JP2008044609A5 - - Google Patents

Description

Solar radiation shield for vehicle window and vehicle window

  The present invention relates to a solar shading for vehicle windows used for sunroofs, panoramic roofs, back windows, rear side windows, and front windows of automobiles, trains, heavy machinery and the like.

Conventionally, as a safety glass for automobiles, a laminated glass is constructed by sandwiching a solar radiation shielding film between two sheet glasses, and the solar energy incident on the laminated glass is cut off to reduce the cooling load and the heat of human heat. The one for the purpose is proposed.
For example, Patent Documents 1 to 3 propose a heat ray shielding plate in which a heat ray reflective film obtained by vapor-depositing a metal or metal oxide on a transparent resin film is bonded to a transparent molded body such as glass, an acrylic plate, or a polycarbonate plate. ing.
However, this heat ray reflective film itself is very expensive and requires a complicated process such as an adhesion process, resulting in high costs. Moreover, since the adhesiveness of a transparent molded object and a reflective film is not good, there exists a fault that peeling of a film arises by a time-dependent change.

  In addition, many heat ray shielding plates have been proposed in which a metal or metal oxide is directly deposited on the surface of the transparent molded body. However, when manufacturing this heat ray shielding plate, there is an apparatus that requires high vacuum and high-precision atmosphere control. Since it is necessary, it has a problem that mass productivity is poor and versatility is poor.

In addition, for example, Patent Documents 4 and 5 disclose organic near infrared absorption represented by phthalocyanine compounds and anthraquinone compounds in thermoplastic transparent resins such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, polyethylene resin, and polystyrene resin. Heat ray shielding plates and films in which agents are kneaded have been proposed.
However, in order to sufficiently shield the heat rays, a large amount of near-infrared absorber must be blended, and if it is blended in a large amount, the problem that the visible light transmission ability is lowered remains. In addition, since organic compounds are used, application to buildings and automobile window materials that are constantly exposed to direct sunlight has difficulty in weather resistance and is not necessarily appropriate.

  In addition, as a laminated glass, in Patent Document 6, a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle size of 0.1 μm or less is interposed between a pair of glass plates. Laminated glass is disclosed.

  In Patent Document 7, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, and Ta are provided between at least two plate glasses. , W, V, Mo metal, oxides, nitrides, sulfides thereof, Sb and F dopes, or laminated glass in which an intermediate layer in which these composites are dispersed is disclosed.

Patent Document 8 discloses an automotive window glass in which fine particles composed of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and a glass component composed of organic silicon or an organic silicon compound are interposed between transparent plate members. Is disclosed.

  Further, in Patent Document 9, an intermediate layer composed of three layers is provided between at least two transparent glass plates, and the intermediate layer of the second layer among the intermediate layers is Sn, Ti, Si, Zn, Zr. , Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, oxide, nitride, sulfide, Sb or F dope, or a composite thereof A laminated glass in which a product is dispersed and an intermediate layer between the first layer and the third layer is used as a resin layer has been proposed.

Further, the present applicant has an intermediate layer having a solar radiation shielding function interposed between two plate 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 vinyl. A solar radiation-shielding laminated glass composed of an intermediate film containing a resin, or the solar radiation-shielding film containing the fine particles formed on the surface of which the intermediate layer is located on the inner side of at least one plate glass; Patent Document 10 proposes a laminated glass for solar radiation shielding composed of an intermediate film containing a vinyl-based resin interposed between a plurality of sheet glasses.
Patent Document 10 discloses that the optical properties of solar shading laminated glass to which hexaboride fine particles alone or 6 boride fine particles and ITO fine particles and / or ATO fine particles are applied have a maximum transmittance in the visible light region. In addition, since it exhibits strong absorption in the near-infrared region and has a minimum transmittance, it has a visible light transmittance of 70% or more and a solar transmittance of 50 compared to the conventional laminated glass described in Patent Documents 4-7. It is disclosed that it is improved to the% level.

These solar-shielding windows are as bright as possible and are intended to improve the solar-shielding properties. However, they are bright in the sunroof, panoramic roof, back window, rear side window, front window, and heavy equipment sunroof. Rather, there is a need for a design that focuses on how to economically block the heat of sunlight.
In order to make a practical laminated glass in such a vehicle window part, a glass having a reduced visible light transmittance and a color tone of dark blue, gray, bronze (red brown), or dark green has been proposed. However, if the above conditions are satisfied, the solar radiation transmittance / visible light transmittance, which is a measure of the solar radiation shielding property, cannot be made smaller than 1, the solar radiation shielding property is inferior, and there is still room for improvement. Had.
JP-A 61-277437 Japanese Patent Laid-Open No. 10-146919 Japanese Patent Laid-Open No. 2001-179887 JP-A-6-256541 JP-A-6-264050 JP-A-8-217500 JP-A-8-259279 Japanese Patent Laid-Open No. 4-160041 Japanese Patent Laid-Open No. 10-297945 JP 2001-89202 A

The present invention has been made paying attention to the problems as described above, and the problem is that dark blue, gray, bronze (red brown), which has a low visible light transmittance and high color tone, are required. An object of the present invention is to provide a solar panel for vehicle windows and a vehicle window, which are dark green and have a low solar radiation transmittance / visible light transmittance, which is a measure of solar radiation shielding properties, less than 1 .

That is, the first invention of the present invention is a vehicle window solar radiation shield containing fine particles having a heat ray shielding function used for a vehicle window, wherein the fine particles having the heat ray shielding function are lanthanum hexaboride, nitriding At least one fine particle selected from titanium and tungsten oxide, antimony-doped tin oxide, tin-doped indium oxide, general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3) 0.0) mixed with at least one fine particle selected from the composite tungsten oxide, and the solar light shielding material has a visible light transmittance in the range of 5% to 40%, The solar radiation shielding body for vehicle windows, characterized in that the solar radiation transmittance and visible light transmittance of the solar radiation shielding body satisfy the following (Equation 1), and further the transmission color of the solar radiation shielding body satisfies the following (Equation 2). .
(Expression 1) Solar transmittance / visible light transmittance <1
(Formula 2) -14 <a ^* <2, -8 <b ^* <2

A second aspect of the present invention is a vehicle window solar radiation shield containing fine particles having a heat ray shielding function used for a vehicle window, wherein the fine particles having the heat ray shielding function are lanthanum hexaboride, titanium nitride, At least one kind of fine particles selected from tungsten oxide, antimony-doped tin oxide, tin-doped indium oxide, general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) ) And at least one kind of fine particles selected from the composite tungsten oxide and iron oxide fine particles are mixed, and the visible light transmittance of the solar radiation shield is in the range of 5% to 40%. The solar radiation shielding for vehicle windows, wherein the solar radiation transmittance and visible light transmittance of the solar radiation shielding body satisfy the following (Equation 3), and further, the transmission color of the solar radiation shielding body satisfies the following (Equation 4): Is the body.
(Expression 3) Solar radiation transmittance / visible light transmittance <1
(Formula 4) -2 <a ^* <14, 2 <b ^* <12

The third invention of the present invention is the vehicle window solar radiation shield according to the first or _second invention, wherein the tungsten oxide is WO ₂ or W ₁₈ O ₄₉ .

In the fourth invention of the present invention, the element M contained in the composite tungsten oxide fine particles is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. The vehicle window solar radiation shield according to the first and second aspects of the invention.

  According to a fifth aspect of the present invention, there is provided the solar radiation shielding body for vehicle windows according to the first to fourth aspects, wherein a diameter of the fine particles having a heat ray shielding function is 300 nm or less.

  According to a sixth aspect of the present invention, in the first to fifth aspects, the fine particles having a heat ray shielding function are surface-treated with at least one selected from a silane compound, a titanium compound, and a zirconia compound. It is a solar radiation shielding body for vehicle windows as described.

  The seventh invention of the present invention further includes at least one selected from zinc oxide fine particles, cerium oxide fine particles, and titanium oxide fine particles, and the solar radiation shielding body for vehicle windows according to the first to sixth inventions, It is.

  According to an eighth aspect of the present invention, there is provided the solar radiation shielding body for vehicle windows according to the first to seventh aspects of the present invention, wherein the fine particles having a heat ray shielding function are contained in a polycarbonate resin molded body.

