WO2015025963A1

WO2015025963A1 - Heat ray shielding material

Info

Publication number: WO2015025963A1
Application number: PCT/JP2014/072056
Authority: WO
Inventors: 強臣宮古
Original assignee: 王子ホールディングス株式会社
Priority date: 2013-08-23
Filing date: 2014-08-22
Publication date: 2015-02-26
Also published as: JPWO2015025963A1

Abstract

Provided is a heat ray shielding material which exhibits excellent visible light transmission performance, heat ray shielding performance and electromagnetic wave transmission performance, while having excellent appearance, and which can be used as a window plate and the like. A heat ray shielding material (1A) which is provided with bases (2, 5) and a metal layer (4a). This heat ray shielding material (1A) is characterized in that: the metal layer (4a) is formed by arranging a plurality of island-like metal coating films; each metal coating film has a diameter of 0.05-0.50 mm; the distance between any two metal coating films is 0.02-0.23 mm; the area ratio of the portions that are not covered by the metal coating films is 11-80%; the visible light transmittance thereof is 45% or more; and the electromagnetic wave shielding ratio thereof is 10 dB or less.

Description

Heat ray shielding material

The present invention relates to a heat ray shielding material that can be used as a window plate or the like.

Conventionally, the development of transparent materials with heat ray shielding performance has been promoted as one of the energy-saving measures for buildings, buildings, and other transportation systems such as trains, passenger cars, and ships. For example, a glass plate or a film having a heat insulating function for transmitting visible light of sunlight falling from a window but blocking heat rays while preventing indoor heat from being released to the outside has been developed.

As a method for imparting a function of shielding heat rays to a glass plate or film, a method of uniformly forming a metal layer such as aluminum on a film or the like is widely employed.

However, such a uniform metal layer generally reflects electromagnetic waves, which may cause a problem that it becomes difficult to use a mobile phone, a mobile TV, or the like indoors or in a vehicle. Therefore, development of glass plates and films having functions of shielding heat rays and transmitting electromagnetic waves has been promoted.

For example, Patent Document 1 discloses a radio wave transmissive heat ray reflector in which an insulating transparent substrate is coated with a conductive coating divided into a plurality of stripes or lattices. Patent Document 2 discloses a heat ray reflective glass having a radio wave low reflection characteristic in which divided grooves are formed so as to be 1/20 times or less of the wavelength λ of radio waves. Patent Document 3 discloses a base film in which a blocking layer that blocks a wavelength at a specific frequency is laminated.

Japanese Patent Laid-Open No. 7-242441 Japanese Patent Laid-Open No. 5-50548 JP 2008-68519 A

However, the radio wave transmissive heat ray reflecting plate described in Patent Document 1 has a problem in terms of appearance as a product because of the large size of the conductor coating. In addition, the disclosed embodiments have a small area ratio of the portion not covered with the transparent conductive film or a small distance between the conductor film portions, and thus the electromagnetic wave permeability and industrial productivity are improved. Somewhat inferior.

In addition, the heat ray reflective glass described in Patent Document 2 is mainly intended to reduce radio wave reflectivity, and in the disclosed embodiment, the width of the stripe-shaped coating film is considerably large, so that the appearance as a product. It could be a problem.

In addition, the base film described in Patent Document 3 is for selectively transmitting electromagnetic waves having a specific wavelength, and since the width and interval of the slits existing between the shielding layers are large, It was a problem.

The present invention has been made in view of such circumstances, and it is an object to provide a heat ray shielding material that is excellent in visible light transmission performance, heat ray shielding performance, electromagnetic wave transmission performance, and excellent in appearance. To do.

In order to solve the above problems, the present inventor has proceeded with studies on the form of the metal layer provided on the substrate. As a metal layer, a substrate on which a metal film is uniformly formed on the entire surface cannot transmit electromagnetic waves. Therefore, when the metal layer is a layer formed by arranging a large number of island-shaped metal films, the conductivity of the entire substrate is lost. As a result, electromagnetic waves can be transmitted through the gaps between the island-shaped metal films, and it has become possible to impart electromagnetic wave transmission performance to the substrate. Moreover, the visible light transmission performance of the substrate could be improved by providing a gap between the island-shaped metal films.

However, when the gap between the island-shaped metal films is made too narrow, the surface resistance value becomes small and the electromagnetic wave transmission performance of the base material is lowered. On the other hand, when the island-shaped metal film is made small and the gap between the island-shaped metal films is excessively widened, the electromagnetic wave transmission performance of the base material is improved, but the heat ray shielding performance of the base material is lowered. Furthermore, there is a concern that the island-shaped metal film may be too large, or depending on the shape and arrangement of the island-shaped metal film, the metal film can be easily seen with the naked eye, which impairs the merchantability of the appearance of the base material. .

Based on such a situation, the present inventor has succeeded in identifying the arrangement method of the island-shaped metal film that can satisfy any of visible light transmission performance, heat ray shielding performance, electromagnetic wave transmission performance and appearance. Thus, the present invention has been completed. That is, the present invention has the following configuration.

(1) A heat ray shielding material comprising a base material and a metal layer, wherein the metal layer is formed by arranging a number of island-like metal films, and the diameter of the metal film is 0.05 to 0.50 mm. The distance between the metal films is 0.02 to 0.23 mm, the area ratio of the portion not covered with the metal film is 11 to 80%, and the visible light transmittance is 45% or more. The electromagnetic wave shielding rate is 10 dB or less.

(2) The heat ray shielding material includes a metal layer on one surface of the substrate and a resin layer having a multilayer structure on the other surface, and the thickness per layer of the multilayer structure is 50 to 1000 nm. It is preferable.

(3) In the heat ray shielding material, the base material is preferably a resin material having a multilayer structure, and the thickness per layer of the multilayer structure is preferably 50 to 1000 nm.

(4) It is preferable that there are two base materials, and the metal layer is sandwiched between the two base materials.

(5) The visible light reflectance is preferably 25% or less.

(6) The heat ray shielding coefficient is preferably 0.9 or less.

(7) The metal layer is preferably composed of a plurality of metal layers.

(8) It is preferable that the said metal layer contains silver.

(9) It is preferable that the heat transmissivity is less than 5.9 W / m ² K.

(10) The ultraviolet transmittance is preferably 5% or less.

(11) It is preferable that the diameter of the metal film is 0.15 to 0.50 mm and the distance between the metal films is 0.04 to 0.23 mm.

The heat ray shielding material of the present invention is excellent in visible light transmission performance, heat ray shielding performance and electromagnetic wave transmission performance, and is excellent in appearance.

It is a table | surface which shows the structure and physical property of a comparative example. It is a table | surface which shows the performance of a comparative example. It is a table | surface which shows the structure and physical property of an Example and a comparative example. It is a table | surface which shows the performance of an Example and a comparative example. It is a table | surface which shows the structure and physical property of an Example and a comparative example. It is a table | surface which shows the performance of an Example and a comparative example. It is a table | surface which shows the structure and physical property of an Example and a reference example. It is a table | surface which shows the performance of an Example and a reference example. It is a table | surface which shows the structure and physical property of an Example and a comparative example. It is a table | surface which shows the performance of an Example and a comparative example. It is a table | surface which shows the structure and physical property of an Example and a comparative example. It is a table | surface which shows the performance of an Example and a comparative example. It is a table | surface which shows the structure and physical property of an Example and a comparative example. It is a table | surface which shows the performance of an Example and a comparative example. It is typical sectional drawing which shows the layer structure of 1 A of heat ray shielding materials of 1st Embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding material 1B of 1st Embodiment. It is a typical sectional view showing layer composition of heat ray shielding material 1C of a 1st embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding material 10 of 2nd Embodiment. It is an example of the arrangement | positioning method of the island-shaped metal film of the heat ray shielding material of 1st Embodiment, and is a circular staggered arrangement. It is an example of the arrangement | positioning method of the island-shaped metal film of the heat ray shielding material of 1st Embodiment, and is a square parallel type arrangement | positioning. It is an example of the arrangement | positioning method of the island-shaped metal film of the heat ray shielding material of 1st Embodiment, and is a hexagonal staggered arrangement. It is a schematic diagram which shows the manufacturing method of the heat ray shielding material 10 of 2nd Embodiment. It is a typical sectional view showing the layer composition of heat ray shielding material 20A of a 3rd embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding material 20B of the comparative example of 3rd Embodiment. It is a typical sectional view showing layer composition of heat ray shielding material 20C of a comparative example of a 3rd embodiment. It is a typical sectional view showing layer composition of heat ray shielding material 20D of a 3rd embodiment. It is a typical sectional view showing the layer composition of heat ray shielding material 20E of a 3rd embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding material 30 of 4th Embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding material 40 of 5th Embodiment. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 2nd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 3rd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the Example of 3rd Embodiment, and a comparative example. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the comparative example of 3rd Embodiment. It is a spectrum figure of the transmittance | permeability and reflectance of the heat ray shielding material of the comparative example of 3rd Embodiment.

Embodiments of the present invention will be described. However, embodiments of the present invention are not limited to the following embodiments.

(Electromagnetic wave, visible light, near infrared, far infrared, ultraviolet)
In the present embodiment, the electromagnetic wave refers to an electromagnetic wave having a wavelength of 10 mm to 10 km and a frequency of about 30 KHz to 30 GHz. The electromagnetic wave region is used for radio broadcasting, television broadcasting, wireless communication, cellular phone, satellite communication, and the like.
In the present embodiment, visible light means light that can be recognized with the naked eye among electromagnetic waves, and generally refers to electromagnetic waves having a wavelength of 380 to 780 nm. Near-infrared light is an electromagnetic wave having a wavelength of approximately 800 to 2500 nm and has a wavelength close to red visible light. Near-infrared rays are contained in sunlight and act to heat an object. On the other hand, far-infrared rays are electromagnetic waves having a wavelength of about 5 to 20 μm (5000 to 20000 nm), are not included in sunlight, and have a wavelength close to that emitted from an object near room temperature. Ultraviolet rays are electromagnetic waves having a wavelength of about 10 to 380 nm.
In the present embodiment, the heat ray means near infrared rays.

The heat ray shielding material of the present embodiment is configured to handle electromagnetic waves having five wavelengths of electromagnetic waves, visible rays, near infrared rays, far infrared rays, and ultraviolet rays. That is, the heat ray shielding material according to the present embodiment allows electromagnetic waves to pass between the outside and the inside of the room so that a mobile phone, a mobile TV, or the like can be used indoors or in a vehicle. Moreover, the heat ray shielding material of the present embodiment partially transmits visible light from the outside to the inside of the room to keep the room bright. Near-infrared light is reflected and absorbed by a metal layer to shield it from entering the room from outside, so that the room does not get hot in the summer. Far-infrared rays are emitted from the room, and are reflected by the metal layer so that the indoor heat does not go out of the room in winter or the like. Ultraviolet rays are reflected and absorbed by the metal layer and shielded from entering the room from the outside so that the articles in the room do not deteriorate over time.

The heat ray shielding material of this embodiment can be used mainly as a window plate or the like. The heat ray shielding material of this embodiment includes a base material and a metal layer. The metal layer is formed by arranging a number of island-shaped metal films, the diameter of the metal film is 0.05 to 0.50 mm, and the distance between the metal films is 0.02 to 0.23 mm. The area ratio of the portion not covered with the metal film is 11 to 80%. And the heat ray shielding material of this embodiment is characterized by having a visible light transmittance of 45% or more and an electromagnetic wave shielding rate of 10 dB or less.

The heat ray shielding material of the present embodiment includes a base material and a metal layer and can be used as a window plate. Here, the substrate may be one sheet or two or more sheets. When two or more substrates are used, the materials, thicknesses, and shapes of the individual substrates may be the same or different.

Therefore, the heat ray shielding material of the present embodiment may be of a type in which a metal layer is directly formed on a base material that can be used as a normal window plate, or a metal layer is formed on a thin sheet-like base material. In addition, it may be of a type that is bonded to a base material as a window plate with an adhesive or the like.

Furthermore, the form of the substrate is not particularly limited. Various forms such as a glass sheet, a glass plate, a resin film, a resin plate, a fabric, a nonwoven fabric, a transparent or translucent paper, and a molded product can be used. However, in order to form and arrange a number of island-shaped metal films on the surface of the substrate in an orderly manner, it is preferably a film or sheet having a flat surface. The substrate as the window plate is preferably a glass plate or a resin plate.

Moreover, the heat ray shielding material of the present embodiment can be laminated with various functional layers such as an adhesive layer, a hard coat layer, and a protective layer in addition to the base material and the metal layer. As a result, more effective characteristics can be imparted.

Hereinafter, the present embodiment will be described by classifying it into more specific embodiments. That is, the first to fifth embodiments and their modifications will be described.

<The heat ray shielding material of the first embodiment>
As described above, the heat ray shielding material of the first embodiment includes a base material and a metal layer, and the metal layer is formed by arranging a number of island-shaped metal films. Two types of base materials are used as the base material, a metal layer is formed on the surface of the first base material, and heat ray shielding is installed on the window plate that is the second base material via an adhesive layer or the like. It is a material. The heat ray shielding material of the first embodiment will be further described with three specific examples.

