JP2003002689A - Glass article glass substrate for display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass article which has an excellent performance for preventing the diffusion of metal ions and has no problem of coloration caused by a metal colloid, and to provide a glass substrate using the glass article and used for a high quality display. SOLUTION: The glass article has an insulative metal ion diffusion-preventing film including at least one thin film comprising a composite oxide film mainly containing tin, silicone and oxygen on the surface of an alkali-containing glass substrate 1. The glass substrate for display has the insulative metal ion diffusion-preventing film 2 including at least one thin film comprising the composite oxide film mainly containing tin, silicone and oxygen, and an electrode film 3 containing silver, which are formed in this order on the surface of the alkali-containing glass substrate 1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention forms a metal ion diffusion preventive film which is excellent in the ability to prevent alkali or metal in a glass from singly or mutually diffusing when a metal film is formed on the surface of an alkali-containing glass. The present invention relates to a glass article and a glass substrate for a display using the glass article.

[0002]

2. Description of the Related Art In a flat panel display such as a plasma display (PDP), a field emission display (FED), a liquid crystal display (LCD), an electroluminescence display (ELD), it is usually 2
After forming members such as electrodes on one glass substrate and then bonding them together, it is used in particular.
Transparent electrodes such as O and SnO ₂ are used. Further, particularly in a large-sized display, a metal such as Ag or Cr / Cu / Cr is used as an auxiliary electrode in order to reduce the wiring resistance of the electrode.

Conventionally, as a glass substrate for PDP,
A soda lime silicate glass substrate formed into a plate shape having a thickness of 1.5 to 3.5 mm or an alkali-containing glass having a high strain point is used. Usually, such a glass is suitable for mass production and is formed by the float method having excellent smoothness. Float glass is exposed to a hydrogen atmosphere during the forming process, so that it is generally known that a reduced layer of several microns is formed on the glass surface, and Sn ²⁺ derived from molten Sn is present in this layer.

On the other hand, in the manufacturing process of PDP, generally, after heat treatment of holding Ag at 550 to 600 ° C. for 20 to 60 minutes after Ag is applied as a bus electrode on the surface of a glass substrate through a transparent electrode, it is repeated several times. Be done.

In this heat treatment step, Ag ⁺ ions diffuse into the transparent electrode and reach the glass surface, so that N ⁺ in the glass
Ion exchange occurs with the a ⁺ ion. Then, as a result, Ag ⁺ ions penetrate into the glass, and the penetrated Ag ^+
+ Ions are reduced by Sn ²⁺ existing in the reduction layer,
It produces a colloid of metallic Ag. Therefore, there is a problem that the Ag colloid causes the substrate glass to be colored yellow.

The problem of coloring due to such a metal colloid can occur not only when Ag is used, but also when a metal electrode film of Cu, Au or the like, which easily diffuses, is formed. In addition to the PDP, there is a problem of coloring due to Ag colloid not only in the PDP but also in the rear glass for automobiles in which the Ag electrode is formed in a stripe shape to prevent fogging.

Therefore, conventionally, when an alkali-containing glass is used as a display substrate, the exchange reaction of the alkali in the glass with Ag or the like used as an electrode in PDP or the like is prevented, and the glass is colored by Ag colloid. Various metal films, nitride films, or Si for preventing
It has been proposed to form a metal ion diffusion preventive film made of an oxide film such as O ₂ , ZrO ₂ , Al ₂ O ₃ and TiO ₂ (Japanese Patent Laid-Open Nos. 9-245652 and 10-1145).
No. 49, No. 10-302648, No. 11-1.
09888 and 11-130471).

[0008]

However, none of the conventionally proposed metal ion diffusion preventive films have sufficient metal ion diffusion preventive performance, and particularly in the case of a nitride film,
There is a drawback in that the metal ion diffusion preventing performance is deteriorated by being oxidized by the heat treatment in the DP manufacturing process.

The present invention solves the above-mentioned problems of the prior art, is excellent in the ability to prevent diffusion of metal ions, is free from the problem of coloring due to metal colloids, and a glass substrate for high quality display using such a glass article. The purpose is to provide.

[0010]

The glass article of the present invention comprises:
It is characterized in that it has an insulating metal ion diffusion preventing film including at least one thin film made of a composite oxide film containing tin, silicon and oxygen as main components on the surface of an alkali-containing glass substrate.

