WO2003037056A1 - Substrat dote d'un film de protection electromagnetique - Google Patents

Substrat dote d'un film de protection electromagnetique Download PDF

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Publication number
WO2003037056A1
WO2003037056A1 PCT/JP2002/010983 JP0210983W WO03037056A1 WO 2003037056 A1 WO2003037056 A1 WO 2003037056A1 JP 0210983 W JP0210983 W JP 0210983W WO 03037056 A1 WO03037056 A1 WO 03037056A1
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WO
WIPO (PCT)
Prior art keywords
layer
thickness
silver
film
substrate
Prior art date
Application number
PCT/JP2002/010983
Other languages
English (en)
Japanese (ja)
Inventor
Tadashi Ohnishi
Keiji Sato
Yasutaka Tsuda
Katsuto Tanaka
Original Assignee
Central Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001328715A external-priority patent/JP2003133787A/ja
Priority claimed from JP2002290283A external-priority patent/JP2004128220A/ja
Application filed by Central Glass Company, Limited filed Critical Central Glass Company, Limited
Publication of WO2003037056A1 publication Critical patent/WO2003037056A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3639—Multilayers containing at least two functional metal layers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
    • C03C17/3676—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electromagnetic shield
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/867—Means associated with the outside of the vessel for shielding, e.g. magnetic shields
    • H01J29/868—Screens covering the input or output face of the vessel, e.g. transparent anti-static coatings, X-ray absorbing layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels
    • H01J2329/86—Vessels
    • H01J2329/868—Passive shielding means of vessels
    • H01J2329/869—Electromagnetic shielding

Definitions

  • the present invention relates to an electromagnetic wave or remote control generated from the front of a display such as a plasma display panel (hereinafter referred to as PDP), a force sort ray tube (CRT), a liquid crystal display (LCD) and an electorite luminescence (EL).
  • PDP plasma display panel
  • CTR force sort ray tube
  • LCD liquid crystal display
  • EL electorite luminescence
  • the PDP emits electromagnetic waves (frequency: 30 to 1000 MHz) harmful to the human body or near infrared rays (wavelength: 850 to 1000 nm) that may cause the remote control of the home appliance to malfunction, these must be Need to be shielded.
  • a filter substrate for a DPP coated with a transparent conductive film is mounted on the front of the DPP for the purpose of shielding electromagnetic waves and near infrared rays on a glass substrate. .
  • the protective plate for PDP in which the multilayer conductive film laminated
  • An electromagnetic wave filter for a DPP having an electromagnetic shielding film is described.
  • a silver layer to which P d or the like is added is used as the silver layer, which is disadvantageous in cost and P d or the like is added to the silver layer.
  • the resistance value is increased as compared to other metal layers having the same film thickness.
  • the electromagnetic shielding film described in JP-A-11-307987 is In order to secure moisture resistance, a silver film to which an expensive Pd is added is used as a metal film as described above, but when a large amount of Pd is added, the resistance value of the transparent conductive film contributing to the electromagnetic wave shielding property In addition, problems such as a decrease in electromagnetic wave shieldability occur, which is disadvantageous in cost.
  • the present invention was made in view of the conventional problems, and adopted a multilayer film of a base layer including a silver 3 layer in which a dielectric layer using optical interference and a silver layer were combined.
  • An object of the present invention is to inexpensively provide a well-balanced substrate with an electromagnetic wave shielding film in which image display is easy to view.
  • the transparent substrate surface is covered with a transparent conductive film in which seven layers of dielectric layers and silver layers are alternately and sequentially repeated alternately from the substrate side. Thickness of each of the silver layers is 5N (99. 999%) or more, and the resistance value (sheet resistance) of the transparent conductive film surface is 1. It is characterized by having a 2 ⁇ / hole or less and a visible light transmittance of 60% or more.
  • the electromagnetic wave shielding film coated substrate comprises a transparent substrate, a first dielectric layer of a transparent metal oxide layer / a first silver layer / a first barrier layer of Z n A 1 / Second dielectric layer composed of transparent metal oxide layer / second silver layer / second barrier layer composed of Z n A 1 Third dielectric layer / third silver layer composed of transparent metal oxide layer ZZ n A 1 A third conductive layer composed of a third dielectric layer and a transparent conductive film composed of a fourth dielectric layer composed of a transparent metal oxide layer, wherein each silver layer has a thickness of 9 to 15 nm, Z n A 1
  • the film thickness of the barrier layer comprising the first dielectric layer and the fourth dielectric layer is 1.0 to 3.
  • the film thicknesses of the first dielectric layer and the fourth dielectric layer are 40 to 50 nm, and the second dielectric layer and the third dielectric layer
  • the transparent conductive film has a film thickness of 75 to 85 nm, a resistance value (sheet resistance) of the surface of the transparent conductive film of 2.5 ⁇ / hole or less, a visible light transmittance of 70% or more, and a transparent conductive film Coating
  • the visible light reflectance on the surface side of the transparent conductive film is 4% or less, and any silver layer constituting the transparent conductive film has a purity of silver of 5 N (99. 99 99%) or more.