15 to 17 are schematic cross-sectional views showing three specific examples having different layer configurations of the heat ray shielding material of the first embodiment. FIG. 15 shows the layer structure of the heat ray shielding material 1A of the first embodiment. FIG. 16 shows the layer structure of the heat ray shielding material 1B of the first embodiment. FIG. 17 shows the layer structure of the heat ray shielding material 1C of the first embodiment.

Hereinafter, the heat ray shielding material 1A of the first embodiment, the heat ray shielding material 1B of the first embodiment, and the heat ray shielding material 1C of the first embodiment will be described. However, many explanations are common to the heat ray shielding material 1A of the first embodiment, the heat ray shielding material 1B of the first embodiment, and the heat ray shielding material 1C of the first embodiment.

[Configuration of Heat Ray Shielding Material of First Embodiment]
(Layer structure)
1 A of heat ray shielding materials of 1st Embodiment have the hard-coat layer 6 in the room inner side of the 1st base material 5 which consists of transparent resin (refer FIG. 15). An adhesive layer 3 is provided on the outdoor surface of the first base material 5 so as to be in close contact with the metal layer 4a formed by arranging a large number of island-like metal films and the window plate 2 as the second base material. And a window plate 2 as a second base material. The island-shaped metal film of the metal layer 4a is composed of a single layer of aluminum.

The heat ray shielding material 1B of the first embodiment has a hard coat layer 6 on the indoor side of the first base material 5 made of a transparent resin (see FIG. 16). In addition, an adhesive layer 3 for closely contacting the metal layer 4b formed by arranging a number of island-shaped metal films on the outdoor surface of the first substrate 5 and the window plate 2 as the second substrate. And a window plate 2 as a second base material. The island-shaped metal film of the metal layer 4b is composed of three conductive layers of ITO / Ag / ITO. Here, ITO is an abbreviation for indium tin oxide (tin-doped indium oxide). Three layers of ITO / Ag / ITO are formed by sputtering ITO, Ag, and ITO in order on the first substrate 5.

The heat ray shielding material 1C of the first embodiment includes a metal layer 4c and a hard coat layer 6 formed by arranging a number of island-shaped metal films on the indoor surface of the first base material 5 made of a transparent resin. (See FIG. 17). In addition, on the outdoor side of the first base material 5, there are an adhesive layer 3 for closely contacting the window plate 2 as the second base material and the window plate 2 as the second base material. The island-shaped metal film of the metal layer 4c is made of a single layer of aluminum.

Hereinafter, the above-mentioned “heat ray shielding material 1A”, “heat ray shielding material 1B”, and “heat ray shielding material 1C” will be collectively referred to as “heat ray shielding material 1”. In addition, the above “metal layer 4a”, “metal layer 4b”, “metal layer 4c”, “metal layer 4d” described later, and the like are collectively referred to as “metal layer 4” as appropriate.

Since the metal layer 4 of the heat ray shielding material 1 is installed on the indoor side of the window plate 2 which is the second base material, it is possible to reduce deterioration due to rain and wind. In addition, the metal layer 4 of the heat ray shielding material 1 can also be installed in the outdoor side of the window board 2 which is a 2nd base material. 15, 16, and 17, the description of “indoor” is “outdoor” and the description of “outdoor” is “indoor”. (Indoor) In this case, the hard coat layer 6 exists in the outdoor outermost layer of the heat ray shielding material 1 installed on the outdoor side of the window plate 2 as the second base material.

[Material of Heat Ray Shielding Material of First Embodiment]
Hereinafter, each material which comprises the heat ray shielding material 1 of 1st Embodiment is demonstrated in detail.
Unless otherwise specified, the heat ray shielding material of the second embodiment described later, the heat ray shielding material of the third embodiment, the heat ray shielding material of the fourth embodiment, the heat ray shielding material of the fifth embodiment, and modifications thereof The description of each material that constitutes the same is the same and can be applied in the same manner, and thus the description thereof is omitted.

(Window plate 2)
The window plate 2 is a transparent plate for taking sunlight from the outside into buildings, traffic vehicles, ships, and the like. It can be a base material for the heat ray shielding material 1. In general, a glass plate or a resin plate is used as the window plate 2. Various resins such as acrylic, styrene, hydrogenated cyclic resin, polycarbonate, and polyester can be used for the resin plate.

(Base material)
A base material is a material for maintaining the form as the heat ray shielding material 1, and can be used to form or hold the metal layer 4 constituting the heat ray shielding material on the surface thereof. In addition to the metal layer 4, it has a function of holding the hard coat layer 6, the adhesive layer 3, and the like. The base material may be the window plate 2 (second base material) or the base material 5 (first base material) different from the window plate.

The base material is preferably made of a transparent material so as to transmit visible light. The base material is preferably excellent in mechanical strength, durability, visible light transmittance, handleability, etc. that can stably hold the metal layer.

The materials used as the substrate include inorganic glass and organic resin. A typical example of inorganic glass is soda-lime glass. As the organic resin, various resins such as acrylic, polycarbonate, styrene, polyester, polyolefin, hydrogenated cyclic resin, fluorine, silicone, and urethane can be used. These organic resins can be used properly according to the application and purpose. Among these organic resins, polyesters are preferable from the viewpoints of moldability, handleability, weather resistance, and the like.

When the first base material 5 is used by being adhered to the window plate 2 via the adhesive layer 3 or the like, the thickness is 8 to 800 μm, although it depends on the mechanical properties of the material. Is preferred. More preferably, it is 12 to 400 μm.

(Metal layer 4)
The metal layer 4 is a layer that shields heat rays and ultraviolet rays of sunlight irradiated from the outside mainly by reflection and shields far infrared rays emitted from the room mainly by reflection. Reflection of heat rays, ultraviolet rays, and far-infrared rays is considered to occur because a large number of free electrons in the metal collectively vibrate according to the oscillating electric field of electromagnetic waves.

The metal layer 4 is a layer provided on at least one side of the substrate. It can be installed on either the indoor side surface or the outdoor side surface of the substrate, or both the indoor side surface and the outdoor side surface. However, it is preferable that the metal layer 4 is on the indoor side surface of the base material because it is excellent in far-infrared reflection performance (heat transmissivity described later).

As the metal constituting the metal layer 4, Al, Ag, Sn, Ni, Cu, Cr, In, Pd, Pt, Au, or the like can be used. These metals have excellent conductive performance and can reflect heat rays, far infrared rays, and ultraviolet rays. In addition, a film can be formed on the substrate by a vapor phase method, and an island-shaped metal film can be formed by etching or the like. These metals may be used alone or as an alloy if there is no problem in performance.

The metal film made of these metals usually has insufficient visible light transmission performance. Therefore, as described below, visible light and electromagnetic wave transmission performance can be imparted by arranging a large number of island-shaped metal films.

The metal layer 4 is formed by arranging a number of island-shaped metal films. The diameter of the metal film is 0.05 to 0.50 mm. The thickness is preferably 0.15 to 0.50 mm, more preferably 0.20 to 0.45 mm. Here, the diameter of the metal film refers to an average value of the maximum length of the island-shaped metal film. When the diameter of the metal film is less than 0.05 mm, the shielding performance such as heat rays becomes insufficient. If the diameter of the metal film exceeds 0.50 mm, the metal film can be easily recognized with the naked eye, the metallic luster becomes strong, and the appearance merchantability decreases.

Also, the distance between the metal films is 0.02 to 0.23 mm. The thickness is preferably 0.04 to 0.23 mm, and more preferably 0.05 to 0.2 mm. Here, the distance between the metal films refers to the shortest distance between the end of the island-shaped metal film and the end of the adjacent island-shaped metal film. If the distance between the metal films is less than 0.02 mm, the visible light transmittance may be reduced, and the radio wave permeability may be reduced. In addition, it may be difficult to manufacture by etching. When the distance between the metal films exceeds 0.23 mm, the metal film is easily recognized with the naked eye, and the appearance merchantability is reduced. Moreover, shielding performance, such as a heat ray, becomes insufficient.

The shape of the island-shaped metal film is not particularly limited, and can be a circle, a square, a rectangle, a regular polygon, an ellipse, an irregular shape, or the like. From the viewpoint of ease of production and ease of management of the shape of the metal film, a circle, a square, a rectangle, and a regular polygon are preferable. Further, the manner of arranging a large number of island-shaped metal films may be arranged regularly or randomly. From the viewpoint of ease of production and ease of management of the shape of the metal film, it is preferable to arrange them regularly.

(Surface resistance value)
The ability to reflect far infrared rays depends on the conductive performance of the metal film of the metal layer 4. The conductive performance of the metal film can be quantified as a surface resistance value. The surface resistance value can be measured by a 4-terminal 4-probe method according to JIS K7194. In the first embodiment, the surface resistance value is measured before the island-shaped metal film is formed by etching or the like.
The surface resistance value of the metal film is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less. When the surface resistance value of the metal film is 100 Ω / □ or less, the ability to reflect far-infrared rays becomes excellent, and the heat ray shielding material 1 having a low heat transmissivity can be obtained. The numerical value of the surface resistance value can be adjusted according to the type and thickness of the metal of the metal layer 4.

19 to 21 are examples of how to arrange island-shaped metal films. FIG. 19 shows a circular staggered arrangement. It arranges regularly so that the center of a circular metal membrane may be located in the vertex of an equilateral triangle. The diameter of the metal film is D (mm), and the distance between the metal films is P (mm).

FIG. 20 shows a square parallel arrangement. The square metal film is regularly arranged so that the center of the metal film is located at the vertex of the rectangle. The diameter of the metal film is about 1.41 × W (mm). The distance between the metal films is SP ₁ (mm) in the vertical direction and SP ₂ (mm) in the horizontal direction.

Fig. 21 shows a hexagonal staggered arrangement. The regular hexagonal metal coating is regularly arranged so that the center of the metal film is located at the apex of the regular triangle. The diameter of the metal film is about 1.15 × W (mm), and the distance between the metal films is P (mm).

In the metal layer 4, the area ratio (opening area ratio) of the portion not covered with the metal film is 11 to 80%. When the area ratio of the part not covered with the metal film is 11 to 80%, the electromagnetic wave transmission performance, heat ray shielding performance, visible light transmission performance, far-infrared reflection performance (heat transmissivity described later) Both can be satisfied with a good balance. The area ratio of the portion not covered with the metal film is preferably 15 to 75%, more preferably 18 to 70%, and still more preferably 20 to 65%.

In the circular staggered arrangement of FIG. 19, the area ratio R ₁ (%) of the portion not covered with the metal film can be calculated by the following equation (1).
R ₁ = 100 − {(90.6 × D ² ) / (P + D) ² } (1)

In the square parallel arrangement in FIG. 20, the area ratio R ₂ (%) of the portion not covered with the metal film can be calculated by the following equation (2).
R ₂ = 100-100 × W ² / {(W + SP ₁ ) × (W + SP ₂ )} (2)

In the hexagonal staggered arrangement of FIG. 21, the area ratio R ₃ (%) of the portion not covered with the metal film can be calculated by the following equation (3).
R ₃ = 100-100 × {W ² / (W + P) ² } (3)

The metal layer 4 may be composed of a single metal layer 4 or a plurality of metal layers 4. Since the performance as the metal layer 4 is stabilized and it is easy to obtain a layer having excellent transparency, the metal layer 4 is preferably composed of a plurality of metal layers.

The metal constituting the metal layer 4 is preferably composed of aluminum or silver. Silver is more preferable because of its excellent conductivity and easy formation and etching of a metal film by a vapor phase method.

When the metal layer 4 is composed of a plurality of conductive layers, by using a combination of highly refractive materials such as ITO (indium tin oxide), zinc oxide, tin oxide, tungsten oxide, titanium oxide, and aluminum nitride, The visible light transmittance of the metal layer 4 can be increased. In the heat ray shielding material 1B of the first embodiment, a conductive layer composed of three layers of ITO / Ag / ITO is used as the metal layer 4 (see FIG. 16). Moreover, the heat ray shielding material 10 of 2nd Embodiment mentioned later uses the conductive layer which consists of five layers of ITO / Ag / ITO / Ag / ITO as the metal layer 4 (refer FIG. 18).

The thickness of the metal film constituting the metal layer 4 is preferably 2 to 120 nm, more preferably 4 to 70 nm, and still more preferably 5 to 30 nm. Here, the thickness of the metal film refers to the total thickness of layers made of only metals such as Ag and Al. When the thickness of the metal film is in this range, the heat ray, far-infrared ray, and ultraviolet ray reflection properties are excellent, and the durability and handleability are also excellent.

(Adhesive layer 3)
In the heat ray shielding material 1 of 1st Embodiment, in order to adhere | attach the 1st base material 5 and the window board 2 which is a 2nd base material, the contact bonding layer 3 is provided.

The adhesive layer 3 is used, for example, when the purchaser of the heat ray shielding material product adheres the first base material 5 to the window plate 2 as the second base material, so that both are adhered. It can be. In this case, the adhesive layer has adhesiveness, and can also be referred to as an adhesive layer. A release sheet is affixed to the adhesive layer as necessary for improving the handleability. When installing on the window plate 2 as the second substrate, the release sheet is peeled off. Adhere.

