WO2003037056A1

WO2003037056A1 - Substrate with electromagnetic shield film

Info

Publication number: WO2003037056A1
Application number: PCT/JP2002/010983
Authority: WO
Inventors: Tadashi Ohnishi; Keiji Sato; Yasutaka Tsuda; Katsuto Tanaka
Original assignee: Central Glass Company, Limited
Priority date: 2001-10-26
Filing date: 2002-10-23
Publication date: 2003-05-01
Also published as: TW200300109A

Abstract

A substrate with a well-balanced electromagnetic shield film, excellent in electromagnetic shielding performance, enabling the user to easily see the image display thanks to high visible light transmittance, and low reflectance, and excellent humidity resistance. This substrate with an electromagnetic shield film has, over the surface of a transparent substrate, a transparent conductive film comprising seven layers of dielectric layers and silver layers alternately formed in the order from the substrate side. Each silver layer has a thickness of 18 nm or more and a silver purity of 99.999% or more. The surface resistance value of the transparent conductive film is 1.2 Ω/&square; or less. The visible light transmittance of the substrate is 60% or more.

Description

Background of the Invention

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). Write on a substrate with an electromagnetic wave shielding film that has a near infrared shielding function that causes a malfunction.

Related.

Since 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. As a countermeasure for this, conventionally, it is known that 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. .

For example, in WO 98/13850, an oxide layer mainly composed of Z 主成分 θ containing one or more metals from the substrate side and a metal layer mainly composed of silver alternate (2 n + l) It describes about the protective plate for PDP in which the multilayer conductive film laminated | stacked layer was coat | covered, and in Unexamined-Japanese-Patent No. 11-307987, refractive index is 1.6-2 from a board | substrate side. A layered structure of seven layers in which eight dielectric layers and a silver-based layer are alternately laminated, and the silver-based layer contains 0.1 to 0.5 atomic percent of palladium with respect to silver An electromagnetic wave filter for a DPP having an electromagnetic shielding film is described.

However, according to the invention of W098 / 1 3850, 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. There is a problem that the resistance value is increased as compared to other metal layers having the same film thickness. Moreover, 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.

Summary of the invention

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.

In the electromagnetic wave shielding film coated substrate according to the first aspect of the present invention, 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 Ω / hole or less and a visible light transmittance of 60% or more.

The electromagnetic wave shielding film coated substrate according to the second aspect of the present invention 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. O nm, 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 Ω / 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.

Brief description of the drawings

FIG. 1 is a cross-sectional view of the layer configuration of a transparent conductive film according to an embodiment of the present invention.

Description of the Preferred Embodiment

In the electromagnetic wave shielding film coated substrate of the present invention, the transparent conductive film has a sheet resistance of not more than 1.2 Ω / hole as a sheet resistance and is excellent in electromagnetic shielding performance and has a high visible light transmittance of 60% or more, In addition, since 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 film coated with a transparent conductive film, wherein the film surface has a sheet resistance value of 1.2 Ω or less and a visible light transmittance of 60% or more. It is characterized in that the resistance value (sheet resistance value) is 2.5 Ω / hole or less and the visible light transmittance is 70% or more.

In the electromagnetic wave shielding film coated substrate according to the first aspect of the present invention, 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 Ω / hole or less and a visible light transmittance of 60% or more.

Furthermore, 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. Dielectric layer having a thickness of 70 to 100 nm / second silver layer having a thickness of 20 to 30 nm / third dielectric layer having a thickness of 70 to 105 nm A third silver layer having a film thickness of 18 to 29 nm / a fourth dielectric layer having a film thickness of 35 to 6 3 nm. In the silver layer which determines the electromagnetic wave shielding performance, 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. On the other hand, 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

In particular, 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, and 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 Ω or less, visible light transmittance It is impossible to easily obtain those with 60% or more.

Next, 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, and 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.

Furthermore, as 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. By using n A 1 or the like, a film-coated substrate having good moisture resistance can be obtained without including impurities such as P d in A g. In the electromagnetic shielding film coated substrate according to the second aspect of the present invention, 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 A substrate on which a transparent conductive film comprising a fourth dielectric layer comprising a Z transparent metal oxide layer is laminated, wherein each silver layer has a thickness of 9 to 15 nm and a barrier layer comprising Z nAl The film thickness is 1. to 3. O nm, the thickness of the first dielectric layer and the thickness of the fourth dielectric layer are 40 to 50 nm, and the thickness of the second dielectric layer and the thickness of the third dielectric layer are 7 And 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 Ω /. 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.