  According to a ninth aspect of the present invention, there is provided a solar radiation shielding body for a vehicle window, wherein a scratch-resistant hard coat layer is formed on at least one surface of the polycarbonate resin molded body according to the eighth aspect.

  According to a tenth aspect of the present invention, there is provided a solar shading body for a vehicle window obtained by laminating the solar radiation shielding body according to the eighth or ninth aspect of the invention on another resin molded body.

  The eleventh invention of the present invention is characterized in that the fine particles having a heat ray shielding function described in the first to seventh inventions are contained in one kind selected from polyvinyl butyral resin, polyvinyl acetate resin, and polyvinyl alcohol resin. It is a solar radiation shield for vehicle windows.

  A twelfth aspect of the present invention is a laminated structure in which the solar radiation shield according to the eleventh aspect of the present invention is interposed between two laminated plates as an intermediate film, the laminated plate comprising an inorganic plate glass and a polycarbonate resin molded product. A solar radiation shielding body for a vehicle window, wherein the solar radiation shielding body is at least one selected from a body and a polyethylene terephthalate resin molding.

A thirteenth aspect of the present invention is a vehicle window solar radiation shielding body, wherein at least one of the laminated plates according to the twelfth invention is the solar radiation shielding body according to the eighth to tenth inventions.

A fourteenth aspect of the present invention is the first to thirteenth aspect of the invention, wherein the solar radiation shielding body for vehicle windows has a thickness of 2.5 mm to 30 mm and a maximum projected area of 400 to 60000 cm ^2. It is a solar radiation shield for car windows.

  According to a fifteenth aspect of the present invention, there is provided a vehicle window characterized by using the vehicle window solar shading member described in the first to fourteenth aspects.

  According to the solar radiation shielding body for vehicle window and the vehicle window according to the present invention, dark blue, gray, bronze (red brown), and dark green, which have not been obtained in the past, have low visible light transmittance and high color tone requirements. In addition, it is possible to provide a solar radiation shielding body for vehicle windows and a vehicle window that have a solar radiation transmittance / visible light transmittance, which is a measure of solar radiation shielding, smaller than 1, and that is inexpensive to produce. It can be applied to panoramic roofs, back windows, rear side windows, front windows, sunroofs for heavy machinery, etc., and its uses are wide and industrially useful.

Hereinafter, the present invention will be described in detail.
1. Fine particles having a heat ray shielding function 1) At least one kind of fine particles selected from lanthanum hexaboride, titanium nitride, and tungsten oxide The group consisting of lanthanum hexaboride, titanium nitride, and tungsten oxide absorbs from visible light to near infrared rays In particular, it has an optical characteristic of selectively absorbing near infrared rays of 780 nm to 1200 nm. Moreover, the visible light and near-infrared absorptivity with respect to the addition amount per unit area are very strong, and a heat ray shielding function can be effectively provided to a base material by addition of a small amount. However, there is a drawback that the infrared absorption ability of 1200 nm or more is poor and the energy in the long wavelength region contained in sunlight cannot be shielded.

a) Lanthanum hexaboride The surface of the lanthanum hexaboride used in the present invention is preferably not oxidized, but is usually slightly oxidized, and the surface is often used in the fine particle dispersion step. It is inevitable that oxidation occurs. However, even in that case, the effectiveness of developing the heat ray shielding effect remains unchanged.
In addition, lanthanum hexaboride fine particles have a higher heat ray shielding effect as the crystal completeness increases. However, even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, If the basic bond is composed of a bond between each metal and boron, a heat ray shielding effect is exhibited.
Lanthanum hexaboride is a powder colored grey-black, brown-black, green-black, etc., but in a state where the particle size is sufficiently smaller than the visible light wavelength and dispersed in a heat-ray-shielding transparent resin substrate, heat-ray shielding Visible light permeability occurs in the transparent resin substrate. However, the infrared light shielding ability can be kept strong enough. The reason for this is not understood in detail, but the amount of free electrons in these particles is large, and the absorption energy of the indirect interband transition due to free electrons inside and on the surface of the particles is just in the vicinity of visible to near infrared. In addition, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.
The heat ray shielding ability per unit weight of lanthanum hexaboride is very high, and the effect is exhibited with the use amount of 1/40 or less compared with ITO and ATO. Therefore, since the amount of all fine particles used can be greatly reduced, if a large amount of heat ray shielding particles are blended with the heat ray shielding transparent resin base material, the physical properties, particularly impact strength and toughness of the transparent resin as the base material are reduced. There is no problem in terms of strength.
For lanthanum hexaboride have a absorption in the visible light region when increasing the amount of use, it can be freely controlled absorption in the visible light region by controlling the addition amount, brightness adjustment and Application to privacy, etc. You can also.
It is also possible to use other hexaborides instead of lanthanum hexaboride, such as cerium hexaboride (CeB ₆ ), praseodymium hexaboride (PrB ₆ ), neodymium hexaboride (NdB ₆ ), hexaboride gadolinium (GdB _6), 6 terbium boride (TbB _6), hexaboride dysprosium (DYB _6), 6 holmium boride (HoB _6), 6 yttrium boride (YB _6), hexaboride Samarium (SmB ₆ ), europium hexaboride (EuB ₆ ), erbium hexaboride (ErB ₆ ), thulium hexaboride (TmB ₆ ), ytterbium hexaboride (YbB ₆ ), lutetium hexaboride (LuB ₆ ) , lanthanum hexaboride, cerium _{((La, Ce) B 6} ), 6 strontium boride (SrB _6), 6 etc. calcium boride (CaB _6), but its typical And the like to.

b) Titanium Nitride The surface of TiN used in the present invention is preferably not oxidized, but is usually slightly oxidized, and surface oxidation occurs during the fine particle dispersion process. Is inevitable to some extent. However, even in that case, the effectiveness of developing the heat ray shielding effect remains unchanged. Further, these nitride fine particles have a higher heat ray shielding effect as the crystal completeness is higher, but even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, If the basic bond is composed of a bond between titanium and nitrogen, a heat ray shielding effect is exhibited.
TiN is a powder colored brown black, blue black or the like, but when the particle size is sufficiently smaller than the visible light wavelength and dispersed in the polycarbonate resin, visible light permeability is generated in the film. However, the infrared light shielding ability can be kept strong enough. The reason for this is not understood in detail, but the amount of free electrons in these particles is large, and the absorption energy of the indirect interband transition due to free electrons inside and on the surface of the particles is just in the vicinity of visible to near infrared. In addition, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.
It is also possible to use other nitrides instead of TiN, such as zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN), etc. A typical example is fine particles.

c) tungsten oxide used in the tungsten oxide present invention have the general formula WO _2, or it is preferable that the general formula of W ₁₈ O _49. In particular, since light around 1000 nm is largely absorbed, the transmitted color tone often has a blue color tone.

2) Selected from antimony-doped tin oxide, tin-doped indium oxide, and composite tungsten oxide represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) At least one kind of fine particles It has an optical characteristic of selectively absorbing in the middle infrared ray of 1000 nm or more. However, the absorption capacity of infrared rays per unit area is weak, and a large amount of addition is required to impart heat ray shielding properties to the substrate, resulting in a decrease in mechanical properties of the substrate itself and an increase in material costs. There was a problem.

a) Antimony-doped tin oxide and tin-doped indium oxide Antimony-doped tin oxide and tin-doped indium oxide used in the present invention are silanes having an alkoxyl group and an organic functional group in order to suppress the photocatalytic activity peculiar to metal oxides. The surface treatment is preferably performed with at least one surface treatment agent selected from a coupling agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent. As these surface treatment agents, those having an organic functional group having an affinity for the surface of antimony-doped tin oxide and having an affinity for an alkoxyl group forming a bond and a transparent thermoplastic resin are used. Examples of the alkoxyl group include a methoxy group, an ethoxy group, and an isopropoxyl group, but are not particularly limited as long as they can undergo hydrolysis and form a bond with the surface of the antimony-doped tin oxide. Examples of the organic functional group include alkyl groups, vinyl groups, γ- (2-aminoethyl) aminopropyl groups, γ-glycidoxypropyl groups, γ-anilinopropyl groups, γ-mercaptopropyl groups, and γ-methacryloxy groups. However, it is not particularly limited as long as it has an affinity for a transparent thermoplastic resin.

b) Composite tungsten oxide The composite tungsten oxide used in the present invention is represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and Has a hexagonal crystal structure. In the near-infrared region, particularly in the vicinity of 1000 nm, the transmitted color tone is often blue.
Examples of 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 include M Examples thereof include composite tungsten oxide fine particles in which the element contains one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, and Cu.
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. Moreover, about the range of Z, 2.2 <= Z <= 3.0 is preferable. This is because if the value of Z is 2.45 or more, it is possible to completely avoid the appearance of an undesired WO ₂ crystal phase in the infrared shielding material and to improve the chemical stability of the material. Can be obtained. On the other hand, if the value of Z is 2.999 or less, a sufficient amount of free electrons is generated and an efficient infrared shielding material is obtained, but if it is 2.95 or less, the infrared shielding material is more preferable. Further, even when Z ≦ 3.0, there is supply of free electrons due to the addition of the element M described above. However, from the viewpoint of optical properties, 2.2 ≦ Z ≦ 2.99 is more preferable, and 2.45 ≦ Z ≦ 2.99 is more preferable.
Here, typical examples of the composite tungsten oxide material include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. However, if Y and Z are within the above ranges, useful heat ray shielding characteristics can be obtained.

