JP2021098287A - Heat ray shielding film and heat ray shielding laminated glass - Google Patents

Abstract

To provide a heat ray shielding film which reflects light with suppressed red color.SOLUTION: A heat ray shielding film is provided, comprising at least a substrate film 1 and a metal laminated portion 2 laminated on one surface of the substrate film. The substrate film is composed of a resin, the metal laminated portion is composed of a laminate in which at least a first metal oxide layer 11, a first metal layer 12, a second metal oxide layer 13, a second metal layer 14 and a third metal oxide layer 15 are laminated in this order from the substrate film side, each of the first metal oxide layer, the second metal oxide layer and the third metal oxide layer is composed of tin-doped indium oxide or zinc-doped indium oxide, and each of the first metal layer and the second metal layer is composed of a silver alloy.SELECTED DRAWING: Figure 1

Description

The present invention relates to a heat ray shielding film and a heat ray shielding laminated glass.

Conventionally, as one of the energy-saving measures for buildings such as buildings and houses and transportation such as trains and automobiles, the development of transparent materials having heat ray shielding performance has been promoted. For example, transparent materials for window panels have been developed that transmit visible rays of the sun's rays that fall from windows but block heat rays, while having a heat insulating function to prevent indoor heat from escaping to the outside.

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

However, since such a uniform metal layer generally reflects electromagnetic waves, there may be a problem that it becomes difficult to use a mobile phone, a television, or the like indoors, in a car, or the like. Therefore, the development of glass plates and films having a function of shielding heat rays but transmitting electromagnetic waves has been promoted.

For example, Patent Document 1 describes a structure in which a transparent laminated film having a laminated structure portion of a metal oxide layer and a metal layer is sandwiched between two transparent base materials, and a groove portion is formed in the laminated structure portion. A heat-shielding laminated structure is disclosed. Further, Patent Document 2 discloses a heat-reflecting structure having an alternating laminate in which metal layers and dielectric layers are alternately laminated on a base material such as glass.

Further, Patent Document 3 discloses a heat ray-shielding laminated glass having a structure in which a heat ray-shielding film is sandwiched between two glass plates, and the heat ray-shielding film includes at least one of a base film and a base film. It is provided with a metal laminated portion laminated in a direction, and a plurality of metal laminated portions are arranged in an island shape on one surface of the base film, and the metal laminated portion is arranged on one surface of the base film. By using a film having an area ratio of more than 80% and 95% or less, a heat-shielding laminated glass having excellent heat ray shielding performance and visible light transmission performance, and further excellent electromagnetic wave transmission performance can be obtained. It is stated that it will be done.

Japanese Unexamined Patent Publication No. 2013-209230 Japanese Unexamined Patent Publication No. 2013-256104 JP-A-2019-189515

For example, the heat-shielding laminated glass described in Patent Document 3 is excellent in heat ray-shielding performance, visible light transmission performance, and electromagnetic wave transmission performance, and is suitably used as a heat-shielding laminated glass required for transportation such as automobiles. can do.

By the way, when the heat ray-shielding film or the heat-shielding laminated glass using the heat ray-shielding film is irradiated with light, if the reflected light is tinged with red, the commercial value in appearance is deteriorated. Therefore, it is required to suppress the red color of the reflected light. For example, the heat-shielding laminated glass described in Patent Document 3 can also suppress the red color of the reflected light, but the present inventors have pursued the development of a technique for suppressing the red color of the reflected light to a higher degree.

An object of the present invention is to provide a heat ray-shielding film in which the red color of reflected light is suppressed. Another object of the present invention is to provide a heat-shielding laminated glass using the heat ray-shielding film.

The present inventors have made diligent studies to solve the above problems. As a result, in the heat ray shielding film including the base film made of resin and the metal laminated portion laminated on one surface of the base film, the laminated structure, material, and thickness of the metal laminated portion have a specific relationship. It was found that when set, the red color of the reflected light was highly suppressed. Specifically, in a heat ray shielding film including at least a base film and a metal laminated portion laminated on one surface of the base film, the base film is made of a resin, and the metal laminated portion is at least. , The first metal oxide layer, the first metal layer, the second metal oxide layer, the second metal layer, and the third metal oxide layer are laminated in this order from the base film side. The first metal oxide layer, the second metal oxide layer, and the third metal oxide layer are each composed of tin-doped indium oxide or zinc-doped indium oxide, and the first metal layer and the second metal layer are composed of tin-doped indium oxide or zinc-doped indium oxide, respectively. Each is composed of a silver alloy, the geometrical film thickness of the second metal oxide layer is 60 nm or more and 90 nm or less, and the geometrical film thickness of the first metal oxide layer and the third metal oxide layer is 15 nm, respectively. By setting the thickness to 30 nm or less and the total of the geometric film thickness of the first metal layer and the geometric film thickness of the second metal layer to be 19.0 nm or more and 25 nm or less, the red color of the reflected light is concavely suppressed. I found that. Furthermore, it has been found that the red color of the reflected light is suitably suppressed in the heat ray-shielding laminated glass having a structure in which the heat ray-shielding film is sandwiched between two glass plates. The present invention has been completed by further studies based on such findings.

That is, the present invention includes the following.
Item 1. At least, it includes a base film and a metal laminated portion laminated on one surface of the base film.
The base film is made of resin and is made of resin.
In the metal laminated portion, at least the first metal oxide layer, the first metal layer, the second metal oxide layer, the second metal layer, and the third metal oxide layer are laminated in this order from the base film side. Also, it is composed of a laminated body,
The first metal oxide layer, the second metal oxide layer, and the third metal oxide layer are each composed of tin-doped indium oxide or zinc-doped indium oxide.
The first metal layer and the second metal layer are each made of a silver alloy.
The geometric film thickness of the second metal oxide layer is 60 nm or more and 90 nm or less.
The geometric film thickness of the first metal oxide layer and the third metal oxide layer is 15 nm or more and 30 nm or less, respectively.
A heat ray-shielding film in which the total of the geometric film thickness of the first metal layer and the geometric film thickness of the second metal layer is 19.0 nm or more and 25 nm or less.
Item 2. Item 2. The heat ray-shielding film according to Item 1, which has a visible light transmittance of 65% or more.
Item 3. Item 2. The heat ray shielding film according to Item 1 or 2 ^{, wherein a *} <0 in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of the reflected light.
Item 4. Item 2. The heat ray shielding film according to any one of Items 1 to 3, wherein the heat shielding performance T _{ts is 60% or less.}
Item 5. Item 2. The heat ray-shielding film according to any one of Items 1 to 4, wherein the metal laminated portion is partially laminated on one surface of the base film.
Item 6. Item 2. The heat ray-shielding film according to any one of Items 1 to 5, wherein a plurality of the metal laminated portions are arranged in an island shape on one surface of the base film.
Item 7. A heat ray-shielding laminated glass having a structure in which the heat ray-shielding film according to any one of Items 1 to 6 is sandwiched between two glass plates.

According to the present invention, it is possible to provide a heat ray shielding film in which the red color of reflected light is suppressed. Further, according to the present invention, it is also possible to provide a heat-shielding laminated glass using the heat ray-shielding film.