In the above-described transparent conductive film, in the silver layer that determines the electromagnetic shielding performance, 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. On the other hand, in order to brighten the image and improve visibility, 70% or more of visible light transmittance is secured, and image contrast In order to lower the visible light reflectance to 4% or less in order to increase the film thickness, it is preferable to set each silver layer to 15 nm or less, and in particular, the film thickness of the first silver layer is 9 to 1 O nm, the second More preferably, the film thickness of the silver layer is 13 to 14 nm, and the film thickness of the third silver layer is 11 to 12 nm. If only two silver layers are provided, the surface resistance of the film surface as in the present invention is 2.5 Ω or less, the visible light transmittance is 70% or more, and the visible light reflectance is 4% or less. It is not easy to get what is.

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.

However, the above-mentioned 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. In addition, 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.

For these reasons, 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.

On the other hand, since the zinc oxide layer has high adhesion to the silver layer, and the high bonding force with oxygen, the potential of oxygen in the layer is low, so oxygen does not diffuse easily in the silver layer. Therefore, 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.

In addition, it is important to keep the chemical potential of the oxygen in the oxide layer in contact with the silver layer as low as possible, and it is desirable to add as much argon as possible together with oxygen at the time of film formation of zinc oxide. 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.

In addition, 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. When 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.

Moreover, as a metal oxide layer as a dielectric layer, the above Z n as a zinc oxide layer In addition to the O layer, it is preferable to use a Z n A 1 x O y (x = 1 to 2, y = 1 to 4) 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) In particular, it is preferable to provide it directly on the metal barrier layer described later.

Next, 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. When forming a metal oxide film, in order to form a film in an oxidizing atmosphere (for example, 80% oxygen, 20% argon), a part of the upper layer portion of the alloy layer is converted to an oxide. The upper layer is called a metal barrier layer including the oxidized oxide layer and the remaining alloy layer. That is, 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.

However, since this barrier layer is a light absorbing layer, too thick a layer may lower the light transmittance.

As the metal barrier layer, as described above, 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. For example, the sheet resistance which is the resistance value is 2.5 Ω. In the following cases, 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. In addition, since the visible light transmittance is as high as 60% or more, it is possible to obtain a sufficiently bright image display. Further, since 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. In addition, 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.

In the case of a substrate with an electromagnetic wave shielding film that has a sheet resistance of 2.5 Ω / hole or less and a visible light transmittance of 70% or more, 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.

For the transparent substrate of the present invention, it is possible to use transparent glass, plastic, etc. For example, as a glass substrate, general-purpose plain plate glass, so-called float plate glass, etc. Various functional glass, tempered glass and similar glass, laminated glass, double glass, etc. Furthermore, it can not be overemphasized that it can be used as various plate glass products, such as a flat plate or a bending board. Even if the glass is a laminate with a transparent plastic plate etc., the composition of the glass is, but is not limited to, soda lime glass, aluminosilicate glass, etc. .

The use of tempered glass with enhanced strength (for example, surface compressive stress of about 100 MNZ m ² ) or semi-tempered glass (for example, surface compressive stress of about 40 to 8 OMNZ m ² ) is more preferable because the glass is less likely to break. .

In addition, although 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. For example, when used for PDP, 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).

Hereinafter, the present invention will be specifically described by way of examples. The transparent conductive film was formed by DC magnetron sputtering. However, the present invention is not limited to the embodiments.

The performance evaluation of the sample of the substrate with an electromagnetic wave shielding film obtained in the following Examples and Comparative Examples was evaluated by the following method.

(1) Visible light transmittance, visible light reflectance, reflection tone:

According to JIS R 316, visible light transmittance Tv, visible light reflectance (glass side Rg, film) between wavelengths 380 to 780 nm by a spectrophotometer (model 4000, manufactured by Hitachi, Ltd. Spectrophotometer One) The surface side R f) and the reflection color tones a * and b * (glass side, film side) were measured. (2) Resistance value:

The sheet resistance of the film surface was measured by a four-point probe resistance meter (manufactured by Epson).