3) Bring iron oxide fine particles a ^* b ^* [color tone (D65-10 degrees)] to the plus side. It has the feature that it can be made into bronze color.
Therefore, the inventor of the present invention mixes the two groups of fine particles of 1) and 2) to compensate for the defects of the materials belonging to the two groups, thereby allowing visible light transmission of the solar radiation shield obtained. The rate is in the range of 5% or more and 40% or less, and the following formula 1 is satisfied. Further, the transmitted color of the solar radiation shielding body can satisfy the formula 2.
(Expression 1) Solar transmittance / visible light transmittance <1
(Formula 2) -14 <a ^* <2, -8 <b ^* <2
Also, by mixing the three groups of fine particles of 1), 2) and 3) above, the disadvantages of the materials belonging to the three groups are compensated for each other. ^* B ^* is brought to the plus side, and the color tone can be adjusted to the bronze color side.
Thereby, it can be used for a panoramic roof, a back window, and a rear side window for automobiles having a relatively low transmittance.

  It is necessary that the visible light transmittance of the solar shading body be 5% or more and 40% or less, and if it is less than 5%, the transmittance as a window is too low and the visibility of the outside world is significantly reduced. If it exceeds 40%, inflow of solar heat including visible light into the room will increase, and it will be insufficient to block solar radiation especially in midsummer, and will increase the cooling load to lower the room temperature. It is because it is not preferable.

In the first aspect of the invention, it is preferable that the transmission color of the solar shield belongs to a range of −14 <a ^* <2 and −8 <b ^* <2 in the range of the visible light transmittance. The green component is too strong when a ^* ≦ −14, the red component is too strong when 2 ≦ a ^* , the bluish color is too strong when b ^* ≦ −8, and the yellow color is too strong when 2 ≦ b ^*. Outside of these ranges, it is not preferable because it deviates from the neutral to dark blue / dark green colors preferred by general users.

In the second aspect of the invention, it is preferable that the transmitted color of the solar shading member belongs to the range of −2 <a ^* <14, 2 <b ^* <12. The green component is strong when a ^* ≦ −2. In addition, the red component is too strong at 14 ≦ a ^* , the blue component is too strong at b ^* ≦ 2, and the yellow component is too strong at 12 ≦ b ^*. This is because it deviates from the bronze tint preferred by the present invention.

  The diameter of the fine particles having a heat ray shielding function is desirably 300 nm or less. If it exceeds 300 nm, light scattering in the visible light region occurs, and the solar radiation shield becomes cloudy, which is not preferable.

  The fine particles having a heat ray shielding function are desirably surface-treated with at least one selected from a silane compound, a titanium compound, a zirconia compound, and an aluminum compound. The weather resistance is improved by coating the surface of the fine particles with the above material. Antimony-doped tin oxide and tin-doped indium oxide have a photocatalytic activity unique to metal oxides, and are preferable from the viewpoint of suppressing the deterioration and preventing deterioration of the polycarbonate resin.

It is desirable that the addition amount per 1 m ² of the heat ray shielding fine particles of the present invention satisfies the following formula 5. In Equation 5, the coefficient applied to each heat ray shielding fine particle is determined by the visible light absorbing ability per unit weight of each heat ray shielding fine particle. For example, when the visible light transmittance of a polycarbonate sheet having a heat ray shielding function is set to the same value, it is experimentally found that the necessary addition amount per 1 m ^{2 of} titanium oxide is 1/160 of tin- doped indium oxide. Yes.
Addition amount of titanium nitride (g / m ² ) × 160 + 6 Addition amount of lanthanum boride (g / m ² ) × 40 + tungsten oxide (g / m ² ) × 40 + composite tungsten oxide (g / m ² ) × 4 + antimony When the value of doped tin oxide (g / m ² ) + tin doped indium oxide (g / m ² ) is 5 or less, the visible light absorption ability is insufficient, and the panorama roof and back for automobiles for the purpose of privacy protection Inappropriate as a window or rear side window. Further, sufficient heat ray shielding ability cannot be obtained. On the other hand, when it is 50 or more, sufficient heat ray shielding ability can be obtained, but absorption of visible light becomes so strong that light from outside the vehicle can hardly be taken in.

(Formula 5)
5 (g / m ² ) <addition amount of titanium nitride (g / m ² ) × 160 + 6 addition amount of lanthanum boride (g / m ² ) × 40 + tungsten oxide (g / m ² ) × 40 + composite tungsten oxide ( g / m ² ) × 4 + antimony-doped tin oxide (g / m ² ) + tin-doped indium oxide (g / m ² ) <50 (g / m ² )

Moreover, it is desirable that the total amount of the fine particles added per 1 m ² is 20 g / m ² or less. When total addition amount per 1 m ² is more than 20 g / m ^2, but also on the thickness of the polycarbonate sheet, may impair the mechanical properties of the polycarbonate resin itself (impact resistance, surface hardness, flexural strength) of. Moreover, material cost will also become high.

The optical characteristic of the solar radiation shielding body for vehicle windows containing fine particles having a heat ray shielding function of the present invention is solar radiation transmittance / visible light transmittance <1. That is, it is desirable that the value of the solar radiation transmittance is smaller than the visible light transmittance. When the solar radiation transmittance / visible light transmittance> 1, the interior of the vehicle becomes too dark in order to sufficiently reduce the solar energy that enters the vehicle from the outside. If a large amount of colored pigment or coloring dye is added to the polycarbonate sheet to reduce the visible light transmittance extremely, the solar transmittance is lowered. However, it has been difficult to satisfy the solar transmittance / visible light transmittance <1. It was.

  In addition, the heat ray shielding fine particles used in the present invention are preferably as small as possible, and considering the infrared absorption ability and the transparency of the resin used, the average particle size is 300 nm or less, more preferably 100 nm or less. is there. Here, the average particle diameter is an average value of the particle diameters of the heat ray shielding fine particles observed with a transmission electron microscope.

In addition to the fine particles having a heat ray shielding function of the present invention, it is possible to further contain at least one selected from zinc oxide fine particles, cerium oxide fine particles, and titanium oxide fine particles as an ultraviolet absorber. Considering the transparency of the resin used, the average particle size is preferably 300 nm or less, more preferably 100 nm or less. Here, the average particle diameter is an average value of the particle diameters of the heat ray shielding fine particles observed with a transmission electron microscope.
Further, in order to suppress the photocatalytic activity of the ultraviolet absorber and improve the dispersibility in the transparent thermoplastic resin, the silane coupling agent is selected from a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent. The surface treatment is preferably performed with at least one surface treatment agent. As these surface treatment agents, those having an organic functional group having affinity for the surface of the ultraviolet absorber and having an alkoxyl group for forming a bond and an affinity for the transparent thermoplastic resin are used. Examples of the alkoxyl group include a methoxy group, an ethoxy group, and an isopropoxyl group, but are not particularly limited as long as they can undergo hydrolysis and form a bond with the surface of the inorganic ultraviolet absorber. Examples of the organic functional group include alkyl groups, vinyl groups, γ- (2-aminoethyl) aminopropyl groups, γ-glycidoxypropyl groups, γ-anilinopropyl groups, γ-mercaptopropyl groups, and γ-methacryloxy groups. However, it is not necessarily limited to these as long as it has an affinity for the transparent thermoplastic resin.
Further, for the purpose of improving the dispersibility of the inorganic ultraviolet absorber in the thermoplastic resin, an organic polymer dispersant can be used in combination with the above coupling agent.