As a material used for the adhesive layer 3, it is possible to use an adhesive or a pressure-sensitive adhesive generally used for glass sticking or the like. Examples include acrylic, silicone, urethane, butadiene, and natural rubber. Among these, acrylic and silicone are preferable from the viewpoint of durability.
The thickness of the adhesive layer 3 is preferably 5 to 50 μm.

(Hard coat layer 6)
In the heat ray shielding material 1 of the first embodiment, the hard coat layer 6 is provided as the outermost layer in order to prevent the surface of the heat ray shielding material 1 from being damaged or the inner layer portion from being destroyed by an external force.
As a material used for the hard coat layer 6, generally, an inorganic hard coat layer, an organic hard coat layer, an organic inorganic hard coat layer, a silicone hard coat layer, or the like can be used. Among these, ultraviolet curable acrylic resins are preferable.
The thickness of the hard coat layer 6 is preferably 0.5 to 20 μm.

(Protective layer)
The heat ray shielding material 1 according to the first embodiment is provided with a protective layer between the metal layer 4 and the adhesive layer 3 on the base material in order to prevent the metal layer 4 from being damaged by an external force or the like during manufacture. May be.
Examples of the protective layer include a coating method and a protective film adhesion method. In the coating method, an organic hard coat agent, an inorganic hard coat agent, a silicone hard coat agent, or the like can be applied and cured. Among these, ultraviolet curable acrylic resins are preferable. The thickness of the protective layer is preferably 0.5 to 20 μm.

In the adhesion method of the protective film, there is a method in which the protective film is bonded onto the metal layer 4 with an adhesive layer. As the protective film, a material such as a PET film can be used similarly to the base material. Examples of the adhesive for the adhesive layer of the protective film include acrylic, silicone, urethane, butadiene, and natural rubber. Among these, acrylic and silicone are preferable from the viewpoint of durability. The thickness of the adhesive layer is preferably 0.5 to 20 μm.

(Metal compounds that absorb heat rays)
In order to further improve the heat ray shielding performance of the heat ray shielding material 1 of the first embodiment, a metal compound that absorbs heat rays in a range that does not affect the visible light transmittance and other performances, the base material 5 and the hard coat It may be added to any one of the layer 6, the adhesive layer 3, and the window plate 2. Further, a layer containing a metal compound that absorbs heat rays may be provided separately. In this case, the layer containing the metal compound that absorbs heat rays is preferably arranged on the indoor side of the heat ray shielding material 1 in terms of performance.

Here, the metal compound that absorbs heat rays is a metal compound having a maximum absorption wavelength peak at 800 to 2500 nm. Specific examples of the metal compound that absorbs heat rays include cesium-containing tungsten oxide, lanthanum hexaboride, antimony-containing tin oxide, tin-containing indium oxide, and gallium-containing zinc oxide. Especially, it is preferable that it is any 1 or more types chosen from a cesium containing tungsten oxide, a lanthanum hexaboride, and an antimony containing tin oxide. Further, cesium-containing tungsten oxide having an excellent ability to absorb heat rays is particularly preferable.

The heat ray shielding material 1 of the first embodiment has a total thickness including the first base material 5, the metal layer 4, the hard coat layer 6, and the adhesive layer 3 excluding the window plate 2 that is the second base material. The thickness is preferably 10 to 800 μm, more preferably 16 to 500 μm.

[Performance of the heat ray shielding material of the first embodiment]
Hereinafter, various performances of the heat ray shielding material 1 of the first embodiment will be described.
Unless otherwise specified, the heat ray shielding material of the second embodiment described later, the heat ray shielding material of the third embodiment, the heat ray shielding material of the fourth embodiment, the heat ray shielding material of the fifth embodiment, and modifications thereof The description of the various performances of the system is the same and can be applied in the same manner, and thus the description thereof is omitted.

(Visible light transmittance)
The heat ray shielding material 1 of the first embodiment transmits visible light having a wavelength of 380 to 780 nm in order to brighten the room. Specifically, the visible light transmittance of the heat ray shielding material 1 is 45% or more. 60% or more is preferable, and 70% or more is more preferable. The visible light transmittance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the visible light transmittance can be adjusted according to the shape, thickness, metal type, material and thickness of the base material and the hard coat layer 6 of the metal layer 4 described above.

(Electromagnetic wave shielding rate)
The heat ray shielding material 1 according to the first embodiment uses an index called an electromagnetic wave shielding rate in order to quantify and evaluate the electromagnetic wave transmission performance. As an evaluation method, the KEC method was adopted. The measurement range of electromagnetic waves is 30 MHz to 1 GHz. A numerical value (dB) at a frequency of 800 MHz was used for the electromagnetic wave shielding rate.
The electromagnetic wave shielding rate is 10 dB or less. When the electromagnetic wave shielding rate is 10 dB or less, there can be no trouble when using a cellular phone, a portable TV, or the like indoors or in a vehicle. The electromagnetic wave shielding rate is preferably 5 dB or less, more preferably 3 dB or less, and even more preferably 1 dB or less.
The numerical value of the electromagnetic wave shielding rate can be adjusted by the shape, thickness, type of metal and the like of the metal film of the metal layer 4 described above.

(Visible light reflectance)
Although the visible light reflectance of the heat ray shielding material 1 of 1st Embodiment is not specifically limited, The one where a numerical value is low is preferable. Specifically, the visible light reflectance is preferably 25% or less. When the visible light reflectance is 25% or less, the metallic luster is small and the appearance as a product is excellent. The visible light reflectance is more preferably 20% or less, and further preferably 10% or less. The visible light reflectance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the visible light reflectance can be adjusted by the shape, thickness, type of metal, and the like of the metal film of the metal layer 4 described above.

(Solar radiation transmittance)
The heat ray shielding material 1 of the first embodiment suppresses transmission of visible light and near infrared light in the wavelength range of 300 to 2500 nm. The solar radiation transmittance of the heat ray shielding material 1 is preferably 60% or less. When the solar transmittance is 60% or less, the heat ray shielding property is excellent. 50% or less is more preferable. The solar radiation transmittance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the solar radiation transmittance can be adjusted by the material, thickness, etc. of each layer constituting the same as in the case of the visible light transmittance described above.

(Solar reflectance)
The heat ray shielding material 1 of the first embodiment preferably has a solar reflectance of 25% or more. When the solar reflectance is 25% or more, the heat ray shielding property is excellent. The solar reflectance is more preferably 30% or more. The solar reflectance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of solar reflectance can be adjusted by the material, thickness, etc. of each layer constituting the same as in the case of the visible light transmittance described above.

(Solar radiation absorption rate)
The heat ray shielding material 1 of the first embodiment preferably has a solar radiation absorption rate of 40% or less. When the solar radiation absorptivity is 40% or less, the temperature of the heat ray shielding material 1 is prevented from rising and the performance is deteriorated, and adverse effects that damage the window plate 2 are also suppressed. The solar radiation absorption rate is more preferably 35% or less. The solar absorptance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the solar radiation absorptance can be adjusted by the material, thickness, etc. of each layer constituting the same as in the case of the visible light transmittance described above.
Note that the sum of the values of solar transmittance, solar reflectance, and solar absorption rate is 100%.

(Chromaticity / Saturation of reflected light)
In the heat ray shielding material 1 of the first embodiment, when the reflected light is tinged with color, the merchantability on the appearance is deteriorated. Therefore, it is preferable that the color is not tinged. That is, in the chromaticity diagram of the L ^* a ^* b ^* color system described in JIS Z8729, it is preferable that the hue a ^* value, b ^* value and chroma C ^* value in reflected light are all small. Specifically, both are preferably 10 or less, and more preferably 5 or less.

(Heat shielding coefficient)
In the first embodiment, in order to quantify and evaluate the heat ray shielding performance of the metal layer 4, an index called a heat ray shielding coefficient is used. The heat ray shielding coefficient is measured using a spectrophotometer according to JIS A5759. The heat ray shielding coefficient is obtained by setting the Ni value to 0.34.
The heat ray shielding coefficient of the heat ray shielding material 1 of the first embodiment is preferably 0.9 or less. When the heat ray shielding coefficient exceeds 0.9, the shielding efficiency of near infrared rays is insufficient in view of the Green Purchasing Law standard of the Ministry of the Environment. The heat ray shielding coefficient is more preferably 0.8 or less, still more preferably 0.7 or less, and particularly preferably 0.6 or less.
The numerical value of the heat ray shielding coefficient can be adjusted by the shape, thickness, metal type, and the like of the metal film of the metal layer 4 described above.

(UV transmittance)
Sunlight that has passed through the heat-shielding material 1 is irradiated to indoor articles, but it is preferable to reduce the ultraviolet transmittance so that the indoor articles are not deteriorated by ultraviolet rays. In the first embodiment, the ultraviolet transmittance is evaluated using light having a wavelength of 380 nm as a measure of the ultraviolet transmittance. The ultraviolet transmittance (380 nm transmittance) can be measured using a spectrophotometer according to JIS A5759.
The ultraviolet ray transmittance (380 nm transmittance) of the heat ray shielding material 1 of the first embodiment is preferably 5% or less. The numerical value of the ultraviolet transmittance can be adjusted by the shape, thickness, type of metal, and the like of the metal film of the metal layer 4 described above.

(Heat flow rate)
In the first embodiment, in order to quantify and evaluate the far-infrared reflection efficiency of the metal layer 4, an index called a heat transmissivity is used. The heat transmissivity can be measured using an infrared reflection measuring instrument in accordance with JIS A5759.
It is preferable that the heat transmissivity of the heat ray shielding material 1 of 1st Embodiment is less than 5.9 W / m < ² > K. The heat ray shielding material 1 excellent in far-infrared reflection efficiency is preferably disposed on the surface layer as much as possible so as not to absorb far-infrared rays.

(Haze)
The heat ray shielding material 1 of the first embodiment preferably has a haze of 1.5% or less. When the haze is 1.5% or less, the visual field is excellent. The haze can be measured using a haze meter (haze meter) according to JIS K7136. The numerical value of haze can be adjusted according to the material, thickness, and the like of each layer constituting the same as in the case of the visible light transmittance described above.

(appearance)
The appearance of the heat ray shielding material 1 according to the first embodiment affects the merchantability as a heat ray shielding material. When the diameter of the metal film that forms the metal layer 4 is larger than 0.50 mm or the distance between the metal films exceeds 0.23 mm, the appearance of the heat ray shielding material 1 is not visible to the naked eye. It becomes easy to recognize and the merchantability of the appearance is lowered. The appearance of the heat ray shielding material 1 is determined by visual observation with the naked eye.

[Method for Manufacturing Heat-ray Shielding Material of First Embodiment]
The heat ray shielding material 1 of 1st Embodiment can be manufactured by forming each layer which comprises the heat ray shielding material 1 on the 1st base material 5 one by one. A representative example of the manufacturing method for forming each layer will be described below.
Unless otherwise specified, the heat ray shielding material of the second embodiment described later, the heat ray shielding material of the third embodiment, the heat ray shielding material of the fourth embodiment, the heat ray shielding material of the fifth embodiment, and modifications thereof Since the description of the manufacturing method is the same and can be applied in the same manner, the description thereof is omitted.

A method for forming the metal layer 4 will be described. First, a predetermined metal film is formed on the entire surface of the substrate 5 by a vapor phase method. As the vapor phase method, a known method such as a vacuum deposition method, a sputtering method, or a CVD method can be appropriately selected.
Next, a resist (photosensitive resin) film is formed on the metal film formed on the entire surface of the base material 5 by a predetermined arrangement of island-shaped metal films. As a method for forming the resist film, a known method such as a printing method or a photolithographic method can be selected. As the printing method, a known method such as gravure printing or screen printing can be selected.
Next, the portion of the metal film where the resist film is not present is removed by etching with acid or alkali. Thereafter, the resist film is peeled off with a solvent, water, or the like, whereby the metal layer 4 having a predetermined island-shaped metal film arrangement can be formed.
In addition to the resist method described above, a method for forming a predetermined island-shaped metal film is a laser in which a laser beam is irradiated onto the metal film in a pattern and the metal film at a specific position is removed by heating. The method can also be used.

The method for forming the adhesive layer 3 will be described. An appropriate amount of an adhesive or pressure-sensitive adhesive polymer is mixed with a solvent to prepare a solution having an appropriate viscosity. The solution is coated on the substrate 5. Then, the adhesive layer 3 can be formed by drying.

The method for forming the hard coat layer 6 will be described. An appropriate amount of a thermosetting resin or a photocurable resin is mixed in a solvent to prepare a solution having an appropriate viscosity. The solution is coated on the substrate 5. After drying, the hard coat layer 6 can be formed by performing a curing reaction using heat or light.

[Use of heat ray shielding material of first embodiment]
Since the heat ray shielding material 1 of the first embodiment transmits electromagnetic waves, a mobile phone, a mobile TV, or the like can be used indoors. Visible light irradiated from the outside is transmitted to some extent, so that the room can be brightened. On the other hand, since the heat ray shielding material 1 of 1st Embodiment shields a heat ray, it can suppress the raise of indoor air temperature. Further, far infrared rays emitted from the room can be prevented from escaping outside the room. Furthermore, ultraviolet rays can be shielded to prevent deterioration of indoor articles over time due to ultraviolet rays.
Unless otherwise specified, the heat ray shielding material of the second embodiment described later, the heat ray shielding material of the third embodiment, the heat ray shielding material of the fourth embodiment, the heat ray shielding material of the fifth embodiment, and modifications thereof This is also the same and can be applied in the same manner, so that the description thereof is omitted.

