JP2010216081A - Heat ray shielding glass louver and window structure including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To control a heat ray shielding function depending on a period of use or an area of use, using heat ray shielding glass. <P>SOLUTION: This heat ray shielding glass louver 30 is characterized as follows: a plurality of heat ray shielding glass 10 are arranged in such a manner that longitudinal directions are parallel to each other and that each glass can freely rotate and stand still by setting the longitudinal direction as the axial center of rotation; and the heat ray shielding glass has a heat ray shielding layer containing a tungsten oxide and/or a composite tungsten oxide. A window structure includes the heat ray shielding glass louver 30. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a louver composed of a glass plate having a heat ray shielding function, and more particularly to a movable heat ray shielding glass louver installed in a window for buildings, vehicles, railways and the like.

  Conventionally, in order to reduce the air conditioning load of buildings such as office buildings and buses, passenger cars, trains, etc., railways, etc., these windows are required to have a function of shielding near infrared rays (heat rays) in sunlight. It has been. As heat shielding glass, kneaded heat ray absorbing glass in which ions such as Fe, Cr and Ti are introduced into the glass itself to give heat ray absorbing property, heat ray reflecting glass in which a metal oxide film is deposited, indium A thin film of a transparent conductive film such as tin oxide (ITO) or tin oxide (ATO), or a heat ray in which a noble metal film / metal oxide film composed mainly of a metal oxide film / Ag film is laminated. Heat ray shielding glass (Patent Document 1) on which a shielding film (also referred to as a Low-E film) is formed has been proposed and put into practical use. Among these, the Low-E film has a function of transmitting near-infrared rays of sunlight having a relatively short wavelength and reflecting far-infrared rays such as heating radiated from the room so as not to escape.

  Further, as a heat ray shielding glass having high heat ray shielding properties and realizing high visible light transmittance, tungsten oxide and / or composite tungsten oxide fine particles are mainly used as a heat ray shielding function, and a UV excitation coloring preventing agent is used. The thing which formed the coating film containing on a glass substrate is proposed (patent document 2).

JP 2001-226148 A JP 2007-269523 A

  However, the heat ray shielding glass described in Patent Document 2 shields the near infrared rays of sunlight when used in a high temperature period such as summer or in a warm area (hereinafter abbreviated as summer). The cooling efficiency of the room can be increased, but there is a problem that it does not become warm when used in a low temperature period such as winter or in a cold area (hereinafter abbreviated as winter). Further, as described above, the Low-E film described in Patent Document 1 has excellent heat insulating properties in winter and can improve heating efficiency. However, in the summer, the near-infrared ray of sunlight is transmitted. It may not contribute to the reduction.

  Therefore, the objective of this invention is providing the thing which can control a heat ray shielding function according to a use time or a use area using a heat ray shielding glass.

  The purpose is to arrange a plurality of heat ray shielding glasses so that their longitudinal directions are parallel to each other, and each glass is rotatable and stationary with the longitudinal direction as a rotation axis, and the heat ray shielding glass is tungsten-oxidized. This is achieved by a heat ray shielding glass louver having a heat ray shielding layer containing an object and / or a composite tungsten oxide. For example, this glass louver can be used for the glass portion at the boundary between the interior of a building (which means the inside of a closed space such as a building, vehicle, or railway) and the outside (which means the outside of the space). When installed outside the room, each heat ray shielding glass is rotated in summer, and the near-infrared light of sunlight is adjusted by adjusting the angle so that the glass surface is perpendicular to the incident direction of sunlight or covering the glass part. Can be blocked by the heat ray shielding layer. Thereby, the temperature rise in the room by near infrared rays can be suppressed, and the cooling efficiency can be increased. Since the heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide has high visible light transmittance, good visible light transmittance is secured even through this glass surface. On the other hand, by rotating each heat ray shielding glass in winter and adjusting each glass surface to an angle that is parallel to the incident direction of sunlight, it is possible not to block the near infrared rays of sunlight. Thereby, heating efficiency can be raised without preventing the effect of warming the room by near infrared rays.