2. Structure of solar shading for vehicle windows As one form of the structure of solar shading for vehicle windows of the present invention, solar radiation for vehicle windows in which the fine particles having a heat ray shielding function of the first and second inventions are contained in a polycarbonate resin molded body. There is a shield.

  A scratch-resistant hard coat layer may be formed on at least one sheet surface of the polycarbonate sheet containing fine particles having a heat ray shielding function. For example, a silicate-based or acrylic-based scratch-resistant hard coat layer can be formed on the sheet. By forming the hard coat layer, it is possible to improve the scratch resistance of the molded body, and the polycarbonate sheet containing fine particles having the heat ray shielding function can be used for an automobile panoramic roof, a back window, and a rear side window. I can do it.

  The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate. As the aromatic polycarbonate, one or more divalent phenolic compounds represented by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane And a polymer obtained by a known method such as interfacial polymerization, melt polymerization, or solid phase polymerization from a carbonate precursor typified by phosgene or diphenyl carbonate.

  Next, the method for dispersing the heat ray shielding fine particles in the polycarbonate resin can be arbitrarily selected as long as the fine particles are uniformly dispersed in the resin. As an example, using a method such as a bead mill, ball mill, sand mill, ultrasonic dispersion, etc., a heat ray shielding fine particle dispersion in which the fine particles are dispersed in an arbitrary solvent is prepared, and the dispersion and polycarbonate resin granules or pellets, If necessary, add other additives such as ribbon blender, tumbler, nauter mixer, Henschel mixer, super mixer, planetary mixer, etc., and Banbury mixer, kneader, roll, kneader ruder, single screw extruder, twin screw A mixture in which fine particles are uniformly dispersed in a polycarbonate resin can be prepared by using a kneading machine such as an extruder and uniformly melting and mixing the solvent while removing the solvent. Further, the solvent of the heat ray shielding fine particle dispersion is removed by a known method, and the obtained powder and the granular material or pellet of the polycarbonate resin and, if necessary, other additives are melt-mixed uniformly. It is also possible to prepare a mixture in which fine particles are uniformly dispersed in a polycarbonate resin. In addition, it is also possible to add a heat ray shielding fine particle powder and a heat-resistant dispersant that are not dispersed directly to the polycarbonate resin and uniformly melt and mix them. The heat ray shielding fine particles are uniformly dispersed in the polycarbonate resin. The method is not limited to these methods.

  Examples of a method for forming a polycarbonate sheet containing fine particles having a heat ray shielding function include arbitrary methods such as injection molding, extrusion molding, compression molding, and rotational molding. In particular, a method of obtaining a molded product by injection molding is preferably employed. The injection molded product is preferably used for a panoramic roof, a back window, and a rear side window of an automobile.

  The polycarbonate sheet containing fine particles having the heat ray shielding function can be used only for automobile panorama roof, back window, rear side window, and other transparent molding such as inorganic glass, resin glass, resin film, etc. It can also be used as a structural material as a heat-shielding transparent laminate that is laminated on the body by any method and integrated. For example, a transparent laminated body having a heat ray shielding function and a heat ray shielding function having a heat ray shielding function and a scattering prevention function by integrating and integrating a polycarbonate sheet containing fine particles having a heat ray shielding function previously formed into a sheet shape on an inorganic glass by a heat lamination method Can be obtained.

  In addition, heat ray shielding ability is achieved by laminating and integrating with other transparent molded bodies simultaneously with the molding of polycarbonate sheets containing fine particles with heat ray shielding function by heat lamination method, coextrusion method, press molding method, injection molding method, etc. It is also possible to obtain a transparent laminate having The transparent laminate having the above-mentioned heat ray shielding ability can be used as a more useful automobile window material by complementing each other's drawbacks while effectively exhibiting the advantages of the mutual molded bodies.

  Furthermore, the polycarbonate sheet containing fine particles having a heat ray shielding function according to the present invention can be blended with general additives. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, and other dyes and pigments generally used for coloring thermoplastic resins in order to give any color tone as necessary. , Hindered phenol and phosphorus stabilizers, release agents, hydroxybenzophenone, salicylic acid, HALS, triazole and triazine UV absorbers, coupling agents, surfactants, antistatic agents, etc. Can be used as additives.

Moreover, as one form of the structure of the solar radiation shielding body for vehicle windows of the present invention, the fine particles having a heat ray shielding function according to the first and second inventions are selected from polyvinyl butyral resin, polyvinyl acetate resin, and polyvinyl alcohol resin. It is also preferable to be used as an intermediate film.
A laminated structure in which the vehicle window solar radiation shield is interposed as an intermediate film between two laminated plates, wherein the laminated plate is selected from at least an inorganic plate glass, a polycarbonate resin molded body, and a polyethylene terephthalate resin molded body. A kind of solar shading for vehicle windows is obtained.
At least one of the laminated plates may be a vehicle window solar radiation shield that is a vehicle window solar radiation shield in which the fine particles having a heat ray shielding function are contained in a polycarbonate resin molded body.

Shape before Symbol vehicle windows for solar radiation-shielding body, it is preferable that the thickness 2.5Mm～30mm, and the maximum projected area is 400~60000cm ^2.
The maximum size that can be manufactured by the current injection molding technology is 60000 cm ² , and if it is larger, manufacturing becomes difficult. However, there may be cases where it is possible to manufacture a larger solar shading body due to innovations in future manufacturing apparatuses and injection molding methods. Moreover, when it becomes 400 cm < ² > or less, it is too small for a vehicle window and is unsuitable. Regarding the thickness, the maximum thickness that can be manufactured by the current injection molding technology is 30 mm, and if it becomes thicker, manufacturing becomes difficult. On the other hand, if the thickness is less than 2.5 mm, the vehicle itself may not have sufficient rigidity when mounted on the vehicle.

  The solar window solar shading body of the present invention having the above-described many forms requires a design that emphasizes how to economically block the heat of solar rays rather than vehicle windows, particularly brightness. It can be applied to sunroofs, panoramic roofs, back windows, rear side windows, front windows and heavy equipment sunroofs.

[Example]
Examples of the present invention will be specifically described below together with comparative examples. However, the present invention is not limited to the following examples. In each example, the dispersed particle size of various fine particles was measured by ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering.
Visible light transmittance and solar light transmittance of the solar radiation shield for vehicle windows were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd.

A TiN fine particle dispersion (liquid A) was prepared by weighing 10% by weight of TiN fine particles, 10% by weight of a dispersant, and 80% by weight of toluene, and pulverizing and dispersing for 6 hours in a paint shaker containing 0.3 mmφZrO ₂ beads. . Here, when the dispersed particle diameter of the TiN oxide fine particles in the TiN fine particle dispersion (liquid A) was measured, it was 80 nm.
Further, a dispersant is added to the liquid A, the weight ratio of the dispersant to the TiN fine particles is adjusted to be dispersant / TiN fine particles = 3, toluene is removed using a spray dryer, and the TiN fine particle dispersed powder is obtained. Obtained (hereinafter abbreviated as A powder).

Next, the obtained powder A was added so that the TiN concentration Porika Bonnet over preparative resin pellet is a thermoplastic resin of 2.0 wt% was uniformly mixed in a blender, melt in a twin-screw extruder The kneaded and extruded strand was cut into pellets to obtain a TiN fine particle-containing polycarbonate masterbatch (hereinafter abbreviated as masterbatch A).

ATO fine particle dispersion (liquid B) was prepared by weighing 10% by weight of ATO fine particles, 10% by weight of dispersing agent and 80% by weight of toluene, and pulverizing and dispersing for 6 hours with a paint shaker containing 0.3 mmφZrO ₂ beads. . Here, when the dispersed particle diameter of the ATO oxide fine particles in the ATO fine particle dispersion (liquid B) was measured, it was 63 nm.
Further, a dispersant is added to the above-mentioned liquid B, and the weight ratio of the dispersant to the ATO fine particles is adjusted to be dispersant / ATO fine particles = 3. Toluene is removed using a spray dryer, and the ATO fine particle dispersed powder is obtained. Obtained (hereinafter abbreviated as B powder).

