JP2012250891A - Laminated glass using heat reflecting film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated glass excellent in stability, hardly changes in external appearance such as cloudiness.SOLUTION: There is provided the laminated glass in which a selective beam transmitting film and a film are arranged in a laminated state between a pair of bonding material layers and the bonding material layers are tightly clamped by a pair of glass substrates and a protection layer for protecting the selective beam transmitting film is formed in close contact with the selective beam transmitting film so as to surround the outer circumferential part thereof.

Description

  The present invention relates to a laminated glass suitable as a window material for vehicles and buildings, and particularly relates to a laminated glass excellent in stability.

  Laminated glass has an integrated structure because an intermediate film such as a resin is sandwiched between a pair of glass plates via a bonding material. Due to its integrated structure, laminated glass is excellent in penetration resistance and scattering prevention, and is therefore widely used as window glass for automobiles, railway vehicles, aircraft, ships, buildings, and the like. These window glasses are required to have a high degree of transparency. In particular, automotive windshields are required to be laminated glass having a visible light transmittance of 70% or more in order to ensure visibility. The In order to have such a function, a laminated glass is known in which a selective light transmission film having selective light transmission performance is sandwiched between a pair of glass plates.

  However, in the conventional technique, there is a problem that the appearance of the laminated glass having the selective light transmission film changes with time. Such a change in appearance is considered to be caused by the fact that the metal layer constituting the selective light transmission film is oxidized by water contained in the glass bonding material. That is, the oxidation of the metal layer destroys the structure of the selective light transmission film and the reflectance of the selective light transmission film fluctuates, so that it is considered that the appearance of the laminated glass changes. Furthermore, since the reflectance is different between the oxidized portion and the non-oxidized portion of the metal layer, the appearance is not uniform.

  Therefore, Patent Document 1 discloses a laminated glass excellent in water resistance and moisture resistance by disposing a protective layer for protecting the selective light transmission film between the selective light transmission film and the bonding material. .

JP-A-5-177756

  However, until now, a laminated glass with little change in appearance and sufficiently stable has not been obtained.

  Then, an object of this invention is to provide the laminated glass excellent in stability by which the external appearance change (for example, cloudiness) was suppressed.

  The present inventors have intensively studied to solve the above problems. As a result, in the laminated glass in which a selective light transmission film and a film are laminated between a pair of bonding material layers, and the bonding material layer is tightly sandwiched between a pair of glass substrates, the selective light transmission film It was found that the above-mentioned problems can be solved by forming a protective layer that protects the surface of the selective light transmission film so as to surround the outer peripheral portion of the selective light transmission film, thereby completing the present invention. It was.

  According to the laminated glass of the present invention, by providing a protective layer that protects the selective light transmissive film, deterioration of the selective light transmissive film is suppressed, so that the laminated glass is excellent in stability and hardly changes in appearance (for example, white turbidity). Glass is provided.

It is a top view of the laminated glass which is one Embodiment of this invention. It is sectional drawing at the time of cut | disconnecting the laminated glass of embodiment shown in FIG. 1 by plane II-II, and shows one Embodiment of this invention. It is sectional drawing of the laminated glass of other embodiment of this invention. It is the model top view which looked at the laminated glass shown by FIG. 2, FIG. 3 from the top. It is sectional drawing of the laminated glass of further another embodiment of this invention. It is sectional drawing of the laminated glass of further another embodiment of this invention. It is the model top view which looked at the laminated glass shown by FIG. 5, FIG. 6 from the top. It is the schematic cross section at the time of manufacturing a laminated glass, and the graph which represented typically the distribution of the water content contained in a joining material layer. It is a schematic cross section at the time of manufacturing a laminated glass. FIG. 8 is a schematic cross-sectional view and a schematic plan view of a bonding surface (contact surface) between a protective layer and a bonding material layer when the laminated glass of the embodiment shown in FIG. 7 is manufactured.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, this invention is not restrict | limited only to the following embodiment. The dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios.

  According to one embodiment of the present invention, a selective light transmission film and a film are laminated between a pair of bonding material layers, and the bonding material layer is formed as a pair of glass substrates (hereinafter referred to as “first glass substrate”). , “Second glass substrate”), and a protective layer that protects the selective light transmissive film surrounds an outer peripheral portion of the selective light transmissive film. A laminated glass formed in close contact with the permeable membrane is provided. That is, according to one aspect of the present invention, the first glass substrate, the first bonding material layer, the selective light transmission film, the film, the second bonding material layer, and the second glass substrate are laminated in this order. Glass is provided. A protective layer for protecting the selective light transmission film is formed in close contact with the selective light transmission film so as to surround an outer peripheral portion of the selective light transmission film.

  FIG. 1 is a plan view of a laminated glass according to an embodiment of the present invention. The laminated glass 1 of the present embodiment is a front window glass of an automobile, is formed according to the shape of the automobile, and has a curved shape according to the shape of the front window. However, the shape of the laminated glass 1 varies depending on the portion to which it is applied, and can have various shapes.

  In general, laminated glass used for window shields of automobiles has many curved surfaces. The laminated glass having such a curved surface shape is manufactured by sandwiching a bonding material layer, a selective light transmission film and a film between glasses previously bent to an arbitrary curvature. On the other hand, what is used for a window material for construction may have a flat plate shape that is not bent.

  FIG. 2 is a cross-sectional view when the laminated glass of the embodiment shown in FIG. 1 is cut along a plane II-II. As shown in FIG. 2, the laminated glass 1 of the present embodiment includes a first glass substrate 11, a first bonding material layer 12, a selective light transmission film 13, a film 14, a second bonding material layer 16 and a second glass. The glass substrates 17 are laminated in order. A protective layer 15 that protects the selective light transmissive film 13 (hereinafter sometimes simply referred to as “protective layer”) is in close contact with the selective light transmissive film 13 so as to surround the outer peripheral portion 23 of the selective light transmissive film 13. The feature is that it is formed. In this embodiment, the selective light transmission film 13 is an alternate laminated body 130 formed by alternately laminating dielectric films 131 and metal films 132 having different refractive indexes. In the laminated glass 1 of this embodiment, the 1st glass substrate 11 is normally arrange | positioned at the vehicle outer side of the motor vehicle which electromagnetic waves, such as a sunlight ray, inject, and the 2nd glass substrate 17 is arranged indoors.