  • Any Z n A 1 barrier layer that constitutes the conductive film It is a substrate with an electromagnetic wave shielding film characterized in that it is a Z n A 1 alloy containing 1 to 10% by weight.
  • FIG. 1 is a cross-sectional view of the layer configuration of a transparent conductive film according to an embodiment of the present invention.
  • the transparent conductive film has a sheet resistance of not more than 1.2 ⁇ / hole as a sheet resistance and is excellent in electromagnetic shielding performance and has a high visible light transmittance of 60% or more,
  • the reflectance is also low, it is possible to provide an electromagnetic wave shielding film-coated substrate having a well-balanced, easy-to-see image display and excellent in moisture resistance at low cost.
  • the electromagnetic wave shielding film coated substrate of the present invention is formed by repeatedly laminating the dielectric layer and the silver layer in this order on the surface of the transparent substrate so that the silver layer is three layers, and the dielectric layer is laminated on the uppermost layer.
  • a transparent conductive film formed by alternately laminating seven layers of dielectric layers and silver layers alternately and sequentially from the substrate side is coated on the transparent substrate surface.
  • the thickness of the silver layer is 18 nm or more, and the purity of silver in each silver layer is 5 N (999.99%) or more.
  • the resistance value of the surface of the transparent conductive film (see It has a resistance of 1.2 ⁇ / hole or less and a visible light transmittance of 60% or more.
  • the transparent conductive film is preferably a first dielectric layer having a thickness of 35 to 6 nm from the substrate side, a first silver layer having a thickness of 18 to 28 nm, and a thickness of 18 to 28 nm.
  • the film thickness of the silver layer influences the electromagnetic wave shielding property, the visible light transmittance and the reflection color tone, and in order to obtain a high electromagnetic wave shielding property of 30 dB or more, A film thickness of 18 nm or more is required.
  • 60% or more of visible light transmittance is ensured to make the image bright and easy to view, and 30 nm or less for each silver layer to avoid red reflected light. It is preferable to
  • the film thickness of the first silver layer is preferably 18 to 28 nm
  • the film thickness of the second silver layer is preferably 20 to 30 nm
  • the film thickness of the third silver layer is preferably 18 to 29 nm. If only two silver layers are provided (five layers including the dielectric layer as a whole), the resistance value of the film surface as in the present invention is a sheet resistance of 1.2 ⁇ or less, visible light transmittance It is impossible to easily obtain those with 60% or more.
  • each dielectric layer is formed of at least a zinc oxide layer or a tin oxide layer, and the thickness of each of these dielectric layers is as follows: the tin oxide layer in the first dielectric layer which is the lowermost layer; 50 nm, zinc oxide layer 5 to 55 nm, tin oxide layer in second dielectric layer 0 to 95 nm, zinc oxide layer 5 to 100 nm, tin oxide layer in third dielectric layer 5
  • the zinc oxide layer is preferably 5 to 100 nm
  • the tin oxide layer in the fourth dielectric layer is preferably 8 to 50 nm
  • the zinc oxide layer is preferably 5 to 55 nm. With a film thickness of 10%, it becomes impossible to make the visible light transmittance 60% or more.
  • the silver layer used in the present invention it is preferable to use silver having a purity of 5N (99. 999%) or more, although any silver layer does not contain any additives, and silver is preferably formed.
  • This is a device that traps the base pressure at the time of the poly cold (by condensing the water vapor present in the vacuum chamber on a low temperature cooling surface called a cryo coil so that a high vacuum can be obtained in the vacuum chamber). It is possible to obtain a high-density structure by applying a high vacuum by using US Polycold Systems Inc. (trade name of manufactured by IN ITAL Co., Ltd.) and the like, and as a silver barrier layer described later.
  • a film-coated substrate having good moisture resistance can be obtained without including impurities such as P d in A g.
  • a first barrier layer comprising a first dielectric layer / a first silver layer / a first silver layer / a Z n AI formed of a transparent metal oxide layer is formed on a transparent substrate.
  • Second dielectric layer consisting of layer / transparent metal oxide layer Z second silver layer third barrier layer consisting of ZnAl / third metal layer consisting of transparent metal oxide layer / third silver layer / third layer consisting of Z nAl Barrier Layer
  • any silver layer constituting the transparent conductive film has a silver purity of 5 N (99. 999%) or more, and any of the silver layers constituting the transparent conductive film.
  • Z n A 1 The rear layer is a substrate with an electromagnetic wave shielding film characterized in that it is a ZnAl alloy containing 1 to 10% by weight of A1, wherein the resistance value (sheet resistance) of the surface of the transparent conductive film is 2.5 ⁇ /. It is characterized by having a visible light transmittance of 70% or more and a visible light reflectance of 4% or less on the side coated with the transparent conductive film.
  • the thickness of the silver layer affects the electromagnetic shielding property, the visible light transmittance and the visible light reflectance, and the high electromagnetic shielding of 30 dB or more
  • Each silver layer needs to have a thickness of 10 nm or more in order to obtain good image quality.