It is an example of the schematic cross-sectional view which shows the layer structure of the heat ray shielding film which concerns on embodiment of this invention. It is an example of the schematic cross-sectional view which shows the layer structure of the heat ray shielding laminated glass which concerns on embodiment of this invention. It is a schematic diagram which shows an example of the manufacturing method of the heat ray shielding laminated glass which concerns on embodiment of this invention. It is an example of how to arrange the island-shaped metal laminated part of the heat ray shielding film which concerns on embodiment of this invention, and is a circular staggered arrangement. This is an example of how to arrange the island-shaped metal laminated portions of the heat ray shielding film according to the embodiment of the present invention, and is a square hole parallel type arrangement. It is an example of how to arrange the island-shaped metal laminated part of the heat ray shielding film which concerns on embodiment of this invention, and is a hexagonal staggered arrangement. This is an example of how to arrange the island-shaped metal laminated portion of the heat ray-shielding film according to the embodiment of the present invention, and is an outer edge-shaped island-shaped portion (metal laminated portion) in which six arcs having the same R value (radius) are combined. Part) is a pattern-like arrangement formed repeatedly at equal intervals. 6 is a cross-sectional image of a metal laminated portion obtained by using a transmission electron microscope (TEM) with respect to the heat ray shielding film obtained in Example 2.

The heat ray shielding film of the present invention includes at least a base film and a metal laminated portion laminated on one surface of the base film, and the base film is made of a resin and has a metal laminated portion. Is a laminate in which at least the first metal oxide layer, the first metal layer, the second metal oxide layer, the second metal layer, and the third metal oxide layer are laminated in this order from the base film side. The first metal oxide layer, the second metal oxide layer, and the third metal oxide layer are each composed of tin-doped indium oxide or zinc-doped indium oxide, and are composed of the first metal layer. The second metal layer and the second metal layer are each made of a silver alloy, and the geometrical film thickness of the second metal oxide layer is 60 nm or more and 90 nm or less, and the first metal oxide layer and the third metal oxide layer are formed. The geometrical film thickness of each of the above is 15 nm or more and 30 nm or less, and the total of the geometrical film thickness of the first metal layer and the geometrical film thickness of the second metal layer is 19.0 nm or more and 25 nm or less. And. Since the heat ray-shielding film of the present invention has this structure, the red color of the reflected light is suppressed.

Further, the heat ray-shielding laminated glass of the present invention has a structure in which a heat ray-shielding film is sandwiched between two glass plates. Since the heat ray-shielding laminated glass of the present invention has this structure, the red color of the reflected light is suppressed.

Hereinafter, the heat ray-shielding film and the heat ray-shielding laminated glass according to the embodiment of the present invention will be described in detail. In this specification, "~" in the numerical range means the above and the following. That is, the notation α to β means α or more and β or less, or β or more and α or less, and includes α and β as a range.

1. 1. Heat ray shielding film The heat ray shielding film according to the present embodiment is a film having heat ray shielding characteristics. Specifically, in the heat ray-shielding film according to the embodiment of the present invention, a metal laminated portion is laminated as a layer for shielding heat rays on at least one surface of a base film made of resin, and the metal laminated portion is formed. Exhibits heat ray shielding characteristics.

The heat ray-shielding film according to the present embodiment can be suitably used not only for applications that require heat ray-shielding characteristics, but also for applications that do not require such characteristics.

The heat ray-shielding film according to the present embodiment can be particularly preferably used for the heat ray-shielding laminated glass, and can suppress the red color of the reflected light of the heat ray-shielding laminated glass. The heat ray-shielding laminated glass is installed as a window plate of, for example, a building, a traffic vehicle, a ship, etc., and has a structure in which a heat ray-shielding film is sandwiched between two glass plates.

(Electromagnetic waves, visible light, near infrared rays, far infrared rays, ultraviolet rays)
In the present embodiment, the electromagnetic wave means an electromagnetic wave in a narrow sense having a wavelength of 10 mm to 10 km and a frequency of about 30 KHz to 30 GHz. It is in the electromagnetic wave region used for radio broadcasting, television broadcasting, wireless communication, mobile phones, satellite communication, etc. In a broad sense, the following visible rays, near infrared rays, far infrared rays, ultraviolet rays and the like are also included in electromagnetic waves.

In the present embodiment, the visible light is an electromagnetic wave that can be recognized by the naked eye, and generally refers to an electromagnetic wave having a wavelength of 380 to 780 nm. The near infrared ray is an electromagnetic wave having a wavelength of about 800 to 2500 nm, and has a wavelength close to that of red visible light. Near infrared rays are contained in sunlight and have the effect of heating 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 are close to the wavelength radiated from an object near room temperature. Further, the ultraviolet ray is an electromagnetic wave having a wavelength of about 10 to 380 nm. In the present embodiment, the heat ray mainly means ultraviolet rays to near infrared rays.

In the heat ray shielding film and the heat ray shielding laminated glass of the present embodiment, as described later, a metal laminated portion is partially arranged on one side of the base film, and five five elements: electromagnetic wave, visible light, near infrared ray, far infrared ray, and ultraviolet ray. The configuration can be configured to handle electromagnetic waves of wavelength consciously. That is, the heat ray-shielding film and the heat ray-shielding laminated glass of the present invention transmit electromagnetic waves to the outside and the room, and are referred to as "indoor, etc." It is possible to use a device using electromagnetic waves such as a mobile phone or a mobile TV in "outdoors, etc." in combination with "outdoors, outdoors, outside the vehicle, etc." In addition, the heat ray-shielding film and the heat ray-shielding laminated glass of the present invention can partially transmit visible light from outdoors or the like to indoors or the like to keep the room bright. Near-infrared rays can be reflected and absorbed by a metal laminated portion or the like to shield them from entering indoors or the like from outdoors or the like, and prevent the indoors from becoming hot in summer or the like. Far-infrared rays are emitted from indoors and the like, and by reflecting them by a metal laminated portion or the like, it is possible to prevent heat from indoors or the like from going out to the outdoors or the like in winter or the like. Ultraviolet rays can be reflected and absorbed by a metal laminated portion or the like to shield them from entering indoors or the like from outdoors or the like so that articles such as indoors do not deteriorate over time.

(Geometric film thickness)
Geometric film thickness has the same meaning as a commonly used film thickness and refers to the physical thickness of the film. The optical film thickness is known as a film thickness different from the geometric film thickness, and the optical film thickness means a value represented by the product of the geometric film thickness and the refractive index. For the geometrical film thickness, a sample for cross-sectional observation was prepared using a focused ion beam (FIB), and a transmission electron microscope (TEM, H-9500 manufactured by Hitachi High-Technologies) was used at an acceleration voltage of 200 kv and a magnification of 1 million times. It is measured by observing a cross-sectional image of the metal laminated portion.

As shown in the schematic view of FIG. 1, the heat ray-shielding film 4 according to the present embodiment is a laminated body including a base film 1 and a metal laminated portion 2 laminated on one surface of the base film 1. ..

(Base film 1)
The base film 1 is a base material for maintaining the form of the heat ray shielding film 4, and has a function of holding the metal laminated portion 2. Therefore, the base film 1 is preferably excellent in mechanical strength, visible light transmittance, processability, and the like. Further, the base film 1 is made of a resin, and is preferably made of a transparent resin so as to transmit visible light. As the resin used as the base film 1, various resins such as acrylic, polycarbonate, styrene, polyester, polyolefin, hydrogenated cyclic resin, fluorine, silicone, and urethane can be used, and can be used for various purposes. It can be used properly according to the purpose. Among these resins, polyester-based resins such as uniaxially and biaxially stretched polyethylene terephthalate (PET) are preferable from the viewpoint of processability. By setting the phase difference of the stretched film to 7,000 nm or more, it is possible to eliminate rainbow (interference) unevenness when sunlight is reflected.