  In the present embodiment, the selective light transmission film 13 and the film 14 are integrally formed. The selective light transmission film 13 having such an integrated structure is produced by, for example, manufacturing a film 14 by a coextrusion method, and alternately laminating dielectric films 131 and metal films 132 using the film 14 as a base material. By applying to the surface, the selective light transmission film 13 can be produced. However, the present invention is not limited to such a form, and an intermediate film may be interposed between the selective light transmission film 13 and the film 14. Such a form can be produced by separately applying the selective light transmission film 13 and the film 14 to a transparent base film and forming a laminated glass. Although the intermediate film and the selective light transmission film 13 (dielectric film 131 and metal film 132) may be laminated one by one, a prepreg in which the selective light transmission film 13 is sandwiched between the intermediate films in advance in terms of improving manufacturing efficiency. It can also be used in the state.

  FIG. 3 is a cross-sectional view of a laminated glass according to another embodiment of the present invention. As shown in FIG. 3, the laminated glass 1 of the present embodiment includes a first glass substrate 11, a first bonding material layer 12, a selective light transmission film 13, a film 14, a second bonding material layer 16 and a second glass. The glass substrates 17 are laminated in order. The protective layer 15 is formed in close contact with the selective light transmission film 13 so as to surround the outer peripheral portion 23 of the selective light transmission film 13. At this time, in the embodiment of FIG. 3, the protective layer 15 is formed so as to surround the outer peripheral portion 24 of the film 14 together with the outer peripheral portion 23 of the selective light transmission film 13.

  FIG. 4 is a schematic plan view of the laminated glass shown in FIGS. 2 and 3 as viewed from above. As shown in FIG. 4, a protective layer is arranged in a frame shape on the outer peripheral edge of the laminated glass 1.

  FIG. 5 is a cross-sectional view of a laminated glass according to another embodiment of the present invention. As shown in FIG. 5, the laminated glass 1 of the present embodiment includes a first glass plate 11, a first bonding material layer 12, a selective light transmission film 13, a film 14, a second bonding material layer 16, and a first glass plate 11. Two glass plates 17 are sequentially laminated. The protective layer 15 is formed in close contact with the selective light transmission film 13 so as to cover at least a part of the peripheral edge 25 of the selective light transmission film 13 and surround the outer peripheral part 23 of the selective light transmission film 13.

  FIG. 6 is a cross-sectional view of a laminated glass according to another embodiment of the present invention. As shown in FIG. 6, the laminated glass 1 of the present embodiment includes a first glass plate 11, a first bonding material layer 12, a selective light transmission film 13, a film 14, a second bonding material layer 16, and a first glass plate 11. Two glass plates 17 are sequentially laminated. The protective layer 15 is formed in close contact with the selective light transmission film 13 so as to cover at least a part of the peripheral edge 25 of the selective light transmission film 13 and surround the outer peripheral part 23 of the selective light transmission film 13. At this time, in the embodiment of FIG. 6, the protective layer 15 is formed so as to surround the outer peripheral portion 24 of the film 14 together with the outer peripheral portion 23 of the selective light transmission film 13.

  FIG. 7 is a schematic plan view of the laminated glass shown in FIGS. 5 and 6 as viewed from above. As shown in FIG. 7, the protective layer is arranged in a frame shape on the outer peripheral edge of the laminated glass 1.

  In this specification, the “outer peripheral portion of the selective light transmitting film” means a peripheral portion (outer peripheral portion of the selective light transmitting film) when the selective light transmitting film is projected from above. Moreover, in this specification, the "peripheral part of a film" means the surrounding part (outer peripheral part of a film) when a film is projected from the upper part.

  In this specification, the “peripheral portion of the selective light transmission film” means an end region (inner peripheral portion of the selective light transmission film) of the selective light transmission film when the selective light transmission film is projected from above. The “inner peripheral portion of the selective light transmitting film” may be referred to as a direction from the outer peripheral portion of the selective light transmitting film toward the center.

  The use of laminated glass is not limited to the above-mentioned front window glass of automobiles, but also for side windows and rear window glasses of automobiles, and also for window glasses of railway vehicles other than automobiles, aircraft, ships, buildings, etc. It can be suitably used.

  Hereinafter, the member which comprises the laminated glass of this embodiment is demonstrated in detail.

[Selective light transmission membrane]
The selective light transmission film used in the present invention has a selective light transmission film formed on one side of the film. The selective light transmission membrane preferably has the following configuration.

  The selective light transmission film is a film having high visible light transmittance and high infrared light reflectance. That is, the selective light transmission film is a thin film having a function of selectively controlling light and heat transmittance. By setting it as such a characteristic, it becomes possible to block the infrared light which causes the indoor temperature rise, ensuring visibility.

  The selective light transmission film has conductivity, that is, has a low electrical resistance, and thus has a high reflectance of infrared light, and functions as a heat ray blocking layer that blocks heat rays from the outside. Infrared light has a large thermal effect, and when absorbed by a substance, it is released as heat, resulting in a temperature rise. From this, it is also called a heat ray, and by blocking these light rays, the temperature rise in the room can be effectively suppressed. For example, it is preferable that the selective light transmission film can reflect electromagnetic waves in near-infrared light (wavelength range 750 nm to 1200 nm), preferably 50% or more, more preferably 70% or more. Thereby, the further heat insulation effect can be expressed. Here, “reflect an electromagnetic wave in the wavelength range Xnm to Ynm of Z% or more” means that the average reflectance in the wavelength range of Xnm to Ynm is Z% or more, and the integration of the reflection spectrum from Xnm to Ynm. It can be calculated from the value.

  The selective light transmission film used in the present invention is composed of a dielectric film, a metal film, or an alternately laminated body in which a dielectric film and a metal film are alternately laminated. An alternating laminate composed of a dielectric film and a metal film is excellent in reflection characteristics of electromagnetic waves (infrared light) having a wavelength range of 1000 nm or more. Electromagnetic waves (infrared light) having a wavelength range of 1000 nm or more are particularly easily converted into heat, causing a temperature rise of the substance. The selective light transmission film is preferably composed of an alternating laminate in which dielectric films and metal films are alternately laminated. Below, a preferable alternating laminated body is described.