Next, the obtained powders B were added to ATO concentration Porika Bonnet over preparative resin pellet is a thermoplastic resin is 2.0 wt% was uniformly mixed in a blender, melt in a twin-screw extruder The kneaded and extruded strand was cut into pellets to obtain an ATO fine particle-containing polycarbonate masterbatch (hereinafter abbreviated as masterbatch B).

Then diluted master batch A and the master batch B in Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, the TiN amount 0. 06g ^/ m 2, ATO additive amount was adjusted to be 9.6 g / ^{m 2,} to obtain a solar radiation-shielding body 1 according to the first embodiment TiN fine particles and the ATO fine particles were uniformly dispersed in the entire resin. Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 75 nm.
As shown in Table 1, the solar radiation transmittance (ST) when the visible light transmittance (VLT) was 31.7% was 19.1%.

The solar radiation shielding body 2 according to Example 2 was obtained in the same manner as in Example 1 except that the addition amount of TiN was 0.09 g / m ² and that the ATO addition amount was 14.4 g / m ² . . The dispersion particle size of the solar radiation shielding particles was 78 nm.
As shown in Table 1, the solar radiation transmittance was 15.9% when the visible light transmittance was 22.1%.

The solar shading body 3 according to Example 3 was obtained in the same manner as in Example 1 except that the addition amount was 0.11 g / m ² and the ATO addition amount was 1.92 g / m ² . . Moreover, the dispersion particle diameter of the fine particles of the sunscreen was 73 nm.
As shown in Table 1, the solar radiation transmittance was 25.2% when the visible light transmittance was 31.9%.

A ZnO fine particle dispersion was prepared by weighing 10% by weight of ZnO fine particles, 10% by weight of a dispersant and 80% by weight of toluene, and pulverizing and dispersing for 3 hours in a paint shaker containing 0.3 mmφZrO ₂ beads. Further, a dispersant is added to the ZnO fine particle dispersion, and the weight ratio of the dispersant to the ZnO fine particles is adjusted to be dispersant / ZnO fine particles = 3. Toluene is removed using a spray dryer, A dust was obtained.

Then, the resulting ZnO fine particle dispersion powder was added as concentration in Porika Bonnet over preparative resin pellet is a thermoplastic resin is 2.0 wt%, followed by uniformly mixing with a blender, a twin The extruded strand was melt-kneaded with a machine and cut into pellets to obtain a polycarbonate masterbatch containing ZnO fine particles.

Next, the solar radiation shielding body 4 which concerns on Example 4 was obtained by the method similar to Example 3 except having added the said ZnO fine particle containing polycarbonate masterbatch 10 wt% instead of the masterbatch A. Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 70 nm.
As shown in Table 1, the solar radiation transmittance was 24.2% when the visible light transmittance was 30.0%.

WO ₂ fine particles 10% by weight, dispersing agent 10% by weight, were weighed 80 weight% toluene, WO ₂ fine particle dispersion by 6 hours pulverized and dispersed in a paint shaker containing the 0.3MmfaiZrO ₂ beads (C solution) Prepared. Here, the measured dispersed particle size of the WO ₂ fine particles in the WO ₂ fine particle dispersion (C solution) in was 55 nm.

Furthermore, adding a dispersing agent to the solution C, the weight ratio of the dispersant and WO ₂ fine particles was adjusted to be dispersants / WO ₂ fine particles = 3, using a spray dryer to remove toluene, WO ₂ fine particles Dispersed powder was obtained (hereinafter abbreviated as C powder).

Next, the obtained powder C, was added to the Porika Bonnet over preparative resin pellets of a thermoplastic resin WO ₂ concentration of 2.0 wt% was uniformly mixed in a blender, a twin-screw extruder The extruded strand was cut into pellets to obtain a polycarbonate master batch containing WO ₂ fine particles (hereinafter abbreviated as “master batch C”).

Then, the master batch B and the master batch C was diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, WO ₂ addition amount 0 .44g ^/ m 2, ATO additive amount was adjusted to be 1.93 g / ^{m 2,} to obtain a solar radiation-shielding body 5 according to example 5 of WO ₂ fine particles and the ATO were uniformly dispersed in the entire resin. The dispersion particle diameter of the solar radiation shielding particles was 80 nm.
As shown in Table 1, the solar radiation transmittance was 28.7% when the visible light transmittance was 30.5%.

An ITO fine particle dispersion (liquid D) was prepared by weighing 10% by weight of ITO fine particles, 10% by weight of a dispersant, and 80% by weight of toluene, and pulverizing and dispersing for 6 hours with a paint shaker containing 0.3 mmφZrO ₂ beads. . Here, when the dispersed particle diameter of the ITO fine particles in the ITO fine particle dispersion (D liquid) was measured, it was 75 nm.

  Furthermore, a dispersant is added to the liquid D, and the weight ratio of the dispersant to the ITO fine particles is adjusted to be dispersant / ITO fine particles = 3. Toluene is removed using a spray dryer, and the ITO fine particle dispersed powder is obtained. Obtained (hereinafter abbreviated as D powder).

Next, the obtained powder D was added so that the ITO concentration to Porika Bonnet over preparative resin pellet is a thermoplastic resin of 2.0 wt% was uniformly mixed in a blender, melt in a twin-screw extruder The kneaded and extruded strand was cut into pellets to obtain an ITO fine particle-containing polycarbonate masterbatch (hereinafter abbreviated as masterbatch D).

Then, the master batch C and the master batch D were diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, WO ₂ addition amount 0 .44g ^/ m 2, ITO addition amount was adjusted to be 1.95 g / ^{m 2,} to obtain a solar radiation-shielding body 6 according to example 6 of WO ₂ fine particles and the ITO were uniformly dispersed in the entire resin. The dispersion particle diameter of the solar radiation shielding particles was 77 nm.
As shown in Table 1, the solar radiation transmittance was 23.1% when the visible light transmittance was 30.9%.

LaB ₆ fine particles 10% by weight, dispersing agent 10% by weight, were weighed 80 weight% toluene, LaB ₆ fine particle dispersion by 6 hours pulverized and dispersed in a paint shaker containing the 0.3MmfaiZrO ₂ beads (E solution) Prepared. Here, the measured dispersed particle size of the LaB ₆ fine particles in the LaB ₆ fine particle dispersion in (E solution) was 68 nm.
Furthermore, adding a dispersing agent to the solution E, the weight ratio of the dispersant and the LaB ₆ fine particles are adjusted so that the dispersant / LaB ₆ fine particles = 3, using a spray dryer to remove toluene, ITO fine particles fraction Dust was obtained (hereinafter abbreviated as E powder).

Next, the obtained E powder was added so that the LaB ₆ concentration Porika Bonnet over preparative resin pellet is a thermoplastic resin of 2.0% by weight, followed by uniformly mixing with a blender, a twin screw extruder The melt-kneaded and extruded strands were cut into pellets to obtain LaB ₆ fine particle-containing polycarbonate masterbatch (hereinafter abbreviated as “masterbatch E”).

Then, the master batch A and the master batch B and the master batch E were diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, LaB ₆ Adjustment was made so that the addition amount was 0.06 g / m ² , the TiN addition amount was 0.06 g / m ² , and the ATO addition amount was 1.94 g / m ² , and LaB ₆ fine particles, TiN fine particles, and ATO fine particles were resin. The solar shading body 7 according to Example 7 that was uniformly dispersed throughout was obtained. Moreover, the dispersion particle diameter of the fine particles of the solar shield was 85 nm.
As shown in Table 1, the solar radiation transmittance was 27.4% when the visible light transmittance was 37.8%.

W ₁₈ O ₄₉ fine particles 10% by weight, dispersing agent 10% by weight, were weighed 80 weight% toluene, _W 18 _{O 49} fine particle dispersion by 6 hours pulverized and dispersed in a paint shaker containing the 0.3MmfaiZrO ₂ Beads (F solution) was prepared. _Here, the measured dispersed particle size of the _W 18 _{O 49} fine particles in the _W 18 _{O 49} fine particle dispersion (F solution) in was 69 nm.