The thickness of the base film 1 is preferably 8 to 800 μm, although it depends on the mechanical properties of the resin and the like. More preferably, it is 12 to 400 μm.

(Metal laminated part 2)
The metal laminated portion 2 is a layer having a property of shielding heat rays and ultraviolet rays mainly by reflection and far infrared rays emitted from indoors or the like mainly by reflection among sunlight radiated from outdoors or the like. It is thought that the reflection of heat rays, ultraviolet rays, and far infrared rays occurs because a large number of free electrons in the metal collectively vibrate in accordance with the oscillating electric field of electromagnetic waves.

The metal laminated portion 2 is a portion containing metal provided on one surface of the base film 1. The metal laminated portion 2 can be installed on either the indoor side or the outdoor side of the base film 1, but the metal laminated portion 2 on the indoor side of the base film 1 has an effect of improving the heat ray shielding performance. It is preferable because it is excellent. The metal laminated portion 2 may be formed directly on one surface of the base film 1, or may be formed on another base film layer, and then bonded to the base film 1 by an adhesive layer or the like. May be good.

The metal laminated portion 2 includes at least the first metal oxide layer 11, the first metal layer 12, the second metal oxide layer 13, the second metal layer 14, and the third metal oxide layer from the base film 1 side. It is composed of a laminated body in which 15 are laminated in this order.

The first metal oxide layer 11, the second metal oxide layer 13, and the third metal oxide layer 15 are each composed of tin-doped indium oxide or zinc-doped indium oxide. Tin-doped indium oxide (indium tin oxide, hereinafter referred to as "ITO") and zinc-doped indium oxide (indium-zinc oxide, hereinafter referred to as "IZO") are excellent in transparency and stability. .. By using a highly refracting material as the first metal oxide layer 11, the second metal oxide layer 13, and the third metal oxide layer 15, it is possible to improve the visible light transmission performance of the metal laminated portion 2. Become. Further, ITO and IZO have conductivity, have a high film forming speed at the time of film formation, and are excellent in mass productivity.

The first metal layer 12 and the second metal layer 14 are each made of a silver alloy. Examples of the silver alloy include an alloy in which silver contains several mass% (for example, 0.5 to 3 mass%) of Au, Pt, Pd, Cu, Ni, and Sn.

In the metal laminated portion 2, the first metal layer 12 and the second metal layer 14 are made of a silver alloy. Therefore, in the heat ray shielding film 4, the metal laminated portion 2 is laminated on the entire surface of one surface of the base film 1 (that is, the first metal layer 12 and the second metal layer 14 are present on the entire surface). In this case, the electromagnetic wave transmission performance is usually not sufficient. On the other hand, as described below, by partially laminating the metal laminated portion 2 on the surface of the base film 1, it is possible to impart the transmission performance of visible light and electromagnetic waves to the heat ray shielding film 4.

In addition, the silver alloy has excellent conductivity and can reflect heat rays, far infrared rays, and ultraviolet rays. Further, the silver alloy can form a film on the base film 1 or the like by the vapor phase method, and can form the island-shaped metal laminated portion 2 as described later by etching or the like. is there.

In the metal laminated portion 2, the geometrical film thickness of the second metal oxide layer 13 is 60 to 90 nm, which is preferable from the viewpoint of preferably suppressing the red color of the reflected light and preferably providing various performances described later. Is 60 to 85 nm, more preferably 60 to 80 nm, still more preferably 60 to 75 nm.

In the metal laminated portion 2, the geometrical film thicknesses of the first metal oxide layer 11 and the third metal oxide layer 15 are 15 to 30 nm or less, respectively, and the red color of the reflected light is suitably suppressed, which will be described later. From the viewpoint of preferably providing various performances, it is preferably 20 to 30 nm, more preferably 22 to 28 nm, and further preferably 22 to 26 nm.

From the viewpoint of appropriately suppressing the red color of the reflected light and appropriately providing various performances described later, the geometrical film thickness of the second metal oxide layer 13 in the metal laminated portion 2 is the first metal oxide layer 11. The total of the geometrical film thickness of the first metal layer 12 and the geometrical film thickness of the first metal layer 12 is preferably 1.2 times or more, more preferably 1.2 to 1.8 times, still more preferably 1.2 to 1. It is 6 times.

In the metal laminated portion 2, the total of the geometrical film thickness of the first metal layer 12 and the geometrical film thickness of the second metal layer 14 is 19.0 to 25 nm or less, and the red color of the reflected light is suitably suppressed. From the viewpoint of preferably providing various performances described later, the thickness is preferably 19.0 to 23 nm, more preferably 19.0 to 21 nm.

In the metal laminated portion 2, the geometrical film thicknesses of the first metal layer 12 and the second metal layer 14 are preferable from the viewpoint of preferably suppressing the red color of the reflected light and preferably providing various performances described later. Is 6 to 15 nm, more preferably 8 to 14 nm.

In the metal laminated portion 2, the total of the geometrical film thickness of the first metal oxide layer 11, the geometrical film thickness of the second metal oxide layer 13, and the geometrical film thickness of the third metal oxide layer 15 is reflection. It is preferably 100 to 130 nm, more preferably 110 to 125 nm, from the viewpoint of suitably providing various performances described later while preferably suppressing the red color of light.

The metal laminated portion 2 includes at least the first metal oxide layer 11, the first metal layer 12, the second metal oxide layer 13, the second metal layer 14, and the third metal oxide layer from the base film 1 side. 15 is a laminated body having five or more layers in the thickness direction, which are laminated in this order. In this laminated body, the metal layer and the metal oxide layer are alternately formed, the total number of the metal layer and the metal oxide layer is 5 or more, and the metal layer is further sandwiched between the metal oxide layers. Thereby, the optical characteristics can be optimized. As a preferable specific example of the layer structure of the metal laminate 2, a laminate in which IZO / AgPd / IZO / AgPd / IZO are laminated in order; a laminate in which ITO / AgPd / ITO / AgPd / ITO are laminated in order, and the like 5 The layer structure can be mentioned.

The total thickness of the metal laminated portion 2 is preferably 110 to 265 nm, more preferably 125 to 200 nm.

Further, a non-conductive layer such _{as a SiO x} layer or a TiO _x layer may be formed on the metal laminated portion 2 to improve the adhesion to the base material. The x is preferably 1.8 to 2.0, and the thickness thereof is preferably 2 to 40 nm, more preferably 3 to 15 nm. When it is less than 2 nm, the _{effect of forming the SiO x} layer described later is slight, and when it exceeds 40 nm, problems such as cracks at the time of bending the film occur, which is not economically advantageous. Durability is also improved, such as suppressing deterioration of the metal layer, which is considered to be due to the barrier property of the SiO _{x layer.}

Further, a top layer may be formed on the uppermost layer of the metal laminated portion 2 in order to improve durability and scratch resistance. Examples of the material having good etching property include an oxide containing amorphous gallium, indium, and tin, respectively. Its thickness is preferably 2 to 50 nm, more preferably 4 to 20 nm. When it is less than 2 nm, the layer forming effect is slight, and when it exceeds 20 nm, it is not economically advantageous.