Preferred embodiments of the heat ray shielding glass louver of the present invention are as follows.
(1) The heat ray shielding glass has a rectangular plate shape.
(2) When the heat ray shielding glass is rotated about the longitudinal direction as a rotation axis, each glass is disposed so as to overlap at least partly with the adjacent glass. Thereby, the near infrared rays of sunlight can be more reliably blocked in summer.
(3) The said heat ray shielding glass is arrange | positioned so that the rotating shaft center of a longitudinal direction may become a horizontal direction.
(4) The heat ray shielding glass is integrally bonded by sandwiching an intermediate film between two transparent substrates, and the heat ray shielding layer and the intermediate film, or the intermediate film, between the intermediate film and the transparent substrate, or A heat ray shielding layer, a plastic film, and an intermediate film are provided.

By making the heat-shielding glass into a laminated glass having such a configuration, the weather resistance and impact resistance of the glass louver can be increased, so that it can be made a more effective heat-shielding glass louver when installed outdoors. it can.
(5) The two transparent substrates are both glass plates.
(6) The intermediate film is a layer (PVB layer) of a composition containing polyvinyl butyral or a layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer.
(7) The tungsten oxide is represented by the general formula WyOz (W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999). Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I, one or more elements selected from W, W represents tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3).

  Moreover, the said objective is achieved by the window structure containing the structure where the heat ray shielding glass louver of this invention is installed in the outdoor side of the glass window in the boundary of the room | chamber interior and the outdoor.

  Thereby, a heat ray shielding function can be controlled according to a use time or a use area, and indoor air-conditioning efficiency can be improved.

  The heat ray shielding glass louver of the present invention is installed outside the glass window of buildings such as office buildings and buses, passenger cars, trains, etc., and glass windows of railways, etc. Since the shielding function can be controlled and the air-conditioning efficiency of these buildings and the like can be improved, the air-conditioning load can be reduced, contributing to energy saving and cost reduction.

  Therefore, the window structure of the present invention is a window structure that can reduce the air conditioning load and contribute to energy saving and cost reduction.

It is a schematic sectional drawing which shows a typical example of the heat ray shielding glass which comprises the heat ray shielding glass louver of this invention. It is a schematic perspective view which shows a typical example of the heat ray shielding glass louver of this invention. It is a schematic sectional drawing which shows a typical example of the window structure of this invention, (a) is a summer use condition, (b) is a schematic sectional drawing which shows the winter use condition.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing a typical example of the heat ray shielding glass 10 constituting the heat ray shielding glass louver of the present invention.

  In FIG. 1, the heat ray shielding glass 10 has a rectangular plate shape. In the present invention, the shape of the heat ray shielding glass 10 is not particularly limited as long as it can be used for the heat ray shielding glass louver. The shape of the heat ray shielding glass 10 may be an elliptical plate shape or a rod shape having a rectangular or elliptical cross section. A rectangular plate shape as shown in FIG. 1 is preferable in terms of easy production, the ability to efficiently shield near infrared rays, and visibility. In the present invention, “glass” in the heat ray shielding glass means the whole transparent substrate. Accordingly, the heat ray shielding glass means a transparent substrate provided with heat ray shielding properties.

In the heat ray shielding glass 10 shown in FIG. 1, an intermediate film 12A, a plastic film 13, a heat ray shielding layer 14 containing tungsten oxide and / or composite tungsten oxide, an intermediate film 12B, and a glass plate 11B on a glass plate 11A. Are sequentially laminated and integrated. This heat ray shielding glass is generally bonded and integrated by sandwiching a plastic film 13 having a heat ray shielding layer 14 on the surface between the two glass plates 11A and 11B via the intermediate films 12A and 12B. Is. The fine particles W of the tungsten oxide and / or the composite tungsten oxide contained in the heat ray shielding layer 14 do not block visible light, and do not block near infrared rays (in particular, near infrared rays in the vicinity of 850 to 1150 nm where the amount of radiation from sunlight is large). ) Is excellent in blocking function and exhibits excellent heat ray shielding properties. The content of fine particles of tungsten oxide and / or composite tungsten oxide in the heat ray shielding layer 14 is not particularly limited, but generally 0.1 to 50 g and 0.5 to 20 g are preferable per 1 m ² . 1-10 g is preferable. By including the composite tungsten oxide fine particles in such a range, it is possible to achieve both the heat ray cut characteristics and transparency of the obtained laminate.

  The heat ray shielding layer 14 is preferably a layer in which fine particles of tungsten oxide and / or composite tungsten oxide are dispersed in a binder resin composition. The intermediate films 12A and 12B are preferably a layer of a composition containing polyvinyl butyral (PVB layer) or a layer of a composition containing an ethylene / vinyl acetate copolymer (EVA layer), and may be a laminate thereof. The EVA layer is preferably a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide. The positions of the plastic film 13 and the heat ray shielding layer 14 may be reversed. Further, only the heat ray shielding layer 14 may be provided without providing the plastic film 13.