  It is preferable that the selective light transmission film 13 includes an alternate laminate 130 in which dielectric films 131 and metal films 132 are alternately laminated. Such an alternately laminated film diffracts and reflects heat rays (especially infrared rays) by plasmon resonance of the metal film, thereby achieving an excellent heat ray blocking function and high heat insulation performance.

  A normal metal totally reflects an electromagnetic wave having a frequency lower than the plasma frequency, that is, an electromagnetic wave on the long wavelength side, and reflects visible light and near infrared rays to have a metallic luster. However, in an alternate laminate in which metal films are sandwiched between dielectric films, the energy of the metal band gap changes at the interface between the dielectric film and the metal layer. For this reason, plasma vibration generated at the interface between the metal layer and the dielectric film is suppressed, and the visible light reflectance is reduced, that is, the visible light transmittance is improved. At this time, visible light reflectivity and heat ray reflectivity can be controlled by controlling the number of laminated metal films and dielectric films, the thickness, and the refractive index.

  At this time, the visible light reflection characteristics can be controlled by controlling the number of laminated metal films and dielectric films, the thickness, and the refractive index. In addition, radio wave permeability can be controlled by controlling the number of laminated metal films and the thickness.

  The number of laminated dielectric films in the alternately laminated body may be determined according to the number of laminated metal films so that the dielectric films alternately sandwich the metal films. Preferably, from the viewpoint of improving transparency and heat insulating properties, it is preferable that both sides of the metal film are sandwiched between dielectric films, that is, the number of laminated dielectric films is set to the number of laminated metal films + 1. In such a case, n layers of metal films are alternately sandwiched between n + 1 layers of dielectric films, resulting in a total number of stacks (2n + 1 layers).

  As a preferred form, the multilayer film has 3 to 11 layers. When the number of layers in the multilayer film is less than 3, reflection in the near infrared region is insufficient. On the other hand, when the number of layers is 12 or more, the manufacturing cost may increase, the plastic film may curl due to an increase in film stress, and handling may be difficult, and there may be a problem in durability. Furthermore, in order to ensure sufficient visible light transmittance, the alternate laminate is more preferably provided with two or more metal films.

  The film thickness of the metal film and dielectric film depends on the wavelength range of light for which reflection is to be suppressed, the refractive index of the dielectric, and the phase change at the interface between the dielectric film and the metal film. What is necessary is just to calculate so that it may be canceled by interference.

  Since the total thickness of the metal film affects visible light transmittance (transparency), the total thickness of each layer is preferably 50 nm or less, and more preferably 30 nm or less. More preferably, it is 20 nm or less. In this case, if the dielectric film does not absorb visible light, very high transparency can be secured. The lower limit of the total thickness of the metal film is not particularly limited, but is preferably 3 nm or more from the viewpoint of film formability.

  The thickness of each metal film is preferably 50 nm or less. The plasmon phenomenon is a physical phenomenon in which light is generated in a surface layer of 50 nm or less, and when it exceeds 50 nm, metal bulk characteristics are generated, and the visible light transmittance may be remarkably reduced. More preferably, the thickness of the metal film is 30 nm or less from the viewpoint of effectively reflecting electromagnetic waves (especially infrared rays having a wavelength of 1000 nm or more) that are easily converted into heat while ensuring transparency, and having excellent heat ray blocking properties. More preferably, it is 15 nm or less. The lower limit of the thickness of the metal film is not particularly limited, but is preferably 3 nm or more, more preferably 6 nm or more in terms of easy uniform film formation and excellent heat ray blocking properties based on infrared reflection.

  The film thickness of the dielectric film is designed so as not to reflect light in the visible light region (especially around 550 nm), and therefore may be designed by multilayer film interference of dielectric-metal layers using the following formula.

  As a material (metal) of the metal film 132 constituting the alternating laminate, any metal having resonance in the infrared region may be used. Specifically, gold (Au), silver (Ag), copper (Cu), platinum It is at least one selected from the group consisting of (Pt), iridium (Ir), palladium (Pd), nickel (Ni), and alloys thereof. The alloy is not particularly limited, and a conventionally known alloy can be used. Preferred is a simple substance of Ag or Al, or an alloy thereof, which has a uniform visible light spectrum and no coloration, and more preferably an Ag alloy (silver alloy) having high corrosion resistance. As a silver alloy, silver (Ag) added with one or more metals such as aluminum (Al), gold (Au), copper (Cu), palladium (Pd), neodymium (Nd), bismuth (Bi) It is.

  The material of the dielectric film 131 constituting the alternating laminate is not particularly limited as long as it is a transparent dielectric material, but preferably has a refractive index of 1.4 to 3.0. The higher the refractive index, the more visible light transmission can be improved by interference reflection.

  Specifically, the dielectric film includes silicon oxide, titanium oxide, niobium oxide, zinc oxide, aluminum oxide, tungsten oxide, zirconium oxide, tin oxide, indium tin oxide (ITO), antimony tin oxide (ATO), fluoride. Examples thereof include transparent inorganic dielectric materials such as calcium and magnesium fluoride, acrylic resins such as polymethyl (meth) acrylate and polynorbornene acrylate, and transparent thermoplastic resins such as polyester resins such as polyethylene terephthalate and polyethylene naphthalate. Note that the dielectric material is not limited to a complete insulator, and may be a material having a slight infrared absorbing property such as ITO or ATO.

  Among these, silicon oxide, titanium oxide, niobium oxide, zinc oxide, aluminum oxide, tungsten oxide, tin oxide, and indium oxide can be used by continuously and alternately laminating metal films and dielectric films by dry processes such as vapor deposition and sputtering. It is preferably at least one selected from the group consisting of tin (ITO), antimony tin oxide (ATO), calcium fluoride, and magnesium fluoride. More preferably, the dielectric film is selected from the group consisting of silicon oxide, titanium oxide, niobium oxide, zinc oxide, aluminum oxide, tungsten oxide, zirconium oxide, tin oxide, indium tin oxide (ITO), and antimony tin oxide (ATO). It is formed from at least one selected metal oxide. More preferred are inorganic oxides having a refractive index of 1.8 or more, such as titanium oxide, niobium oxide, zinc oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO). These inorganic oxides can particularly improve the visible light transmittance by interference in the above-described film thickness design. Particularly preferred are indium tin oxide (refractive index 2.2 to 3.0) and titanium oxide (2.3 to 2.4), which have a high refractive index.