<Modification of the heat ray shielding material of the first embodiment>
The heat ray shielding material of the first embodiment is a heat ray shielding material of a type in which a metal layer is formed on the surface of a first base material and is installed on a window plate as a second base material via an adhesive layer or the like. However, a type in which the metal layer is directly formed on the window plate using only the window plate as the substrate without using the first substrate may be used. For example, a metal layer is formed on the surface of a temporary support, and this is laminated and pressure-bonded on the surface of the base material on which the metal layer is formed, and the temporary support is peeled off to transfer the metal layer to the base material. You may print directly with the method and the ink containing a metal in a base material. As described above, a transparent glass plate or a transparent resin plate can be used as the window plate as the base material.

Moreover, the heat ray shielding material of the first embodiment uses two types of base materials, a first base material and a window plate that is a second base material. However, if the first base material has sufficient mechanical strength, durability, handleability, etc. that can stably hold the metal layer, the window plate as the second base material is bonded. You don't have to. In this case, only the first substrate is used as the substrate.

Also, in the heat ray shielding material of the first embodiment, the first base material having a metal layer formed on the surface and the second base material that is a window plate are attached via an adhesive layer. However, when laminating the first base material and the second base material, it is possible to use a method in which the first base material and the second base material are stacked as they are, or mechanically fitted, or pressed from both sides without using an adhesive layer.

<The heat ray shielding material of 2nd Embodiment>
The heat ray shielding material of the second embodiment has two or more base materials as window plates as compared with the heat ray shielding material of the first embodiment, and the metal layer is sandwiched between these two or more base materials. It is a heat ray shielding material which has. The substrate as the window plate may be at least two, and may be three or more.

[Configuration of Heat Ray Shielding Material of Second Embodiment]
FIG. 18 is a schematic cross-sectional view showing a layer configuration of the heat ray shielding material 10 of the second embodiment.
The heat ray shielding material 10 according to the second embodiment includes a metal layer 4d formed by arranging a large number of island-shaped metal films on the indoor surface of the first base material 5 made of a transparent resin, and a second base material. And an adhesive layer 3a for closely contacting the window plate 2a (see FIG. 18). In addition, on the outdoor side of the base film 5, there is an adhesive layer 3 a for tightly contacting the window plate 2 a that is the third base material. Therefore, the heat ray shielding material 10 has a sandwich structure in which the metal layer 4d is sandwiched between two window plates 2a that are base materials from both sides via an adhesive layer or the like. The island-shaped metal film of the metal layer 4d is composed of five conductive layers of ITO / Ag / ITO / Ag / ITO. The five layers of ITO / Ag / ITO / Ag / ITO are formed by sequentially sputtering ITO, Ag, ITO, Ag, and ITO on the first substrate 5.

The heat ray shielding material 10 of the second embodiment has a configuration in which a metal layer 4d is formed on a base material 5 and is further sandwiched by two window plates 2a through two adhesive layers 3a. Therefore, no matter which side is the outdoor side, deterioration due to rain and wind can be reduced.

[Material of Heat Ray Shielding Material of Second Embodiment]
In the heat ray shielding material 10 of the second embodiment, when a glass plate is used as the material of the two window plates 2a as the base material, a so-called laminated glass is formed. When the materials constituting the laminated glass are strongly bonded using the two adhesive layers 3a, the laminated glass can be provided with excellent penetration resistance, impact resistance, and scattering prevention effects. The adhesive layer 3a is not particularly limited as long as it is a resin film that is generally used as an intermediate film of laminated glass, and preferably has no absorption in the visible light region or the infrared region.

The material used for the adhesive layer 3a of the heat ray shielding material 10 of the second embodiment is different from the material used for the adhesive layer 3 of the heat ray shielding material of the first embodiment. For example, the adhesive layer 3a of the heat ray shielding material 10 according to the second embodiment is applied or laminated on a base material as a resin having no adhesiveness at room temperature, and then heat-treats after laminating each material constituting the heat ray shielding material. In this way, the adhesive exhibits adhesiveness and adhesiveness, and can bond the respective layers.

Examples of such an adhesive include polyvinyl butyral resin (PVB resin), ethylene-vinyl acetate copolymer resin (EVA resin), and the like. An ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a colorant, an adhesion adjusting agent, and the like may be appropriately added to the resin forming the adhesive layer 3a. These resins may be used alone or in combination of two or more. The adhesive layer 3a may be manufactured using a known method, but a commercially available product may be used. Examples of commercially available products include plasticized PVB manufactured by Sekisui Chemical Co., Ltd. and Mitsubishi Plastics, EVA resin manufactured by DuPont and Takeda Pharmaceutical, and modified EVA resin manufactured by Tosoh. The adhesive layer 3a may be composed of a single layer of the above resin film, or may be composed of two or more layers laminated.

The thickness of the adhesive layer 3a of the heat ray shielding material 10 of the second embodiment is preferably 100 to 1000 μm. It does not restrict | limit especially as a method of producing the laminated glass of 2nd Embodiment, What is necessary is just to use the manufacturing method of a general laminated glass. Specifically, in the laminated glass of the second embodiment, the adhesive layer 3a, the base material on which the metal layer is formed, and the adhesive layer 3a are laminated and pre-adhered between the glass plates, and then bubbles remaining after the pre-adhesion are removed. It can be manufactured by a process of removing by pressure bonding at high temperature and high pressure.

When the

adhesive layers

3, 3a and the metal layer 4 are in contact with each other as in the first embodiment and the second embodiment described above, a metal film is used as the material used for the

adhesive layers

3, 3a. In order to prevent deterioration, a neutral pH is preferable. Specifically, a chemical structure that does not contain a carboxylic acid is preferable. Moreover, you may add a rust preventive material to the material used for the

contact bonding layers

3 and 3a.

[Method for Manufacturing Heat-ray Shielding Material of Second Embodiment]
A method for producing the heat ray shielding material 10 of the second embodiment will be described.
The method for forming the metal film on the substrate 5 and the method for forming the predetermined island-shaped metal film are the same as those in the method of manufacturing the heat ray shielding material of the first embodiment, and thus the description thereof is omitted. .

Next, adhesive layers 3a are formed on both surfaces of the base material 5 provided with the metal layer 4, respectively. An appropriate amount of the polymer adhesive is mixed with a solvent to prepare a solution having an appropriate viscosity. The solution is coated on the substrate 5 or the metal layer 4. Thereafter, the adhesive layer 3a can be formed by drying. Further, as described above, a protective layer may be provided between the metal layer 4 and the adhesive layer 3a.

The method in particular of bonding the base material 5 provided with the metal layer 4 and the contact bonding layer 3a and the glass plate 2a is not restrict | limited, What is necessary is just to use the manufacturing method of a general laminated glass. A specific example will be described next.
FIG. 22 is a schematic diagram showing a method for manufacturing the heat ray shielding material 10 according to the second embodiment.

First, as shown in FIG. 22A, a base material 9 having an adhesive layer on both sides is laminated between two glass plates 2a. The laminated glass plate 2a and the base material 9 having adhesive layers on both surfaces move on the roller 21 and move to the next step.

Next, as shown in FIG. 22 (b), the laminated glass plate 2 a and the base material 9 having the adhesive layers on both surfaces are heated to about 90 ° C. by the heater 23 in the sealed chamber 22. Subsequently, by passing a pair of pressure-bonding rolls 24, the laminated glass plate 2a and the base material 9 having an adhesive layer on both surfaces are temporarily pressure-bonded.

Next, as shown in FIG. 22 (c), the heat ray shielding material 10 that has been temporarily press-bonded is accommodated in the autoclave 25. In autoclave 25, it is pressurized to about 1 MPa and heated to about 130 ° C., thereby removing bubbles remaining after temporary pressure bonding, and the adhesive layer of heat ray shielding material 10 is sufficiently bonded to the glass plate, The heat ray shielding material 10 is manufactured.

<Modification of Heat Ray Shielding Material of Second Embodiment>
In order to further improve the heat ray shielding performance of the heat ray shielding material, the present inventor has studied the relationship with the wavelength of light. As a result, the transmittance in the wavelength region (800 to 2500 nm) of near-infrared or higher near visible light. Has been found to be effective. And in order to reduce the transmittance | permeability of the said wavelength range, it discovered that it was effective to provide the adhesive layer containing the glass plate containing an iron ion, or a heat ray absorptive metal compound fine particle.

That is, in the first modification of the heat ray shielding material of the second embodiment, the glass plate on the indoor side of the two glass plates that are the base material of the heat ray shielding material contains iron ions. In order to improve the shielding performance in the wavelength range of 800 to 2500 nm, it is effective that the glass plate on the indoor side of the two glass plates contains iron ions.

Also, in the second modification of the heat ray shielding material of the second embodiment, the indoor adhesive layer constituting the heat ray shielding material contains heat ray absorbing metal compound fine particles. Also in this case, in order to improve the shielding performance in the wavelength range of 800 to 2500 nm, it is effective that the indoor adhesive layer contains the heat ray absorbing metal compound fine particles among the plurality of adhesive layers of the heat ray shielding material. It is.

(First modification of the heat ray shielding material of the second embodiment)
FIG. 18 is a schematic cross-sectional view showing the layer configuration of the first modification of the heat ray shielding material 10 of the second embodiment, with the upper side being the indoor side and the lower side being the outdoor side. In the 1st modification of the heat ray shielding material 10 of 2nd Embodiment, the indoor side glass plate 2a contains the iron ion (not shown) among the two glass plates 2a which are base materials.

(Iron ion-containing glass plate)
The glass plate containing iron ions is soda lime glass mainly composed of silicon dioxide (SiO ₂ ), sodium oxide (Na ₂ O), calcium oxide (CaO), and iron content is Fe ₂ O _3. A glass plate containing 0.3 to 0.9% by mass and having iron reduced at a high reduction rate is preferable. As a standard for a high reduction rate of iron, the content ratio of divalent iron ions to trivalent iron ions (Fe ²⁺ / Fe ³⁺ ) is 50 to 250%. By reducing the iron content and increasing the content ratio of divalent iron ions, the absorptance in the infrared region can be increased. As a method for reducing the iron content, it can be prepared by melting in an electric melting furnace or the like using powders such as silica sand, feldspar, soda ash, and bengara as soda lime glass raw materials and carbon as a reducing agent. The reduction rate of iron can be measured by a redox measuring device.

By using a glass plate containing iron ions as the indoor glass plate 2a, it is possible to improve the shielding performance in the wavelength region of 800 to 2500 nm. As a result, the heat ray shielding coefficient as the heat ray shielding material 10 can be pushed down by the combined effect of the heat ray shielding material 10 with the metal layer 4d.

(Second modification of the heat ray shielding material of the second embodiment)
FIG. 18 is a schematic cross-sectional view illustrating a layer configuration of a second modification of the heat ray shielding material 10 of the second embodiment. In the 2nd modification of the heat ray shielding material 10 of 2nd Embodiment, the contact bonding layer 3a of the indoor side of the heat ray shielding material 10 contains a heat ray absorptive metal compound fine particle (not shown). That is, the heat ray absorbing metal compound fine particles described below are uniformly contained in the adhesive used for the adhesive layer 3a.

(Heat-absorbing metal compound fine particles)
The heat ray absorbing metal compound is a metal compound having a maximum absorption wavelength peak in the infrared region. Specific examples of heat-absorbing metal compounds include cesium-containing tungsten oxide, lanthanum hexaboride, cerium hexaboride, antimony-containing tin oxide, tin-containing indium oxide, aluminum-containing zinc oxide, indium-containing zinc oxide, tin-containing zinc oxide. And silicon-containing zinc oxide, gallium oxide-containing zinc oxide, and the like. Among these, at least one selected from cesium-containing tungsten oxide, lanthanum hexaboride, antimony-containing tin oxide, and tin-containing indium oxide is preferable, and tin-containing indium oxide is particularly preferable.

The heat ray absorbing metal compound is contained in the adhesive layer 3a as fine particles. The average particle diameter of the fine particles is preferably 100 nm or less. When it exceeds 100 nm, the scattering of visible light by the fine particles becomes remarkable, and the transparency may be lowered. More preferably, it is 10 to 80 nm.

The content of the heat ray absorbing metal compound fine particles is preferably 0.1 to 3% by mass with respect to the adhesive. When it is less than 0.1% by mass, the heat ray shielding performance is not sufficiently exhibited. On the other hand, if it exceeds 3% by mass, the visible light transmittance is lowered or the haze is increased.

It is possible to improve the heat ray shielding performance by using the adhesive layer containing the heat ray absorbing metal compound fine particles as the indoor adhesive layer 3a. As a result, the heat ray shielding coefficient as the heat ray shielding material 10 can be pushed down by the combined effect of the heat ray shielding material 10 with the metal layer 4d.