  • each silver layer in order to brighten the image and improve visibility, 70% or more of visible light transmittance is secured, and image contrast
  • An amorphous film consisting of a tin oxide layer as an oxide layer is chemically and mechanically strong, and because of its amorphous loose structure, its adhesion to glass is also strong, and internal stress is also strong. It is hard to occur. Therefore, it is desirable to coat directly on the glass.
  • the thickness of the tin oxide layer in the first dielectric layer is preferably at least 8 nm or more in order to increase adhesion to glass and to eliminate the influence of alkali ions.
  • the dielectric layer is not limited to the zinc oxide layer or the tin oxide layer described above, and titanium oxide, S n Z n O, Z n A l, ITO, or the like can also be used.
  • tin oxide layer has poor adhesion to silver, in particular, and peeling at the tin oxide layer Z silver layer interface is likely to occur.
  • tin oxide has a weak bond with oxygen as its ionization tendency shows, and since the chemical potential of oxygen in the film is high, oxygen is easily diffused in the silver layer, the electrical resistance is increased, and high electromagnetic wave shielding is achieved. hard.
  • the tin oxide layer is preferably not in contact with the silver layer.
  • the tin oxide layer may contain an element as an amorphous film component which improves the chemical and mechanical properties and strengthens the adhesion to glass.
  • the layer immediately below the silver layer is preferably a zinc oxide layer.
  • the zinc oxide layer contains a known element (A1, Sn, etc.) as a component of the film that does not reduce the adhesion with the silver layer and makes it difficult for oxygen to diffuse in the silver layer. It is good.
  • the desired argon addition rate varies depending on equipment, but is approximately 10 to 30%. This value is determined by adding argon gradually from the oxygen atmosphere, observing whether the voltage applied to the target suddenly rises or the current suddenly drops, and then reducing argon a little.
  • the zinc oxide layer is dense and has the effect of preventing the diffusion of corrosive gases in the air, and also has the function of absorbing ultraviolet rays contained in sunlight, but its chemical durability is low.
  • a zinc oxide layer is used as the upper layer, it is desirable to further provide a tin oxide layer which is an amorphous oxide on the upper layer.
  • the above Z n as a zinc oxide layer
  • This Z n Al x O y layer prevents the oxidation of the silver layer, especially when heat treatment is performed at a high temperature above the softening point of the glass after forming a conductive film for bending and / or strengthening (including semi-reinforcing)
  • a metal barrier layer is preferably provided immediately above the silver layer to prevent oxidation of the silver layer. It is important to improve the moisture resistance, because the silver layer is likely to be oxidized due to moisture in the air, and if oxidation occurs, the resistance value is increased and a desired electromagnetic wave shielding property can not be obtained.
  • the metal barrier layer is not particularly limited in its components, but a Z n A 1 alloy layer containing 1 to 10% by weight of A 1 having high adhesion to both the silver layer and the dielectric layer is used. desirable.
  • the metal barrier layer referred to here is an alloy layer whose entire thickness is immediately after depositing a metal barrier layer directly on the silver layer, but then, for example, a dielectric layer is formed on the alloy layer.
  • the film thickness of the metal barrier layer indicates the film thickness when the Z n A 1 alloy layer is formed first.
  • the function of the metal barrier layer is as follows: when depositing the oxide layer of the second dielectric layer or the third dielectric layer, the effect of the oxidizing atmosphere does not affect the lower silver layer. Protect the silver layer of Furthermore, it also has the function of preventing moisture in the air from entering the film after film formation and oxidizing silver, thereby improving the moisture resistance of the silver layer. In addition, when the oxide dielectric layer is formed directly on the silver layer, irregularities are formed at the silver / dielectric interface, and the irregularities cause light scattering and the light transmittance is significantly reduced. The metal barrier layer also prevents the decrease in light transmittance to prevent the formation of the asperities.
  • this barrier layer is a light absorbing layer, too thick a layer may lower the light transmittance.
  • a Z n A 1 alloy is preferable, and in particular, A Z n A 1 alloy containing 1. 0 to 1. 0 wt% of oxygen has a high bonding strength with oxygen and traps oxygen and other corrosive ions that have diffused most effectively in the silver layer. Especially preferred. It is natural that the thicker the film thickness of this metal barrier layer is, the longer the strong effect is, but if it is too thick, the visible light transmittance is lowered. However, since a part of the metal barrier layer is oxidized when depositing the oxide next time, in order to make the visible light transmittance 60% or more, the first Venus barrier before oxidation is oxidized.
  • the thickness of the layer is preferably 1.3 to 3.5 nm, more preferably about 1.6 to 3. O nm. Furthermore, the thickness of the metal barrier layer for making visible light transmittance 70% or more needs to be 1. o to 3. O nm.
  • the transparent conductive film coated on the surface of the substrate with the electromagnetic wave shielding film of the present invention provides higher electromagnetic wave shielding performance as the resistance value becomes lower.
  • the sheet resistance which is the resistance value is 2.5 ⁇ .