  In a more preferred embodiment of the present invention, the metal is silver or a silver compound, and the dielectric is ITO. Although the present invention effectively suppresses the selective light transmission film from coming into contact with water, the selective light transmission film is an alternating laminate, the dielectric is ITO (indium-tin oxide), and the metal is Particularly effective in the case of silver or a silver alloy. When silver is deposited on ITO using silver or a silver alloy, a phenomenon occurs in which small silver particles become coarse and become large particles in the presence of water (Ostwald ripening). Therefore, this causes a portion where silver does not exist, and a uniform multilayer film becomes non-uniform. Moreover, since the part which silver does not exist does not have a heat reflective function, performance also deteriorates. With the configuration of the present invention, Ostwald ripening can be effectively suppressed.

  A metal film or a dielectric film can be formed on a plastic film by sputtering. As a film formation method other than sputtering, a metal film may be formed by vapor deposition or ion plating, and a dielectric film is formed by CVD, vapor deposition, ion plating, or the like. May be.

  In addition, in the laminated glass for window shields for automobiles, it is important that Tvis (visible light transmittance) determined by safety standards is 70% or more. On the other hand, the heat insulating property is indicated by an index called Tts (solar heat acquisition rate), and is preferably lower in terms of energy saving. Specifically, Tts (sunlight acquisition rate) is preferably 50% or less, and more preferably 45% or less. In particular, when Tvis ≧ 70% and Tts ≦ 45%, the energy saving effect is remarkably improved.

[Protective layer]
The present invention has a protective layer that shields (protects) the selective light transmission membrane from external substances.

  In the present invention, the protective layer is formed in close contact with the selective light transmission film so as to surround the outer periphery of the selective light transmission film, so that the intrusion of water from the peripheral part of the selective light transmission film can be suppressed. Thereby, deterioration of the metal layer contained in the selective light transmission film can be suppressed.

  In the present invention, the protective layer is further formed so as to cover at least a part of the peripheral portion of the selective light transmission film, so that in the adjacent bonding material layer, the bonding material layer considered to have the largest water content. Intrusion of water from the peripheral edge, that is, the peripheral edge of the selective light transmission film can be suppressed. Thereby, deterioration of the metal layer contained in the selective light transmission film can be suppressed.

The material used for the protective layer is required to be transparent and impervious to water. In the present specification, transparent means that the visible light transmittance is 70% or more as measured by the JIS R3106-98 method. Further, impervious to water means that the moisture permeability is 80 g / m ² · 24 hr or less as measured by JIS Z0208-76 method. If the visible light transmittance of the protective layer is 70% or more, it is suitable for a windshield glass of a car. Preferably, the visible light transmittance is 75% or more. When the moisture permeability is 80 g / m ² · 24 hr or less, the ability as a protective layer against water is sufficient.

  Suitable materials for the protective layer include compounds selected from the group consisting of ethylene-vinyl acetate copolymer resins, vinylidene chloride-vinyl chloride copolymer resins, vinylidene chloride-acrylonitrile copolymer resins. It will be. Preferably, an ethylene-vinyl acetate copolymer resin is the main component.

  In the present invention, the protective layer blocks the selective light transmission membrane from coming into contact with water. Therefore, the protective layer is formed in close contact with the selective light transmission film so as to surround the outer periphery of the selective light transmission film. Therefore, it is possible to prevent water from entering from the cross-sectional direction. At this time, the width of the protective layer surrounding the outer periphery of the selective light transmission film is preferably 0.01 to 10% of the hydraulic diameter of the selective light transmission film, more preferably 0.05 to 7%. 0.1 to 5% is more preferable. By covering the outer periphery of the selective light transmission film within the above range, the range to be protected can be sufficiently covered. The width of the protective layer covering the outer periphery of the selective light transmission film is indicated by d1 in FIG. In a more preferred form, the protective layer is formed to cover at least a part of the peripheral edge of the selective light transmission film. At this time, the protective layer covers 0.01 to 10% of the hydraulic diameter of the selective light transmission film from the outer periphery of the selective light transmission film toward the center (that is, covers the inner peripheral part of the selective light transmission film). It is preferable to cover 0.05 to 7%, and it is more preferable to cover 0.1 to 5%. By covering the peripheral edge portion of the selective light transmission film within the above range, contact with a portion having a high water content in the bonding material layer described below can be avoided. The width of the protective layer covering the peripheral edge (inner peripheral part) of the selective light transmission film is indicated by d2 in FIG. Moreover, when a protective layer covers a film outer peripheral part with a selective light transmission film | membrane, the width | variety of the protective layer mentioned above is preferable. In addition, a hydraulic diameter is calculated | required by dividing what multiplied the area of the target object 4 times by the perimeter (outside length) of the target object.

  In addition, the protective layer allows the selective light transmission film to be in contact with all the parts that are not in contact with the bonding material layer and the film, so that the contact between the selective light transmission film and water can be suppressed. Deterioration can be further suppressed. As described above, the selective light transmission membrane is preferably covered with a bonding material layer, a film and a protective layer. In some cases, for example, when a wiring or the like exists between the selective light transmission film and the protective layer or another member, the selective light transmission film may not be covered with the protective layer.

  A cross section of the selective light transmission film can be given as a part where water and the metal contained in the selective light transmission film are easily contacted. In other parts, a dielectric film exists on the metal film, and can act as a protective layer against contact with water. In the laminated glass of the present invention, the protective layer is formed in close contact with the cross section of the selective light transmission film so as to surround the outer periphery of the selective light transmission film, so that the selective light transmission film is effectively in contact with water. Is suppressed.