In the first modification of the second embodiment, the case where the indoor side glass plate 2a of the heat ray shielding material 10 contains iron ions is exemplified. Moreover, in the 2nd modification of 2nd Embodiment, the case where the indoor side adhesion layer 3a of the heat ray shielding material 10 contained the heat ray absorptive metal compound fine particle was illustrated. Therefore, these two modifications may be combined. That is, iron ions are contained in the glass plate 2a on the indoor side of the heat ray shielding material 10, and heat ray absorbing metal compound fine particles are contained in the adhesive layer 3a on the indoor side. Such a heat ray shielding material 10 can exhibit both the effects of both modifications, and is more preferable.

As described above, the present inventors have found that it is effective to increase the reflectance in the near-infrared wavelength region (800 to 1200 nm) close to visible light in order to further improve the heat ray shielding performance. Therefore, it has been found that a method of installing a transparent resin layer having a multilayer structure is effective as a method different from the method shown in the modification of the second embodiment. Further, the present inventor has effective to use a transparent resin layer having a multilayer structure with a thickness of 50 to 1000 nm per layer in order to increase the reflectance in the wavelength region of 800 to 1200 nm. I found out.
That is, as one of the elements constituting the heat ray shielding material, it is possible to further improve the heat ray shielding performance by introducing a transparent resin layer having a multilayer structure by coating with a multilayer film or a liquid crystal resin. I found.

Here, as a method for introducing a transparent resin layer having a multilayer structure into a heat ray shielding material, a method of laminating a resin layer having a multilayer structure on one surface of a substrate, and a resin material having a multilayer structure as the substrate itself There is a method. Therefore, these two embodiments will be described below as a third embodiment and a fourth embodiment, respectively.

<The heat ray shielding material of 3rd Embodiment>
The heat ray shielding material of 3rd Embodiment is equipped with the base material and the metal layer, The metal layer is provided in one surface of the said base material, The resin layer which has a multilayer structure in the other surface of the said base material It has. The multilayer structure has a thickness of 50 to 1000 nm per layer.

[Configuration of Heat Ray Shielding Material of Third Embodiment]
FIG. 23 is a schematic cross-sectional view showing the layer configuration of the heat ray shielding material 20A of the third embodiment.
In the heat ray shielding material 20 </ b> A of the third embodiment, the adhesive layer 3, the transparent resin layer 8 having a multilayer structure, the adhesive layer 3, and the second base material are sequentially provided on the outdoor side of the first base material 5. Window plate 2 is laminated. On the other hand, a metal layer 4 is formed on the indoor side of the first base material 5. The metal layer 4 is formed by arranging a large number of island-shaped metal films.

[Material for Heat-ray Shielding Material of Third Embodiment]
(Transparent resin layer 8 having a multilayer structure)
The transparent resin layer 8 having a multilayer structure is a layer having a particularly excellent reflectance in the near-infrared wavelength region (800 to 1200 nm) close to visible light among sunlight irradiated from outside.

There are several methods for forming the transparent resin layer 8 having a multilayer structure on the substrate 5. Specifically, there are a method using a multilayer film and a method using a liquid crystal resin coating.

The multilayer film is a film having a structure in which the same or different polymers having different refractive indexes are alternately laminated. The thickness per layer of the multilayer structure can be adjusted by changing the extrusion thickness and the stretching ratio at the time of co-extrusion.
A method for producing a multilayer film having such a structure is described in, for example, JP-T 9-506837, JP-A 2007-307893, JP-A 2008-273186, JP-A 2013-209246, and the like. Yes. As the resin constituting the multilayer film, acrylic, polycarbonate, styrene, polyester, and polyolefin resins can be used. In particular, polyester resins such as PET, PBT, and PEN are preferable.

It is known that a liquid crystal resin forms a multilayered layer by coating a solution on a base film. For example, when a chiral agent is added to an acrylic resin nematic liquid crystal and UV cured, a cholesteric liquid crystal layer is formed. The thickness per layer can be adjusted by changing the addition amount of the chiralizing agent. A method for producing a liquid crystal resin layer having such a structure is described in, for example, Japanese Patent Application Laid-Open Nos. 2010-286663 and 2012-13963.

The transparent resin layer 8 having a multilayer structure has a high reflectance in a wavelength region of 800 to 1200 nm because the thickness per layer of the multilayer structure is 50 to 1000 nm. When the transparent resin layer 8 having a multilayer structure is irradiated with heat rays, the heat rays are usually reflected at each interface of the multilayer structure having a different refractive index. In a multilayer thin film structure, in order for reflection to occur from individual layers and the phase of each reflected light to be aligned to increase the reflectance, it is effective that the thickness per layer of the multilayer structure is in the above range. . The thickness per layer of the multilayer structure is preferably 70 to 300 nm.

Also, in order to have a specifically high reflectance in the wavelength region of 800 to 1200 nm, the number of layers in the multilayer structure is preferably 50 to 600 layers, more preferably 100 to 400 layers. preferable. When the number of layers in the multilayer structure exceeds 600, the wavelength region having a high reflectance is widened, and the light in the visible light region is also reflected. Therefore, the visible light transmittance is reduced.
The heat shrinkage of the multilayer film is preferably 1% or less when left in a drying oven at 130 to 150 ° C. for 30 minutes. When this value exceeds 1%, it becomes a factor that wrinkles are easily formed when adhering to the base film 5 or adhering to laminated glass described later, and the metal layer is cracked or peeled off.

<The comparative example and modification of the heat ray shielding material of 3rd Embodiment>
FIG. 24 is a schematic cross-sectional view showing a layer structure of a heat ray shielding material 20B of a comparative example of the third embodiment. Although it has the metal layer 4 on one surface of the 1st base material 5, the metal layer is not formed by arrange | positioning many island-shaped metal films. Further, the transparent resin layer 8 having a multilayer structure is not provided. The heat-shielding material 20B is constituted as a whole by being bonded to the window plate 2 as the second base material with the adhesive layer 3.
FIG. 25 is a schematic cross-sectional view showing a layer configuration of a heat ray shielding material 20C of a comparative example of the third embodiment. The heat ray shielding material 20 </ b> C has the transparent resin layer 8 having a multilayer structure, but does not have the metal layer 4. The transparent resin layer 8 having a multilayer structure is bonded to the window plate 2 as a base material by the adhesive layer 3.
FIG. 26 is a schematic cross-sectional view illustrating a layer configuration of a heat ray shielding material 20D according to a modification of the third embodiment. The heat ray shielding material 20D has a hard coat layer 6 in the outermost layer on the indoor side in addition to the layer configuration of the heat ray shielding material 20A of FIG.
FIG. 27 is a schematic cross-sectional view showing a layer configuration of a heat ray shielding material 20E according to a modification of the third embodiment. Of the layer configuration of the heat ray shielding material 20D, the heat ray shielding material 20E has four layers of the metal layer 4, the base material 5, the adhesive layer 3, and the transparent resin layer 8 having a multilayer structure, and the directions to the inside and the outside are reversed. ing. At this time, unlike the heat ray shielding material 20E, the heat ray shielding material 20D is preferable because the metal layer 4 is on the indoor side of the transparent resin layer 8 having a multilayer structure, and is excellent in the effect of improving the heat ray shielding performance.

<Heat ray shielding material of the fourth embodiment>
The heat ray shielding material of the fourth embodiment includes a base material and a metal layer, and the base material is a resin material having a multilayer structure. The multilayer structure has a thickness of 50 to 1000 nm per layer.

[Configuration of Heat Ray Shielding Material of Fourth Embodiment]
FIG. 28 is a schematic cross-sectional view showing the layer structure of the heat ray shielding material 30 of the fourth embodiment.
In the heat ray shielding material 30 of the fourth embodiment, the adhesive layer 3 and the window plate 2 as the second base material are sequentially laminated on the outdoor side of the transparent resin layer 8a having a multilayer structure as the base material. Yes. On the other hand, a metal layer 4 and a hard coat layer 6 are sequentially laminated on the indoor side of the transparent resin layer 8a having a multilayer structure as a base material. The metal layer 4 is formed by arranging a large number of island-shaped metal films.

A fourth embodiment in which the arrangement of the metal layer 4 and the transparent resin layer 8a having a multilayer structure is reversed with respect to the heat ray shielding material 30, and the metal layer 4 is formed outside the transparent resin layer 8a having the multilayer structure. There exists a modification (not shown). At this time, it is preferable that the metal layer 4 is on the indoor side of the transparent resin layer 8a having a multilayer structure because the effect of improving the heat ray shielding performance is superior. Further, it is possible to reversely read indoors and outdoors as in the case of the first embodiment.

However, unlike the third embodiment, the transparent resin layer 8a having the multilayer structure of the fourth embodiment is a layer having a function as a base material. Therefore, the transparent resin layer 8a having the multilayer structure of the fourth embodiment also has a function of holding the metal layer 4, the adhesive layer 3, and the like, and is excellent in mechanical strength, visible light transmittance, workability, and the like. Is preferred. Therefore, the transparent resin layer 8a having a multilayer structure is preferably manufactured by a method using a multilayer film rather than a method using a liquid crystal resin coating.

<The heat ray shielding material of 5th Embodiment>
Similarly to the heat ray shielding material of the second embodiment, the heat ray shielding material of the fifth embodiment has two or more base materials as window plates, and these two or more base materials as window plates are metal. It has the structure which pinches | interposes a layer. Furthermore, it has the

transparent resin layers

8 and 8a which have the multilayer structure used in 3rd Embodiment or 4th Embodiment as the component. That is, the second embodiment has a configuration in which the

transparent resin layers

8 and 8a having a multilayer structure characteristic in the third embodiment and the fourth embodiment are combined.

[Configuration of Heat Ray Shielding Material of Fifth Embodiment]
FIG. 29 is a schematic cross-sectional view showing the layer configuration of the heat ray shielding material 40 of the fifth embodiment.
Various combinations of the third embodiment or the fourth embodiment with respect to the second embodiment exist. The heat ray shielding material 40 shown in FIG. 29 shows an example thereof, and is an example when the base material is a resin material having a multilayer structure.

In the heat ray shielding material 40 of the fifth embodiment, the adhesive layer 3a and the window plate 2a as the second base material are sequentially laminated on the outdoor side of the transparent resin layer 8a having a multilayer structure as the base material. Yes. On the other hand, on the indoor side of the transparent resin layer 8a having a multilayer structure as a base material, a metal layer 4, an adhesive layer 3a, and a window plate 2a as a third base material are laminated in order. Therefore, the heat ray shielding material 40 has a sandwich structure in which the metal layer 4 is sandwiched between two window plates 2a that are base materials from both sides via an adhesive layer or the like. The metal layer 4 is formed by arranging a large number of island-shaped metal films.

The heat ray shielding material 40 is formed on the transparent resin layer 8a having a multilayer structure in which the metal layer 4 is a base material, and is further sandwiched by two window plates 2a through two adhesive layers 3a. Because of this configuration, it is possible to reduce deterioration due to rain and wind, regardless of which side is the outdoor side.

5th Embodiment will comprise what is called a laminated glass, when a glass plate is used as a raw material of the window plate 2a. When the laminated glass is constituted using the adhesive layer 3a, the laminated glass can be provided with excellent penetration resistance, impact resistance, and scattering prevention effects.
In addition, since the material, manufacturing method, modification, and the like constituting the heat ray shielding material 40 are the same as those in the case of the heat ray shielding material of the second embodiment, the description thereof is omitted.

This embodiment will be described more specifically with reference to the following examples.

Example 1
A composition A having the following composition was coated on one surface of an easily-adhesive PET film (U40, 100 μm thickness) using a bar coater and dried in a hot air oven at 100 ° C. for 2 minutes. Thereafter, the coated surface was cured by irradiating with ultraviolet rays (integrated light amount 300 mJ / cm ² ) with a high-pressure mercury lamp, thereby forming a hard coat layer having a thickness of about 4 μm.

<Composition A>
Dipentaerythritol polyacrylate-based ultraviolet curable resin (Arakawa Chemical Co., Ltd., Beam Set 700) 83.3 parts by mass Photopolymerization initiator (BASF, Irgacure 184) 1 part by mass Toluene 320 parts by mass

Aluminum was deposited on the surface of the PET film opposite to the hard coat layer using a deposition method under a vacuum of 5 × 10 ⁻⁵ Torr. On the produced aluminum film, a resist dissolved in a solvent was printed by gravure printing so as to have the predetermined island-like arrangement shown in FIG. In the shape of the metal film in each figure, a circle means a circular staggered type (see FIG. 19), a square means a square parallel type (see FIG. 20), and a hexagon means a hexagonal staggered type (see FIG. 21). After the resist was dried at 200 ° C., the aluminum film on the portion where the resist was not printed was dissolved and removed using an aqueous hydrochloric acid solution. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the aluminum film. After washing with water and drying, a metal layer having a predetermined island-like metal film disposed on the surface of the PET film opposite to the hard coat layer was formed.

On the other hand, a composition B having the following composition was applied on a silicone-treated separator (manufactured by Mitsubishi Plastics, MRQ # 38, 38 μm thickness) using an applicator. Then, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 22 μm.