  As long as the heat ray shielding glass 10 in the present invention is a heat ray shielding glass having a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide, tungsten oxide and A glass plate coated with a heat ray shielding layer containing composite tungsten oxide and / or a plastic film having a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide is attached to one glass plate via an adhesive layer. Film tempered glass may also be used. Moreover, the laminated glass which adhere | attached the two glass plates 11A and 11B with the heat ray cut layer 14 may be sufficient if the heat ray shielding layer 14 has a function of an intermediate film and can adhere a glass plate. A conventional interlayer film can be used, and a laminated glass structure as shown in FIG. 1 is preferable in terms of weather resistance, impact resistance, and the like.

  The glass plates 11A and 11B may be transparent substrates and may be the same or different. For example, glass plates such as green glass, silicate glass, inorganic glass plate, and non-colored transparent glass plate, as well as plastics such as polyethylene terephthalate (PET), polyethylene aphthalate (PEN), polyethylene butyrate, polymethyl methacrylate, etc. A substrate or film may be used. In terms of weather resistance, impact resistance, etc., the two transparent substrates are preferably glass plates. The thickness of the transparent substrate is generally about 1 to 20 mm.

  The heat ray shielding glass 10 is generally chamfered to prevent danger and is mainly installed outdoors as will be described later, so that it is waterproofed with a resin coat or the like.

  Next, the heat ray shielding glass louver of the present invention will be described. FIG. 2 is a schematic perspective view showing a typical example of the heat ray shielding glass louver 30 of the present invention. As shown in the drawing, the heat ray shielding glass louver 30 includes the frame 20 (the transparent view is indicated by a broken line), the fixture 21, and the rectangular heat ray shielding glass 10 described in FIG. The frame 20 is generally made of metal such as stainless steel and has a bearing 23 that is paired with the shaft 22 of the fixture 21. The fitting 21 is generally made of a metal such as stainless steel, and is fitted to the shaft 22 paired with the bearing 23 and the width and thickness of the heat ray shielding glass 10 for fixing the heat ray shielding glass 10. Part 24. Both ends of the heat ray shielding glass 10 are fixed by fixing means such as springs and screws at the fitting portions 24 of the fixture 21, and as shown in the drawing, a plurality of the heat ray shielding glasses 10 are arranged in the longitudinal direction. It arrange | positions so that it may mutually become parallel. A shaft 22 of the fixture 21 is attached to a bearing 23 of the frame 20, and each heat ray shielding glass 10 is attached to the frame 20 so as to be rotatable and stationary with the shaft 22 as a rotation axis.

  The interval between the plurality of heat ray shielding glasses 10 is not particularly limited as long as it can block near infrared rays of sunlight in summer. In order to block near-infrared rays of sunlight more reliably, when each heat ray shielding glass 10 is rotated, the plate surface of each glass 10 is disposed so that at least a part of the plate surface of the adjacent glass 10 overlaps. Is preferred. In this case, by adjusting the rotation angle of the heat ray shielding glass 10 so that the plate surfaces of all the glasses 10 overlap at least partially with the plate surfaces of the adjacent glasses 10, the range surrounded by the frame 20 is heat ray shielded. The glass plate 10 can be covered with no gaps. Although the range in which each heat ray shielding glass 10 overlaps does not have a restriction | limiting in particular, Generally it is 5-20 mm. The frame 20 is preferably provided with interlocking means (not shown) such as gears so that the rotation angles of all the heat ray shielding glasses 10 can be adjusted to the same angle. Moreover, it is preferable that a control means capable of mechanical or electronic remote operation is provided.

  In the heat ray shielding glass louver 30 of the present invention, the heat ray shielding glass 10 is installed so as to be freely rotatable and stationary with the horizontal direction as a rotation axis in FIG. 2, but the longitudinal direction of the glass 10 is installed in the vertical direction. The direction may be the rotation axis. In order to adjust the angle of the plate surface of the heat ray shielding glass 10 in accordance with the incident direction of sunlight, it is preferable to use the horizontal direction as a rotation axis as shown in FIG. In FIG. 2, the heat ray shielding glass 10 is attached to the frame 20 only by the shaft 22 of the fixture 21. However, if the heat ray shielding glass 10 is disposed so as to be freely rotatable and stationary with the longitudinal direction as the rotation axis. Well, any attachment means may be used. For example, a means for fixing the heat ray shielding glass 10 to an arm that is rotatably and stationaryly attached to the frame 20 can be used.

