TWI686361B - Method for manufacturing glass plate with film - Google Patents

Abstract

The present invention is a method for manufacturing a film-attached glass plate, which is a method for manufacturing a film-attached glass plate in which a laminated film is formed on a glass plate, the laminated film is black when viewed from the glass plate side, and a plurality of films are laminated Wherein the step of forming the laminated film includes: an inorganic film forming step S1 of forming an inorganic film containing at least a precious metal on the glass plate; a heating step S2 of heating the inorganic film; forming electroless plating on the inorganic film Electroless plating process S3 of the metallized film; and electrolytic plating process S4 of forming the electrolytically plated metal film on the aforementioned electroless plated metal film. Next, in the electrolytic plating process S4, a pyrophosphate inorganic substance bath is used.

Description

Method for manufacturing glass plate with film

The invention relates to a method for manufacturing a film-attached glass plate.

As is well known, in recent years, with the development of electronic devices and the like, substrates for flat panel displays (FPD) such as liquid crystal displays and electroluminescent displays or sensors, sensors, and semiconductor package covers such as solid-state imaging devices or laser diodes have been used Components, and even thin-film compound solar cell substrates, etc., span a variety of glass plates.

However, in a display device such as a TV, a personal computer, a smartphone, etc., if an electrode is formed on a transparent substrate such as a glass plate, the transparent substrate side is placed on the screen so that the user side becomes the user side At this time, there is a possibility that the electrode is visually recognized by the user, or that the image appears black. Next, in order to solve the problems shown above, it has been proposed to blacken the transparent substrate side of the electrode (for example, Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-89689

On the other hand, in order to produce an electrode on a glass plate, the method used when forming a metal film on a glass plate generally includes vapor deposition or sputtering.

However, in vapor deposition or sputtering, a reduced-pressure environment is often required, manufacturing equipment becomes large-scale, and manufacturing costs are high. In addition, during vapor deposition or sputtering, the temperature around the glass plate is often high during the process. Therefore, stress occurs in the glass plate and the metal film, which may cause the metal film to peel off. In addition, during vapor deposition or sputtering, the surface roughness of the formed metal film may increase.

Regarding the problems shown above, the inventors of the present application proposed a film-coated glass plate that can be manufactured without using vapor deposition or sputtering. The film-attached glass plate refers to a film-attached glass plate in which a laminated film is formed on a glass plate, the laminated film is black when viewed from the glass plate side, and a plurality of films are laminated, and the laminated film is provided with: An inorganic film containing at least a precious metal on the glass plate; an electroless plated metal film formed on the inorganic film; and an electrolytic plated metal film formed on the electroless plated metal film.

However, in this film-attached glass plate, there is a possibility that the following problems may occur.

When the film-coated glass plate is used for manufacturing elements such as a touch panel, the laminated film of the film-coated glass plate must be finely processed. However, in this processing project, usually most of the ultrasonic washing Etching, heat treatment and other processes that exert a force to peel the laminated film. Therefore, if the film adhesion of the laminated film is weak, there is a possibility that the device yield may be reduced.

In addition, the laminated film system may not only be peeled off from various parts due to long-term use of the device in the manufacturing process, but the long-term reliability of the device may be reduced at this time.

In view of the above-mentioned circumstances, the present invention aims to improve the film adhesion of a laminated film in a film-attached glass plate having a laminated film that is black when viewed from the glass plate side as a technical problem.

In order to solve the aforementioned problems, the inventors of the present invention have carefully studied the results and obtained the knowledge that the electrode is easily peeled off at the interface between the electroless plated metal film and the electrolytically plated metal film in the laminated film of the film-attached glass plate. In addition, the reason why the electrode is easily peeled off at this part is that the sulfuric acid inorganic substance bath used when the metal film is formed by electrolytic plating is strongly acidic, and therefore it is known that the surface of the electroless plated metal film corrodes. Based on such knowledge, the inventor of the present case completed the invention of the present case.