  • the electromagnetic wave shielding performance at a wavelength of 1 GHz is 3 O dB or more, and it becomes possible to sufficiently shield the electromagnetic waves emitted from devices such as PDP.
  • the visible light transmittance is as high as 60% or more, it is possible to obtain a sufficiently bright image display.
  • the visible light ray reflectance on the glass surface side is about 12% or less, there is an advantage that the image penetration of the surrounding scenery is small, the image display is easy to view, and the red reflected light can be avoided.
  • it has excellent performance in the moisture resistance test (described later) for evaluating the degree of oxidation of the silver layer, and defects such as spots due to silver oxidation do not occur even in a hot and humid environment. It also has durability.
  • the visible light reflectance on the glass surface side is 4% or less, so the surrounding scenery It has the advantages of low image reflection and enabling image display with excellent contrast.
  • transparent glass plastic, etc.
  • a glass substrate general-purpose plain plate glass, so-called float plate glass, etc.
  • the composition of the glass is, but is not limited to, soda lime glass, aluminosilicate glass, etc. .
  • tempered glass with enhanced strength for example, surface compressive stress of about 100 MNZ m 2
  • semi-tempered glass for example, surface compressive stress of about 40 to 8 OMNZ m 2
  • the sputtering method of the conductive film of the present invention is preferable from the viewpoint of productivity, other film forming methods such as vacuum evaporation, ion plating, PC VD (plasma CVD) It is also possible to form a film by a method or the like.
  • the electromagnetic wave shielding film coated substrate of the present invention can be used as an electromagnetic wave shielding film coated substrate having a shielding function of near infrared rays which cause an erroneous operation of a remote control or an electromagnetic wave generated from the front of a display such as PDP or CRT.
  • a display such as PDP or CRT.
  • the surface and the back of the electromagnetic wave shielding film coated substrate of the present invention are anti-reflective by an adhesive etc., moisture proof of silver based transparent conductive film, prevention of scattering when broken glass, adhesion It is possible to attach a transparent film that has the function of adjusting the chromaticity of the entire film by adding a dye to the layer, and attach it to the front of the PDP (the electromagnetic shielding film is on the PDP side).
  • the transparent conductive film was formed by DC magnetron sputtering.
  • the present invention is not limited to the embodiments.
  • the sheet resistance of the film surface was measured by a four-point probe resistance meter (manufactured by Epson).
  • step difference measuring device dektak3 (made by S1 o an).
  • the sample was exposed to an atmosphere of 30 ° C.-90% RH for 2 weeks, and a sample having a size of at least 0.2 mm and no film defect or change in chromaticity was accepted.
  • the resistance value (sheet resistance) of the film surface of the transparent conductive film is 1.2 ⁇ or less, and the visible light transmittance is 60% or more.
  • the resistance value (sheet resistance) of the film surface of the transparent conductive film in Example 6 to Example 9 and Comparative Example 3 to Comparative Example 6 corresponds to a substrate with an electromagnetic wave shield film. 2.
  • a float glass substrate (visible light transmittance: 90.4%, with a black frame print on the rim of the glass and busbars, semi-reinforced) with a size of 1 00 Omm x 5 80 111] 11 approximately 3 111 111 (thick)
  • a film was formed in the following order using a sputtering device.
  • the pressure before film formation is Exhausting of the inside of the vacuum chamber 1 was sufficiently performed to 5 ⁇ 10 ⁇ 5 Torr.
  • a transport roll is installed below the target in the vacuum chamber 1, and when the glass substrate reciprocates on the roll, a predetermined metal layer or metal oxide is applied from the evening get to which power is applied. The layer is deposited on a glass plate.
  • the atmosphere is maintained at an inert atmosphere of Ar 100%, and the silver layer as the first silver layer is made 20 nm by the silver-gold, and it is made the first metal barrier layer by the 4A1-Zn target.
  • the 4 A 1 1 Zn alloy layer was deposited to a thickness of 1.6 nm.
  • the atmosphere is maintained at an inert atmosphere of Ar 100%, and the silver layer is used as a second metal barrier layer with a silver as an upper silver layer of 25 nm and a 4 A 1 Zn as a second metal barrier layer. of 4A 1-Z n alloy layer 1.
  • the transparent conductive film is formed by successively forming the second layer of 8.4 nm, the third layer of Z n Z layer of 34.4 nm, and the eighth pass of the fourth layer of S n 0 2 layer of 4.2 nm.
  • the coated substrate with the electromagnetic wave shielding film was discharged from the film forming chamber.
  • Table 1 shows the film configuration of each sample.
  • a substrate sample with an electromagnetic shielding film of the present invention was produced.
  • resistance value sheet resistance
  • visible light transmittance 64.2%
  • electromagnetic wave shielding property 30 to 1 000 MHz
  • an AR film with an AR (anti-reflection) treatment having an adhesive on the front and back of the substrate with an electromagnetic wave shielding film coated with the transparent conductive film obtained above is an AR film with anti-reflection treatment (Nippon Oil & Fat
  • the substrate was made of TAC resin
  • the adhesive was made of acrylic resin
  • the electromagnetic wave shielding filter was made.