In the heat ray shielding film 4 of the present embodiment, the metal laminated portion 2 may be laminated on the entire surface of one surface of the base film 1, or the metal laminated portion 2 may be partially laminated on one surface of the base film 1. It may be laminated. By partially laminating the metal laminated portion 2 on one surface of the base film 1, it is possible to impart the transmission performance of visible light and electromagnetic waves to the heat ray shielding film 4.

It is preferable that a plurality of metal laminated portions 2 are arranged in an island shape on one surface of the base film 1. The diameter of the metal laminated portion 2 is preferably 170 to 500 μm, more preferably 190 to 500 μm, further preferably 190 to 500 μm, more preferably 200 to 500 μm, and particularly preferably 300 to 500 μm. Here, the diameter of the metal laminated portion 2 means an average value of the maximum transfer lengths of the island-shaped metal laminated portions 2. If the diameter of the metal laminated portion 2 is less than 170 μm, the shielding performance of heat rays and the like becomes insufficient. When the diameter of the metal laminated portion 2 exceeds 500 μm, the metal laminated portion 2 can be easily recognized by the naked eye, the metallic luster becomes strong, and the commercial value of the appearance deteriorates.

The distance (gap) between the metal laminated portions 2 is preferably 7 to 32 μm, more preferably 13 to 30 μm, still more preferably 20 to 30 μm, and particularly preferably 25 to 30 μm. Here, the distance between the metal laminated portions 2 means the shortest distance between the end portion of the island-shaped metal laminated portion 2 and the end portion of the adjacent island-shaped metal laminated portion 2. If the distance between the metal laminated portions 2 is less than 7 μm, the visible light transmittance may decrease. In addition, it may be difficult to manufacture by etching. When the distance between the metal laminated portions 2 exceeds 32 μm, the metal laminated portions 2 are easily recognized by the naked eye, and the commercial value of the appearance is deteriorated. In addition, the shielding performance of heat rays and the like becomes insufficient.

Further, from the viewpoint of forming a heat ray-shielding film having excellent heat ray-shielding performance and visible light transmission performance while suitably suppressing the red color of the reflected light, the individual areas of the metal laminated portions 2 arranged in an island shape are set to be different. preferably 0.025~0.217mm ^2, more preferably 0.034~0.217mm ^2, more preferably 0.034~0.217mm ^2, particularly preferably 0.090~0.217mm ^2.

The shape of the island-shaped metal laminated portion 2 is not particularly limited, and can be circular, square, rectangular, regular polygon (triangle, quadrangle, pentagon, hexagon, etc.), oval, irregular shape, or the like. Further, from the viewpoint of suppressing the generation of bright lines when the heat ray shielding film 4 is exposed to light (particularly sunlight), the outer edge of each island-shaped metal laminated portion 2 when the heat ray shielding film 4 is viewed in a plan view. The shape preferably includes a curve. From the viewpoint of more effectively suppressing the generation of the emission line, the outer edge shape is preferably formed by a combination of curves (for example, the outer edge shape is composed of only curves), and in particular, the same or different. It is preferably formed by a combination of arcs. FIG. 7 illustrates a pattern-like arrangement in which a large number of island-shaped portions (metal laminated portions) having a shape obtained by combining six arcs having the same outer edge shape and having the same R value (radius) are repeatedly formed at equal intervals. There is. From the viewpoint of ease of manufacturing and ease of managing the shape of the metal laminated portion 2, a shape combining a circle, a square, a polygon, a rectangle, and an arc is preferable. Further, the method of arranging the plurality of island-shaped metal laminated portions 2 may be regularly arranged or irregularly arranged. From the viewpoint of ease of manufacturing and ease of controlling the shape of the metal laminated portion 2, it is preferable to arrange them regularly. Further, the shape of the plurality of island-shaped metal laminated portions 2 may be one type (that is, the same shape) or two or more types, but preferably one type or two types, and more. One type is preferable. In particular, it is preferable that the plurality of island-shaped metal laminated portions 2 have the same shape and can be arranged at equal intervals (for example, FIGS. 6 and 7). As shown in FIG. 7, the outer edge shape of each island-shaped metal laminated portion 2 includes a curved line, and the outer edge shape allows a plurality of metal laminated portions 2 to be arranged at equal intervals while suppressing bright lines. It is particularly preferable from the viewpoint of ease of manufacturing and ease of controlling the shape of the metal laminated portion 2.

FIGS. 4 to 7 are examples of how to arrange the island-shaped metal laminated portion 2 of the heat ray shielding film according to the present embodiment. FIG. 4 shows a circular staggered arrangement. In the circular staggered arrangement, the circular metal laminated portions 2 are regularly arranged so that the center is located at the apex of the equilateral triangle. The diameter of the metal laminated portion 2 is D (μm), and the distance between the metal laminated portions 2 is P (μm).

FIG. 5 shows a square hole parallel type arrangement. In the square hole parallel type arrangement, the square metal laminated portions 2 are regularly arranged so that the center is located at the apex of the rectangle. The diameter of the metal laminated portion 2 is the length of the diagonal line of the square, and is about 1.41 × W (μm). The distance between the metal laminated portions 2 is SP ₁ (μm) in the vertical direction and SP ₂ (μm) in the horizontal direction.

FIG. 6 shows a hexagonal staggered arrangement. In the hexagonal staggered arrangement, the metal laminated portions 2 of the regular hexagon are regularly arranged so that the center is located at the apex of the equilateral triangle. The diameter of the metal laminated portion 2 is the distance between two opposing sides, and is about 1.15 × W (μm). The distance between the metal laminated portions 2 is P (μm).

The arrangement of the schematic diagram of FIG. 7 is as described above. Similar to FIGS. 4 to 6, the island-shaped portions (metal laminated portions 2) as shown in the schematic diagram of FIG. 7 are also regularly arranged. Further, the diameter of these metal laminated portions 2 and the distance between the metal laminated portions 2 can be designed by using a CAD system or the like.

In the heat ray shielding film 4, from the viewpoint of improving the heat ray shielding performance and the visible light transmitting performance, the area ratio of the portion where the metal laminated portion 2 is arranged is preferably 80 to 95%, more preferably 85.3 to 95. It is 0.0%.

For example, in the circular staggered arrangement of FIG. 4, the area ratio R ₁ (%) of the portion where the metal laminated portion 2 is arranged can be calculated by the following formula (1).
R ₁ = (90.6 × D ² ) / (P + D) ² ... (1)

Further, for example, in the square hole parallel type arrangement shown in FIG. 5, the area ratio R ₂ (%) of the portion where the metal laminated portion 2 is arranged can be calculated by the following formula (2).
R ₂ = {100 x W ² } / {(W + SP ₁ ) x (W + SP ₂ )} ... (2)

Further, for example, in the hexagonal staggered arrangement of FIG. 6, the area ratio R ₃ (%) of the portion where the metal laminated portion 2 is arranged can be calculated by the following formula (3).
R ₃ = 100 × {W ² / (W + P) ² } ・ ・ ・ (3)

The area ratio of the metal laminated portion 2 in the arrangement shown in the schematic view of FIGS. 4 to 7 can be designed by using a CAD system or the like.

[Performance of heat ray shielding film]
Hereinafter, various preferable performances that the heat ray-shielding film 4 of the present embodiment can have will be described.