    Next, the window structure including the heat ray shielding glass louver of the present invention will be described. 3A and 3B are schematic cross-sectional views showing a typical example of the window structure 50 of the present invention. FIG. 3A shows a usage state in summer, and FIG. 3B shows a usage state in winter. The glass window 40 is a glass window at the boundary between indoors and outdoors of buildings such as office buildings and the like, vehicles such as buses, passenger cars, trains, and railways. In the present invention, the “glass” of the glass window 40 means the whole transparent substrate. The heat ray shielding glass louver 30 is as described with reference to FIG. 2, and is installed outside the glass window 40 in the window structure 50 of the present invention. As shown in FIG. 3A, in the summer, each heat ray shielding glass 10 of the heat ray shielding glass louver 30 is rotated so that the plate surfaces of all the glasses 10 are adjusted to an angle that is perpendicular to the incident direction of sunlight. ing. Thereby, permeation | transmission of the near infrared rays of sunlight to the room | chamber interior can be interrupted | blocked by the heat ray shielding layer of the heat ray shielding glass 10. FIG. The tungsten oxide and / or the composite tungsten oxide contained in the heat ray shielding layer according to the present invention does not substantially block visible light and has a large amount of radiation from sunlight (particularly near infrared light in the vicinity of 850 to 1150 nm). It has an excellent blocking function and exhibits excellent heat ray shielding properties. Therefore, the temperature rise in the room due to near infrared rays can be suppressed, and the cooling efficiency can be improved.

  In addition, as shown in FIG. 3B, in the winter season, each heat ray shielding glass 10 is rotated and adjusted so that the plate surface of each glass 10 is parallel to the incident direction of sunlight. Thereby, permeation | transmission of the near infrared rays of sunlight to the room | chamber interior is not interrupted | blocked by the heat ray shielding layer of the heat ray shielding glass 10. FIG. Therefore, heating efficiency can be improved without impeding the effect of warming the room by the near infrared rays of sunlight. Furthermore, by adjusting the angle of the heat ray shielding glass 10 to an appropriate angle, it is possible to adjust the amount of transmission of near infrared rays of sunlight and contribute to temperature control in the room.

  In the window structure 50 of the present invention, since the heat ray shielding glass louver 30 of the present invention is installed, the glass window 40 is a normal glass such as green glass, silicate glass, inorganic glass plate, and non-colored transparent glass plate, Alternatively, a transparent substrate made of plastic such as polymethyl methacrylate may be used. Further, the glass window 40 may be laminated glass to improve impact resistance and penetration resistance, and may be laminated glass to enhance heat insulation effect, and to suppress far-infrared radiation such as heating heat from indoors in winter. Alternatively, a Low-E film may be provided.

  The window structure 50 of the present invention only needs to include a structure in which the heat ray shielding glass louver 30 of the present invention is installed on the outdoor side of the glass window 40 at the boundary between the room and the outdoor. In FIG. 3, the heat ray shielding glass louver 30 is installed on the outermost part of the outdoor side, but a glass window may be installed on the outdoor side. Further, an integrated window structure in which the heat ray shielding glass louver 30 is provided between two transparent substrates may be used.

Hereinafter, each structure of the heat ray shielding glass which concerns on this invention is demonstrated.
[Heat ray shielding layer]
As described above, the heat ray shielding layer constituting the heat ray shielding glass according to the present invention is a layer in which fine particles of tungsten oxide and / or composite tank stainless oxide are dispersed in a binder resin composition.

  The tungsten oxide is an oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is the tungsten oxide. The element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, 1 or more elements selected from Ta, Re, Be, Hf, Os, Bi, and I). As a result, free electrons are generated in WyOz, including the case of z / y = 3.0, and free electron-derived absorption characteristics are expressed in the near infrared region, which is effective as a near infrared absorbing material near 1000 nm. . In the present invention, composite tungsten oxide is preferable.

In the tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), the preferable composition range of tungsten and oxygen is When the composition ratio of oxygen is less than 3 and the infrared shielding material is described as WyOz, 2.2 ≦ z / y ≦ 2.999. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of WO ₂ which is not intended in the infrared shielding material and to obtain chemical stability as a material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated and an efficient infrared shielding material can be obtained.

