JPS61220238A - Composite alloy for sealing - Google Patents

Abstract

PURPOSE:To simplify manufacture of the electrode of a display tube or the like by providing the surface of a sealing alloy plate containing Cr with a metal layer generating no oxidation coating due to preoxidation coating treatment, while removing said layer except only the required part to be left in order to form the oxidation coating. CONSTITUTION:Both sides of a sealing alloy plate 1 such as a 15-30% Cr-Fe alloy plate and a 40-48% Ni - 4-8% Cr-Fe alloy plate are coated with a metal layer 2 generating no oxidation coating due to preoxidation coating treatment by a plating method or the like. Next, the metal layer 2 on the required spot sealed with glass is removed by a screen printing method or the like. Further, the whole is subjected to preoxidization coating treatment for forming an oxidation coating 3 followed by dissolving removing the remaining metal layer 2 with an acid solution or the like. Then, glass 4 is sealed on an oxidation coating 3 as an electrode for a display tube of a display unit or the like. Accordingly, a machining process for removing the unrequired oxidation coating can be omitted, thus curtailing manufacturing processes.

Description

Detailed Description of the Invention Field of Application This invention relates to a sealing alloy plate, particularly to a sealing alloy plate used for electrodes for display tubes, etc., and to prevent unnecessary oxide coatings during the production of electrodes, etc. The present invention relates to a composite alloy for sealing which allows the removal process to be omitted.

BACKGROUND ART In general, the sealing alloys used for electrodes for display tubes, etc., have the following characteristics: ■The coefficient of thermal expansion is close to that of soft glass; ■The adhesion of the oxide film to the base material is good.■ It is required to satisfy properties such as excellent punchability and workability, and currently, 15-30C is used as a sealing alloy.
r-Fa gold alloy, 40-48NL-4-8Cr-F
θ alloy is used.

This sealing alloy is rolled to the required thickness, then punched or etched into the required dimensions and shape, for example.
When manufacturing electrodes for display tubes, in order to improve the adhesion to the glass of the lead part that is sealed to the glass part of the display tube, the sealing alloy plate is coated with a wet H with a dew point of +10°C to +40°C.
2. Preliminary oxide coating treatment is performed at 1000°C to 1250°C in an atmosphere, but an oxide film is formed on the sheet metal surface, and cutting is performed to remove the unnecessary oxide film on the surfaces of the encapsulating side lead part and the external lead part. There is a need.

However, since the above-mentioned alloy plate is extremely thin and the oxide film has a dense structure and is firmly adhered, cutting the alloy plate requires a large amount of process and time.

Purpose of the Invention The present invention is directed to a composite alloy plate for sealing used for electrodes for display tubes such as displays or support plates for cathode ray tubes, etc., which can omit the process of removing unnecessary oxide films during the production of electrodes, etc. It is aimed at composite alloy plates.

Structure and Effects of the Invention The present invention is a composite alloy for sealing, characterized in that a metal layer or an alloy layer that does not form an oxide film by preliminary oxidation film treatment is provided on both main surfaces of a Cr-containing sealing alloy plate. .

The composite alloy for sealing according to the present invention is manufactured by removing the metal or alloy layer on the surface of the composite alloy plate at the required locations for sealing, and then applying a preliminary oxide coating treatment to improve adhesion to glass. Since the oxide film is formed only on the required sealing alloy parts, the process of removing the oxide film and cutting unnecessary parts, which were previously impossible and unavoidable, can be omitted, reducing the manufacturing process of sealing material. This has a great effect on simplification and cost reduction.

Therefore, depending on the application, purpose of use, etc., C
In order to expose the surface of the r-containing sealing alloy, the metal layer or alloy layer that does not form an oxide film due to preliminary oxidation film treatment on the surface of the composite alloy may be removed by a partial removal process such as photoetching, There is an advantage that a sealing material having oxide films in the required number of locations can be easily manufactured.

In addition, to remove the metal or alloy layer remaining on the surface after forming the required oxide film, for example, it can be easily removed by immersing it in an acid solution depending on the surface layer material, and other methods can be used. It also has the advantage that it does not adversely affect the next process, such as providing a layer or pattern.