That is, the method for manufacturing a film-attached glass plate of the present invention is a method for manufacturing a film-attached glass plate in which a laminated film is formed on a glass plate, the laminated film is black when viewed from the aforementioned glass plate side, and a plurality of films are laminated The method for manufacturing the film-attached glass plate is characterized in that the step of forming the laminated film includes: an inorganic film forming step of forming an inorganic film containing at least a precious metal on the glass plate; and forming electroless plating on the inorganic film Electroless plating process of metallized film; and electrolytic plating process of forming electrolytically plated metal film on the aforementioned electroless plated metal film, in the aforementioned electrolytic plating process, pyrophosphate inorganic substance bath is used.

In this configuration, a pyrophosphate inorganic substance bath is used in the electrolytic plating process. The pyrophosphate inorganic substance bath is neutral or weakly alkaline, so the possibility of surface corrosion of the electroless plating metal film is low. Therefore, the adhesion between the electroless plated metal film and the electrolytic plated metal film is improved, and further, the film adhesion of the laminated film is improved. Therefore, according to the method for manufacturing a film-attached glass sheet of the present invention, in a film-attached glass sheet in which a laminated film that is black when viewed from the glass sheet side is formed, the film adhesion of the laminated film can be improved.

In the above configuration, it is preferable that the electroless plated metal film is nickel.

Since the nickel film formed by electroless plating has good adhesion to the inorganic film, the film adhesion of the laminated film can be improved.

Preferably, the electrolytic plating metal film is copper, and in the electrolytic plating process, a copper pyrophosphate bath is used.

Copper-based conductivity is excellent, and workability such as fine wiring having a width of several μ or low cost is suitable as a material for electrode wiring materials. The copper pyrophosphate bath is usually used by adding an acid or an alkaline solution to form a weakly alkaline pH of about 8.5. Therefore, it is possible to form a copper film with good adhesion without dissolving a metal film of electroless plating such as a nickel film as a base electrode for electrolytic plating. In addition, the copper film-based film surface is excellent in smoothness, uniform dyeability, and film thickness uniformity.

In the above configuration, it is preferable that the inorganic film A heating process for heating the inorganic film is provided between the forming process and the electroless plating process.

If the inorganic film is heated in the heating process, the inorganic film becomes strong, and the film peeling at the interface between the film intermediate portion of the inorganic film or the inorganic film and the electroless plated metal film can be suppressed. As a result, the adhesion of the inorganic film is improved, and in addition, the adhesion of the laminated film can be improved. The reason why the inorganic film becomes strong due to heating is presumed to be due to the formation of a strong alloy in the inorganic film due to heating.

As described above, according to the present invention, in a film-attached glass plate having a laminated film that is black when viewed from the glass plate side, the film adhesion of the laminated film can be improved.

1‧‧‧Coated glass plate

2‧‧‧ laminated film

3‧‧‧glass plate

4‧‧‧Inorganic film

5‧‧‧ Electroless plating metal film

6‧‧‧ Electroplating metal film

S1‧‧‧Inorganic film formation project

S2‧‧‧Heating project

S3‧‧‧Electroless plating project

S4‧‧‧Electrolytic plating project

FIG. 1 is a schematic cross-sectional view showing a film-coated glass plate according to an embodiment of the present invention.

2 is a flowchart showing a method of manufacturing a film-attached glass plate according to an embodiment of the present invention.

The form for implementing the present invention will be described below based on the drawings.

FIG. 1 is a schematic cross-sectional view showing a film-coated glass plate according to an embodiment of the present invention. In this film-attached glass plate 1, a laminated film 2 formed by laminating plural films is formed on a glass plate 3. The laminated film 2 includes: an inorganic film 4 formed on the glass plate 3 containing at least a precious metal; and an electroless plated metal film formed on the inorganic film 4 by electroless plating using the inorganic film 4 as a catalyst 5; and electrolytic plating metal film 6 formed on the electroless plating metal film 5 by electrolytic plating. Next, the laminated film 2 is black when viewed from the glass plate 3 side. Examples of the precious metal contained in the inorganic film 4 include gold, silver, platinum, palladium, and ruthenium.

The laminated film 2 of the film-attached glass plate 1 is used by users who are patterned into a predetermined wiring shape. Next, in this patterning, the laminated film 2 is etched with an acidic etching solution. For the acidic etching solution, hydrogen peroxide sulfate, ferric chloride, or copper chloride can be used. In particular, by mixing an etching solution of hydrogen peroxide in an oxalic acid-based solution, the laminated film 2 of the present invention can be etched once.