(Saturation of transmitted light and reflected light)
In the heat ray shielding film 4 of the present embodiment, the red color of the reflected light is suppressed. More specifically, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the reflected light, a *} <0 is preferable, -15 <a ^* <0 is more preferable, and -10 <a. ^* <0 is more preferable. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the transmitted light, a *} <0 is preferable, -15 <a ^* <0 is more preferable, and -10 <a ^* <0. It is more preferable to have. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the reflected light, -15 <b *} <15 is preferable, and -10 <b ^* <10 is more preferable. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the transmitted light, -15 <b *} <15 is preferable, and -10 <b ^* <10 is more preferable. As for the reflected light, the light reflected by the heat ray shielding film is measured by using the light source D65 in accordance with JIS Z8722 (2009). As for the transmitted light, the light transmitted through the heat ray shielding film 4 is measured by using the light source D65 in accordance with JIS Z8722 (2009). A commercially available ultraviolet-visible near-infrared spectrophotometer is used as the measuring device. The chromaticity a ^* and b ^* are calculated from the chromaticity diagram ^{of the L *} a ^* b ^* color system described in JIS Z8730 (2009). The ^{smaller the absolute value of a *,} the more it is evaluated that the red color is suppressed, and ^{when a *} <0 for the reflected light, it is evaluated that the red color is particularly preferably suppressed, and the appearance as a product is particularly excellent. It becomes a thing. More specifically, when ^{the absolute values of a *} and b ^* are 0, the color becomes achromatic and the appearance is particularly excellent, but even when there is a tint (not achromatic), red is a stimulating color. Therefore, it can be said that the appearance is particularly excellent when a ^{* <0 (that is, green).}

(Visible Light Transmittance)
The heat ray-shielding film 4 of the present embodiment preferably transmits visible light having a wavelength of 380 to 780 nm. The visible light transmittance of the heat ray shielding film 4 is preferably 65% or more, and more preferably 70% or more. When the visible light transmittance is 70% or more, the field of view is particularly excellent. The visible light transmittance can be measured in accordance with JIS A5759, for example, using an ultraviolet visible near infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. It can be adjusted by the constituent materials and thicknesses of the base film 1 and the metal laminated portion 2 constituting the heat ray shielding film 4.

(Visible light reflectance)
The heat ray-shielding film 4 of the present embodiment preferably has a visible light reflectance of 15% or less, more preferably 12.5% or less, and further preferably 10% or less. When the visible light reflectance is 10% or less, the metallic luster is low and the appearance as a commercial product is particularly excellent. The visible light reflectance can be measured in accordance with JIS A5759 (2008), for example, using an ultraviolet visible near infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. The numerical value of the visible light reflectance can be adjusted according to the material and thickness of each of the constituent layers, as in the case of the visible light transmittance described above.

(Haze)
The heat ray-shielding film 4 of the present embodiment preferably has a haze of 1.3 or less. When the haze is 1.3 or less, the field of view is particularly excellent. The haze can be measured according to JIS K7136 (2000), for example, using a haze meter (cloudiness meter) NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The numerical value of the haze can be adjusted according to the material and thickness of each of the constituent layers, as in the case of the visible light transmittance described above.

(Heat shield performance T _ts )
_{T ts} is used as an index of the heat shielding performance of the heat ray shielding film 4. T _ts is measured according to ISO13837: 2008. Specifically, it is _{calculated from the formula of T ts} = 27.6 + 0.724 × (solar transmittance) −0.276 × (solar reflectance). This transmission and reflection spectra are measured using a spectrophotometer. The T _ts is preferably 60% or less, more preferably 55% or less, and even more preferably 53% or less.

(Electromagnetic wave shielding rate)
In the heat ray shielding film 4 of the present embodiment, an index called an electromagnetic wave shielding rate is used in order to quantify and evaluate the electromagnetic wave transmission performance. The KEC method is adopted as the evaluation method. The measurement range of electromagnetic waves is 30 MHz to 1 GHz. For the electromagnetic wave shielding rate, a numerical value (dB) at a frequency of 800 MHz is used.

The electromagnetic wave shielding rate is preferably 5 dB or less. When the electromagnetic wave shielding rate is 5 dB or less, there can be little trouble when using a mobile phone, a mobile TV, or the like indoors. The electromagnetic wave shielding rate is more preferably 3 dB or less.

The numerical value of the electromagnetic wave shielding rate can be suitably adjusted by the area ratio of the portion where the metal laminated portion 2 is arranged, in addition to the material and thickness of each layer constituting the heat ray shielding film 4.

As described above, the heat ray-shielding film 4 of the present embodiment can be designed to transmit electromagnetic waves, so that a device using electromagnetic waves such as a mobile phone or a mobile television can be preferably used indoors or the like. .. Since visible light emitted from the outdoors or the like is transmitted to some extent, it is possible to brighten the indoors or the like. On the other hand, since the heat ray shielding film 4 shields heat rays, it is possible to suppress an increase in temperature indoors or the like. In addition, far infrared rays radiated from indoors or the like can be prevented from escaping to the outdoors or the like. Further, ultraviolet rays can be shielded to prevent articles such as indoors from being deteriorated with time by ultraviolet rays.

[Manufacturing method of heat ray shielding film]
A method for producing the heat ray shielding film 4 according to the present embodiment will be described. The metal laminated portion 2 is formed on the base film 1. First, a predetermined film is formed on the entire surface of the base film 1 by the 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.

In the case where the metal laminated portion 2 is partially laminated on one surface of the base film 1, for example, the predetermined predetermined metal laminated portion 2 described above is placed on the metal laminated portion 2 formed on the entire surface of the base film 1. A resist (photosensitive resin) film is formed by the method of arranging the island-shaped metal laminated portions 2. As a method for forming the resist film, a known method such as a printing method or a photolithography method can be selected. As the printing method, a known method such as gravure printing or screen printing can be selected.

Next, the metal laminated portion 2 in the portion where the resist film does not exist is etched with an acid or an alkali to remove it. Then, by peeling the resist film with a solvent, water, or the like, the metal laminated portion 2 having a predetermined island-shaped metal laminated portion 2 arrangement can be formed.

2. Heat ray-shielding laminated glass FIG. 2 is an example of a schematic cross-sectional view showing a layer structure of the heat ray-shielding laminated glass according to the present embodiment. In the heat ray-shielding laminated glass 10 of the present embodiment, the heat ray-shielding film 4 according to the above-described embodiment is sandwiched between the two glass plates 5A and 5B. The heat ray shielding film 4 is provided with a base film 1 made of resin and a metal laminated portion 2 on one surface thereof. Further, adhesive layers 3B and 3A are provided on the other surface of the base film 1 and on the metal laminated portion 2, respectively. The heat ray-shielding film 4 is bonded to the two glass plates 5A and 5B by the adhesive layers 3A and 3B, respectively. In FIG. 2, the upper side is the indoor side and the lower side is the outdoor side. Hereinafter, each layer constituting the heat ray-shielding laminated glass 10 of the present embodiment will be described in detail. The details of the heat ray shielding film 4 according to the present embodiment are as described above, and the description thereof will be omitted below.

(Glass plate)
In the heat ray-shielding laminated glass 10 of the present embodiment, the glass plates 5A and 5B are transparent plates for taking in sunlight from the outside world inside a building, a traffic vehicle, a ship, or the like. Generally, a so-called inorganic glass plate or a resin plate made of an organic resin is used. Soda-lime glass is a typical example of inorganic glass. As the transparent organic resin, various resins such as acrylic, styrene, hydrogenated cyclic resin, polycarbonate, and polyester can be used.