An insulating metal ion diffusion preventive film including at least one thin film composed of a composite oxide film containing tin, silicon and oxygen as main components is excellent in metal ion diffusion preventing performance and is contained in glass. It is possible to effectively prevent the elution of the generated alkali and the diffusion of metal ions of the metal film formed on the surface into the glass.

The insulating metal ion diffusion preventive film including at least one thin film made of a composite oxide containing tin, silicon and oxygen as main components has a high surface resistance and is suitable for display substrates and rear glass for automobiles. It can provide sufficient insulation required.

In a composite oxide film containing tin, silicon and oxygen as main components, the ratio of silicon / tin (ratio of the number of atoms) in the film,
The distribution of the ratio of silicon / tin in the depth direction varies depending on the raw material used and the manufacturing conditions and is appropriately selected.

The characteristics of the composite oxide film containing tin, silicon and oxygen as main components differ depending on the silicon / tin ratio. When this ratio is small, the metal ion diffusion preventing ability is high and the insulating property is low, and when this ratio is large, the metal ion diffusion preventing ability is low and the insulating property is high. Since the required characteristics of display substrates differ depending on the application and manufacturing process, in order to obtain the desired characteristics, in order to control the characteristics of the composite oxide film containing tin, silicon, and oxygen as the main components, the silicon in the film should be controlled. The / tin ratio is designed to include the depth profile.

For example, if it is desired to prioritize the metal ion diffusion preventing ability, the silicon / tin ratio may be designed to be small near the surface, and if it is desired to prioritize the insulating property, silicon near the surface may be designed. It may be designed so that the ratio of / tin is large.

It is considered that the reason why the characteristics change depending on the silicon / tin ratio is that tin oxide has a high ability to prevent diffusion of metal ions and silicon oxide has a high insulating property.

A small amount of elements such as phosphorus and boron may be added to the composite oxide film containing tin, silicon and oxygen as main components.

The insulating metal ion diffusion preventive film is formed by laminating a composite oxide film containing tin, silicon and oxygen as main components and a tin oxide film, or a composite containing tin, silicon and oxygen as the main components. A stack of an oxide film and a silicon oxide film can be used. The combination of these and the order of lamination are appropriately selected.

The glass article of the present invention is generally used by forming an electrode film, preferably an electrode film containing Ag, on the insulating metal ion diffusion preventing film.

In this case, the surface resistance of the insulating metal ion diffusion preventing film is preferably in the range of 1.0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω / □, and this surface resistance is the glass substrate for PDP. Generally required thermal stability, ie after heat treatment at 550 ° C. for 1 hour and / or 6
It is preferable that the temperature is within the above range even after holding at 85C and 85RH% for 168 hours.

The glass substrate for a display of the present invention comprises an alkali-containing glass substrate, and an insulating metal ion diffusion preventive film including at least one thin film made of a composite oxide film containing tin, silicon and oxygen as main components on the surface of the glass substrate. A glass substrate for a display having a film formed thereon, wherein the surface resistance of the insulating metal ion diffusion preventing film is 1.50 even after heat treatment at 550 ° C. for 1 hour and / or after holding at 65 ° C. and 85 RH% for 168 hours. It is characterized in that it is 0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω / □, and due to the excellent metal ion diffusion preventing performance of the insulating metal ion diffusion preventing film, there is no problem of coloring due to metal colloid. , Is a glass substrate for a display of remarkably high quality.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a cross-sectional view of a glass article according to an embodiment of the present invention, in which an insulating metal ion diffusion preventing film 2 is formed on a glass substrate 1, and the insulating metal ion diffusion preventing film 2 is formed on the insulating metal ion diffusion preventing film 2. The metal electrode film 3 is formed on.

The glass substrate 1 is made of alkali-containing glass. The following are examples of suitable main compositions of the alkali-containing glass.

SiO ₂ 50 to 73% by mass Al ₂ O _{3 0 to} 15% by mass R ₂ O 6 to 24% by mass R'O 6 to 27% by mass R ₂ O is Li ₂ O, Na ₂ O, K ₂ O total,
R'O is the total of CaO, MgO, SrO, and BaO.

In the present invention, the insulating metal ion diffusion preventing film 2 includes at least one thin film composed of a composite oxide film containing tin, silicon and oxygen as main components.