The material of the glass plate 3 is not particularly limited, and includes, for example, soda lime glass, non-alkali glass, etc. In addition, it may be aluminosilicate glass used as a strengthened glass.

The thickness of the glass plate 3 is not particularly limited, for example, 10 μm to 300 μm, preferably 20 μm to 200 μm, and most preferably 50 μm to 100 μm. If the thickness of the glass plate 3 is less than 10 μm, the glass plate may be warped or wrinkled due to the stress of the electroless plating metal film 5. In addition, if the thickness of the glass plate 3 exceeds 300 μm, the glass plate 3 is hardly flexible, so it may not be possible to use electronics such as displays with curved screens The possibility of machines.

Examples of the inorganic film 4 containing at least noble metal include, for example, tin chloride, zinc chloride, copper chloride, etc. that are easily adsorbed on the glass plate 3 to give gold sodium sulfite, silver chloride, and platinum (IV) chloride Acid 6 hydrate, palladium chloride, ruthenium chloride, etc. The inorganic film 4 may contain, in addition to the above-mentioned precious metals, metals such as nickel, cobalt, and copper that become electroless plating catalysts.

The thickness of the inorganic film 4 is, for example, 0.07 μm to 1.0 μm, more preferably 0.1 μm to 0.7 μm, and most preferably 0.2 μm to 0.5 μm. If the thickness of the inorganic film 4 is less than 0.07 μm, there is a possibility that the plating speed of electroless plating is very slow. If the thickness of the inorganic material film 4 exceeds 1.0 μm, when the laminated film 2 is viewed from the glass plate 3 side, there is a possibility that the inorganic material film 4 does not become black due to the influence of the red color.

The thickness of the electroless plated metal film 5 is, for example, 0.05 μm to 5.0 μm, more preferably 0.1 μm to 1.0 μm, and most preferably 0.2 μm to 0.5 μm. If the thickness of the electroless plating metal film 5 is less than 0.05 μm, there is a possibility that the laminated film 2 does not become black when viewed from the glass plate 3 side. If the thickness of the electroless plating metal film 5 exceeds 5.0 μm, the film formation takes time, and there is a possibility that the production efficiency is lowered.

The thickness of the electrolytic plating metal film 6 is, for example, 0.1 μm to 5.0 μm, more preferably 0.3 μm to 3.0 μm, and most preferably 0.5 μm to 2.0 μm. If the thickness of the electrolytically plated metal film 6 is less than 0.1 μm, the resistance of the electrolytically plated metal film 6 may be too high. If the thickness of the electrolytic plating metal film 6 exceeds 5.0 μm, there is a possibility that the manufacturing cost will increase.

In this embodiment, the metal of the electroless plating metal film 5 is nickel. However, the present invention is not limited to this. From the viewpoint of a metal material that can be finely etched, the electroless plating metal film 5 is preferably copper or nickel. The copper resistance is low, and the thickness uniformity is good in electroless plating. In addition, the nickel system has the advantage of lower reflectivity (black) than copper, and is suitable for display devices with a small area. In addition, the electroless nickel plating film has the advantage of having good adhesion to the inorganic film 4.

If the electroless plated metal film 5 is made of copper, a low-resistivity laminated film 2 with good film thickness uniformity can be obtained in a short time. In addition, if the electroless plated metal film 5 is made of copper, the fine processing by etching becomes easier.

In the present embodiment, the metal of the electrolytic plating metal film 6 is copper, and electrolytic plating is performed with a copper pyrophosphate bath to form an electrolytic plating metal film 6 having a low volume resistance of about 2 to 3 μΩ‧cm. However, the present invention is not limited to this. The electrolytically plated metal film 6 has a low resistance like tin or copper, and is a metal that can be plated with a pyrophosphate inorganic substance bath. It can be used as a wiring material on the electroless plated metal 5.

Next, a method of manufacturing the film-attached glass plate 1 of this embodiment will be described.

As shown in FIG. 2, in the manufacturing method of the film-attached glass plate 1 of the present embodiment, the process of forming the laminated film 2 includes: inorganic film forming process S1, heating process S2, electroless plating process S3, and electrolysis Plating project S4 as the main project.

First, in the inorganic film forming process S1, on the glass plate 3. An inorganic film 4 containing at least a noble metal is formed on it.