  From the viewpoint of stability, the composite tungsten oxide fine particles are generally MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, One or more elements selected from Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, (0.001 ≦ x / Y ≦ 1, 2.2 ≦ z / y ≦ 3) The alkali metal is a group 1 element of the periodic table excluding hydrogen, and the alkaline earth metal is the second element of the periodic table. Group elements and rare earth elements are Sc, Y and lanthanoid elements.

  In particular, from the viewpoint of improving optical characteristics and weather resistance as an infrared shielding material, the M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Some are preferred. The composite tungsten oxide is preferably treated with a silane coupling agent. Excellent dispersibility is obtained, and an excellent infrared cut function and transparency are obtained.

  If the value of x / y indicating the added amount of the element M is larger than 0.001, a sufficient amount of free electrons is generated, and a sufficient infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding effect also increases, but the value of x / y is saturated at about 1. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the fine particle-containing layer.

  Regarding the value of z / y indicating the control of the amount of oxygen, in the composite tungsten oxide represented by MxWyOz, the same mechanism as that of the infrared shielding material represented by WyOz described above works, and z / y = Even in 3.0, since there is a supply of free electrons due to the addition amount of the element M described above, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable. It is.

  Further, when the composite tungsten oxide fine particles have a hexagonal crystal structure, the transmission of the fine particles in the visible light region is improved and the absorption in the near infrared region is improved.

When the cation of the element M is added to the hexagonal void, the transmission in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be added as long as the additive element M exists in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0. .33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  Besides hexagonal crystals, tetragonal and cubic tungsten bronzes also have an infrared shielding effect. These crystal structures tend to change the absorption position in the near infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. For this reason, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible light region and shield light in the infrared region. Moreover, it is preferable from the viewpoint of improving weather resistance that the surface of the composite tungsten oxide fine particles of the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al.

  The particle diameter of the composite tungsten oxide fine particles used in the present invention is preferably 800 nm or less (average particle diameter), particularly 400 nm or less from the viewpoint of maintaining transparency. This is because particles smaller than 800 nm do not completely block light due to scattering, can maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the particle size is 200 nm or less, preferably 100 nm or less.

  The average particle diameter of the heat-absorbing material is a number-average value obtained by observing the cross section of the heat-absorbing layer with a transmission electron microscope at a magnification of about 1,000,000 and obtaining the projected area equivalent circle diameter of at least 100 heat-absorbing materials. And

  The composite tungsten oxide fine particles are produced, for example, as follows.

  The tungsten oxide fine particles represented by the general formula WyOz and / or the composite tungsten oxide fine particles represented by MxWyOz are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. Can do.

  The tungsten compound starting material is obtained by dissolving tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride in alcohol and then drying. Tungsten oxide hydrate powder, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or ammonium tungstate It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous solution and a metal tungsten powder.

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

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

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has sufficient coloring power and is efficient as infrared shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 to 650 ° C. in a reducing gas atmosphere, and then heat-treated at a temperature of 650 to 1200 ° C. in an inert gas atmosphere. . The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

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

  The composite tungsten oxide fine particles of the present invention are preferably surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Silane coupling agents are preferred. Thereby, the affinity with the binder resin is improved, and various physical properties are improved in addition to transparency and heat ray shielding properties.

  Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane and trimethoxyacrylsilane can be mentioned. Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and trimethoxyacrylsilane are preferred. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable to use 5-20 mass parts of content of the said compound with respect to 100 mass parts of microparticles | fine-particles.

  As the binder resin contained in the binder resin composition, known thermoplastic resins, ultraviolet curable resins, and thermosetting resins can be used. For example, synthetic resins such as silicone resin, fluorine resin, olefin resin, acrylic resin, polyester resin, epoxy resin, urethane resin, phenol resin, resorcinol resin, urea resin, melamine resin, and furan resin can be given. A silicone resin, a fluororesin, an olefin resin, and an alkyl resin are preferable in terms of weather resistance. A thermoplastic resin and an ultraviolet curable resin are preferable, and an ultraviolet curable resin is particularly preferable. The ultraviolet curable resin is preferable because it can be cured in a short time and has excellent productivity. The binder resin composition contains a thermal polymerization initiator and a photopolymerization initiator depending on the curing method. Furthermore, you may contain hardening | curing agents, such as a polyisocyanate compound. Moreover, when adding the function of an intermediate film to a heat ray shielding layer, the PVB resin composition or EVA resin composition similar to the below-mentioned intermediate film can be used as a binder resin composition.