  • the AR film has functions of preventing reflection and protecting the transparent conductive film and preventing breakage and scattering of the glass substrate.
  • the transparent conductive film was connected to a bus bar provided on the upper surface of a black frame printed on the periphery of the surface of the glass substrate.
  • the resistance value is 0.94 ⁇
  • the visible light transmittance is 64%
  • the near infrared transmittance (950 nm) is 0.05%
  • the moisture resistance there is no remarkable film defect or color change having a size of 0.2 mm or more, and the moisture resistance is very good
  • the PDP cover filter particularly for household class B type It had sufficient performance as an electromagnetic wave filter.
  • AgPd contains 1 atomic% of Pd
  • the film thickness of the 4 A 1-Z n alloy layer which is a metal barrier layer provided immediately above the second and third silver layers is 1.6 nm and 2.8 nm, respectively.
  • the same procedure as in Example 1 was followed except for the change.
  • Example 1 The procedure was the same as in Example 1 except that the film thickness was changed as shown in Table 1 in comparison with Example 1. As a result of evaluating the obtained sample, as shown in Table 1, it showed excellent performance. The moisture resistance was also passed.
  • Example 1 4 Replacement 3 ⁇ 4 (SIJ26) The procedure was the same as in Example 1 except that the film thickness was changed as shown in Table 1 in comparison with Example 1. As a result of evaluating the obtained sample, as shown in Table 2, it showed excellent performance. The moisture resistance was also passed.
  • Example 2 Compared to Example 1, all the same as Example 1 except that the film thickness of the 4 A 1 -Z n alloy layer which is a metal barrier layer provided immediately above the second silver layer was changed to 1.6 nm. I went to. As a result of evaluating the obtained sample, as shown in Table 2, it showed excellent performance. The moisture resistance was also passed.
  • Example 2 Compared to Example 1, the material of the metal barrier layer provided immediately above the silver layer was changed to T i, and the film thickness of the second 4 A 1-Z n alloy layer was changed to 1.6 nm. The same procedure as in Example 1 was followed except for the above. As a result of evaluating the obtained sample, as shown in Table 2, the transmittance was low and the moisture resistance was also poor.
  • Example 1 Compared to Example 1, all Example 1 and Example 1 were used except that the metal barrier layer provided immediately above the silver layer was made of a material of Ti and that the silver layer contained 1 atomic% of Pd. I went in the same way. As a result of evaluating the obtained samples, as shown in Table 3, although the moisture resistance was excellent, the resistance value was high.
  • Float glass substrate size of visible light transmittance: 90.4%, with black frame print and busbar on the rim of the glass, half size of about 100 0 mm x 5 0 0 111 111 thickness
  • a coating was formed in the following order on the surface of the reinforced product using a sputtering device.
  • a ZnO layer of a second layer was formed to a thickness of 38 nm with a Zn target under the same conditions as the first layer.
  • the atmosphere is maintained in an inert atmosphere of Ar 100%, the silver layer as the first silver layer is 10 nm by silver plating, and the ZnA as the first contact layer is ZnA as the first target.
  • An alloy layer was deposited at 1.6 nm.
  • Z N_ ⁇ as S n 0 2 Layers 1. 8 nm, 3-layer a Z n A 1 x O y layer with the first layer of the second dielectric layer 3.
  • 2-layer The layer was 45 nm, the second layer was an Sn 02 layer, the third layer was a 3.5 nm layer, and the fifth layer was a Zn o layer, 22.4 nm.
  • the atmosphere is maintained at an inert atmosphere of Ar 100%, the silver layer as the second silver layer is 14 nm by the silver getter, the Z as the second metal layer by the Z n A 1 target.
  • n A 1 alloy layer was deposited to a thickness of 1.6 nm.
  • fifth layer was deposited sequentially with 23.2 nm.
  • the atmosphere is maintained at an inert atmosphere of Ar 100%
  • the silver layer as the third silver layer is 12 nm by the silver plate
  • the Z nA as the third barrier layer by the Z nA 1 target As the sixth pass, the atmosphere is maintained at an inert atmosphere of Ar 100%
  • the silver layer as the third silver layer is 12 nm by the silver plate
  • the Z nA as the third barrier layer by the Z nA 1 target An alloy layer was formed to a thickness of 2.2 nm.
  • the S N_ ⁇ two layers as a layer th 1.4 nm, the Z nO layer 1 8. 5 nm, the S N_ ⁇ 2 layer as the 6 th layer 0. 7 nm are sequentially formed as the fifth layer, a transparent conductive
  • the substrate with the electromagnetic wave shielding film coated with the film was taken out from the film forming chamber.
  • the layer configuration of the obtained transparent conductive film is shown in FIG.
  • a substrate sample with an electromagnetic wave shielding film of the present invention was produced.
  • the surface resistance 2.5 ⁇ / hole
  • electromagnetic wave shielding property (30 to L 000 MHz): 30 dB or more
  • visible light transmittance 70% visible It had excellent characteristics with a light reflectance of 4%.