In the composite oxide film containing tin, silicon and oxygen as main components, the ratio of silicon / tin in the film is 0.05 to 0.9.
It is preferably 5. Also, in the depth direction of the film, silicon /
The proportion of tin may vary.

The film thickness of this composite oxide film is 10 to 400 n.
m, particularly preferably in the range of 50 to 300 nm.
When the film thickness is less than 10 nm, it is difficult to obtain sufficient metal ion diffusion preventing ability, and when the film thickness exceeds 400 nm, it is not preferable in terms of productivity.

Insulating metal ion diffusion preventive film 2 of the present invention
Includes at least one thin film of a composite oxide film containing tin, silicon, and oxygen as main components, and can be a laminate including the composite oxide film.

As a laminated structure, silicon / silicon is formed in the depth direction of the film.
A laminate of two kinds of complex oxide films having different tin ratios, a laminate of a composite oxide film containing tin, silicon and oxygen as main components and a film containing tin oxide as the main component, or tin and silicon. And a composite oxide film containing oxygen as a main component and a film containing silicon oxide as a main component are preferably laminated. In such a laminated structure, the total film thickness is preferably less than 500 nm.

Insulating metal ion diffusion preventive film 2 of the present invention
Has a surface resistance of 1.0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω
/ □ is preferred, and the surface resistance is 550 ° C,
Heat treatment for 1 hour and / or 1 at 65 ° C, 85RH%
It is more preferable that the content is within the above range even after the holding for 68 hours.

Surface resistance of 1.0 × 10 ^{8 to} 1.0 × 10
By setting it to ¹⁶ Ω / □, the glass article according to the present invention can be suitably used as a glass substrate for a display, which does not cause problems such as leak current and charging of the substrate.

Further, as the glass substrate for a display, when used as a display, and the influence of the processing temperature in the manufacturing process of the display panel, for example, Ag.
It does not change even under the firing conditions of the electrode, and it is preferable to maintain the above range, and heat treatment at 550 ° C for 1 hour
Alternatively, it is desired to be within the above range even after holding at 65 ° C. and 85 RH% for 168 hours.

Such an insulating metal ion diffusion preventive film of the present invention is a so-called physical vapor deposition method such as a sputtering method, an ion plating method or a vacuum vapor deposition method, a so-called chemical vapor deposition method such as a chemical vapor phase method, or a printing method. A film can be easily formed by using the sol-gel method or the like.

When forming an insulating metal ion diffusion preventing film having a laminated structure, the above different film forming methods can be combined.

Among the above-mentioned manufacturing methods, in the thermal decomposition method capable of continuously forming a film, particularly in the glass ribbon forming step in the case of manufacturing a glass plate by the float method, the thermal decomposition reaction is carried out by utilizing the heat of the glass ribbon. The chemical vapor deposition method (hereinafter, referred to as "online CVD method") for advancing is most suitable.

The online CVD method will be specifically described below with reference to the drawings. As shown in FIG. 2, in this apparatus, a glass fiber 10 flows from a melting furnace (float kiln) 11 into a tin float bath (float bath) 12, and moves a predetermined distance from the surface of a glass ribbon 10 that moves in a strip shape on a tin bath 15, A predetermined number of coaters 16 (three coaters 16a, 16b, 16c in the illustrated embodiment) are arranged. A gaseous raw material is supplied from these coaters 16, and a film is continuously formed on the glass ribbon 10. The glass ribbon 10 on which the film is formed is pulled up by the roller 17 and sent to the slow cooling kiln 13. The glass plate gradually cooled in the slow cooling kiln 13 is cut by a float-type general-purpose cutting device (not shown) to form a glass plate of a predetermined size. It should be noted that 98% by volume of nitrogen and 2% by volume of hydrogen were supplied to the tin float bath space so that the inside of the tin float bath space was maintained at a slightly higher pressure than the outside of the bath, and a non-oxidizing atmosphere was provided inside the bath. Hold on.

As a raw material for forming a composite oxide film containing tin, silicon and oxygen as main components by an online CVD method, a vapor composed of a tin compound, a silicon compound and an oxidizing agent is diluted with an inert gas to a predetermined concentration. The gas used is.

As the tin compound, monobutyltin trichloride, dimethyltin dichloride, tetraethyltin, tin tetrachloride and the like are preferable. As the silicon compound, tetramethyl orthosilicate, tetraethyl orthosilicate, dibutoxydiacetoxysilane and the like are suitable. As the oxidizer, oxygen, water vapor, ozone, carbon monoxide and the like are suitable. As the inert gas, nitrogen, helium, argon or the like can be used.