  The heat ray shielding layer preferably contains 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 to 300 parts by mass of the (composite) tungsten oxide with respect to 100 parts by mass of the binder resin. The thickness of the heat ray shielding layer is generally 0.1 to 50 μm, preferably 0.1 to 10 μm, particularly preferably 0.1 to 5 μm.

[Interlayer film]
As described above, the intermediate film constituting the heat ray shielding glass according to the present invention is generally an EVA layer or a PVB layer, or a laminated film thereof.

  The PVB resin composition constituting the PVB layer generally contains a PVB resin, a plasticizer, an ultraviolet absorber, and the like. As the PVB resin, those having a polyvinyl acetal unit of 70 to 95% by weight, a polyvinyl acetate unit of 1 to 15% by weight and an average degree of polymerization of 200 to 3000, particularly 300 to 2500 are preferred.

  Examples of the plasticizer for the PVB resin composition include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers.

  Monobasic acid esters include organic acids such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and tris. Esters obtained by reaction with ethylene glycol are preferred, in particular triethylene-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol-di-capronate, triethylene glycol- Di-n-octoate is preferred. An ester of the above organic acid with tetraethylene glycol or tripropylene glycol can also be used.

  As the polybasic acid ester plasticizer, for example, an ester of an organic acid such as adipic acid, sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable. Kate, dioctyl azelate and dibutyl carbitol adipate are preferred.

  As the phosphoric acid plasticizer, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like are preferable.

  In the PVB resin composition, if the amount of the plasticizer is small, the film formability is deteriorated, and if it is too large, the durability during heat resistance is impaired. Therefore, the plasticizer is generally added in an amount of 5 to 50 with respect to 100 parts by mass of the polyvinyl butyral resin. It is preferable to include 10 parts by mass, particularly 10 to 40 parts by mass.

  In the PVB resin composition of the present invention, a benzophenone compound, a triazine compound, a benzoate compound, a hindered amine compound, or the like can be used as an ultraviolet absorber (UV absorber). Benzophenone compounds are preferred because yellowing is suppressed.

  Preferred examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, particularly 2-hydroxy-4-n-octylbenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone is preferred.

  In a PVB layer, it is preferable to use the said ultraviolet absorber 0.05-1.0 mass part (especially 0.1-0.2 mass part) with respect to 100 mass parts of PVB.

  Furthermore, the PVB resin composition may contain an alkali or alkaline earth metal salt of a fatty acid (generally used as an adhesion modifier).

  Examples of alkaline earth metal salts of the fatty acids include magnesium formate, magnesium acetate, magnesium lactate, magnesium stearate, magnesium octylate, calcium formate, calcium acetate, calcium lactate, calcium stearate, calcium octylate, barium formate, acetic acid Barium, barium lactate, barium stearate, barium octylate, etc .; examples of alkali metal salts of fatty acids include potassium formate, potassium acetate, potassium lactate, potassium stearate, potassium octylate, sodium formate, sodium acetate, sodium lactate , Sodium stearate, sodium octylate and the like.

  Additives such as stabilizers and antioxidants may be added to the PVB resin composition to further prevent deterioration.

  EVA used for the EVA resin composition constituting the EVA layer generally has a vinyl acetate content of 23 to 38% by mass, and particularly preferably 23 to 28% by mass. When the vinyl acetate content is less than 23% by mass, the transparency of the resin obtained when crosslinked and cured at a high temperature is insufficient, and when it exceeds 38% by mass, the impact resistance and penetration resistance are insufficient. It becomes a trend. Moreover, it is preferable that EVA has a melt flow index (MFR) of 1.5 to 20.0 g / 10 min, particularly 2.0 to 8.0 g / 10 min. This facilitates pre-bonding.

  The EVA resin composition contains an ultraviolet absorber and an organic peroxide in the EVA, and may further contain various additives such as a crosslinking aid, an adhesion improver, and a plasticizer as necessary. it can.

  Examples of the ultraviolet absorber contained in the EVA resin composition include benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds. From the viewpoint of suppressing yellowing, benzophenone compounds are preferred.

  In the EVA layer, it is preferable to use 0.01 to 1.5 parts by mass (particularly 0.5 to 1.0 part by mass) of the ultraviolet absorber with respect to 100 parts by mass of EVA.