In order to improve the heat ray shielding performance, a glass plate containing iron ions can be used as a glass plate for reducing the transmittance in the near infrared wavelength region (800 to 2500 nm). The glass plate containing iron ions is _{soda lime glass containing silicon dioxide (SiO 2} ), sodium oxide (Na ₂ O), and calcium oxide (Ca O) as main components, and the 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 guideline for a high iron content reduction rate, Fe ²⁺ / Fe ³⁺ is 50 to 250%. By reducing the iron content and increasing the content of divalent iron ions, the absorption rate in the infrared region can be increased. As a method for reducing iron content, powders such as silica sand, feldspar, soda ash, and red iron oxide as raw materials for soda-lime glass and carbon as a reducing agent can be used and melted in an electric melting kiln or the like. The iron content reduction rate can be measured by a redox measuring device.

The thickness of one glass plate is not particularly limited, and examples thereof include about 0.1 to 10 mm, preferably about 1 to 5 mm.

(Adhesive layers 3A, 3B)
In the heat ray-shielding laminated glass 10 of the present embodiment, adhesive layers 3B and 3A are provided on the metal laminated portion 2 forming one side of the heat ray-shielding film 4 and on the base film 1 forming the other side, respectively. It has a configured structure. The heat ray shielding film 4 is bonded to the glass plates 5A and 5B by these adhesive layers 3A and 3B, respectively.

The adhesive layers 3A and 3B are not particularly limited as long as they are resin films that are generally used as an intermediate film of laminated glass, but those that do not absorb in the visible light region or the infrared region are preferable.

The adhesive used for the adhesive layers 3A and 3B is, for example, applied or laminated on the base film 1 or the like as an adhesive that is not adhesive at room temperature, and after laminating each material constituting the heat ray-shielding laminated glass 10. , It is an adhesive that develops adhesiveness and adhesiveness by heat treatment and makes it possible to bond each layer.

Specific examples of the adhesive used for the adhesive layers 3A and 3B include polyvinyl acetal resins such as polyvinyl butyral resin (PVB resin) and ethylene-vinyl acetate copolymer resin (EVA resin). ..

The adhesive used for the adhesive layers 3A and 3B may be manufactured by a known method, or a commercially available product may be used. Examples of commercially available products include plasticized PVB manufactured by Sekisui Chemical Co., Ltd. and Mitsubishi Resin Co., Ltd., EVA resin manufactured by DuPont and Takeda Pharmaceutical Company Limited, and modified EVA resin manufactured by Tosoh Co., Ltd.

The thickness of the adhesive layers 3A and 3B is preferably 100 to 1000 μm, respectively.

As the adhesive used for the adhesive layers 3A and 3B, an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a coloring agent, an adhesive adjusting agent, a heat ray absorbing / reflecting agent and the like are appropriately used. It may be added and blended. When the adhesive layers 3A and 3B and the metal laminated portion 2 are present in contact with each other, the adhesive used for the adhesive layers 3A and 3B has a neutral pH so as not to deteriorate the metal laminated portion 2. preferable. Specifically, those having no carboxylic acid as a chemical structure are preferable. Moreover, you may add a rust preventive material.

(Protective layer)
In order to prevent the metal laminated portion 2 from being damaged by an external force or the like during manufacturing, the heat ray-shielding laminated glass 10 is provided with a protective layer between the metal laminated portion 2 on the base film 1 and the adhesive layer 3A. It may be provided.

Examples of the protective layer include a coating method and a method of adhering a protective film. In the coating method, an organic hard coating agent, an inorganic hard coating agent, a silicone hard coating agent, or the like can be applied and cured to form the product. Of these, an ultraviolet curable acrylic resin is preferable. The thickness of the protective layer is preferably 0.5 to 20 μm.

In the method of adhering the protective film, there is a method of adhering the protective film on the metal laminated portion 2 by an adhesive layer. As the protective film, a material such as a PET film can be used as in the base film 1. Examples of the adhesive for the adhesive layer include acrylic type, silicone type, urethane type, butadiene type, and natural rubber type. Among these, acrylic type and silicone type are preferable from the viewpoint of durability. The thickness of the adhesive layer is preferably 0.5 to 20 μm.

The heat ray shielding laminated glass 10 can be used for automobiles, railroad vehicles, aircraft, ships, buildings and the like. The heat ray shielding laminated glass 10 can be used for other purposes. The heat ray shielding laminated glass 10 is preferably a laminated glass for vehicles or buildings.

[Performance of heat ray shielding laminated glass]
Hereinafter, various performances of the heat ray-shielding laminated glass 10 of the present embodiment will be described. Since the heat ray-shielding laminated glass 10 of the present embodiment uses the heat ray-shielding film 4 according to the present embodiment described above, it is possible to exhibit the same performance as the various performances of the heat ray-shielding film 4 described above.

(Saturation of transmitted light and reflected light)
In the heat ray shielding laminated glass 10 of this embodiment, the red color of the reflected light is suppressed. More specifically, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the reflected light, a *} <0 is preferable, -15 <a ^* <0 is more preferable, and -10 <a. ^* <0 is more preferable. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the transmitted light, a *} <0 is preferable, -15 <a ^* <0 is more preferable, and -10 <a ^* <0. It is more preferable to have. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the reflected light, -15 <b *} <15 is preferable, and -10 <b ^* <10 is more preferable. Further, in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of ^{the transmitted light, -15 <b *} <15 is preferable, and -10 <b ^* <10 is more preferable. As for the reflected light, the light reflected from the heat ray-shielding laminated glass 10 is measured by using the light source D65 in accordance with JIS Z8722 (2009). As for the transmitted light, the light transmitted through the heat ray shielding laminated glass 10 is measured by using the light source D65 in accordance with JIS Z8722 (2009). A commercially available ultraviolet-visible near-infrared spectrophotometer is used as the measuring device. The chromaticity a ^* and b ^* are calculated from the chromaticity diagram ^{of the L *} a ^* b ^* color system described in JIS Z8730 (2009). The ^{smaller the absolute value of a *,} the more it is evaluated that the red color is suppressed, and ^{when a *} <0 for the reflected light, it is evaluated that the red color is particularly preferably suppressed, and the appearance as a product is particularly excellent. It becomes a thing. More specifically, when ^{the absolute values of a *} and b ^* are 0, the color becomes achromatic and the appearance is particularly excellent, but even when there is a tint (not achromatic), red is a stimulating color. Therefore, it can be said that the appearance is particularly excellent when a ^{* <0 (that is, green).}

(Visible Light Transmittance)
The heat ray-shielding laminated glass 10 of the present embodiment preferably transmits visible light having a wavelength of 380 to 780 nm. The visible light transmittance of the heat ray-shielding laminated glass 10 is preferably 65% or more, and more preferably 70% or more. When the visible light transmittance is 70% or more, the field of view is particularly excellent. The visible light transmittance can be measured in accordance with JIS A5759, for example, using an ultraviolet visible near infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. The numerical values of the visible light transmittance are the materials and thicknesses of the glass plates 5A and 5B, the base film 1 constituting the heat ray shielding film 4, the constituent materials and thicknesses of the metal laminated portion 2, and the adhesive layers 3A and 3B. It can be adjusted according to the constituent material and thickness of.