  Moreover, the peripheral part of a selective light transmission film | membrane can be considered as a site | part which water and the metal contained in a selective light transmission film | membrane easily contact. In the peripheral part of the selective light transmission film, the water content increases in the production of laminated glass as compared with other parts. 8A to 8C are a schematic cross-sectional view when manufacturing the laminated glass 3 and a graph schematically showing the distribution of the water content contained in the bonding material layer. As the bonding material, polyvinyl butyral (hereinafter sometimes abbreviated as “PVB”) is generally used as described later. PVB contains water in order to adjust the adhesion to glass. Before heating and pressing (FIG. 8A), the water content contained in PVB (bonding material layers 32 and 36) is substantially uniform (graph in FIG. 8A). When the laminated glass is manufactured, the first bonding material layer 32, the selective light transmission film 33, the film 34, and the second bonding material layer 36 are sandwiched between the first glass substrate 31 and the second glass substrate 37. Then, pressure heating is performed (FIG. 8B). By being pressurized in the direction of the arrow 38, the water in the PVB moves in the direction of the arrow (the arrow in the bonding material layers 32 and 36), and the water is pushed out from the glass center, and the end of the glass ( It slips out to the peripheral edge (FIG. 8B). At the end of the heating and pressurization (FIG. 8C), the water content of PVB at the center of the glass is small and the water content at the end (peripheral edge) of PVB (bonding material layer) is large (FIG. 8 (C) Graph). Therefore, the PVB on the peripheral edge of the selective light transmission film 33 has a large water content. Similarly, air is pushed out by moving in the direction of the arrow.

  As described above, in a preferred embodiment of the present invention, the protective layer is formed so as to cover at least a part of the peripheral edge portion of the selective light transmission film. For this reason, in the adjacent bonding material layer, it is possible to suppress the permeation of water from the peripheral portion of the bonding material layer considered to have the largest water content, that is, the peripheral portion of the selective light transmission film.

  Further, when the laminated glass is produced, the sandwiched film is stretched by heating. FIG. 9 is a schematic cross-sectional view when the laminated glass 3 is manufactured. In order to produce a laminated glass, the first glass substrate 31 and the second glass substrate 37 are alternately laminated with a first bonding material layer 32, a dielectric film 331 and a metal film 332 (selective light transmission film). Then, the film 34 and the second bonding material layer 36 are sandwiched and heated under pressure (FIG. 9A). An alternating laminate 330 (selective light transmission film) is formed on the film 34, but the alternating laminate 330 (selective light transmission film) is not subjected to tensile stress before heating and pressing. The alternating laminated body 330 (selective light transmission film) is subjected to tensile stress due to stretching of the film 34 as shown in FIG. Therefore, the alternate laminated body 330 (selective light transmission film) is pulled from the film 34, and the dielectric layer 331 made of ceramics is finely cracked even though the highly ductile metal layer 332 is not affected. There is a fear. For example, when the pressure heating is completed, the dielectric layer 331 has a fine crack. Furthermore, in the alternate laminated body 330 (selective light transmission film) in contact with the PVB end portion (peripheral portion) having a high water content described above, there is a concern that water may penetrate from cracks in the dielectric layer 331. Even when the laminated glass of the present invention is subjected to tensile stress due to heat and pressure, the protective layer is formed in close contact with the peripheral edge of the selective light transmission film, so that PVB having a high water content and the selective light transmission film Therefore, the selective light-transmitting membrane is effectively prevented from coming into contact with water.

  In the present invention, the selective light transmission film is formed on the film, but the protective layer covers the peripheral edge of the selective light transmission film, and the protective layer may be formed between the film and the selective light transmission film. Good. A protective layer may be formed between the film and the bonding material layer.

  As described above, according to the present invention, the protective layer adheres to the selective light transmission film and the outer peripheral portion and the peripheral portion so that the contact between the selective light transmission membrane and water is suppressed, and the stability with time is improved. Glass is obtained.

  10 is a schematic cross-sectional view and a schematic plan view of a contact surface between a protective layer and a selective light transmission film when the laminated glass of the embodiment shown in FIG. 7 is manufactured. 10 (A) to 10 (C) are schematic diagrams for explaining unevenness on the surface of the protective layer when producing a laminated glass, and an enlarged state of the bonding surface (contact surface) between the protective layer and the bonding material layer. Show.

  According to the method for producing a laminated glass of the present invention, the protective layer and the bonding material are bonded by heating and pressing the bonding surface of the protective layer on which the convex portion is formed and the bonding surface of the bonding material layer. Joining the layers.

  In the laminated glass of the present invention, after heating and pressurizing, the constituent elements are in close contact with each other without any gap, but before the heating and pressurizing, the surface of the protective layer is uneven and a space is formed. This space is in communication, and the exit exists on the glass outer peripheral side of the protective layer. The communicating space is crushed by heat and pressure, and is closely attached without a gap. Even if there are voids due to fine irregularities on the bonding surface (contact surface) between the selective light transmission film and the protective layer before heating and pressing, and the bonding surface (contact surface) between the protective layer and the bonding material layer It is pushed out from the communicating space during heating and pressurization.

  The protective layer used in the present invention preferably has a convex portion between the bonding material layers (bonding surface), that is, an uneven surface. In this specification, “the protective layer has a convex portion” means that the surface of the protective layer is at least one selected from the group consisting of a concave portion, a convex portion, an uneven portion, a groove portion (notch portion), and a bank portion. It means having a shape.