<Composition B>
Acrylic neutral adhesive (manufactured by Soken Chemical Co., Ltd., SK Dine 2975) 100 parts by mass Curing agent (manufactured by Soken Chemical Co., Ltd., Y-75) 0.2 parts by mass Triazine UV absorber (manufactured by BASF, Tinuvin 477) 3 parts by mass Parts 100 parts by mass of toluene

Furthermore, the adhesive layer was laminated with the surface on which the metal layer of the PET film was formed. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a 3 mm thick alkali glass plate to produce a heat ray shielding material, and various performances were evaluated.

(Examples 2 to 5)
The thickness of the metal layer (aluminum film), the shape of the metal film, the diameter of the metal film, the distance between the metal films, and the opening area ratio (the area ratio of the portion not covered with the metal film) are shown in FIG. Except for the changes, a heat ray shielding material was produced in the same manner as in Example 1, and various performances were evaluated.

(Examples 6 and 7)
In the same manner as in Example 1, an easy-adhesion PET film having a hard coat layer formed on one side was produced. On the surface opposite to the hard coat layer of the PET film, using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 30 nm thick ITO film, a 10 nm thick Ag film, and a 30 nm thick ITO film The films were sequentially laminated to form a metal film having a three-layer structure.

A resist (photosensitive resin) film is thermally laminated on the prepared metal film, exposed and developed by a photolithography method, and the resist is formed to have the predetermined island-like arrangement shown in FIG. did. After the resist was dried at 120 to 160 ° C., the metal film on the portion where the resist was not printed was dissolved and removed using an aqueous solution of ferric chloride. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the metal film. After washing with water and drying, a metal layer having a predetermined island-like metal film disposed on the surface of the PET film opposite to the hard coat layer was formed.
Thereafter, in the same manner as in Example 1, a heat ray shielding material was produced, and various performances were evaluated.

(Examples 8 and 9)
On one side of an easy-adhesive PET film (manufactured by Teijin Ltd., HB, 100 μm thickness), using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 40 nm thick ITO film, a 10 nm thick Ag film, A 70 nm thick ITO film, a 12 nm thick Ag film, and a 35 nm thick ITO film were sequentially laminated to form a metal film having a five-layer structure.

A resist film was heat-laminated on the produced metal film, exposed and developed by a photolithography method, and a resist was formed to have a predetermined island-like arrangement shown in FIG. After the resist was dried at 120 to 160 ° C., the metal film on the portion where the resist was not printed was dissolved and removed using an aqueous solution of ferric chloride. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the metal film. It washed with water and dried and formed the metal layer by which the predetermined island-like metal membrane | film | coat was arrange | positioned on the single side | surface of PET film.

On the other hand, a sheet of PVB (polyvinyl butyral film, Sekisui Chemical Co., Ltd., S-LEC TB) having a thickness of 380 μm was placed as an adhesive layer on two alkali glass plates having a thickness of 3 mm. Thereafter, it was dried in a hot air oven at 100 ° C. for 2 minutes to adhere the alkali glass plate and PVB, thereby producing two alkali glass plates having an adhesive layer on one side.

A single alkali glass plate having an adhesive layer was placed on a flat table with the adhesive layer facing upward. On top of that, the above PET film was placed with the layer on which the metal layer was formed facing upward. Further thereon, another alkali glass plate having an adhesive layer was placed with the adhesive layer on the lower side. The obtained multilayer sheet was temporarily pressure-bonded through a roll laminator having a metal roll heated at 60 ° C. Thereafter, the multilayer sheet temporarily bonded was put in an autoclave and subjected to main pressure bonding by autoclaving under conditions of 130 ° C., 13 atm, and 1 hour to produce a heat ray shielding material in the form of laminated glass (see FIG. 18). . Thereafter, various performances were evaluated.

(Example 10)
In the same manner as in Example 1, first, aluminum was vapor-deposited on one surface of the easy-adhesion PET film using a vapor deposition method under a vacuum of 5 × 10 ⁻⁵ Torr. Next, a resist is printed on the prepared aluminum film in the same manner as in Example 1 so as to have the predetermined island-like arrangement shown in FIG. A metal layer in which a metal film was disposed was formed.

Next, the surface of the PET film on which the metal layer on which the island-shaped metal film was arranged was formed, the composition A was applied using a bar coater, and the procedure described in Example 1 was performed to obtain a thickness of about 4 μm. A hard coat layer was formed. In the same manner as in Example 1, an adhesive layer was laminated on the surface of the PET film opposite to the surface on which the metal layer and the hard coat layer were formed. Thereafter, in the same manner as in Example 1, a heat ray shielding material was produced, and various performances were evaluated.

(Examples 11, 13, and 14)
A heat ray shielding material was prepared in the same manner as in Example 10 except that the thickness of the metal layer (aluminum film), the diameter of the metal film, the distance between the metal films, and the opening area ratio were changed to the values described in FIG. Various performances were evaluated.

(Examples 12 and 15)
Except that the composition A was changed to the following composition C, Example 12 was prepared in the same manner as in Example 11, and Example 15 was prepared in the same manner as in Example 14 to produce a heat ray shielding material and evaluated various performances. Went.

<Composition C>
Solid content of dipentaerythritol polyacrylate-based ultraviolet curable resin (Arakawa Chemical Co., Ltd., Beam Set 700) 83.3 parts by mass Cs _0.33 WO ₃ (Sumitomo Metal Mining Co., Ltd., YMF-02A, average particle size 20 nm) 20 mass% toluene dispersion 9.0 mass parts as solid content Photopolymerization initiator (BASF, Irgacure 184) 1 mass part Toluene 320 mass parts

(Examples 16 and 17)
In Example 16, a heat ray shielding material was produced in the same manner as in Example 7 except that the diameter of the metal film, the distance between the metal films, and the opening area ratio were changed to the numerical values described in FIG. Went. In Example 17, a heat ray shielding material was produced in the same manner as in Example 6 except that the configuration of the metal layer was changed to the same as that in Example 9, and various performances were evaluated.

(Comparative Examples 1 to 14)
Comparative Examples 1 to 13 were heat ray shieldings produced in Examples 1 to 6, Example 8, and Examples 10 to 15, respectively, without forming the metal film into a predetermined island-shaped metal film using a resist. It is a material. The comparative example 14 is the heat ray shielding material produced in Example 1 without forming a metal film. Each performance was evaluated.

(Comparative Examples 15 to 17)
Comparative Examples 15 and 16 were heat ray shielding materials in which a heat ray shielding material was produced in the same manner as in Example 1 except that the diameter of the metal coating, the distance between the metal coatings, and the opening area ratio were changed to the numerical values shown in FIG. It is. Comparative Example 17 is a heat ray shielding material produced without forming a metal film into a predetermined island-shaped metal film using a resist while forming a metal layer in the same manner as in Example 16. Each performance was evaluated.

(Examples 18 to 34, Comparative Examples 18 to 20)
Examples 18 to 23, 25 to 27, and 29 to 34 are heat ray shielding materials prepared in Examples 1 to 15 without being bonded to an alkali glass plate, respectively. These have a configuration corresponding to a modification of the first embodiment. Similarly, Examples 24 and 28 are heat ray shielding materials that were manufactured without being bonded to an alkali glass plate in the same manner as in Examples 18 to 23 and the like, although the structure of the metal layer was partially different. . Similarly, Comparative Examples 18 and 19 are heat ray shielding materials produced in Comparative Examples 15 and 16 without being bonded to an alkali glass plate, respectively. Similarly, the comparative example 20 is a heat ray shielding material manufactured without being bonded to an alkali glass plate in the same manner as in the example 23 and the like, although the structure of the metal layer is partially different. Each performance was evaluated.

<Performance evaluation method>
In Examples and Comparative Examples, surface resistance value, electromagnetic wave shielding rate, visible light transmittance, visible light reflectance, solar transmittance, solar reflectance, solar absorption rate, chromaticity / saturation of reflected light, heat ray shielding coefficient, The performance was evaluated under the conditions described below for the ultraviolet transmittance, thermal conductivity, haze, and appearance. In addition, evaluation was performed about the transmitted light and reflected light by irradiating a predetermined light ray from the outdoor side of the heat ray shielding material.

(Surface resistance value)
It was measured by JIS K7194 4 terminal 4 probe method (Dia Instruments Co., Ltd., Loresta MCP-T610).

(Electromagnetic wave shielding rate)
Using a sample of 15 cm × 15 cm, the electromagnetic wave shielding rate was measured in the frequency range of 30 MHz to 1 GHz by the KEC method. The numerical value of the electromagnetic wave shielding rate was a value (dB) at a frequency of 800 MHz.

(Visible light transmittance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Visible light reflectance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar radiation transmittance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar reflectance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar radiation absorption rate)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Chromaticity and saturation of reflected light)
From the chromaticity diagram of the L ^* a ^* b ^* color system described in JIS Z8729, chromaticity a ^* , b ^* , and saturation C ^* were calculated. The saturation C ^* is calculated by the following formula.
C ^* = {(a ^* ) ² + (b ^* ) ² } ^1/2
Based on JIS Z8722, it measured about the light which reflected the heat ray shielding material using the light source D65. As a measuring apparatus, SE2000 manufactured by Nippon Denshoku Co., Ltd. was used.

(Heat shielding coefficient)
The heat ray shielding coefficient is measured using a spectrophotometer according to JIS A5759. The heat ray shielding coefficient was determined by setting the Ni value to 0.34. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(UV transmittance)
In accordance with JIS A5759, the transmittance of light having a wavelength of 380 nm was measured. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Heat flow rate)
The heat transmissivity is measured using an infrared reflectometer in accordance with JIS A5759. When the heat transmissivity is less than 5.9 W / m ² K, it is determined that the far-infrared reflection efficiency is excellent. In this example, an infrared reflection measuring machine (manufactured by Shimadzu Corporation, FTIR8700) was used.

(Haze)
The haze was measured using a haze meter (Nippon Denshoku Co., Ltd., NDH7000) in accordance with JIS K7136.

(appearance)
The appearance of the heat ray shielding material is determined by visual observation with the naked eye. When the metal film could not be recognized with the naked eye, it was judged as ◯, and when the metal film could be recognized with the naked eye, it was judged as x.

The results obtained in Examples and Comparative Examples are shown in FIGS. As a reference, the performance of a single alkali glass plate is shown as Comparative Example 14. In the column of “surface resistance value”, the column “over” indicates that the metal layer is formed of an island-shaped metal film or there is no metal layer, so that the measurement terminals are electrically insulative. It is shown that. In FIG. 1 to FIG. 6, the column with “-” indicates that measurement could not be performed. The same applies to FIGS.

3 and 4, the heat ray shielding materials of Examples 1 to 5 have the layer configuration of the first embodiment (FIGS. 15 and 1A), and the thickness of the metal layer, the arrangement of the metal film, the area ratio of the opening, The diameter of the metal film and the distance between the metal films are different. Each of the examples satisfies the provisions of claim 1 and is a heat ray shielding material having excellent visible light transmission performance, heat ray shielding performance, electromagnetic wave transmission performance, and ultraviolet ray shielding performance, and an excellent appearance. .

The heat ray shielding materials of Examples 6, 7, 16, and 17 have the layer configuration of the first embodiment (FIGS. 16 and 1B), and three layers of ITO / Ag / ITO or ITO / Ag / ITO / Ag / ITO. And having a multi-layer metal layer composed of five layers. In addition, Examples 8 and 9 have the layer configuration of the second embodiment (FIGS. 18 and 10), and have a multilayer metal layer composed of five layers of ITO / Ag / ITO / Ag / ITO. It has the structure pinched | interposed into a window plate. Examples 6 to 9, 16, and 17 are superior to Examples 1 to 5 in terms of visible light transmittance and visible light reflectance.

The heat ray shielding materials of Examples 10 to 15 have the layer configuration of the first embodiment (FIGS. 17 and 1C). Compared with Examples 1 to 5, it is a heat ray shielding material that has an excellent heat transmissibility and an excellent far-infrared reflection efficiency. In particular, Example 12 and Example 15 are superior to the corresponding Examples 11 and 14, respectively, because the hard coat layer contains cesium-containing tungsten oxide, so that the heat ray shielding coefficient is superior. Yes.

In Comparative Examples 1 to 13, the metal layer was not formed by arranging a large number of island-shaped metal films, and all of the values were excessive in electromagnetic wave shielding rate.
Comparative Example 15 and Comparative Example 16 have the layer configuration of the first embodiment (FIGS. 15 and 1A), but satisfy the provisions of the present invention in terms of the opening area ratio, the diameter of the metal film, and the distance between the metal films. Not done. Comparative Example 15 was inferior in visible light transmission performance and appearance, and Comparative Example 16 was inferior in heat ray shielding performance. In Comparative Example 17, the metal layer was not formed by arranging a large number of island-shaped metal films, and the numerical value was excessive in the electromagnetic wave shielding rate.

Each of Examples 18 to 34 and Comparative Examples 18 to 20 in FIGS. 5 and 6 is a heat ray shielding material not bonded to an alkali glass plate, Examples 1 to 17 in FIGS. 3 and 4 and Comparative Examples. 15 and 16 have almost the corresponding performance.

(Laminated film B1)
A metal layer having a five-layer structure was formed on one surface of an easily adhesive PET film (Toray Industries, Inc., U40, 50 μm thickness, hereinafter referred to as “PET film”). Specifically, using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 40 nm thick ITO film, a 10 nm thick Ag film, a 70 nm thick ITO film, a 12 nm thick Ag film, A metal layer having a five-layer structure was formed by sequentially laminating an ITO film having a thickness of 35 nm.