(Visible light reflectance)
The heat ray-shielding laminated glass 10 of the present embodiment preferably has a visible light reflectance of 15% or less, more preferably 12.5% or less, and further preferably 10% or less. When the visible light reflectance is 10% or less, the metallic luster is low and the appearance as a commercial product is particularly excellent. The visible light reflectance can be measured in accordance with JIS A5759 (2008), for example, using an ultraviolet visible near infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. The numerical value of the visible light reflectance can be adjusted according to the material and thickness of each of the constituent layers, as in the case of the visible light transmittance described above.

(Haze)
The heat ray-shielding laminated glass 10 of the present embodiment preferably has a haze of 1.3 or less. When the haze is 1.3 or less, the field of view is particularly excellent. The haze can be measured according to JIS K7136 (2000), for example, using a haze meter (cloudiness meter) NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The numerical value of the haze can be adjusted according to the material and thickness of each of the constituent layers, as in the case of the visible light transmittance described above.

(Heat shield performance T _ts )
_{T ts} is used as an index of the heat shield performance of the heat shield laminated glass 10. T _ts is measured according to ISO13837: 2008. Specifically, it is _{calculated from the formula of T ts} = 27.6 + 0.724 × (solar transmittance) −0.276 × (solar reflectance). This transmission and reflection spectra are measured using a spectrophotometer. The T _ts is preferably 60% or less, more preferably 55% or less, and even more preferably 51% or less.

(Electromagnetic wave shielding rate)
In the heat ray shielding laminated glass 10 of the present embodiment, an index called an electromagnetic wave shielding rate is used in order to quantify and evaluate the electromagnetic wave transmission performance. The KEC method was adopted as the evaluation method. The measurement range of electromagnetic waves is 30 MHz to 1 GHz. For the electromagnetic wave shielding rate, a numerical value (dB) at a frequency of 800 MHz is used.

The electromagnetic wave shielding rate is preferably 5 dB or less. When the electromagnetic wave shielding rate is 5 dB or less, there can be little trouble when using a mobile phone, a mobile TV, or the like indoors or the like. The electromagnetic wave shielding rate is more preferably 3 dB or less.

The numerical value of the electromagnetic wave shielding rate can be suitably adjusted by the area ratio of the portion where the metal laminated portion 2 is arranged, in addition to the material and thickness of each layer constituting the heat ray shielding laminated glass 10.

Since the heat ray-shielding laminated glass 10 of the present embodiment can be designed to transmit electromagnetic waves, devices using electromagnetic waves such as mobile phones and mobile televisions can be preferably used indoors or the like. Since visible light emitted from the outdoors or the like is transmitted to some extent, it is possible to brighten the indoors or the like. On the other hand, since the heat ray-shielding laminated glass 10 shields heat rays, it is possible to suppress an increase in temperature indoors or the like. In addition, far infrared rays radiated from indoors or the like can be prevented from escaping to the outdoors or the like. Further, ultraviolet rays can be shielded to prevent articles such as indoors from being deteriorated with time by ultraviolet rays.

Further, since the heat ray-shielding laminated glass 10 of the present embodiment has a structure sandwiched between two glass plates 5, deterioration due to rain and wind can be reduced regardless of which side is the outdoor side or the like.

[Manufacturing method of heat ray shielding laminated glass]
A method for producing the heat ray-shielding laminated glass 10 of the present embodiment will be described. First, the above-mentioned heat ray shielding film 4 is prepared. Next, the adhesive layers 3A and 3B are formed on both sides of the base film 1 provided with the metal laminated portion 2. The pressure-sensitive adhesive polymer is mixed with the solvent in an appropriate amount to prepare a solution having an appropriate viscosity. The solution is coated on the base film 1 or the metal laminate 2. After that, the adhesive layers 3A and 3B can be formed by drying. Further, as described above, a protective layer may be provided between the metal laminated portion 2 and the adhesive layer 3A.

The method of bonding the heat ray shielding film 4 and the glass plate 5 is not particularly limited, and a general method for producing laminated glass may be used. A specific example will be described below. FIG. 3 is a schematic view showing a method for manufacturing a heat ray-shielding laminated glass according to an embodiment of the present invention.

First, as shown in FIG. 3A, a heat ray shielding film 4 having adhesive layers on both sides is laminated between two glass plates 5. The laminated glass plate 5 and the heat ray shielding film 4 move on the roller 21 to move to the next step.

Next, as shown in FIG. 3B, the laminated glass plate 5 and the heat ray shielding film 4 are heated to about 90 ° C. by the heater 23 in the closed chamber 22. Subsequently, the laminated glass plate 5 and the heat ray shielding film 4 are temporarily crimped by passing through a pair of crimping rolls 24.

Next, as shown in FIG. 3C, the temporarily crimped heat ray-shielding laminated glass 10 is housed in the autoclave 25. By pressurizing to about 1 MPa and heating to about 130 ° C. in the autoclave 25, air bubbles remaining after temporary crimping are removed, and the adhesive layer of the heat ray shielding film 4 is sufficiently bonded to the glass plate 5. , Heat ray shielding laminated glass 10 is manufactured.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. Unless otherwise specified, parts and% indicate "parts by mass" and "% by mass", respectively.

[Examples 1 and 2 and Comparative Example 1-3]
<Manufacturing of heat ray shielding film>
Sputtering on one side of a polyethylene terephthalate film (easy-adhesive biaxially stretched PET film, Cosmoshine A4300 manufactured by Toyo Boseki Co., Ltd., thickness 50 μm) as a base film so as to have the geometrical film thickness shown in Table 1, respectively. Using the method, the first metal oxide layer, the second metal oxide layer, and the IZO film as the third metal oxide (manufactured by Idemitsu Kosan Co., Ltd.), respectively, and the first metal layer and the first metal layer, respectively. An AgPd film (silver containing 1 atomic% of palladium) as a two metal layer was laminated on the entire surface in the order of an IZO film, an AgPd film, an IZO film, an AgPd film, and an IZO film to obtain each laminated film. The conditions of the sputtering method were under a vacuum of 0.4 Pa. For the geometrical film thickness, a sample for cross-sectional observation was prepared using a focused ion beam (FIB), and a transmission electron microscope (TEM, H-9500 manufactured by Hitachi High-Technologies) was used at an acceleration voltage of 200 kv and a magnification of 1 million times. The measurement was performed by observing a cross-sectional image of the metal laminated portion. For reference, FIG. 8 shows a cross-sectional image of the metal laminated portion obtained by using a transmission electron microscope (TEM) for the heat ray shielding film obtained in Example 2.

Next, on the outermost surface (IZO film surface) of each of the obtained laminated films, a resist dissolved in a solvent is gravure-printed to have the same R value (radius) as shown in the schematic diagram of FIG. Printing was performed so that a large number of island-shaped portions (metal laminated portions) having an outer edge shape in which six arcs were combined were repeatedly formed at equal intervals in a pattern-like arrangement. The diameter of each island-shaped part (distance between two opposing sides μm), gap (μm), area (μm ² ), and area ratio (%) of the part where the island-shaped part is arranged are shown in Table 4 and, respectively. The values are set to be as shown in Table 5. The diameter, gap, area, and area ratio of each island-shaped portion in Tables 4 and 5 are the measured values (metal laminated portion) of the island-shaped portion (metal laminated portion) of the five-layer structure (metal layer and metal oxide layer), respectively. The average value described later).