  The protective layer may be provided with one convex portion or a plurality of convex portions at one place. Examples of the planar shape of the convex portion include a triangle; an arbitrary quadrangle including a square, a rectangle, and a trapezoid; an arbitrary polygon; an arbitrary smooth closed curve including a circle, an oval, an ellipse, and the like. As a cross-sectional shape of the convex portion when the convex portion is cut along the height direction, a triangle; an arbitrary quadrangle including a square, a rectangle, a trapezoid; an arbitrary polygon; A part of a smooth curve can be exemplified. Moreover, one recessed part may be provided in one place of the protective layer, and the several recessed part may be provided. Examples of the planar shape of the concave portion include an arbitrary smooth closed curve including a triangle; an arbitrary quadrangle including a square, a rectangle, and a trapezoid; an arbitrary polygon; a circular, an oval, an ellipse, and the like. As a cross-sectional shape of the recess when the recess is cut along the depth direction, a triangle; an arbitrary quadrangle including a square, a rectangle, a trapezoid; an arbitrary polygon; an arbitrary smooth including a circle, an oval, an ellipse, etc. A part of the curve can be exemplified. What is necessary is just to comprise the convex part of a protective layer from the combination of the recessed part and convex part which were demonstrated above. The groove portion (notch portion) or bank portion is preferably linear, but is not limited thereto. Further, the protective layer used in the present invention has a shape in which the groove forms a passage, for example, a structure in which the groove is perpendicular to the side of the glass outer peripheral portion (having an angle of 90 °) (FIG. 10A). ), A structure in which the groove has an angle of more than 0 ° and less than 90 ° with respect to the side of the glass outer periphery, and two opposing grooves (or banks) have an angle of 90 ° with respect to the side of the glass outer periphery The lattice-like structure, and the diagonal structure (FIG. 10 (B)) in which two opposing grooves (or banks) have an angle of more than 0 ° and less than 90 ° with respect to the side of the glass outer peripheral portion, and the protrusions are independent. As an existing shape, an emboss structure (FIG. 10C) can be selected as appropriate. Note that having two opposite grooves (or banks) means that the grooves (or banks) intersect, and the two grooves (or banks) intersect, so that the banks are convex pyramid-shaped. Part (square conical shape). The size of the irregularities may be any size that can be processed, and in the case of an irregular structure, the pitch (width) is preferably 0.1 to 1 mm and the height is preferably 0.05 to 0.5 mm.

  The protective layer adheres to the bonding material layer by heating and pressing. At this time, since the protective layer has an uneven surface, even if there is a gap at the interface between the protective layer and the bonding material layer, a passage that can be easily pushed out of the glass is secured, and each of the protective layer and the bonding material is heated. Air in the passage is easily pushed out by deformation due to pressure.

  That is, it is deformed by heating and pressurization at the time of producing laminated glass, and the gap is crushed and air is pushed out. This makes it difficult for a gap to remain on the interface between the bonding material layer and the protective layer. There was a gap at the part where the bonding material layer and the protective layer were in contact before heating and pressing, and it was removed by heating and pressing. Specifically, the air in the gap could not be pushed out of the cross section of the laminated glass. In such a case, water may accumulate in the gap. Therefore, it is preferable to previously provide a groove (recess) passage between the surface of the protective layer and the surface of the bonding material layer so as to escape to the end of the glass (in the direction of the outer periphery) before heating and pressing. Even if a gap exists before heating and pressurization, the air in this gap can be efficiently extracted from the passage by heating and pressurization. Further, when the protective layer has an uneven surface, the surface of the bonding material layer in contact with the protective layer is preferably a smooth surface in order to improve the appearance.

[the film]
The film used for the laminated glass of the present invention is used as a substrate (substrate) for a selective light transmission film, that is, a support for the selective light transmission film.

  The film may be transparent or opaque, and various resin films can be used. However, when used for a window of a building or a vehicle, particularly when used for a windshield of an automobile, it should be transparent. Is preferred.

  Specific examples include polyolefin film (polyethylene, polypropylene, etc.), polyester film (polyethylene terephthalate (PET), polyethylene naphthalate, etc.), polyvinyl chloride film, cellulose acetate film, polyimide film, tack film, nylon film, polycarbonate. A film, a polymethyl methacrylate film, a polyether sulfone film, a polyarylate film, a cycloolefin polymer film, or the like can be used. Preferred are polyester films such as polyethylene terephthalate (PET) film and polyethylene naphthalate film, polyimide film, tack film, nylon film, polycarbonate film, polymethyl methacrylate, polyether sulfone, polyarylate, and cycloolefin polymer, and more preferred. Is a polyester film. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. Among the polyesters having these as main constituent components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Of these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymer polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  Also, among the above films, plastic films produced by stretching methods such as PET films have relatively high strength, so that defects such as film breaks that occur during handling at the time of processing can be suppressed. The formation of spherical crystals by heating can be suppressed, and the cloudiness is suppressed, which is preferable.

  The thickness of the film used in the present invention is usually 10 to 500 μm, preferably 20 to 200 μm, and more preferably 25 to 100 μm. Two or more substrates may be stacked, and in this case, the types of the substrates may be the same or different.

[Bonding material layer]
The bonding material layer is composed of a bonding material, and is a layer for bonding the glass substrate, the selective light transmission film, and the film. That is, the bonding material layers (12, 16) are interposed between two or more glass plates, and have a function of bonding and integrating them. Because the laminate that constitutes the laminated glass is strongly bonded by the bonding material layer, the laminated glass can be given excellent penetration resistance, impact resistance, and anti-scattering effects. However, it is preferable that the bonding material has no absorption due to a functional group other than the OH group in the visible light region or the infrared light region. Specifically, it is formed from polyvinyl butyral resin (PVB resin), ethylene-vinyl acetate copolymer resin (EVA resin), silicone resin, polyurethane resin, or the like. Of these, polybutyl vinyl resin is particularly preferable, but the type of the bonding material is appropriately determined according to the purpose and application of use, and is not limited in the present invention. These resins may be used alone or in combination of two or more. Although it is convenient to use it alone, in particular, in order to improve durability, it is also effective to use a plurality of bonding materials. In addition to the above resin, the bonding material layer may be appropriately mixed with an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a coloring agent, an adhesion adjusting agent, and the like.

The bonding material 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 Monsanto, EVA resin manufactured by DuPont and Takeda Pharmaceutical Company Limited, and modified EVA resin manufactured by Tosoh Corporation. In general, the bonding material layer may be composed of a single layer of the above resin, or may be used in a state where two or more layers are laminated. Further, the first bonding material layer 12 and the second bonding material layer 15 may be made of the same type of resin, or may be made of different types of resin.

  The bonding material layer may contain fine particles of a transparent conductive oxide material having a heat ray absorbing ability such as indium tin oxide (ITO) and antimony tin oxide (ATO), but it is preferable not to contain these fine particles. This is because these fine particles absorb heat once and then radiate heat to the indoor side by re-radiation, which causes an increase in the temperature of the room over time. From this point of view, when these fine particles are dispersed, it is preferably applied to the second bonding material layer disposed on the indoor side. In the second bonding material layer, most of the heat rays are blocked by the selective light transmission film, so that the influence of re-radiation by the fine particles can be minimized and the heating efficiency in winter can be increased.