(3) Film thickness:

It measured by the level | step difference measuring device dektak3 (made by S1 o an).

(4) Electromagnetic shielding:

Measured according to US military standard M I L-st d 285.

(5) Moisture resistance:

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.

In Examples 1 to 5 and Comparative Example 1 and Comparative Example 2, the resistance value (sheet resistance) of the film surface of the transparent conductive film is 1.2 Ω 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 substrate with an electromagnetic wave shielding film with a visible light transmittance of 70% or more, which is 5 Ω / hole or less.

Example 1

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) On the surface, a film was formed in the following order using a sputtering device. '

First, after attaching each metal target of S n, Z n (3 units), silver, and Z n A 1 (eight percent content 4 percent) to the force sorter in the sputtering apparatus in advance, the pressure before film formation is Exhausting of the inside of the vacuum chamber 1 was sufficiently performed to ⁵ × 10 −5 Torr. In this method, 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. As a first pass, oxidizing atmosphere the atmosphere in the deposition chamber _{(0 2: A r = 9} : 1) To retain the S n0 ₂ layer as a first layer of the first dielectric layer by S n target 5. After 3 nm of film formation, 41.7 nm of second layer of Zn 0 layer was formed by Zn wetting under the same conditions as the first layer.

As the second pass, 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.

3 pass as film forming chamber atmosphere again oxidizing atmosphere (〇 _2: Ar == 9: 1) to hold, to form a metal oxide layer of the second dielectric layer. As the first layer of the second dielectric layer, 4A 1−Z n 層 layer is 8.2 nm, S n 0 ₂ layer as the _second layer is 16.4 nm, and Z θθ layer as the third layer is 65. A film of 4 nm was sequentially formed.

As the fourth pass, 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. 4 nm, 5 pass the again oxidizing atmosphere of the deposition chamber atmosphere maintained at _{(0 2:: Ar = 9} 1), the third dielectrics layer 1 8.5 nm as the layer Z n A 1 x Oy layer, 16.9 nm as the second layer SnO ₂ layer as the _second layer 67.6 nm as the third layer The atmosphere is maintained at an inert atmosphere of Ar 100%, and a silver target is used to form a silver layer as a top silver layer 23 nm, 4 A 1-Zn as a second metal barrier layer. With the Z n alloy layer at 1.8 nm and the seventh pass, the atmosphere in the deposition chamber is again maintained in the oxidizing atmosphere (0 ₂ : Ar = 8: 2) and used as the first layer of the fourth dielectric layer. Layer with a thickness of 4.2 nm and a second layer of S n 〇 _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.

When a Z n A 1 x O y layer is formed in an oxidizing atmosphere on the upper layer of the 4 A 1-Z n alloy layer of the first metal barrier layer and the second metal barrier layer, the 4 A 1-Z n alloy is The layer was oxidized. Table 1 shows the film configuration of each sample. As described above, a substrate sample with an electromagnetic shielding film of the present invention was produced. As a result of evaluating the characteristics of the obtained electromagnetic wave shielded film coated substrate, as shown in Table 2, resistance value (sheet resistance): 0.94 Ω / hole, visible light transmittance: 64.2%, electromagnetic wave shielding property ( 30 to 1 000 MHz): 40 dB or more, moisture resistance was also pass, and had excellent characteristics.

Next, 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, and 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.

As a result of evaluating the characteristics of the produced electromagnetic wave shielded filter, the resistance value is 0.94 Ω, the visible light transmittance is 64%, the near infrared transmittance (950 nm) is 0.05%, As a result of evaluating 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, and the PDP cover filter, particularly for household class B type It had sufficient performance as an electromagnetic wave filter.

table 1

(Note) AgPd: Ag contains 1 atomic% of Pd

13 replacement forms (Rule 26) Table 2

Example 2

In comparison with Example 1, 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.

As a result of evaluating the obtained samples, as shown in Table 1, it showed excellent performance. The moisture resistance was also passed.

Example 3

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 4

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 5

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.

Comparative example 1

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.

Comparative example 2

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.

Example 6

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.