Thereafter, a resist dissolved in a solvent was printed on the produced metal layer by gravure printing so as to have the island-like arrangement shown in FIG. Here, the diameter of the metal film was 360 μm, the distance between the metal films was 40 μm, and the opening area ratio was 19%.

After the resist was dried at 200 ° C., the metal film of the portion where the resist was not printed was dissolved and removed using an aqueous ferric chloride solution. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the metal film. After washing with water and drying, a metal layer in which a metal film having a predetermined five-layer structure was disposed was formed on the PET film.

On the other hand, a composition D having the following composition was coated on a separator treated with silicone (manufactured by Mitsubishi Plastics, MRQ # 38, 38 μm thickness, hereinafter referred to as “separator”) using an applicator. Thereafter, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 1 μm.

<Composition D>
Acrylic neutral adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 2975) 100 parts by mass Curing agent (manufactured by Soken Chemical Co., Ltd., Y-75) 0.2 parts by mass
100 parts by mass of toluene

Furthermore, the adhesive layer was laminated with the surface of the PET film on which the metal layer was formed. The separator was peeled off, and the exposed adhesive layer and a 50 μm-thick PET film as a protective film were bonded together to produce a laminated film B1.

(Laminated film B2)
A metal layer having a five-layer structure was formed on one surface of the PET film. Specifically, using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 35 nm thick ITO film, a 9 nm thick Ag film, a 60 nm thick ITO film, a 9 nm thick Ag film, A 30 nm thick ITO film was sequentially laminated to form a metal layer having a five-layer structure. Thereafter, etching was performed on the produced metal layer in the same manner as B1, thereby forming a metal layer in which a metal film having a five-layer structure having a predetermined shape described in FIG. 21 was disposed. Here, the diameter of the metal film was 250 μm, the distance between the metal films was 60 μm, and the opening area ratio was 35%.

On the surface of the PET film on which the metal layer was formed, the composition A was applied using a bar coater and dried in a hot air oven at 80 ° C. for 2 minutes. Thereafter, the coated surface was cured by irradiating with ultraviolet light (integrated light amount 500 mJ / cm ² ) with a high-pressure mercury lamp, and a protective layer having a thickness of about 4 μm was formed to produce a laminated film B2.

(Example 36)
A sheet of PVB (polyvinyl butyral film, manufactured by Sekisui Chemical Co., Ltd., S-LEC PVB0.38) having a thickness of 380 μm as an adhesive layer on a float glass plate (thickness 2 mm) of soda-lime glass (hereinafter referred to as “PVB sheet”) To be described).

On the other hand, instead of soda lime glass, a glass plate (thickness 2 mm) of soda lime glass containing iron ions was used, and a PVB sheet as an adhesive layer was placed on the iron ion containing glass plate in the same manner as described above.

A glass plate having an adhesive layer was placed on a flat table so that the adhesive layer was on the upper side. On top of that, the laminated film B1 was placed so that the metal layer was on the upper side. Further thereon, an iron ion-containing glass plate having an adhesive layer was placed so that the adhesive layer was on the lower side. The obtained laminate was passed through the production line described in FIG. That is, in the sealed chamber 22, the obtained laminate was heated to about 90 ° C. using the heater 23. Then, the glass plate 2a laminated | stacked and the base material 9 which has an adhesive layer on both surfaces were temporarily crimped | bonded by letting a pair of crimping | compression-bonding rolls 24 pass.

Next, the heat-shielding material 10 that was temporarily bonded was stored in the autoclave 25. The autoclave 25 is pressurized to about 1 MPa and heated at about 130 ° C. for 30 minutes to remove bubbles remaining after the temporary pressure bonding, and the base material 9 having an adhesive layer on both sides is sufficiently adhered to the glass plate 2a by the adhesive layer. The bonded heat ray shielding material 10 was manufactured. The configuration according to the configuration shown in FIG. 18 was assumed.

(Example 37)
Unlike Example 36, a float glass plate (thickness 2 mm) of soda-lime glass was used as each of the two glass plates without using an iron ion-containing glass plate. A PVB sheet having a thickness of 380 μm as an adhesive layer was placed on one glass plate.

On the other glass plate, a sheet of PVB polyvinyl butyral film (S-LEC SCF (L), 780 μm thickness) containing tin-containing indium oxide fine particles was placed as an adhesive layer.

A glass plate having an adhesive layer was placed on a flat table with the adhesive layer facing upward. On top of that, the laminated film B1 was placed so that the metal layer was on the upper side. Further thereon, a glass plate having an adhesive layer containing heat-absorbing metal compound fine particles was placed with the adhesive layer facing down. The obtained laminate was passed through the production line described in FIG. That is, in the sealed chamber 22, the obtained laminate was heated to about 90 ° C. using the heater 23. Then, the base material 9 which has the laminated | stacked glass plate 2a and an adhesive layer on both surfaces was temporarily crimped | bonded by letting a pair of crimping | compression-bonding rolls 24 pass.

Next, the heat-shielded laminated glass 10 that was temporarily press-bonded was stored in the autoclave 25. The autoclave 25 is pressurized to about 1 MPa and heated at about 130 ° C. for 30 minutes to remove bubbles remaining after the temporary pressure bonding, and the base material 9 having an adhesive layer on both sides is sufficiently adhered to the glass plate 2a by the adhesive layer. The bonded heat ray shielding material 10 was manufactured. The configuration according to the configuration shown in FIG. 18 was assumed.

(Example 38)
In Example 37, the heat ray shielding material 10 was produced in the same manner as in Example 37 except that the laminated film B2 was used instead of the laminated film B1.

(Example 39)
In Example 36, it was manufactured in the same manner as in Example 36 except that a glass sheet of soda-lime glass (thickness 2 mm) was used as the two glass sheets without using the iron ion-containing glass sheet. Thus, the heat ray shielding material 10 was manufactured.

(Example 35)
In Example 36, except that the iron ion-containing glass plate was not used, and as the two glass plates, a soda-lime glass float glass plate (thickness 2 mm) was used, and the configuration of the metal layer was partially changed. Were manufactured in the same manner as in Example 36 to manufacture the heat ray shielding material 10.

(Reference Example B1, Reference Example B2)
For reference, the performance of the above laminated film B1 and laminated film B2 was also evaluated.

The results obtained for Examples 35 to 39 and Reference Examples B1 and B2 are shown in FIGS.

7 and 8, the heat ray shielding materials of Examples 36 to 38 have a glass plate containing iron ions or an adhesive layer containing heat ray absorbing metal compound fine particles on the indoor side of the metal layer. The heat ray shielding materials of Examples 35 and 39 do not have a glass plate containing iron ions or an adhesive layer containing heat ray absorbing metal compound fine particles. All of them had good performance in heat ray shielding coefficient, visible light transmittance, visible light reflectance, solar transmittance, solar reflectance, solar absorption rate, and electromagnetic wave shielding rate. In particular, the heat ray shielding materials of Examples 36 to 38 were extremely excellent with a heat ray shielding coefficient of 0.60 or less.

The laminated film B1 and laminated film B2 of the reference example do not have a glass plate containing iron ions or an adhesive layer containing heat ray-absorbing metal compound fine particles. Compared with Examples 36 to 38, heat ray shielding The coefficient was inferior.

30 to 35 are spectrum diagrams of transmittance and reflectance of the heat ray shielding materials of Examples and Reference Examples. A solid line is a spectrum of transmitted light, and a broken line is a spectrum of reflected light. 30 and 31 show the spectra of Example 36 and Example 37, respectively. On the other hand, FIG. 32 shows the spectrum of Example 39, which shows the characteristics of only the metal layer having an island-shaped metal film. The transmittance in the near infrared and near-wavelength region (800 to 1800 nm) close to visible light was slightly high, resulting in slightly inferior heat ray shielding coefficient.

On the other hand, FIGS. 33, 34, and 35 are spectra of reference examples, respectively. FIG. 33 is a spectrum of a laminated glass having a structure in which only a 380 μm-thick PVB sheet is sandwiched between two iron ion-containing glass plates (thickness 2 mm) and bonded. In FIG. 34, only a sheet of PVB (polyvinyl butyral film, 760 μm thickness) containing tin-containing indium oxide fine particles as an adhesive layer is sandwiched between two soda-lime glass float glass plates (thickness 2 mm). It is a spectrum of the laminated glass of the structure only bonded together. FIG. 35 shows a configuration in which only a sheet of PVB (760 μm thick) containing tin-containing indium oxide fine particles is sandwiched between two iron ion-containing glass plates (thickness 2 mm) and bonded together. It is the spectrum of glass. These reference examples have only a glass plate containing iron ions, only an adhesive layer containing heat-absorbing metal compound fine particles, or both, and do not have a metal layer. All of them had a characteristic of absorbing from visible light to the near infrared region, and reflected light was slight.

In Examples 36 and 37, the heat ray shielding coefficient is obtained by absorbing iron ions or heat ray absorbing metal compound fine particles in a wavelength region of near infrared or higher near visible light that is not sufficiently shielded by the metal layer alone. Improvements have been made.

(Comparative Example 21)
A metal layer having a three-layer structure was formed on one surface of an easy-adhesion PET film (Toray Industries, Inc., U40, 100 μm thickness, hereinafter referred to as “PET film”). Specifically, using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 50 nm thick ITO film, an 11 nm thick Ag film, and a 50 nm thick ITO film are sequentially laminated on one surface of the PET film. Thus, a metal layer having a three-layer structure was formed.
On the other hand, the composition B was applied onto a silicone-treated separator (Mitsubishi Plastics, MRQ # 38, 38 μm thickness, hereinafter referred to as “separator”) using an applicator. Then, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 22 μm.

Furthermore, the adhesive layer was laminated with the surface of the PET film on which the metal layer was formed. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a 3 mm thick alkali glass plate (hereinafter referred to as “glass plate”) to produce a heat ray shielding material F1, and various performances were evaluated. (See FIGS. 24 and 20B).

(Multilayer film C, Multilayer film D)
Some multilayer films as transparent resin layers having a multilayer structure used in the present embodiment are commercially available, and they were obtained and used for experiments.
As a multilayer film in which 200 layers are alternately laminated in the thickness direction, there is nano90 (non-adhesive product) manufactured by 3M. The multilayer film has a thickness of 50 μm, and the average thickness per layer of the multilayer structure is 250 nm (hereinafter referred to as “multilayer film C”).
As a multilayer film in which 1000 layers are alternately laminated in the thickness direction, there is Picasas GL-30 manufactured by Toray. This is because the thickness of the multilayer film is 100 μm, and the average thickness per layer of the multilayer structure is 100 nm (hereinafter referred to as “multilayer film D”).

(Comparative Example 22)
A 50 nm thick ITO film, an 11 nm thick Ag film, and a 50 nm thick ITO film were sequentially laminated on one surface of the PET film by sputtering under a vacuum of 5 × 10 ⁻⁵ Torr. A metal layer having a three-layer structure was formed.
Furthermore, the composition A was coated on the surface of the PET film on which the metal layer was formed using a bar coater and dried in a hot air oven at 100 ° C. for 2 minutes. Thereafter, the coated surface was cured by irradiating with ultraviolet rays (integrated light amount 300 mJ / cm ² ) with a high-pressure mercury lamp, thereby forming a hard coat layer having a thickness of about 4 μm.

On the other hand, composition A was applied onto two separators using an applicator. Thereafter, it was dried in a hot air oven at 100 ° C. for 2 minutes to form two adhesive layers having a thickness of about 22 μm.
One of the adhesive layers was laminated with the surface of the PET film on which the metal layer and the hard coat layer were not formed.
Another adhesive layer was laminated with one surface of the multilayer film C.
After standing for 7 days, the separator of the PET film was peeled off and bonded to the surface of the multilayer film C where the adhesive layer was not formed. Furthermore, the separator of the multilayer film C was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F3, and various performances were evaluated (see FIGS. 24 and 20B).

(Example 46)
A 50 nm thick ITO film, an 11 nm thick Ag film, and a 50 nm thick ITO film were sequentially laminated on one surface of the PET film by sputtering under a vacuum of 5 × 10 ⁻⁵ Torr. A metal layer having a three-layer structure was formed.
Thereafter, a resist dissolved in a solvent was printed on the produced metal layer by gravure printing so as to have the island-like arrangement shown in FIG. Here, the diameter of the metal film was 300 μm, the distance between the metal films was 33 μm, and the opening area ratio was 19%.
After drying the resist at 120 ° C., the portion of the metal film where the resist was not printed was dissolved and removed using an aqueous ferric chloride solution. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the metal film. After washing with water and drying, a metal layer in which a metal film having a predetermined three-layer structure was disposed was formed on the PET film (hereinafter referred to as “circular zigzag-arranged three-layer metal layer”).

On the other hand, the composition A was coated on the separator using an applicator. Then, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 22 μm.
Further, the adhesive layer was laminated with the surface of the PET film on which the metal layer was formed. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F4, and various performances were evaluated.