Next, after the resist was dried at 200 ° C., the AgPd film (metal layer) and the IZO film (metal oxide layer) in the portion where the resist was not printed were dissolved and removed using an aqueous ferrous chloride solution. , The surface of the PET film was partially exposed. Next, the resist was then dissolved with an aqueous solution of sodium hydroxide and stripped from the surface of the IZO membrane. After washing and drying with water, each heat ray-shielding film in which a large number of island-shaped portions (metal laminated portions) having a predetermined shape of a five-layer structure (metal layer and metal oxide layer) were arranged on the PET film was obtained.

[Manufacturing of heat ray shielding laminated glass]
PVB (polyvinyl butyral film, manufactured by Sekisui Kagaku Kogyo Co., Ltd., S-LEC PVB 0. A 38 mm) sheet (hereinafter referred to as "PVB sheet") was placed. The heat-shielding film is placed on the heat-shielding film with the metal laminated portion on the lower side, a PVB sheet as an adhesive layer is placed, and finally a glass plate is placed, and the laminated plate in which the heat-shielding film is sandwiched between the adhesive layers is placed. Obtained.

This laminated board was passed through the production line shown in FIG. That is, in the closed chamber 22, the obtained laminated board was heated to about 90 ° C. using the heater 23. After that, the laminated glass plates 5 and the heat ray shielding film 4 were temporarily crimped by passing through a pair of crimping rolls 24.

Next, the temporarily crimped heat ray-shielding laminated glass 10 was housed in the autoclave 25. By pressurizing to about 1 MPa in the autoclave 25 and heating at about 130 ° C. for 30 minutes, air bubbles remaining after temporary crimping are removed, and the heat ray shielding film 4 is sufficiently bonded to the glass plate 5 by an adhesive layer. Shielding laminated glass 10 was manufactured. A heat ray-shielding laminated glass having a structure similar to that shown in FIG. 2 was obtained.

<Performance evaluation method>
In Examples and Comparative Examples, the diameter of the island-shaped portion, the gap between the island-shaped portions, the visible light transmittance, the visible light reflectance, the heat shielding performance T _ts , the haze, the chromaticity of the transmitted light and the reflected light, the electromagnetic wave shielding rate, The performance of the light and the appearance was evaluated under the conditions described below. The evaluation was performed on the transmitted light and the reflected light by irradiating a predetermined light beam from the outdoor side or the like. Regarding the optical measurement of the heat ray shielding film, according to JIS A 5759 (2008) building window glass film, a heat ray shielding film and a glass plate (thickness 3 mm) were used using an adhesive material (HJ-9150W manufactured by Nitto Denko Co., Ltd.). ) And the measurement was performed. Table 2 shows the results for the heat ray-shielding film without the island-shaped part, and Table 3 shows the results for the heat ray-shielding laminated glass without the island-shaped part. Table 4 shows the results of the above, and Table 5 shows the results of the heat ray-shielding laminated glass having the island-shaped portion formed.

(Average value of island-shaped diameter and gap)
The diameter of the island-shaped portion of the heat ray-shielding film and the length of the gap were measured using a digital microscope VHX-1000 manufactured by KEYENCE CORPORATION, and the average value of 10 points was shown.

(Saturation of transmitted light and reflected light)
As for the reflected light, the light reflected by the heat ray shielding film was measured by using the light source D65 in accordance with JIS Z8722 (2009). As for the transmitted light, the light transmitted through the heat ray shielding film 4 was measured by using the light source D65 in accordance with JIS Z8722 (2009). As a measuring device, an ultraviolet visible near infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation was used. The chromaticity a ^* and b ^* were calculated from the chromaticity diagram ^{of the L *} a ^* b ^* color system described in JIS Z8730 (2009).

The ^{smaller the absolute value of a *,} the more it is evaluated that the red color is suppressed, and ^{when a *} <0 for the reflected light, it is evaluated that the red color is particularly preferably suppressed, and the appearance as a product is particularly excellent. It becomes a thing. More specifically, as described above, when ^{the absolute values of a *} and b ^* are 0, the color becomes achromatic, and the appearance is particularly excellent. Since red is a stimulating color, it can be said that the appearance is particularly excellent ^{when a * <0 (that is, green).}

(Visible Light Transmittance)
The visible light transmittance of the heat ray shielding film and the heat ray shielding laminated glass conforms to JIS A5759. In this example, an ultraviolet-visible near-infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation was used.

(Visible light reflectance)
The visible light reflectance of the heat ray shielding film and the heat ray shielding laminated glass conforms to JIS A5759. In this example, an ultraviolet-visible near-infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation was used.

(Haze)
The haze of the heat ray shielding film and the heat ray shielding laminated glass was measured using a haze meter (cloudiness meter) NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136.

(Heat shield performance T _ts )
Thermal barrier performance T _ts of the heat ray-shielding film and heat-ray shielding laminated glass, ISO13837: 2008 was measured in accordance with. It _{was calculated from the formula of T TS} = 27.6 + 0.724 × (solar transmittance) −0.276 × (solar reflectance). Regarding the solar transmittance and the solar reflectance, first, the spectral transmittance and the spectral reflectance were measured using an ultraviolet-visible near-infrared spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, and JIS R3106: 1998. Each was calculated based on.

(Electromagnetic wave shielding rate)
The electromagnetic wave shielding rate of the heat ray shielding film and the heat ray shielding laminated glass was measured in the frequency range of 30 MHz to 1 GHz by the KEC method using a sample of 15 cm × 15 cm. The numerical value of the electromagnetic wave shielding rate was a value (dB) having a frequency of 800 MHz.

1 Base film 2 Metal laminated part 3A, 3B Adhesive layer 4 Heat ray shielding film 5, 5A, 5B Glass plate 10 Heat ray shielding laminated glass 11 1st metal oxide layer 12 1st metal layer 13 2nd metal oxide layer 14th 2 metal layer 15 3rd metal oxide layer

Claims (7)

At least, it includes a base film and a metal laminated portion laminated on one surface of the base film.
The base film is made of resin and is made of resin.
In the metal laminated portion, at least the first metal oxide layer, the first metal layer, the second metal oxide layer, the second metal layer, and the third metal oxide layer are laminated in this order from the base film side. Also, it is composed of a laminated body,
The first metal oxide layer, the second metal oxide layer, and the third metal oxide layer are each composed of tin-doped indium oxide or zinc-doped indium oxide.
The first metal layer and the second metal layer are each made of a silver alloy.
The geometric film thickness of the second metal oxide layer is 60 nm or more and 90 nm or less.
The geometric film thickness of the first metal oxide layer and the third metal oxide layer is 15 nm or more and 30 nm or less, respectively.
A heat ray-shielding film in which the total of the geometric film thickness of the first metal layer and the geometric film thickness of the second metal layer is 19.0 nm or more and 25 nm or less. The heat ray shielding film according to claim 1, wherein the visible light transmittance is 65% or more. The heat ray shielding film according to claim 1 or 2 ^{, wherein a *} <0 in the CIE L ^* a ^* b ^* chromaticity coordinate diagram of the reflected light. The heat ray-shielding film according to any one of claims 1 to 3, wherein the heat-shielding _{performance T ts is 60% or less.} The heat ray-shielding film according to any one of claims 1 to 4, wherein the metal laminated portion is partially laminated on one surface of the base film. The heat ray-shielding film according to any one of claims 1 to 5, wherein a plurality of the metal laminated portions are arranged in an island shape on one surface of the base film. A heat ray-shielding laminated glass having a structure in which the heat ray-shielding film according to any one of claims 1 to 6 is sandwiched between two glass plates.

Images