In this embodiment, the inorganic film 4 is formed as follows, for example. The glass plate 3 is immersed in a solution containing one or more kinds of tin, zinc, and copper, and the metal ions are adsorbed on the surface of the glass plate 3, and then immersed in an aqueous solution containing a precious metal. Thereby, due to the difference in ionization tendency, metal ions such as tin, zinc, and copper are replaced with precious metal ions, and a film mainly composed of a precious metal or a precious metal compound is formed on the glass plate 3. Next, the glass plate 3 on which the film is formed is immersed in a reducing solution. Thereby, the precious metal near the surface of the film is reduced to a state having a catalyst action of electroless plating. The inorganic film 4 formed by this is a substance that can be etched by an etching solution of copper or nickel.

Next, in the heating process S2, the inorganic film 4 formed in the inorganic film forming process S1 is heated. Specifically, for example, the glass plate 3 on which the inorganic film 4 is formed is put into a heating furnace in the atmosphere. The heating in the heating process S2 may be once or plural times.

If the heating in the heating project S2 is performed only once, the heating temperature is preferably 120 to 500°C, preferably 200 to 400°C, and most preferably 250 to 330°C. If the heating temperature is less than 120°C, the inorganic film 4 may not become very strong. If the heating temperature exceeds 500°C, the cost of the heating process S2 may increase and the glass substrate may shrink or deform.

If there is only one heating in the heating project S2, the heating time is preferably 1 to 60 minutes, preferably 5 to 60 minutes, and preferably 15 to 30 minutes. If the heating time is less than 1 minute, for the inorganic film 4 To become very strong, it is necessary to have a device that collectively heats the inorganic film 4 like a laser annealing device or a flash lamp annealing device, and there is a possibility that the manufacturing cost will increase. If the heating time exceeds 60 minutes, the cost of the heating process S2 may increase.

After the heating process S2, in the electroless plating process S3, the electroless plating metal film 5 is formed on the inorganic substance film 4 heated in the heating process S2 by electroless plating.

Next, in the electrolytic plating process S4, the electrolytic plating metal film 6 is formed on the electroless plating metal film 5 formed in the electroless plating process S3 by electrolytic plating. In the electrolytic plating in this electrolytic plating process S4, a pyrophosphate inorganic substance bath is used.

The method of electrolytic plating using a pyrophosphate inorganic substance bath may use the method of a well-known technique.

For example, in order to form a copper film as the electrolytic plating metal film 6, if a 1 liter copper plating bath is manufactured, 300 g of potassium pyrophosphate is dissolved in about 700 mL of water. Next, 70 g of copper pyrophosphate was added to completely dissolve it. An additional 2mL of ammonia was added. Finally, appropriate addition of polyphosphoric acid or potassium hydroxide, thereby adjusting the pH in the range of 8.2 ~ 8.8. Thereafter, the temperature was raised to 55°C, and oxygen-free copper was used as the anode, and the copper was electrolytically plated.

Among them, if a tin film is formed by electrolytic plating, a tin pyrophosphate bath is used, and if a zinc film is formed by electrolytic plating, a zinc pyrophosphate bath is used.

In the manufacturing method of the film-attached glass plate 1 of this embodiment configured as above, the following effects can be enjoyed.

Coke used in electrolytic plating of electrolytic plating project S4 Since the phosphoric acid inorganic substance bath is neutral or weakly alkaline, the surface of the electroless plating metal film 5 is less likely to corrode. Therefore, the adhesion between the electroless plated metal film 5 and the electrolytic plated metal film 6 is improved, and further, the film adhesion of the laminated film 2 is improved. Therefore, according to the manufacturing method of the film-attached glass plate 1 of this embodiment, in the film-attached glass plate 1 on which the laminated film 2 is formed, the film adhesion of the laminated film 2 can be improved.