Furthermore, by adding a dispersant to said solution F, the weight ratio of the dispersant and W ₁₈ O ₄₉ fine particles are adjusted so that the dispersant / W ₁₈ O ₄₉ fine particles = 3, the toluene was removed using a spray dryer W ₁₈ O ₄₉ fine particle dispersed powder was obtained (hereinafter abbreviated as F powder).

Then added resulting F powder such that W ₁₈ O ₄₉ concentration Porika Bonnet over preparative resin pellet is a thermoplastic resin of 2.0% by weight, followed by uniformly mixing with a blender, a twin The melt was kneaded with a machine and the extruded strand was cut into pellets to obtain a polycarbonate master batch containing W ₁₈ O ₄₉ fine particles (hereinafter abbreviated as “master batch F”).

Then, the master batch B and the master batch F were diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, W ₁₈ O ₄₉ addition amount Was adjusted to 0.43 g / m ² and the ATO addition amount was 2.01 g / m ^2, and the solar radiation shielding body 8 according to Example 8 in which W ₁₈ O ₄₉ fine particles and ATO were uniformly dispersed throughout the resin was obtained. Obtained. Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 61 nm.
As shown in Table 1, the solar radiation transmittance was 28.1% when the visible light transmittance was 31.8%.

C s _0.33 WO ₃ fine particles 10% by weight, dispersing agent 10% by weight, were weighed 80 weight% toluene, C _{s 0} by 6 hours pulverized and dispersed in a paint shaker containing the 0.3MmfaiZrO _{2 beads. 33} WO ₃ fine particle dispersion (liquid G) was prepared. Here, the measured dispersed particle size of the C _{s 0.33} WO ₃ fine particles in the _{C s 0.33} WO ₃ fine particle dispersion (G liquid) in was 77 nm.

Furthermore, adding a dispersing agent to the solution G, the weight ratio of the dispersant and C _{s 0.33} WO ₃ fine particles was adjusted to be dispersants / _{C s 0.33} WO ₃ fine particles = 3, a spray drier Then, toluene was removed to obtain C s _0.33 WO ₃ fine particle dispersed powder (hereinafter abbreviated as G powder).

Then added to C s _0.33 WO ₃ concentration G powder Porika Bonnet over preparative resin pellet is a thermoplastic resin obtained is 2.0% by weight, followed by uniformly mixing with a blender, The melt was kneaded with a twin screw extruder, and the extruded strand was cut into pellets to obtain a polycarbonate master batch containing C s _0.33 WO ₃ fine particles (hereinafter abbreviated as “master batch G”).

Then diluted master batch A and the master batch G in Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, the TiN amount 0. _{^{06g / m 2, C s 0.33}} WO 3 amount was adjusted to be 2.4 g / ^{m 2,} in example 9, TiN fine particles and the C _{s 0.33} WO ₃ were uniformly dispersed in the entire resin The solar radiation shielding body 9 which concerns was obtained. The dispersion particle diameter of the solar radiation shielding particles was 79 nm.
As shown in Table 1, the solar radiation transmittance was 15.7% when the visible light transmittance was 31.7%.

The solar radiation according to Example 10 was performed in the same manner as in Example 9 , except that the addition amount of TiN was 0.15 g / m ² and that of C s _0.33 WO ₃ was adjusted to 6.0 g / m ^2. A shield 10 was obtained. The dispersion particle diameter of the solar radiation shielding particles was 66 nm.
As shown in Table 1, the solar radiation transmittance was 7.1% when the visible light transmittance was 10.1%.

Fe ₂ O ₃ fine particles 10% by weight, dispersing agent 10% by weight, were weighed 80 weight% toluene, _Fe 2 _{O 3} fine particle dispersion by 6 hours pulverized and dispersed in a paint shaker containing the 0.3MmfaiZrO ₂ Beads (Liquid H) was prepared. Here, the measured dispersed particle size of the _Fe 2 _{O 3} fine particles in the _Fe 2 _{O 3} fine particle dispersion (H solution) in was 50nm.
Furthermore, adding a dispersing agent to the H solution, the weight ratio of the dispersant and Fe ₂ O ₃ fine particles was adjusted to be dispersants / Fe ₂ O ₃ fine particles = 3, the toluene was removed using a spray dryer , Fe ₂ O ₃ fine particle dispersed powder was obtained (hereinafter abbreviated as H powder).

Then added and the resulting H powder as the Porika Bonnet over preparative resin pellets of a thermoplastic resin is Fe ₂ O ₃ concentration of 2.0 wt% were uniformly mixed in a blender, twin The melt was kneaded with a machine, and the extruded strand was cut into pellets to obtain a Fe ₂ O ₃ fine particle-containing polycarbonate master batch (hereinafter abbreviated as “master batch H”).

Then, the master batch A and the master batch G masterbatch H was diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, TiN added The amount was adjusted to 0.06 g / m ² , C s _0.33 WO ₃ added amount to 2.4 g / m ² , and Fe ₂ O ₃ added amount to 0.6 g / m ^2. A solar shading body 11 according to Example 11 in which s _0.33 WO ₃ and Fe ₂ O ₃ fine particles were uniformly dispersed throughout the resin was obtained. The dispersion particle diameter of the Fe ₂ O ₃ fine particles of the solar radiation shielding body was 81 nm.
As shown in Table 1, the solar radiation transmittance was 25.0% when the visible light transmittance was 26.6%.

3% by weight of TiN fine particles and 97% by weight of isopropyl alcohol are weighed, pulverized and dispersed for 6 hours with a paint shaker containing 0.3 mmφZrO ₂ beads, added with methyltrimethoxysilane, and stirred with a mechanical stirrer for 1 hour. After mixing, isopropyl alcohol was removed using a spray dryer, and TiN fine particles subjected to surface treatment with a silane compound were obtained.
3% by weight of ATO fine particles and 97% by weight of isopropyl alcohol were weighed, pulverized and dispersed for 6 hours with a paint shaker containing 0.3 mmφZrO ₂ beads, methyltrimethoxysilane was added, and the mixture was stirred with a mechanical stirrer for 1 hour. After mixing, isopropyl alcohol was removed using a spray dryer, and ATO fine particles subjected to surface treatment with a silane compound were obtained.

A solar radiation shield 12 according to Example 12 was obtained in the same manner as in Example 1 except that TiN fine particles surface-treated with a silane compound and ATO fine particles surface-treated with a silane compound were used.
Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 83 nm.
As shown in Table 1, the solar radiation transmittance was 19.2% when the visible light transmittance was 31.5%.

50% by weight of Aronix M-400 manufactured by Toagosei Co., Ltd., 5% by weight of Irgacure 651 manufactured by Ciba Specialty, and 45% by weight of toluene were mixed to prepare a scratch-resistant hard coat solution. The scratch-resistant hard coat solution was applied to the surface of the solar radiation shield 1 produced in the same manner as in Example 1 using a bar coater # 20, dried at 70 ° C. for 1 minute, and then 140 mW with a high-pressure mercury lamp. / cm ² of irradiation with UV light to form a scratch resistance hard coating layer to obtain a solar radiation-shielding body 13.
As shown in Table 1, the solar radiation transmittance was 18.9% when the visible light transmittance was 31.2%.
When the pencil hardness was measured, it was confirmed that the pencil hardness of the solar shading body 13 was improved to 2H by forming the scratch-resistant hard coat layer. The solar shield 1 produced in Example 1 had a pencil hardness F.

  By forming a scratch-resistant hard coat layer on the surface of the solar shield, it is possible to improve the scratch resistance of the solar shield, and the solar shield can be used for vehicles, automobile windows, etc. I can do it.

TiN fine particle dispersion (liquid A) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, and toluene is removed with a stirring type vacuum dryer. TiN plasticizer dispersion (A plasticizer liquid) ) Was produced.
Similarly, ATO fine particle dispersion (liquid B) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, and toluene is removed with a stirring type vacuum dryer, and ATO plasticizer dispersion (B plastic) Preparation).

A plasticizer liquid and B plasticizer liquid are added to polyvinyl butyral resin, triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the mixture is kneaded with a roll to form a 0.5 mm thick sheet. formed was adjusted so that the amount is 0.06 g ^/ m 2, ATO added TiN additive amount is 9.60 g / ^{m 2,} an intermediate layer of TiN fine particles and the ATO were uniformly dispersed in the entire resin (intermediate film a) Got.