  As the organic peroxide contained in the EVA resin composition, any organic peroxide can be used in combination as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  Examples of this organic peroxide include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di- t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone pero Side, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxy isobutylene and 2,4-dichlorobenzoyl peroxide Can be mentioned.

  The EVA layer is used to improve or adjust various physical properties of the film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), and in particular to improve mechanical strength. It preferably contains a group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound.

  The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group. Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.

  Examples of amides include diacetone acrylamide.

  Examples of polyfunctional compounds (crosslinking aids) include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and the aforementioned triallyl cyanurate and triallyl isocyanurate. it can.

Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. (Ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether can be mentioned.

  A silane coupling agent can be added to the EVA resin composition as an adhesion improver in order to further enhance the adhesive force between the EVA layer and the glass plate or transparent plastic substrate or film.

  Examples of this silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Mention may be made of β- (aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of EVA.

  The plasticizer contained in the EVA resin composition is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of EVA.

  The EVA layer according to the present invention is, for example, a method for obtaining an EVA resin film by molding a composition containing the above-mentioned EVA, an organic peroxide, an ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering) or the like. Can be manufactured. Similarly to the above, the PVB layer according to the present invention is obtained by, for example, molding a composition containing the PVB, the ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering) or the like to obtain a PVB resin film. It can be manufactured by a method.

  Alternatively, a layered product can be obtained by dissolving the above composition in a solvent and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film. The PVB layer and the EVA layer may be formed using respective resin films, or may be formed by using a PVB / EVA composite resin film by two-layer extrusion molding of PVB resin and EVA resin or the like. Moreover, the other resin composition is applied to any one of the resin films, for example, the EVA resin composition is applied to a PVB resin film formed in advance to form a two-layer laminated film. You may do it. A three-layer laminated film for bonding can be formed in the same manner.

[Plastic film]
The plastic film constituting the heat ray shielding glass according to the present invention is generally a transparent plastic film. The material is not particularly limited as long as it is transparent (meaning “transparent to visible light”). Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. The thickness of the plastic film is preferably 10 to 400 μm, particularly 20 to 200 μm. Further, in order to improve the adhesiveness, the plastic film surface may be subjected in advance to an adhesion treatment such as a corona treatment, a plasma treatment, a flame treatment, and a primer layer coating treatment.

  In order to produce the heat ray shielding glass according to the present invention, first, a plastic film having a heat ray shielding layer is prepared. This can be done by applying a coating solution in which fine particles of (composite) tungsten oxide are dispersed in a binder resin as described above on a plastic film and drying it (by further curing with heat, light, etc. if necessary). )Obtainable. In this case, drying is preferably performed by heating the resin composition applied on the plastic film at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  Next, an EVA resin film is formed as an intermediate film as described above, and the plastic film on which the heat ray shielding layer is formed is sandwiched between the two glass plates via the EVA resin film (glass plate / EVA). Resin film / plastic film / EVA resin film / glass plate on which a heat ray shielding layer is formed), and this laminate (laminated glass) is degassed and then pressed and integrated under heating. good. Such a laminated glass can be obtained, for example, by a vacuum bag method or a nip roll method. Since the EVA layer is soft, it can be performed by pressure bonding by a nip roll method, and the production of the laminate is facilitated. The temperature of the nip roll is preferably 80 to 140 ° C.

  In producing the heat ray shielding glass, the EVA layer is generally crosslinked at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. For this cross-linking, after deaeration in a state of being sandwiched between glass plates, for example, pre-compression is performed at a temperature of 80 to 120 ° C., and heat treatment is performed at 100 to 150 ° C. (especially around 130 ° C.) for 10 minutes to 1 hour. Is done. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

Hereinafter, the present invention will be described in more detail with reference to examples.
(1) Production of heat ray shielding glass (production of interlayer film)
An EVA sheet having a thickness of 0.7 mm was obtained as an intermediate film (transparent adhesive layer) by a calendar molding method using the following composition as a raw material. The kneading of the blend was carried out at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass,
Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100 parts by mass Cross-linking agent (Perbutyl E; manufactured by Nippon Oil & Fats Co., Ltd. t-butylperoxy-2-ethylhexyl monocarbonate): 2.2 parts by mass Silane Coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 part by mass Ultraviolet absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.5 part by mass

(Preparation of PET film with heat ray shielding layer)
The following coating solution for forming a heat ray cut layer was applied on a PET film (200 μm) with a bar coater and dried at 120 ° C. for 2 minutes to form a heat ray cut layer having a thickness of 1 μm.