When the insulating metal ion diffusion preventing film having a laminated structure is formed by the online CVD method, continuous film formation can be performed by supplying different raw material gases to the respective coaters. For example, in order to form tin oxide as the first layer and a complex oxide film containing tin, silicon and oxygen as main components as the second layer in this order, the first coater (16a)
To form a tin oxide film, and a second coater (16b) to form a composite oxide film containing tin, silicon, and oxygen as main components.

When the metal electrode film 3 made of Ag or the like is formed on the insulating metal ion diffusion preventing film 2, the film thickness is 3 to.
It is preferably about 12 μm.

[0042]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples.

(Example 1) In the production of a float glass having a thickness of 3 mm, from a coater installed in a float bath,
A mixed gas consisting of vapor of monobutyltin trichloride and tetraethyl orthosilicate, water vapor, and oxygen and nitrogen was supplied to the surface of the glass ribbon to form a 100-nm-thick composite oxide film containing tin, silicon, and oxygen as main components. The ribbon on which the film was formed was gradually cooled and washed, and then cut.
When the composition of the film was examined by XPS, it was a composite oxide containing tin, silicon and oxygen as main components, and the ratio of silicon / tin in the film was about 0.15 on the surface of the film and about 0. 63
Met. Print Ag paste on the surface of this film,
After firing at 0 ° C. for 1 hour to form an Ag electrode having a thickness of 8 μm, the degree of coloring was visually observed under a halogen lamp (500 W). In addition, without Ag paste printing, 5
After baking at 50 ° C for 1 hour, cooling to room temperature and then 6
It was held at 5 ° C. and 85 RH% for 168 hours, after which the surface resistance was measured. The results are shown in Table 1.

Example 2 A soda lime glass plate having a thickness of 3 mm, which had been cut into a size of 100 × 100 mm in advance, was placed on a mesh belt, passed through a heating furnace, and heated to about 600 ° C. While further transporting this heated glass plate, a mixed gas consisting of dimethyltin dichloride, dibutoxydiacetoxysilane, water vapor, oxygen and nitrogen was supplied from a coater installed above the glass transport path, and a film thickness was formed on the glass plate. A 160-nm-thick film containing tin, silicon, and oxygen as main components was formed, and this glass plate was gradually cooled, and then washed and dried. When the composition of the film was examined by XPS, it was a composite oxide containing tin, silicon and oxygen as main components, and the ratio of silicon / tin in the film was about 0.15, which was almost constant in the depth direction. It was In the same manner as in Example 1, the degree of coloring after forming the Ag electrode and the surface resistance of the sample without the Ag electrode were measured. The results are shown in Table 1.

(Example 3) In the production of a float glass having a thickness of 3 mm, from a coater installed in a float bath,
70 nm of dimethyltin dichloride vapor, steam, mixed gas consisting of oxygen and nitrogen is supplied to the surface of the glass ribbon.
A film containing tin oxide as a main component was formed. A 100 nm-thick composite oxide film containing tin, silicon, and oxygen as main components was formed on the surface of the film containing tin oxide as a main component using the same source gas as in Example 1 with a coater installed further downstream. did. The ribbon in which the tin oxide film and the composite oxide film were laminated in this order was gradually cooled and washed, and then cut. In the same manner as in Example 1, the degree of coloring after forming the Ag electrode and the surface resistance of the sample without the Ag electrode were measured. The results are shown in Table 1.
It was shown to.

(Example 4) In the production of a float glass having a thickness of 3 mm, a coater installed in a float bath was used to deposit 100 nm containing tin, silicon and oxygen as main components as in Example 1.
A thick complex oxide film was formed. A mixed gas composed of monosilane, ethylene, oxygen, and nitrogen was supplied to the surface of the composite oxide from a coater installed further downstream to form a 100-nm-thick film containing silicon oxide as a main component. The ribbon in which the composite oxide film and the silicon oxide film were laminated in this order was gradually cooled and cut through a washing process. In the same manner as in Example 1, Ag
The degree of coloring after forming the electrode and the surface resistance of the sample without the Ag electrode were measured. The results are shown in Table 1.