Among them, when the amount of phosphorus contained in the electroless plated nickel film as the electroless plated metal film 5 is more than 4% in terms of at% (atomic percentage), the acid resistance is high, and the metal When electrolytic plating is performed, even if a sulfuric acid inorganic plating bath that is strongly acidic is used, it is not easily corroded in the bath. As a result, the electrolytic plating metal film 6 can be formed in the sulfuric acid inorganic bath with good adhesion. However, in applications where fine processing such as patterning is necessary, the electroless nickel plating film must be etched with an acidic etching solution. Therefore, the phosphorus concentration in the nickel film must be reduced to 4% or less (preferably 3.5% the following). However, in the case of electrolytic plating of metals, if a sulfuric acid inorganic plating bath that is strongly acidic is used, the electroless plating nickel film with a phosphorus concentration of 4% or less starts from the immersion in the plating bath until the electrolytic plating begins As a result, the film surface is corroded, and there is a possibility that the adhesion with the electrolytic plating metal film 6 formed thereon becomes weak. Therefore, when forming the laminated film 2 having an electroless nickel film with a phosphorus concentration of 4% or less, the method of manufacturing the film-attached glass plate 1 of this embodiment using a pyrophosphate inorganic substance bath is particularly effective.

In addition, due to the softness of the inorganic film 4, an electroless plated metal film 5 with a large stress is formed on the inorganic film 4, or is caused by a difference in thermal expansion rate between the glass plate 3 and the electroless plated metal film 5 due to heat treatment of Stress or the hydrogen contained in the electroless plated metal film 5 is to be applied to the inorganic film 4 to form a film expansion force. There is an interface between the inorganic film 4 or the interface between the inorganic film 4 and the electroless plated metal film 5 Possibility of film peeling.

Regarding this problem, in the present embodiment, since the inorganic film 4 is heated in the heating process S2, the inorganic film 4 becomes strong, and it is possible to suppress the film intermediate portion of the inorganic film 4 or the inorganic film 4 and the electroless plating metal The film at the interface of the film 5 peeled off. Thereby, the adhesiveness of the inorganic film 4 improves, and the adhesiveness of the laminated film 2 can also be improved. The reason why the inorganic film 4 is strong due to heating is presumed to be that a strong alloy is formed in the inorganic film 4 due to heating. For example, if silver and tin are present in the inorganic film 4, silver and tin are considered to form a strong alloy.

The present invention is not limited to the above-mentioned embodiment, and various modifications can be made within the scope of the technical idea. For example, in the above embodiment, the manufacturing method of the film-attached glass plate 1 is provided with the heating process S2, but the heating process S2 may not be provided. In addition, in the above-mentioned embodiment, the electroless plated metal film 5 is nickel, but may also be other metals such as copper. In addition, in the above-mentioned embodiment, the laminated film 2 of the film-attached glass plate 1 is used for patterned users, but it may also be used for unpatterned applications, such as decoration or shading.

Claims (4)

A method for manufacturing a film-attached glass plate, which is a method for manufacturing a film-attached glass plate in which a laminated film is formed on a glass plate, the laminated film is black when viewed from the aforementioned glass plate side, and a plurality of films are laminated, the attached The method of manufacturing a film glass plate is characterized in that the step of forming the laminated film includes: an inorganic film forming step of forming an inorganic film containing at least a precious metal on the glass plate; and an electroless plating metal film formed on the inorganic film Electroless plating process; and an electrolytic plating process of forming an electrolytic plating metal film on the aforementioned electroless plating metal film, wherein the aforementioned electroless plating metal film is copper or nickel, and coke is used in the aforementioned electrolytic plating process Phosphoric acid inorganic bath. A method for manufacturing a film-attached glass plate, which is a method for manufacturing a film-attached glass plate in which a laminated film is formed on a glass plate, the laminated film is black when viewed from the aforementioned glass plate side, and a plurality of films are laminated, the attached The method of manufacturing a film glass plate is characterized in that the step of forming the laminated film includes: an inorganic film forming step of forming an inorganic film containing at least a precious metal on the glass plate; and an electroless plating metal film formed on the inorganic film Electroless plating process; and electrolytic plating process of forming an electrolytic plating metal film on the aforementioned electroless plating metal film, the aforementioned electroless plating metal film is nickel, and pyrophosphate inorganics are used in the aforementioned electrolytic plating process bath. For example, the manufacturer of the film-coated glass plate in the scope of patent application In the method, the electrolytic plating metal film is copper, and in the electrolytic plating process, a copper pyrophosphate bath is used. The method for manufacturing a film-attached glass plate according to any one of the first to third patent applications, further comprising heating the inorganic film between the inorganic film forming process and the electroless plating process engineering.

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