Furthermore, this interlayer film A was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar shading body 14. The dispersion particle diameter of the fine particles of the solar radiation shielding body was 69 nm.
Moreover, as shown in Table 1, the solar radiation transmittance was 19.0% when the visible light transmittance was 30.8%.

The solar radiation shielding body 15 according to Example 15 was obtained in the same manner as in Example 13 except that the TiN addition amount was 0.09 g / m ² and the ATO addition amount was adjusted to 14.4 g / m ² . . The dispersion particle size of the solar radiation shielding particles was 78 nm.
As shown in Table 1, the solar radiation transmittance was 15.7% when the visible light transmittance was 21.1%.

The solar radiation shielding body 16 according to Example 16 was obtained in the same manner as in Example 1 except that the addition amount was 0.11 g / m ² and the ATO addition amount was 1.92 g / m ² . . Moreover, the dispersion particle diameter of the fine particles of the sunscreen was 73 nm.
As shown in Table 1, the solar radiation transmittance was 25.0% when the visible light transmittance was 30.9%.

WO ₂ fine particle dispersion (C solution), plasticizer triethylene glycol - weighed 50 wt% di-2-ethyl butyrate, the toluene was removed at a stirring type vacuum drier, WO ₂ plasticizer dispersion liquid (C plasticity Preparation).
A plasticizer liquid and C plasticizer liquid are added to polyvinyl butyral resin, triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the mixture is kneaded with a roll to form a 0.5 mm thick sheet. formed, adjusted to WO ₂ addition amount 0.44 g ^/ m 2, ATO additive amount is 1.93 g / ^{m 2,} an intermediate layer (intermediate film WO ₂ fine particles and the ATO were uniformly dispersed in the entire resin D) was obtained.

Furthermore, this interlayer film D was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar radiation shielding body 17. The dispersion particle diameter of the solar radiation shielding particles was 77 nm.
As shown in Table 1, the solar radiation transmittance was 28.4% when the visible light transmittance was 30.5%.

ITO fine particle dispersion (liquid D) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, toluene is removed with a stirring type vacuum dryer, ITO plasticizer dispersion (D plasticizer liquid) ) Was produced.

C plasticizer liquid and D plasticizer liquid are added to polyvinyl butyral resin, triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the mixture is kneaded with a roll to form a 0.5 mm thick sheet. formed, WO ₂ addition amount is 0.44 g ^/ m 2, ITO addition amount was adjusted to be 1.95 g / ^{m 2,} an intermediate layer (intermediate film WO ₂ fine particles and the ITO were uniformly dispersed in the entire resin E) was obtained.

Furthermore, this intermediate film E was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressed in accordance with a normal laminated glass manufacturing method, whereby a solar shading body 18 was obtained. Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 81 nm.
As shown in Table 1, the solar radiation transmittance was 22.4% when the visible light transmittance was 30.1%.

A LaB ₆ fine particle dispersion (E liquid) and a plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, and toluene is removed with a stirring type vacuum dryer, and a LaB ₆ plasticizer dispersion (E plastic Preparation).

Add A liquid plasticizer, B plasticizer liquid and E plasticizer liquid to polyvinyl butyral resin, add triethylene glycol-di-2-ethylbutyrate as plasticizer, knead this mixture with a roll, 0.5 mm the thickness of the formed into a sheet, was adjusted to LaB ₆ addition amount is 0.06 g ^/ m 2, TiN addition amount is 0.06 g ^/ m 2, ATO addition amount 1.94 g / ^{m 2,} and, LaB An intermediate film (intermediate film F) in which ₆ fine particles, TiN fine particles, and ATO were uniformly dispersed throughout the resin was obtained.

Furthermore, this interlayer film F was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar radiation shield 19. The dispersion particle diameter of the solar radiation shielding particles was 79 nm.
As shown in Table 1, the solar radiation transmittance was 27.3% when the visible light transmittance was 37.5%.

W ₁₈ O ₄₉ fine particle dispersion (liquid F) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, toluene is removed with a stirring type vacuum dryer, and W ₁₈ O ₄₉ plasticizer is dispersed. A liquid (F plasticizer liquid) was prepared.
B liquid plasticizer and F plasticizer liquid are added to polyvinyl butyral resin, triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the mixture is kneaded with a roll to form a 0.5 mm thick sheet. Formed and adjusted so that W ₁₈ O ₄₉ addition amount is 0.43 g / m ² and ATO addition amount is 2.01 g / m ² , and W ₁₈ O ₄₉ fine particles and ATO fine particles are uniformly dispersed throughout the resin. An intermediate film (intermediate film G) was obtained.
Further, this interlayer film G was sandwiched between two float glass sheets having a thickness of 2 mm, and heated and pressed in accordance with a normal laminated glass manufacturing method, so that a solar shading body 20 was obtained. The dispersion particle diameter of the solar radiation shielding particles was 79 nm.
As shown in Table 1, the solar radiation transmittance was 29.1% when the visible light transmittance was 31.4%.

Cs _0.33 WO ₃ fine particle dispersion (liquid G) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, toluene is removed with a stirring type vacuum dryer, and Cs _0.33 WO _Three plasticizer dispersion liquid (G plasticizer liquid) was produced.

Add the A liquid plasticizer and G plasticizer liquid to the polyvinyl butyral resin, add triethylene glycol-di-2-ethylbutyrate as the plasticizer, knead this mixture with a roll, and form a 0.5 mm thick sheet. The TiN fine particles and the Cs _0.33 WO ₃ fine particles are added to the entire resin by adjusting the TiN added amount to 0.06 g / m ² and the Cs _0.33 WO ₃ added amount to 2.4 g / m ² . An intermediate film (intermediate film H) uniformly dispersed was obtained.

Further, this interlayer film H was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressure-bonded in accordance with a normal laminated glass manufacturing method to obtain a solar shading body 21. Moreover, the dispersion particle diameter of the fine particles of the solar radiation shielding body was 75 nm.
As shown in Table 1, the solar radiation transmittance was 15.6% when the visible light transmittance was 31.3%.

Solar radiation shielding according to Example 22 in the same manner as in Example 20, except that the amount of TiN added was adjusted to 0.15 g / m ² and the amount of Cs _0.33 WO ₃ added was adjusted to 6.00 g / m ^2. Body 22 was obtained. The dispersion particle size of the solar radiation shielding particles was 72 nm.
As shown in Table 1, the solar radiation transmittance was 7.0% when the visible light transmittance was 10.1%.

Fe ₂ O ₃ fine particle dispersion (liquid H) and plasticizer triethylene glycol-di-2-ethylbutyrate 50% by weight are weighed, toluene is removed with a stirring type vacuum dryer, and Fe ₂ O ₃ plasticizer is dispersed. A liquid (H plasticizer liquid) was prepared.

A liquid plasticizer, G plasticizer liquid and H plasticizer liquid are added to polyvinyl butyral resin, triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and this mixture is kneaded with a roll, 0.5 mm Formed into a thick sheet, TiN addition amount is 0.06 g / m ² , Cs _0.33 WO ₃ addition amount is 2.4 g / m ² , Fe ₂ O ₃ addition amount is 0.6 g / m ² , Thus, an intermediate film (intermediate film J) in which TiN fine particles, Cs _0.33 WO ₃ fine particles, and Fe ₂ O ₃ were uniformly dispersed throughout the resin was obtained.

Further, this interlayer film J was sandwiched between two float glass sheets having a thickness of 2 mm, and was heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar radiation shield 23. The dispersion particle diameter of the solar radiation shielding particles was 67 nm.
As shown in Table 1, the solar radiation transmittance was 24.8% when the visible light transmittance was 26.5%.

The interlayer film H was sandwiched between a float glass having a thickness of 2 mm and the solar radiation shield 6 and heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar radiation shield 24.
As shown in Table 1, the solar radiation transmittance was 11.6% when the visible light transmittance was 17.9%.

The intermediate film H was sandwiched between a float glass having a thickness of 2 mm and a polyethylene terephthalate film having a thickness of 0.5 mm, and was heated and pressure-bonded according to a normal laminated glass manufacturing method to obtain a solar radiation shield 25.
As shown in Table 1, the solar radiation transmittance was 16.2% when the visible light transmittance was 31.9%.