  The bonding material can be used in the form of a film, powder, or solution. When the bonding material is used in the form of a film, it is effective to use a film (bonding material) in which one surface is an uneven surface and the other surface is a smooth surface in order to improve the appearance. When forming the laminated glass, the smooth surface of the film (bonding material) which is a bonding material is used on the selective light transmission film and the film side, and the uneven surface side is used on the glass side. In a powder or solution state, it functions as a bonding material by being heated and compressed after being applied to a selective light transmission film, film or glass.

[First glass substrate and second glass substrate]
It does not specifically limit as the 1st glass substrate 11 and the 2nd glass substrate 17, What is necessary is just to select according to the light transmission performance and heat insulation performance which are requested | required for a use, and it may be inorganic glass or organic glass. .

  The inorganic glass plate is not particularly limited, and examples thereof include various types of inorganic glass such as float plate glass, polished plate glass, mold plate glass, meshed plate glass, wire-containing plate glass, heat ray absorbing plate glass, and colored plate glass. Examples of the organic glass include glass plates made of resins such as polycarbonates, polystyrenes, and polymethyl methacrylates. These organic glass plates may be a laminate formed by laminating a plurality of sheet-shaped ones made of the resin. Regarding the color, not only the transparent glass plate but also glass plates of various colors such as general-purpose green, brown and blue used for vehicles and the like can be used. The first glass plate 11 and the second glass plate 16 may be the same type of glass plate or different types of glass plates.

  However, it is desirable that the first glass substrate 11 disposed on the outdoor side is difficult to absorb visible light or infrared light. Preferably, the glass has an electromagnetic wave absorption of less than 5% and a visible light transmittance of 85% or more, specifically a glass having an electromagnetic wave absorption of 750 nm or more of less than 5% and a transmittance of 380 nm to 780 nm of 85% or more. Is preferred. If glass that absorbs heat rays such as visible light or infrared rays is used on the outdoor side, the indoor temperature may increase due to re-radiation of the absorbed heat. Specifically, it is preferable to use clear glass or the like.

  On the other hand, the second glass substrate 17 disposed on the indoor side is not particularly limited, and may absorb visible light or infrared light. Since the selective light transmission film 13 is arranged on the vehicle exterior side of the second glass substrate 17 and the infrared rays are blocked by this, the amount of infrared absorption of the second glass substrate 17 can be reduced, and the influence of re-radiation is small. It is. Specifically, it is preferable to use green glass in addition to clear glass. Among these, it is preferable to use green glass because it has ultraviolet absorption performance.

  There is no restriction | limiting in particular about the thickness of a glass substrate, What is necessary is just to set suitably according to a use. Usually, the glass substrate has a thickness of 1.5 to 2.5 mm. For example, in the use of a windshield (window shield) of a transportation vehicle, the glass substrate generally has a thickness of 2.0 to 2.3 mm. It is preferable to use a substrate.

  In addition, although the laminated glass 1 of embodiment shown in FIG. 2 contains two glass substrates (the 1st glass substrate 11 and the 2nd glass substrate 17), in this invention, it contains three or more glass plates. May be. Even when three or more glass substrates are included, the laminated body may be bonded and integrated into a laminated glass by interposing a bonding material layer between the glass substrates, as in FIG.

  It does not restrict | limit especially as a method of producing the laminated glass of this invention, What is necessary is just to use the manufacturing method of a general laminated glass. Specifically, the laminated glass of the present embodiment is obtained by laminating the selective light transmission film 13, the protective layer 15, and the bonding material layers (12, 16) between the glass plates (11, 17) and pre-adhering them. The air bubbles remaining after the pre-adhesion can be manufactured by a process of removing by heating and pressurizing (pressure bonding with high temperature and pressure). In addition, according to the manufacturing method of the present invention, the protective layer and the bonding material layer are formed by bringing the bonding surface of the protective layer on which the convex portion is formed and the bonding surface of the bonding material layer into close contact with each other by heating and pressing. And a step of joining. About the shape of the convex part of a protective layer, since it mentioned above, it abbreviate | omits.

The heating and pressurization can be appropriately adjusted according to the used bonding material, protective layer, glass, film and selective light transmission membrane, but the heating is preferably 90 to 160 ° C, more preferably 100 to 150 ° C, The pressurization is preferably performed at 5 to 16 kg / cm ² , more preferably 10 to 14 kg / cm ² .

  Conventionally, there are many glasses having a metal film attached to the surface. Such glass is (1) easy to peel off by using a wiper or the like, (2) it is necessary to produce a batch because a film needs to be attached according to each glass, (3) metal film on the glass surface There is a problem that water easily enters and gets rusted. The laminated glass of the present invention can be manufactured continuously and is advantageous in terms of cost. In addition, even when used for a front window where a wiper or the like is used, peeling and rust are prevented and excellent durability is achieved. .

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

[Example 1]
A selective light transmission film made of ITO (30 nm) / silver (15 nm) / ITO (30 nm) / silver (15 nm) / ITO (30 nm) is formed on one side of a PET film having a thickness of 50 μm and a 15 cm square by DC magnetron sputtering. Formed. An ethylene-vinyl acetate copolymer resin sheet having a thickness of 52 μm and a width of 0.5 cm at a position in contact with the outer periphery (cross section) of the film (manufactured by Tatsuno Chemical Co., Ltd., product name Midea, visible light transmittance of 86.6%) , Moisture permeability 20g / m ² · 24hr) is enclosed as a protective layer and sandwiched between the center of two polybutyl vinyls with a thickness of 0.38mm and 16cm square, and is further covered with a transparent plate glass with a thickness of 2mm and 16cm square. After sandwiching, pressure-bonding was performed at 130 ° C. and 10 Kg / cm ² to produce a laminated glass 1. About this laminated glass, the durability test mentioned later was done and the external appearance change of the laminated glass was investigated visually.