(Combination)
Silicone resin (solid content 20% by mass, toluene 80% by mass,
KR-251 manufactured by Shin-Etsu Chemical Co., Ltd.) 75 parts by mass Cesium tungsten oxide (Cs _0.33 WO ₃ ,
Solid content 20% by mass, MIBK 80% by mass) 100 parts by mass

(Production of heat ray shielding glass)
The PET film with a heat ray shielding layer obtained above was laminated on both sides with a glass plate via an EVA sheet, placed in a rubber bag, vacuum degassed, and pre-pressed at a temperature of 110 ° C. Next, this pre-press-bonded glass was put in an oven and pressurized for 30 minutes under the condition of a temperature of 130 ° C. to produce a laminated glass (glass plate / EVA / film with heat ray shielding layer / EVA / glass plate). .

(2) Production of heat ray shielding glass louver The produced heat ray shielding glass was cut into strips, chamfered, and waterproofed with a resin coat to produce a rectangular glass plate having a width of 90 mm and a length of 720 mm. The 18 pieces of the heat ray shielding glass were attached to a frame having a width of 780 mm and a height of 1370 mm to produce a heat ray shielding glass louver as shown in FIG. The overlapping width of each heat ray shielding glass was 10 mm.

  The heat ray shielding glass louver was installed outside the glass window facing the outside of the office. In summer, when the angle of the heat ray shielding glass plate surface is adjusted to be perpendicular to the incident direction of sunlight, the visible light transmittance does not change, but the near infrared ray is well shielded and the cooling efficiency is improved. I was able to. In winter, the angle of the surface of the heat-shielding glass was adjusted to be parallel to the incident direction of sunlight. As a result, room temperature was improved by the near infrared rays of sunlight, and heating efficiency was improved.

  In addition, this invention is not limited to said embodiment and Example, A various deformation | transformation is possible within the range of the summary of invention.

  Air conditioning loads on buildings such as office buildings, buses, passenger cars, trains, etc., and railways can be reduced regardless of summer or winter.

DESCRIPTION OF SYMBOLS 10 Heat ray shielding glass 11A, 11B Glass plate 12A, 12B Intermediate film 13 Plastic film 14 Heat ray shielding layer 20 Frame 30 Heat ray shielding glass louver 40 Glass window 50 Window structure

Claims (9)

  A plurality of heat ray shielding glasses are arranged so that their longitudinal directions are parallel to each other, and each glass is rotatably and stationary with the longitudinal direction as a rotation axis, and the heat ray shielding glass is made of tungsten oxide and / or A heat ray shielding glass louver comprising a heat ray shielding layer containing a composite tungsten oxide. The heat ray shielding glass louver according to claim 1, wherein the heat ray shielding glass has a rectangular plate shape. 3. The heat ray shielding glass louver according to claim 1, wherein when the heat ray shielding glass is rotated about the longitudinal direction as a rotation axis, each glass is disposed so as to overlap at least partly with an adjacent glass.   The heat ray shielding glass louver according to any one of claims 1 to 3, wherein the heat ray shielding glass is disposed so that a longitudinal axis of rotation thereof is in a horizontal direction.   The heat ray shielding glass is bonded and integrated by sandwiching an intermediate film between two transparent substrates, and the heat ray shielding layer and the intermediate film or the heat ray shielding layer is interposed between the intermediate film and the transparent substrate. The heat ray shielding glass louver according to claim 1, wherein a plastic film and an intermediate film are provided.   The heat ray shielding glass louver according to claim 3, wherein the two transparent substrates are both glass plates.   The heat ray shielding glass louver according to claim 3 or 4, wherein the intermediate film is a layer of a composition containing polyvinyl butyral (PVB layer) or a layer of a composition containing an ethylene / vinyl acetate copolymer (EVA layer).   The tungsten oxide is represented by the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is represented by the general formula MxWyOz ( Where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, One or more elements selected from Hf, Os, Bi, and I, W represents tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3 The heat ray shielding glass according to any one of claims 1 to 5 represented by: Through bar.   The window structure containing the structure where the heat ray shielding glass louver of any one of Claims 1-6 is installed in the outdoor side of the glass window in the boundary of an indoor and an outdoor.

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