  • an AR film with AR (anti-reflection) treatment with an adhesive on the front and back of the substrate with an electromagnetic wave shielding film coated with the transparent conductive film obtained above is an AR film (Rose 1 ook made by NOF Corp.)
  • the base material was made of TAC resin
  • the adhesive was made of acrylic resin, to prepare an electromagnetic wave filter.
  • the AR film has functions of preventing reflection, protecting the transparent conductive film, and preventing breakage and scattering of the glass substrate.
  • the transparent conductive film was connected to a bus bar provided on the upper surface of a black frame printed on the periphery of the surface of the glass substrate.
  • the surface resistance 2.5 ⁇
  • the electromagnetic wave shielding property (30 to: L 000 MHz): 30 dB or more
  • the visible light reflection Rate Near-infrared transmittance (950 nm): 2.8%
  • moisture resistance 60 ° C, 90% RH, 1 000 h
  • the film thickness of the first dielectric layer is 4111111, the thickness of the first silver layer is 9.511111, and the thickness of the first barrier layer is 1 6 nm, the thickness of the second dielectric layer is 80 nm, the thickness of the second silver layer is 13.5 nm, the thickness of the second dielectric layer is 1.6 nm, and the thickness of the third dielectric layer is 82 nm
  • the transparent conductive film is formed by adjusting the film forming time so that the thickness of the third silver layer is 11. 5 nm, the thickness of the third barrier layer is 2.2 nm, and the thickness of the fourth dielectric layer is 42 nm. Shielding film coated The attached substrate was manufactured.
  • the film thickness of the first dielectric layer is 41 nm
  • the thickness of the first silver layer is 10 nm
  • the thickness of the first barrier single layer is the same under the same film forming conditions as in Example 6. 2.
  • the second dielectric layer thickness is 76 nm
  • the second silver layer thickness is 14 nm
  • the second barrier layer thickness is 2.0 nm
  • the third dielectric layer thickness is 78 nm
  • the transparent conductive film is coated by adjusting the deposition time so that the thickness of the third silver layer is 12 mm
  • the thickness of the third barrier layer is 2.6 nm
  • the thickness of the fourth dielectric layer is 41 nm.
  • a substrate with an electromagnetic shielding film was fabricated.
  • the film thickness of the first dielectric layer is 41 nm
  • the thickness of the first silver layer is 9 nm
  • the thickness of the first barrier layer is 1 under the same film forming conditions as in Example 6. 6 nm, thickness of second dielectric layer 76 nm, thickness of second silver layer 13 nm, thickness of second barrier layer 1.6 nm, thickness of third dielectric layer 7811111, third
  • the transparent conductive film was coated by adjusting the film formation time so that the thickness of the silver layer was 11 nm, the thickness of the third barrier layer was 2.2 nm, and the thickness of the fourth dielectric layer was 41 nm.
  • a substrate with an electromagnetic shielding film was made.
  • Table 3 shows the thickness, visible light transmittance, visible light reflectance, and surface resistance of each layer of the transparent conductive films of Examples 6 to 9.
  • the film thickness of the first dielectric layer is 35 nm
  • the thickness of the first silver layer is 10 nm
  • the thickness of the first barrier layer is 1.6 nm
  • thickness of second dielectric layer 70 nm thickness of second silver layer 14 nm
  • thickness of second barrier single layer 1.6 nm
  • thickness of third dielectric layer 70 nm third The film thickness is 12 nm
  • the thickness of the third barrier layer is 2.2 nm
  • the thickness of the fourth dielectric layer is 35 nm.
  • the film thickness of the first dielectric layer is 41 nm
  • the thickness of the first silver layer is 10 nm
  • the thickness of the first barrier layer is O under the same film forming conditions as in Example 6.
  • nm, thickness of second dielectric layer 76 nm, thickness of second silver layer 14 nm, thickness of second barrier layer 0 nm, thickness of third dielectric layer 78 nm, thickness of third silver layer The film formation time was adjusted so that the thickness of the third barrier layer was 0 nm and the thickness of the fourth dielectric layer was 41 nm, and a substrate with an electromagnetic shielding film coated with a transparent conductive film was fabricated.
  • the film thickness of the first dielectric layer is 41 nm, the thickness of the first silver layer is 10 nm, and the thickness of the first barrier single layer is 3.40 under the same film forming conditions as in Example 6. 2 nm, the thickness of the second dielectric layer is 76 nm, the thickness of the second silver layer is 14 nm, the thickness of the second barrier layer is 3.2 nm, the thickness of the third dielectric layer is 78 nm, the third silver layer A substrate with an electromagnetic wave shielding film coated with a transparent conductive film by adjusting the film forming time so that the film thickness is 12 nm, the thickness of the third barrier layer is 3.2 nm, and the thickness of the fourth dielectric layer is 41 nm. Was produced.
  • Example 2 The same film forming conditions and film thickness as in Example 1 except that the same film forming substrate as in Example 6 is used and the A 1 content of the Z n A 1 jacket attached in advance to the force sword of the sputtering apparatus is 15 wt%.