[Example 2]
In Example 1, instead of ethylene-vinyl acetate copolymer resin, vinylidene chloride-vinyl chloride copolymer resin (manufactured by Asahi Kasei Chemicals Corporation, product name Saran film UB, visible light transmittance%, moisture permeability / m ² · 24 hr. The laminated glass 2 was obtained in the same manner except using

[Example 3]
In Example 1, laminated glass was used in the same manner except that vinylidene chloride-acrylonitrile copolymer resin (visible light transmittance 94%, moisture permeability 50 g / m ² · 24 hr) was used instead of ethylene-vinyl acetate copolymer resin. 3 was obtained.

[Example 4]
In Example 1, 14 cm of a selective light transmission film is formed in the center of a 15 cm square film, and a protective layer having a thickness of 50 μm and a width of 0.5 cm is provided at a position of 0.5 cm width where no film is formed. Was placed in the center of a 15 cm square polybutyl vinyl sheet and sandwiched between 15 cm square transparent plate glasses to obtain a laminated glass 4.

[Example 5]
In Example 1, the size of the film is 5 cm square, the size of polybutyl vinyl is 6 cm square, the size of the glass is 6 cm square, a protective layer is added to the periphery of the film, and the selective light transmitting film on the film A laminated glass 5 was obtained in the same manner except that it also covered a range of 0.05 cm from the end of the surface on which the film was formed (in the direction from the outer periphery to the center).

[Example 6]
In Example 1, in addition to the periphery of the film, the protective layer also covers a range of 0.7 cm from the end of the surface on which the selective light transmission film is formed (in the direction from the outer periphery toward the center). Similarly, laminated glass 6 was obtained.

[Example 7]
In Example 2, the protective layer has a convex portion on the entire surface in contact with the polybutyl vinyl (joining material) in the direction perpendicular to the glass surface, and the convex portion has a height toward the glass surface. A laminated glass 7 was obtained in the same manner except that a groove having a pitch of 0.2 mm and a pitch of 0.2 mm was used so that the passage formed by the grooves was directed toward the outer peripheral portion of the glass. .

[Example 8]
In Example 2, the protective layer has a convex portion on the entire surface in contact with the polybutyl vinyl (joining material) in the direction perpendicular to the glass surface, and the convex portion has a height toward the glass surface. 0.2 mm, 0.3 mm wide pyramid-shaped convex part (square square shape), and the passage formed by the concave part (groove part) by the pyramidal convex part is 90 ° with respect to the side of the outer peripheral part of the glass A laminated glass 8 was obtained in the same manner except that a glass that had been processed so as to have an angle toward the direction was used.

[Example 9]
In Example 8, the path formed by the concave portion (groove portion) by the pyramidal convex portion is processed so that it has an angle of 45 ° with respect to the side of the glass outer peripheral portion (diagonal shape). A laminated glass 9 was obtained in the same manner except that it was used.

[Comparative Example A]
In Example 1, the laminated glass A was similarly formed except that the protective layer was formed so as to cover the entire surface of the selective light transmission film on the film (that is, the protective layer was not formed on the outer peripheral portion of the selective light transmission film). Got.

[Reference Example B]
In Example 1, after forming the laminated glass, laminated glass B was obtained in the same manner except that the entire periphery was covered with a protective layer so as to surround the outer peripheral portion of the laminated glass.

<Durability test>
The laminated glass obtained in Examples 1 to 9, Reference Example A and Reference Example B was checked for changes in the appearance of the laminated glass after being left for 90 days in an air atmosphere at 50 ° C. and a relative humidity of 95%. The appearance was confirmed visually.

  The cloudiness and spots in the comparative examples and reference examples are considered to be due to the oxidative degradation of Ag by water. As described above, it can be seen that the present invention is more excellent in appearance quality durability than the comparative example and the reference example.

1 Laminated glass,
3 Laminated glass,
11 First glass substrate,
12 1st joining material layer,
13 Selective light transmission membrane,
14 Film 15 Protective layer,
16 second bonding material layer,
17 second glass substrate,
23 The outer periphery of the selective light transmission membrane,
24 The outer periphery of the film,
25 Peripheral portion 130 of selective light transmission film alternating laminate,
131 dielectric film,
132 metal film,
d1 width of the protective layer covering the outer periphery of the selective light transmission film,
d2 width of the protective layer covering the peripheral edge of the selective light transmission film,
31 1st glass substrate,
32 a first bonding material layer,
33 selective light transmission membrane,
34 films,
36 a second bonding material layer;
37 second glass substrate,
38 direction of pressurization,
330 alternating laminates,
331 dielectric film,
332 metal film.

Claims (6)

Between the pair of bonding material layers, a laminated layer of a selective light transmission film and a film, wherein the bonding material layer is closely sandwiched between a pair of glass substrates,
A laminated glass, wherein a protective layer for protecting the selective light transmission film is formed in close contact with the selective light transmission film so as to surround an outer peripheral portion of the selective light transmission film. The selective light transmission film is an alternately laminated body in which dielectric films and metal films are alternately laminated,
The dielectric film is at least one metal oxide selected from the group consisting of silicon oxide, titanium oxide, niobium oxide, zinc oxide, aluminum oxide, tungsten oxide, zirconium oxide, tin oxide, indium tin oxide and antimony tin oxide. Formed from things,
The laminated glass according to claim 1, wherein the metal film is formed of at least one metal selected from the group consisting of gold, silver, copper, platinum, iridium, palladium, and nickel.   The laminated glass of Claim 1 or 2 with which the said protective layer covers at least one part of the peripheral part of the said selective light transmission film | membrane.   4. The laminated glass according to claim 3, wherein the protective layer covers 0.01 to 10% of the hydraulic diameter of the selective light transmission film from the outer periphery of the selective light transmission film toward the center.   The protective layer includes one or more compounds selected from the group consisting of ethylene-vinyl acetate copolymer resin, vinylidene chloride-vinyl chloride copolymer resin, and vinylidene chloride-acrylonitrile copolymer resin. Laminated glass of any one of 1-4.   The method includes the step of bonding the protective layer and the bonding material layer by bringing the bonding surface of the protective layer on which a convex portion is formed and the bonding surface of the bonding material layer into close contact with each other by heat and pressure. The manufacturing method of the laminated glass of any one of -5.

Images