[Comparative Example 1]
Masterbatch B and a blue coloring dye (anthraquinone-based blue dye (trade name: Kura Li Ant Co. Porishinsu Ren Blue RLS)) was diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, a T-die Comparative Example 1 in which the ATO addition amount was adjusted to 1.96 g / m ² , the ATO fine particles were uniformly dispersed throughout the resin, and a blue coloring dye was added. The solar radiation shielding body 26 concerning was obtained. Moreover, the dispersion particle diameter of the ATO fine particles of the solar shield was 84 nm.
As shown in Table 1, the solar radiation transmittance was 39.6% when the visible light transmittance was 31.7%.
The solar radiation transmittance / visible light transmittance = 1.25, and the solar radiation transmittance / visible light transmittance <1 cannot be satisfied.
It is possible to reduce the visible light transmittance by using ATO and blue coloring dye, but the solar radiation transmittance cannot be lowered sufficiently, and to increase the temperature inside the car to use it for the car window. This is unsuitable because it is less effective.

[Comparative Example 2]
The master batch A and the master batch D were diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, the amount of added TiN is 0.016 g / m ² and the amount of ITO added was adjusted to 2.40 g / m ² to obtain a solar shading body 27 according to Comparative Example 2 in which TiN fine particles and ITO fine particles were uniformly dispersed throughout the resin. The dispersion particle diameter of the solar radiation shielding particles was 69 nm.
As shown in Table 1, the solar radiation transmittance was 40.5% when the visible light transmittance was 65.2%.
0.016 g ^/ m 2 (addition amount of ^{TiN) × 160 + 2.4g / m} 2 ( addition amount of ITO) = 4.96, and the following addition amount of the heat ray shielding fine particles are shown in the text (Formula 5) Since it does not satisfy, the visible light transmittance cannot be made sufficiently low, and it is unsuitable for use for a car window for the purpose of privacy protection.
(Formula 5)
5 (g / m ² ) <addition amount of titanium nitride (g / m ² ) × 160 + 6 addition amount of lanthanum boride (g / m ² ) × 40 + tungsten oxide (g / m ² ) × 40 + composite tungsten oxide ( g / m ² ) × 4 + antimony-doped tin oxide (g / m ² ) + tin-doped indium oxide (g / m ² ) <50 (g / m ² )

[Comparative Example 3]
The master batch A and the master batch B were diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, the amount of added TiN is 0.19 g / m ² and the ATO addition amount was adjusted to 19.9 g / m ² to obtain a solar shading body 28 according to Comparative Example 3 in which TiN fine particles and ATO fine particles were uniformly dispersed throughout the resin. The dispersion particle diameter of the solar radiation shielding particles was 76 nm.
As shown in Table 1, the solar radiation transmittance was 3.3% when the visible light transmittance was 3.4%.
0.19 g / m ² (addition amount of TiN) × 160 + 2.4 g / m ² (addition amount of ATO) = 50.3, and the addition amount of each heat ray shielding fine particle satisfies the formula 5 shown in the text. Therefore, the visible light transmittance is too low to be suitable for use in a car window.

Further, since the total addition amount per 1 m ² of the heat ray shielding 蔽微 particles 20.1 g / ^{m 2,} and the has more than 20 g / ^{m 2} or less as shown in the text, is significantly reduced surface strength of the solar radiation-shielding body However, rubbing with nails can easily cause scratches and is unsuitable for use in car windows. Moreover, material cost will also become high.

[Comparative Example 4]
The master batch C was diluted with Porika Bonnet over preparative resin pellet, followed by uniformly mixing with a tumbler, extruded to a thickness of 2.0mm by using the T-die, WO ₂ added amount is 0.44 g / ^{m 2} Thus, a solar radiation shield 29 according to Comparative Example 4 in which the WO ₂ fine particles were uniformly dispersed throughout the resin was obtained. The dispersion particle diameter of the solar radiation shielding particles was 76 nm.
As shown in Table 1, the solar radiation transmittance was 45.7% when the visible light transmittance was 35.9%.
The solar radiation transmittance / visible light transmittance = 1.27, and the solar radiation transmittance / visible light transmittance <1 could not be satisfied. Since WO ₂ is used alone, the absorption of infrared rays of 1000 nm or more is insufficient, and the solar radiation transmittance cannot be lowered sufficiently. It is.

Claims (15)

A solar radiation shielding body for vehicle windows containing fine particles having a heat ray shielding function used for a vehicle window, wherein the fine particles having the heat ray shielding function are selected from lanthanum hexaboride, titanium nitride, and tungsten oxide. From the above fine particles, and antimony-doped tin oxide, tin-doped indium oxide, a composite tungsten oxide represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) The solar radiation shielding body has a visible light transmittance of 5% or more and 40% or less, and is mixed with at least one or more selected fine particles. The solar radiation shielding body for a vehicle window, characterized in that the transmittance satisfies the following (Formula 1), and the transmitted color of the solar radiation shielding body satisfies the following (Formula 2).
(Expression 1) Solar transmittance / visible light transmittance <1
(Formula 2) -14 <a ^* <2, -8 <b ^* <2 A solar radiation shielding body for vehicle windows containing fine particles having a heat ray shielding function used for a vehicle window, wherein the fine particles having the heat ray shielding function are selected from lanthanum hexaboride, titanium nitride, and tungsten oxide. From the above fine particles, and antimony-doped tin oxide, tin-doped indium oxide, a composite tungsten oxide represented by the general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) At least one kind of fine particles selected and iron oxide fine particles are mixed, and the visible light transmittance of the solar radiation shielding body is in the range of 5% to 40%, and the solar radiation of the solar radiation shielding body. A vehicle window solar shading body characterized in that the transmittance and the visible light transmittance satisfy the following (formula 3), and the transmitted color of the solar shading body satisfies the following (formula 4).
(Expression 3) Solar radiation transmittance / visible light transmittance <1
(Formula 4) -2 <a ^* <14, 2 <b ^* <12 The solar radiation shielding body for vehicle windows according to claim 1, wherein the tungsten oxide is WO ₂ or W ₁₈ O ₄₉ .   The element M contained in the composite tungsten oxide fine particles is at least one of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. The solar radiation shielding body for vehicle windows according to 2.   The solar radiation shielding body for vehicle windows according to any one of claims 1 to 4, wherein a diameter of the fine particles having a heat ray shielding function is 300 nm or less.   6. The vehicle window according to claim 1, wherein the fine particles having a heat ray shielding function are surface-treated with at least one selected from a silane compound, a titanium compound, and a zirconia compound. Solar radiation shield. The vehicle window solar radiation shield according to any one of claims 1 to 6, further comprising at least one selected from zinc oxide fine particles, cerium oxide fine particles, and titanium oxide fine particles.   The solar radiation shielding body for vehicle windows according to any one of claims 1 to 7, wherein the fine particles having a heat ray shielding function are contained in a polycarbonate resin molded body.   A solar radiation shielding body for vehicle windows, wherein a scratch-resistant hard coat layer is formed on at least one surface of the polycarbonate resin molded body according to claim 8.   A solar radiation shielding body for vehicle windows, which is obtained by laminating the solar radiation shielding body according to claim 8 on another resin molded body.   A solar radiation shielding body for vehicle windows, wherein the fine particles having a heat ray shielding function according to claim 1 are contained in one kind selected from polyvinyl butyral resin, polyvinyl acetate resin, and polyvinyl alcohol resin.   A laminated structure comprising the solar radiation shielding body according to claim 11 interposed as an intermediate film between two laminated plates, wherein the laminated plate is selected from inorganic plate glass, polycarbonate resin molded body, and polyethylene terephthalate resin molded body. A solar shading body for vehicle windows, characterized in that it is at least one kind.   The solar radiation shielding body for vehicle windows, wherein at least one of the laminated plates according to claim 12 is the solar radiation shielding body according to any one of claims 8 to 10. 14. The vehicle window solar radiation according to claim 1, wherein the vehicle window solar radiation shield has a thickness of 2.5 mm to 30 mm and a maximum projected area of 400 to 60000 cm ^2. Shield.   The vehicle window solar radiation shielding body of any one of Claims 1-14 is used, The vehicle window characterized by the above-mentioned.