First, after attaching metal targets of S n and Z n (3 units), silver, and Z n A 1 (A 1 content rate 4 wt%) to the force sorter in advance in a sputtering device, the pressure before film formation Evacuating the inside of the vacuum chamber 1 was sufficiently performed until the force became 1.5 X 10 " ⁴ Pa or less. In addition, according to this method, a transfer port is provided below the target in the vacuum chamber 1. Set on the roll and power is applied when the glass substrate reciprocates on the roll. A predetermined metal layer or metal oxide layer is formed on a glass plate from a wafer.

As the first pass, the atmosphere of the film forming chamber is maintained in an oxidizing atmosphere (02: Ar = 9: 1), and the Sn target as the first layer of the first dielectric layer is 3 nm by the Sn target. After film formation, 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.

As the second pass, 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. (1) An alloy layer was deposited at 1.6 nm.

As the third pass, the atmosphere of the film forming chamber was maintained again in the oxidizing atmosphere (0 ₂ : A r = 9: 1) to form the metal oxide layer of the second dielectric layer. Z N_〇 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. As 3 nm, 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.

As the fourth pass, 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.

As the fifth pass, the atmosphere of the deposition chamber is again maintained in the oxidizing atmosphere (0 ₂ : A r = 9: 1), and the Z nA l _x o _y layer as the first layer of the third dielectric layer is selected. Snm layer as _second layer: 1.8 nm, Zn layer as third layer: 46 nm, _second layer as SnO2 layer: 3.6 nm, fifth layer Was deposited sequentially with 23.2 nm.

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.

As the seventh pass, the atmosphere in the deposition chamber is again maintained in the oxidizing atmosphere (0 ₂ : Ar = 9: 1), and the Z n A 1 x Oy layer as the first layer of the fourth dielectric layer is 1 · 3 nm , SnO as the second layer, 0.7 nm as the second layer, and 18.4 nm as the third layer, the _second layer 18.4 nm, 4 The S N_〇 _two layers as a layer th 1.4 nm, the Z nO layer 1 8. 5 nm, the S N_〇 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.

As described above, a substrate sample with an electromagnetic wave shielding film of the present invention was produced. As a result of evaluating the characteristics of the obtained substrate with an electromagnetic wave shielding film, the surface resistance: 2.5 Ω / 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%. Next, 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, and 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.

As a result of evaluating the characteristics of the produced electromagnetic wave shielding filter, the surface resistance: 2.5 Ω, the electromagnetic wave shielding property (30 to: L 000 MHz): 30 dB or more, the visible light transmittance 71%, the visible light reflection Rate: Near-infrared transmittance (950 nm): 2.8% and moisture resistance (60 ° C, 90% RH, 1 000 h) are also evaluated. The result is remarkable with a size of 0.2 mm or more There was no film defect or color change, and it had excellent performance as an electromagnetic wave shielding filter for PDP.

Example 7

Using the same film formation substrate as in Example 6, and under the same film forming conditions as in Example 6, 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.

Example 8

Using the same film formation substrate as in Example 6, 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 the same under the same film forming conditions as in Example 6. 2. 0 nm, 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, and the thickness of the fourth dielectric layer is 41 nm. A substrate with an electromagnetic shielding film was fabricated.

Example 9

Using the same film formation substrate as in Example 6, the film thickness of the first dielectric layer is 41 nm, the thickness of the first silver layer is 9 nm, and 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.

Table 3

Comparative example 3

Using the same film formation substrate as in Example 6, and under the same film forming conditions as in Example 6, the film thickness of the first dielectric layer is 35 nm, the thickness of the first silver layer is 10 nm, and 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, and the thickness of the fourth dielectric layer is 35 nm. A substrate with a shield film was produced.

Comparative example 4

Using the same film formation substrate as in Example 6, 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 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. . Comparative example 5

Using the same film formation substrate as in Example 6, 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.