(Example 40)
A PET film having a metal layer was produced in the same manner as the heat ray shielding material F3 except that a PET film having a circular staggered three-layer metal layer created in the heat ray shielding material F4 was used.
Furthermore, the separator of the multilayer film C was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F5, and various performances were evaluated (see FIGS. 26 and 20D).

(Example 47)
It produced similarly to the heat ray shielding material F5 except having used the multilayer film D instead of the multilayer film C. FIG.
Furthermore, the separator of the multilayer film D was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F7, and various performances were evaluated (see FIGS. 26 and 20D).

(Example 48)
On one side of the PET film, using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr, a 40 nm thick ITO film, 10 nm thick Ag film, 70 nm thick ITO film, 12 nm thick An Ag film and a 35 nm-thick ITO film were sequentially laminated to form a metal layer having a five-layer structure.
Thereafter, a resist dissolved in a solvent was printed on the produced metal layer by gravure printing so as to have the island-like arrangement shown in FIG. Here, the diameter of the metal film was 360 μm, the distance between the metal films was 40 μm, and the opening area ratio was 19%. The obtained metal layer is referred to as “circular staggered arrangement five-layer metal layer”.
Other manufacturing conditions were produced in the same manner as the heat ray shielding material F4. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F8, and various performances were evaluated.

(Example 41)
A PET film having a metal layer formed thereon was prepared in the same manner as the heat ray shielding material F5 except that a PET film having a circular staggered 5-layer metal layer prepared in the heat ray shielding material F8 was used.
Furthermore, the separator of the multilayer film C was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F9, and various performances were evaluated (see FIGS. 26 and 20D).

(Example 42)
Except for the contents described below, the production conditions described in the heat ray shielding material F3 and the heat ray shielding material F8 were used.
A hard coat layer was formed on one surface of the multilayer film C. Furthermore, the adhesive layer formed on the separator was laminated on the surface of the multilayer film C where the hard coat layer was not formed.
The adhesive layer formed on the other separator was laminated on the metal layer of the PET film having the circular staggered five-layer metal layer prepared in the heat ray shielding material F8.
After leaving for 7 days, the separator of the multilayer film C was peeled off and bonded to the surface of the PET film on which the adhesive layer was not formed. Furthermore, the separator of the PET film was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F10, and various performances were evaluated (see FIGS. 27 and 20E).

(Example 43)
A 47 nm thick ITO film, an 11 nm thick Ag film, and a 47 nm thick ITO film are sequentially laminated on one surface of the multilayer film C using a sputtering method under a vacuum of 5 × 10 ⁻⁵ Torr. Thus, a metal layer having a three-layer structure was formed.
Thereafter, a resist dissolved in a solvent was printed on the produced metal layer by gravure printing so as to have the island-like arrangement shown in FIG. Here, the diameter of the metal film was 150 μm, the distance between the metal films was 45 μm, and the opening area ratio was 41.0%.
After drying the resist at 120 ° C., the portion of the metal film where the resist was not printed was dissolved and removed using an aqueous ferric chloride solution. Thereafter, the resist was dissolved using an aqueous solution of sodium hydroxide and peeled off from the surface of the metal film. It was washed with water and dried to form a metal layer on the multilayer film C in which a metal film having a predetermined three-layer structure was disposed.

Further, on the surface of the multilayer film C on which the metal layer was formed, the composition B was applied using a bar coater and dried in a hot air oven at 100 ° C. for 2 minutes. Thereafter, the coated surface was cured by irradiating with ultraviolet rays (integrated light amount 300 mJ / cm ² ) with a high-pressure mercury lamp, thereby forming a hard coat layer having a thickness of about 4 μm.

On the other hand, the composition A was coated on the separator using an applicator. Then, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 22 μm.
Further, the adhesive layer was laminated with the surface of the multilayer film C where the metal layer was not formed. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a glass plate to produce a heat ray shielding material F11, and various performances were evaluated (see FIGS. 28 and 30).

(Example 44)
In the heat ray shielding material F5, the heat ray shielding sheet which did not provide the contact bonding layer on the glass plate side of the multilayer film C was produced.
On the other hand, a sheet of PVB (polyvinyl butyral film, Sekisui Chemical Co., Ltd., S-LETB) having a thickness of 380 μm as a second adhesive layer was placed on each of two glass plates. Thereafter, it was dried in a hot air oven at 100 ° C. for 2 minutes to bond the glass plate and PVB, and two glass plates having an adhesive layer on one side were produced.

A single alkali glass plate having an adhesive layer was placed on a flat table with the adhesive layer facing upward. On top of this, the heat ray shielding sheet was placed with the side on which the multilayer film C was bonded facing up. Further thereon, another alkali glass plate having an adhesive layer was placed with the adhesive layer on the lower side. The obtained multilayer sheet was temporarily pressure-bonded through a roll laminator having a metal roll heated at 60 ° C. Thereafter, the multilayer sheet that had been temporarily press-bonded was placed in an autoclave and autoclaved under conditions of 130 ° C., 13 atm, and 1 hour, thereby being subjected to main press-bonding to produce a laminated glass having a heat ray shielding sheet sandwiched therebetween. Thereafter, various performances were evaluated (see FIGS. 29 and 40).

(Example 45)
In the heat ray shielding material F9, the heat ray shielding sheet which did not provide the contact bonding layer on the glass plate side of the multilayer film C was produced.
Others were produced under the same conditions as in Example 38 to produce a laminated glass with a heat ray shielding sheet sandwiched between them. Thereafter, various performances were evaluated (see FIGS. 29 and 40).

The results obtained in Examples 40 to 48 and Comparative Examples 21 and 22 are shown in FIGS.

36 and 37 are spectrum diagrams of transmittance and reflectance of the heat ray shielding materials of the third embodiment and the comparative example.
T1 and R1 are spectral diagrams of transmittance and reflectance, respectively, of a laminated material in which a multilayer film C and a glass plate are bonded together with an adhesive layer. The multilayer film C has a thickness of 250 nm per layer of the multilayer structure, but it is shown that the transmittance is specifically low and the reflectance is high in the wavelength region of 850 to 1050 nm. T2 and R2 are spectrum diagrams of transmittance and reflectance of the heat ray shielding material F4 (Example 46), respectively. It is shown that the heat ray shielding material having only the circular staggered three-layer metal layer has high transmittance and low reflectance in the near infrared wavelength region (800 to 1200 nm) close to visible light.

T3 and R3 are spectrum diagrams of transmittance and reflectance of the heat ray shielding material F5 (Example 40), respectively. The combination of the multilayer film C and the circular staggered three-layer metal layer shows that the transmittance is kept low and the reflectance is increased in the near-infrared wavelength region (800 to 1200 nm) close to visible light. ing.

38 and 39 are spectrum diagrams of transmittance and reflectance of the heat ray shielding material of the comparative example. T4 and R4 are spectral diagrams of transmittance and reflectance of a laminated material in which a multilayer film D and a glass plate are bonded with an adhesive layer, respectively. The multilayer film D has a thickness of 100 nm per layer of the multilayer structure, but the transmittance decreases in the near-infrared wavelength region (800 to 1200 nm) close to visible light as seen in the multilayer film C. No specific characteristics were found.

9 and 10, the heat ray shielding materials of Examples 40 to 48 have a metal layer formed by arranging a large number of island-like metal films and a transparent resin layer (multilayer film) having a multilayer structure. is there. All have excellent heat ray shielding coefficient of 0.60 or less, visible light transmittance, visible light reflectance, solar transmittance, solar reflectance, solar absorption rate, chromaticity / saturation of reflected light, electromagnetic wave shielding rate Also had good performance.

As can be seen from the comparison between Example 40 and Example 41, in comparison between the circular staggered arrangement three-layer metal layer and the circular staggered arrangement five-layer metal layer, Example 41 having a five-layer metal layer is more It was excellent in heat ray shielding coefficient and visible light reflectance.
As can be seen from the comparison between Example 41 and Example 42, the configuration having a metal layer on the indoor side and a transparent resin layer having a multilayer structure on the outdoor side is superior in heat ray shielding coefficient and solar reflectance. It was.
Example 43 is an example according to the fourth embodiment. This is an example according to the third embodiment, and has almost the same performance when compared with Example 40 having a similar configuration.

9 and 10, Example 44 and Example 45 have a laminated glass structure, and both have excellent heat ray shielding coefficient of 0.60 or less, visible light transmittance, visible light reflection. In terms of rate, solar transmittance, solar reflectance, solar radiation absorption rate, and electromagnetic wave shielding rate, it also had good performance.

Comparative Example 21 and Comparative Example 22 have an excessive electromagnetic shielding rate because the metal layer is present on the entire surface of the heat ray shielding material. Example 46 and Example 48 did not have a transparent resin layer having a multilayer structure, and were slightly inferior to the heat ray shielding coefficient as compared with Example 40. Example 47 has a metal layer formed by arranging a large number of island-shaped metal films and a transparent resin layer (multilayer film D) having a multilayer structure. However, due to the optical characteristics of the multilayer film D, although the heat ray shielding coefficient was relatively low, the visible light transmittance was considerably low and the visible light reflectance was relatively high.

(Examples 49 to 52, Comparative Examples 23 to 30)
As in Examples 23 to 28 and Comparative Example 20, Examples 49 to 52 and Comparative Examples 23 to 30 are heat ray shielding materials prepared without being bonded to an alkali glass plate. These have a configuration corresponding to a modification of the first embodiment. The manufacturing method was performed according to Examples 23 to 28 and Comparative Example 20, and a heat ray shielding material having a metal layer having the contents shown in FIG. 11 was produced. However, it manufactured using SZO (tin containing zinc oxide) instead of ITO used for a metal layer. Each performance was evaluated.
The results obtained in Examples 49 to 52 and Comparative Examples 23 to 30 are shown in FIGS.

As can be seen from FIGS. 11 and 12, the examples satisfying the provisions of the present invention have good performance in heat ray shielding coefficient, visible light transmittance, visible light reflectance, electromagnetic wave shielding rate, appearance, and the like. there were. On the other hand, the comparative example which does not satisfy the provisions of the present invention in terms of the shape of the metal film is inferior in electromagnetic wave shielding rate, appearance and the like.

(Examples 53 to 60, Comparative Example 31, Comparative Example 32)
Each of Examples 53 to 60, Comparative Example 31, and Comparative Example 32 is a heat ray shielding material produced without being bonded to an alkali glass plate, as in Examples 23 to 28 and Comparative Example 20. These have a configuration corresponding to a modification of the first embodiment. The manufacturing method was performed according to Examples 23 to 28 and Comparative Example 20, and a heat ray shielding material having a metal layer having the contents shown in FIG. 13 was produced. However, it manufactured using IZO (indium containing zinc oxide) instead of ITO used for a metal layer. Each performance was evaluated.
The results obtained in Examples 53 to 60, Comparative Example 31, and Comparative Example 32 are shown in FIGS.

As can be seen from FIGS. 13 and 14, the examples satisfying the provisions of the present invention are as follows: heat ray shielding coefficient, visible light transmittance, visible light reflectance, chromaticity / saturation of reflected light, electromagnetic wave shielding rate, and appearance. It had good performance. On the other hand, the comparative example in which a large number of island-shaped metal films are not formed in the metal layer is inferior in the electromagnetic wave shielding rate.

1A, 1B, 1C, 10, 20A, 20B, 20C, 20D, 30, 40 Heat-shielding

material

2, 2a Base material (window plate)
3,

3a Adhesive layer

4, 4a, 4b, 4c, 4d Metal layer 5 Base material 6

Hard coat layer

8, 8a Transparent resin layer having a multilayer structure

Claims

A heat ray shielding material comprising a base material and a metal layer,
The metal layer is formed by arranging a number of island-shaped metal films,
The diameter of the metal film is 0.05 to 0.50 mm;
The distance between the metal films is 0.02 to 0.23 mm,
The area ratio of the portion not covered with the metal film is 11 to 80%,
Visible light transmittance is 45% or more,
A heat ray shielding material having an electromagnetic wave shielding rate of 10 dB or less.
The metal substrate is provided on one surface of the substrate, the resin layer having a multilayer structure is provided on the other surface, and the thickness per layer of the multilayer structure is 50 to 1000 nm. The heat ray shielding material described in 1.
2. The heat ray shielding material according to claim 1, wherein the base material is a resin material having a multilayer structure, and the thickness per layer of the multilayer structure is 50 to 1000 nm.
The heat ray shielding material according to claim 1, wherein there are two base materials, and the metal layer is sandwiched between the two base materials.
The heat ray shielding material according to any one of claims 1 to 4, wherein the visible light reflectance is 25% or less.
6. The heat ray shielding material according to claim 1, wherein the heat ray shielding coefficient is 0.9 or less.
The heat ray shielding material according to any one of claims 1 to 6, wherein the metal layer is composed of a plurality of metal layers.
The heat ray shielding material according to any one of claims 1 to 7, wherein the metal layer contains silver.
The heat ray shielding material according to any one of claims 1 to 8, wherein the heat transmissivity is less than 5.9 W / m 2 K.
The heat ray shielding material according to any one of claims 1 to 9, wherein the ultraviolet ray transmittance is 5% or less.
The metal film has a diameter of 0.15 to 0.50 mm;
The heat ray shielding material according to any one of claims 1 to 10, wherein a distance between the metal films is 0.04 to 0.23 mm.