(Example 5) A tin oxide film and a composite oxide film were laminated in the same manner as in Example 3, and a mixed gas of monosilane, ethylene, oxygen and nitrogen was mixed with a mixed oxide from a coater installed further downstream. It was supplied to the surface to form a film containing silicon oxide as a main component. The ribbon in which the tin oxide film, the composite oxide film, and the silicon oxide film were laminated in this order was gradually cooled and cut through a washing process. In the same manner as in Example 1, the degree of coloring after forming the Ag electrode and the surface resistance of the sample without the Ag electrode were measured. The results are shown in Table 1.

(Comparative Example 1) In the production of a float glass having a thickness of 3 mm, from a coater installed in a float bath,
70 nm of dimethyltin dichloride vapor, steam, mixed gas consisting of oxygen and nitrogen is supplied to the surface of the glass ribbon.
A film containing tin oxide as a main component was formed. In the same manner as in Example 1, the degree of coloring after the Ag electrode was formed and A
The surface resistance was measured on the sample without the g-electrode. The results are shown in Table 1.

(Comparative Example 2) In the production of a float glass having a thickness of 3 mm, from a coater installed in a float bath,
A mixed gas consisting of monosilane, ethylene, oxygen and nitrogen was supplied to the surface of the glass ribbon to form a film containing silicon oxide as a main component and having a thickness of 100 nm. In the same manner as in Example 1, the degree of coloring after forming the Ag electrode and the surface resistance of the sample without the Ag electrode were measured. The results are shown in Table 1.

[0050]

[Table 1]

From Table 1, it can be seen that according to the present invention, Ag colloidal coloring due to diffusion of Ag ions is highly suppressed.

[0052]

As described in detail above, according to the present invention, a glass article which is excellent in insulation and metal ion diffusion preventive property and has no problem of coloring due to a metal colloid, and a glass article using such a glass article. A glass substrate for a quality display is provided.

The glass article of the present invention is industrially very useful as a substrate for displays, rear glass for automobiles, and the like.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a glass article of the present invention.

FIG. 2 is a diagram showing an outline of an apparatus capable of producing the glass article of the present invention.

[Explanation of symbols]

1 glass substrate 2 Insulating metal ion diffusion prevention film 3 metal electrode film 10 glass ribbon 11 melting furnace 12 tin float tank 13 Annealing furnace 15 tin bath 16 coater 17 Laura

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01J 17/16 H01J 17/16 29/86 29/86 Z (72) Inventor Koichiro Kiyohara Central Osaka City, Osaka Prefecture 4-7-28 Kitahama-ku, Nippon Sheet Glass Co., Ltd. F-term (Reference) 2H090 HA04 HB03X HB17X HC13 HD01 JA07 JB02 JD08 LA01 4G059 AA01 AA08 AC20 AC24 DA01 DB09 EA07 EB01 EB03 EB04 BB07 GA01 GA02 GA05 GA12BB01 BB01 A14 5C04 5C04 5C04 5C040 GA01 GA02 GA09 KA04 KA07 KB19 KB29 MA10

Claims (7)

[Claims] 1. A glass article having, on the surface of an alkali-containing glass substrate, an insulating metal ion diffusion preventive film including at least one thin film made of a composite oxide film containing tin, silicon and oxygen as main components. 2. The glass article according to claim 1, wherein the ratio of silicon / tin in the composite oxide film is not constant in the depth direction. 3. The glass article according to claim 1, wherein the ratio of silicon / tin in the composite oxide film is constant in the depth direction. 4. A laminated structure of two or more layers, in which a composite oxide film containing tin, silicon and oxygen as main components and a film containing tin oxide or silicon oxide as main components are formed on the surface of an alkali-containing glass substrate. The glass article according to any one of claims 1 to 3, which further comprises an insulating metal ion diffusion preventing film. 5. The glass according to claim 1, wherein the surface resistance of the insulating metal ion diffusion preventing film is 1.0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω / □. Goods. 6. The surface resistance is 1.0 × 10 ^{8 to} 1.0 × 10 ¹⁶ Ω / □ even after heat treatment at 550 ° C. for 1 hour and / or holding at 65 ° C. and 85 RH% for 168 hours. Item 6. The glass article according to any one of items 1 to 5. 7. A glass substrate for a display, wherein an electrode film containing silver is formed on the surface of the insulating metal ion diffusion preventive film of the glass article according to any one of claims 1 to 6.