  • the substrate with an electromagnetic wave shielding film coated with a transparent conductive film was fabricated.
  • Table 4 shows the thickness, visible light transmittance, visible light reflectance, and surface resistance of each layer of the transparent conductive films of Comparative Examples 3 to 6. '
  • Visible light transmittance (3 ⁇ 4;) 68.7 30.0 63.4 67.5 Visible light reflectance (3 ⁇ 4) 4.2 5.4 ′ 7.2 4.0 Surface resistivity ( ⁇ / mouth) 2.3 8.5 2.6 2.4

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Abstract

L'invention concerne un substrat doté d'un film de protection électromagnétique bien équilibré et présentant une excellente protection électromagnétique, et permettant à un utilisateur de visualiser facilement l'affichage des images grâce à une transmittance lumineuse élevée, à une réflectance faible, et à une excellente résistance à l'humidité. Le substrat décrit dans cette invention présente, sur la surface d'un substrat transparent, un film conducteur transparent comprenant sept couches de couches diélectriques et de couches d'argent formées en alternance dans l'ordre depuis le côté du substrat. Chaque couche d'argent présente une épaisseur égale ou supérieure à 18nm et une pureté de l'argent égale ou supérieure à 99,999 %. La valeur de résistance superficielle du film conducteur transparent est égale ou supérieure à 1,2Φ/<. La transmittance lumineuse du substrat est égale ou supérieure à 60 %.
PCT/JP2002/010983 2001-10-26 2002-10-23 Substrat dote d'un film de protection electromagnetique WO2003037056A1 (fr)

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JP2001-328715 2001-10-26
JP2001328715A JP2003133787A (ja) 2001-10-26 2001-10-26 電磁波シールド膜付き基板
JP2002-290283 2002-10-02
JP2002290283A JP2004128220A (ja) 2002-10-02 2002-10-02 電磁波シールド膜付き基板

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FR2862961A1 (fr) * 2003-11-28 2005-06-03 Saint Gobain Substrat transparent utilisable alternativement ou cumulativement pour le controle thermique, le blindage electromagnetique et le vitrage chauffant.
EP1659845A1 (fr) * 2003-08-25 2006-05-24 Asahi Glass Company Ltd. Corps multicouche de protection electromagnetique et afficheur utilisant ce corps
CN102126833A (zh) * 2011-03-10 2011-07-20 黄骅荣达玻璃有限公司 一种低辐射镀膜玻璃
EP1501768B1 (fr) 2002-05-03 2017-04-19 Vitro, S.A.B. de C.V. Substrat presentant un revetement de gestion thermique pour une unite de vitrage isolant
CN109791338A (zh) * 2016-08-22 2019-05-21 唯景公司 电磁屏蔽电致变色窗
US11462814B2 (en) 2014-11-25 2022-10-04 View, Inc. Window antennas
US11559852B2 (en) 2011-12-12 2023-01-24 View, Inc. Thin-film devices and fabrication
US11561446B2 (en) 2011-09-30 2023-01-24 View, Inc. Fabrication of electrochromic devices
US11579571B2 (en) 2014-03-05 2023-02-14 View, Inc. Monitoring sites containing switchable optical devices and controllers
US11599003B2 (en) 2011-09-30 2023-03-07 View, Inc. Fabrication of electrochromic devices
US11630366B2 (en) 2009-12-22 2023-04-18 View, Inc. Window antennas for emitting radio frequency signals
US11631493B2 (en) 2020-05-27 2023-04-18 View Operating Corporation Systems and methods for managing building wellness
EP2577368B1 (fr) 2010-05-25 2023-07-26 AGC Glass Europe Vitrage de contrôle solaire à faible facteur solaire
US11732527B2 (en) 2009-12-22 2023-08-22 View, Inc. Wirelessly powered and powering electrochromic windows
US11740529B2 (en) 2015-10-06 2023-08-29 View, Inc. Controllers for optically-switchable devices
US11750594B2 (en) 2020-03-26 2023-09-05 View, Inc. Access and messaging in a multi client network
US11796885B2 (en) 2012-04-17 2023-10-24 View, Inc. Controller for optically-switchable windows
US11799187B2 (en) 2014-11-25 2023-10-24 View, Inc. Window antennas
US12061402B2 (en) 2011-12-12 2024-08-13 View, Inc. Narrow pre-deposition laser deletion
US12087997B2 (en) 2019-05-09 2024-09-10 View, Inc. Antenna systems for controlled coverage in buildings

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KR101768257B1 (ko) * 2013-09-02 2017-08-14 (주)엘지하우시스 저방사 코팅 및 이를 포함하는 창호용 건축 자재
CN106435475B (zh) * 2016-09-08 2018-09-14 江苏双星彩塑新材料股份有限公司 一种蓝绿色三银低辐射节能窗膜及其制备方法