Comparative example 6

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. '

Table 4 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Fourth Dielectric Layer Thickness (nm) 35 41 41 41 Third Barrier Single Layer Thickness (nm) 2.2 0 3.2 2.2

Third Ag film thickness (nm) 12 12 12 12 Third dielectric film thickness (nm) 70 78 78 78 Second barrier single-layer film thickness (nm) 1.6 0 3.2 1.6

Second Ag layer thickness (nm) 14 14 14 14 Second dielectric layer thickness (nm) 70 76 76 76 First barrier single layer thickness (nm) 1.6 0 3.2 1.6

First Ag layer film thickness (nm) 10 10 10 10 First dielectric layer film thickness (nm) 35 41 41 41

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 (Ω / mouth) 2.3 8.5 2.6 2.4

Claims

The scope of the claims

1. A transparent conductive film comprising a dielectric layer and a silver layer alternately and repeatedly laminated seven layers sequentially from the substrate side is coated on the transparent substrate surface, and the thickness of each silver layer is 18 nm or more, The silver layer also has a purity of 5 N (99. 999%) or more, and the resistance (sheet resistance) of the surface of the transparent conductive film is 1.2 Ω / hole or less, and the visible light transmittance Is 60% or more. A substrate with an electromagnetic shielding film.

2. The transparent conductive film has a first dielectric layer thickness of 35 to 63 nm and a first silver layer thickness of 18 to 28 nm from the substrate side. Second dielectric layer having a thickness of 00 nm Second silver layer having a thickness of 20 to 30 nm / A third dielectric layer having a thickness of 70 to 105 nm a thickness of 18 to 29 A third silver layer having nm thickness is formed of a fourth dielectric layer having a thickness of 35 to 6 nm. The substrate with an electromagnetic wave shielding film according to claim 1.

3. A special feature of the present invention is to provide a 1.3 to 3.5 nm thick metal barrier layer made of a Z nA 1 alloy containing 1 to 10% by weight of A 1 immediately above each silver layer. A substrate with an electromagnetic wave shielding film according to any one of Items 1 to 2.

4. First dielectric layer Z composed of a transparent metal oxide layer First transparent layer composed of a first metal layer ZZ n A 1 Second transparent layer composed of a transparent metal oxide layer Z Second one Second barrier layer consisting of Ag layer / Z n A1 Third dielectric layer consisting of Z transparent metal oxide layer Z third silver layer ZZ third layer consisting of third barrier layer / transparent metal oxide layer consisting of 1 And the thickness of each silver layer is 9 to 15 nm, and the thickness of the barrier layer made of ZnAl is 1. to 3 respectively. 0 nm, the film thickness of the first dielectric layer and the fourth dielectric layer is 40 to 50 nm, and the film thickness of the second dielectric layer and the third dielectric layer is 75 to 85 nm; The resistance of the film surface (sheet resistance) is 2.5 Ω or less, visible light transmission The visible light reflectance of the surface coated with the transparent conductive film is 4% or less, and the purity of silver of all the silver layers constituting the transparent conductive film is 5 N (99 9 99%) or more, and any of the barrier layers of Z nA 1 constituting the transparent conductive film is a Z nA 1 alloy containing 1 to 10% by weight of A 1. Substrate with electromagnetic wave shield film.

5. The film thickness of the first silver layer is 9 to 1 O nm, the film thickness of the second silver layer is 13 to 14 nm, and the film thickness of the third silver layer is 11 to 12 nm. A substrate with an electromagnetic wave shield film according to item 4.

6. The tin oxide layer in the first dielectric layer is 3 to 50 nm, the zinc oxide layer is 5 to 50 nm, the tin oxide layer in the second dielectric layer is 0 to 85 nm, the zinc oxide layer is 5 to 85 nm, The tin oxide layer in the third dielectric layer is 5 to 85 nm, the zinc oxide layer is 5 to 85 nm, the tin oxide layer in the fourth dielectric layer is 0 to 50 nm, and the zinc oxide layer is 0 to 50 nm The electromagnetic wave shielding film according to any one of claims 4 to 5, characterized in that

7. The substrate with an electromagnetic wave shielding film according to any one of claims 1 to 6, wherein the immediate upper layer of the transparent substrate is made of a tin oxide layer.

8. A substrate provided with an electromagnetic shielding film according to any one of claims 1 to 7, wherein a protective plate made of a resin film is provided on the front surface and Z or the rear surface of the substrate provided with an electromagnetic shielding film.

9. The substrate with an electromagnetic shielding film according to claim 1 or 8, wherein the substrate with an electromagnetic shielding film is attached to the front surface of the plasma display panel.