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JPH11307987A (ja) * 1998-04-16 1999-11-05 Nippon Sheet Glass Co Ltd 電磁波フィルタ
JP2000252682A (ja) * 1999-02-26 2000-09-14 Central Glass Co Ltd 電磁波遮蔽膜付き基板
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* Cited by examiner, † Cited by third party
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EP1501768B1 (fr) 2002-05-03 2017-04-19 Vitro, S.A.B. de C.V. Substrat presentant un revetement de gestion thermique pour une unite de vitrage isolant
EP1659845A4 (fr) * 2003-08-25 2008-07-30 Asahi Glass Co Ltd Corps multicouche de protection electromagnetique et afficheur utilisant ce corps
EP1659845A1 (fr) * 2003-08-25 2006-05-24 Asahi Glass Company Ltd. Corps multicouche de protection electromagnetique et afficheur utilisant ce corps
US7771850B2 (en) 2003-08-25 2010-08-10 Asahi Glass Company, Limited Electromagnetic wave shielding laminate and display device employing it
CN1906136B (zh) * 2003-11-28 2010-10-20 法国圣戈班玻璃厂 可交替或累积用于热控制、屏蔽电磁波和加热窗玻璃的透明基底
JP2007512218A (ja) * 2003-11-28 2007-05-17 サン−ゴバン グラス フランス 熱制御、電磁遮蔽、および加熱窓のために、代替使用または累加使用ができる透明基板
EA015109B1 (ru) * 2003-11-28 2011-06-30 Сэн-Гобэн Гласс Франс Элемент остекления
US7972713B2 (en) 2003-11-28 2011-07-05 Saint-Gobain Glass France Transparent substrate which can be used alternatively or cumulatively for thermal control, electromagnetic armour and heated glazing
US20110236663A1 (en) * 2003-11-28 2011-09-29 Saint-Gobain Glass France Transparent substrate which can be used alternatively or cumulatively, for thermal control, for electromagnetic armour and for heated glazing
CN101921066B (zh) * 2003-11-28 2012-11-28 法国圣戈班玻璃厂 可交替或累积用于热控制、屏蔽电磁波和加热窗玻璃的透明基底
US8440329B2 (en) 2003-11-28 2013-05-14 Saint-Gobain Glass France Transparent substrate which can be used alternatively or cumulatively, for thermal control, for electromagnetic armour and for heated glazing
WO2005051858A1 (fr) * 2003-11-28 2005-06-09 Saint-Gobain Glass France Substrat transparent utilisable alternativement ou cumulativement pour le controle thermique, le blindage electromagnetique et le vitrage chauffant.
FR2862961A1 (fr) * 2003-11-28 2005-06-03 Saint Gobain Substrat transparent utilisable alternativement ou cumulativement pour le controle thermique, le blindage electromagnetique et le vitrage chauffant.
US11630366B2 (en) 2009-12-22 2023-04-18 View, Inc. Window antennas for emitting radio frequency signals
US11732527B2 (en) 2009-12-22 2023-08-22 View, Inc. Wirelessly powered and powering electrochromic windows
EP2577368B1 (fr) 2010-05-25 2023-07-26 AGC Glass Europe Vitrage de contrôle solaire à faible facteur solaire
CN102126833A (zh) * 2011-03-10 2011-07-20 黄骅荣达玻璃有限公司 一种低辐射镀膜玻璃
US11561446B2 (en) 2011-09-30 2023-01-24 View, Inc. Fabrication of electrochromic devices
US11599003B2 (en) 2011-09-30 2023-03-07 View, Inc. Fabrication of electrochromic devices
US11559852B2 (en) 2011-12-12 2023-01-24 View, Inc. Thin-film devices and fabrication
US12061402B2 (en) 2011-12-12 2024-08-13 View, Inc. Narrow pre-deposition laser deletion
US11796885B2 (en) 2012-04-17 2023-10-24 View, Inc. Controller for optically-switchable windows
US11668990B2 (en) 2013-02-08 2023-06-06 View, Inc. Fabrication of electrochromic devices
US11579571B2 (en) 2014-03-05 2023-02-14 View, Inc. Monitoring sites containing switchable optical devices and controllers
US11462814B2 (en) 2014-11-25 2022-10-04 View, Inc. Window antennas
US11670833B2 (en) 2014-11-25 2023-06-06 View, Inc. Window antennas
US11799187B2 (en) 2014-11-25 2023-10-24 View, Inc. Window antennas
US11740529B2 (en) 2015-10-06 2023-08-29 View, Inc. Controllers for optically-switchable devices
CN109791338A (zh) * 2016-08-22 2019-05-21 唯景公司 电磁屏蔽电致变色窗
US12087997B2 (en) 2019-05-09 2024-09-10 View, Inc. Antenna systems for controlled coverage in buildings
US11750594B2 (en) 2020-03-26 2023-09-05 View, Inc. Access and messaging in a multi client network
US11882111B2 (en) 2020-03-26 2024-01-23 View, Inc. Access and messaging in a multi client network
US11631493B2 (en) 2020-05-27 2023-04-18 View Operating Corporation Systems and methods for managing building wellness

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