In this invention, the Cr-containing sealing alloy plate serving as the core material is a 15% to 30% Cr-Fe alloy plate, a 40% to 4% Cr-Fe alloy plate,
8NL 4% to 8% Cr-Fe alloy plate is suitable, and the material of the metal layer or alloy layer provided on both main surfaces of this Cr-containing sealing alloy plate has an oxide film formed by preliminary oxide film treatment. If not, any metal or alloy can be applied, and from the viewpoint of thermal expansion coefficient, thermal conductivity consistency, and cost, F
e 30% to 55% NL alloy plate, Fe, NL, 5 metal plate, etc. are preferable, and may be selected appropriately depending on the purpose and use. Also, the method of depositing the metal or alloy layer is rolling cladding method, Various methods such as plating can be applied depending on the core material and surface layer material. Furthermore, the thickness of the metal layer or alloy layer is preferably as thin as possible since it will be removed in a later process.

In this invention, the reason for using a 15% to 30% Cr Fe alloy plate and a 40% to 48NL 4% to 8% Cr Fe alloy plate is as follows.

In 15% to 30% Cr-Fe alloys, CT is 15
If it is less than wt%, the coefficient of thermal expansion becomes large and the difference with the coefficient of thermal expansion of soft glass becomes too large, which is undesirable.
If it exceeds 0 wt%, workability deteriorates and it becomes difficult to form into a predetermined shape, so Cr is set at 15 wt% to 30 wt%.

Moreover, in the 40%~48NL-4%~8%Cr Fe alloy, NL7! If J is less than 40 wt%, the thermal expansion coefficient becomes small, and the difference in the thermal expansion coefficient of soft glass becomes too large, making it difficult to arrive at the glass. The difference with the coefficient becomes too large, which is undesirable, and Cr is 4w.
If it is less than t%, the coefficient of thermal expansion will be small, and the difference with the coefficient of thermal expansion of soft glass will be too large, and the adhesion of the oxide film to the alloy base will be poor, and if it exceeds awt%, the coefficient of thermal expansion will become large. , the difference between the thermal expansion coefficient and the soft glass becomes too large, which is not preferable.

In addition, any of the above sealing alloys can be heated.

In order to improve cold workability, the content of SL and tln is 0.005 wt% to 1.0 wt%, respectively. Owt% of M, 7. r
.

At least one of Ti, Y or rare earth elements is 0
．． It is also good to contain 0.005 wt% to 1.0 wt%.

Disclosure of the Invention Based on the Drawings FIGS. 1 and 2 are explanatory diagrams showing a method of manufacturing an electrode for a display tube using a composite sealing alloy according to the present invention.

When producing electrodes for display tubes, a metal layer or alloy layer (2) that does not produce an oxide film by preliminary oxide film treatment is applied to both main surfaces of a Cr-containing sealing alloy plate (1) of the required dimensions using a rolling cladding method. After the composite alloy plate for sealing is formed by applying the composite alloy plate by a method such as a pinning method, it is punched or etched into the required size and shape.

Roughly, in order to remove the metal layer or alloy layer (2) at the required points to be sealed to the glass, the portion corresponding to the sealing lead part is partially etched by screen printing, photo etching, etc., and the core material is sealed. The deposited alloy (1) is exposed.

Next, if the metal layer or alloy layer (2) deposited on the surface of the Cr-containing sealing alloy plate (1) is an Fe-30% to 55% NL alloy, and the Fe, NL alloy layer is an alloy, the dew point is +10°C. ~
1000°C to 1250°C in a moist H2 atmosphere at +40°C
℃ pre-oxidation film treatment, metal layer or alloy layer (2
) is a 5 metal or a 5 alloy, the dew point is +10℃ to +4
By applying a preliminary oxide film treatment at 1000 to 1050°C in a moist H2 atmosphere at 0°C, a thickness of 1.5 mm is formed only on the surface of the Cr-containing sealing alloy plate (1) that will become the sealing lead. c+
An oxide film (3) of m to 5 mm is formed.

Oxide film (3) at required locations on Cr-containing sealing alloy plate (1)
After forming the metal layer or alloy layer remaining on the surface (
In order to remove (2), the metal layer or alloy layer (2) can be easily dissolved and removed by, for example, immersing the entire plate in an acid solution depending on the material of the metal layer or alloy layer.

Glass (4) is sealed to the Cr-containing sealing alloy plate (1) on which the oxide film (3) is formed and adhered.

In addition, as shown in Fig. 2, the surface metal layer or alloy layer (
2) is removed by pickling, etc., formed into the desired shape by press processing, subjected to preliminary oxidation coating treatment, and sealed in a glass container (5) without removing the surface metal layer or alloy layer (2). You can also.

An oxide film (
3), the process of removing the oxide film on the surfaces of the external lead part (5) and the encapsulating side lead part (6), which was conventionally unavoidable, is no longer necessary, which reduces and simplifies the manufacturing process of display tube electrodes. It is extremely effective in reducing costs.

In addition, conventionally, the oxide film (3) on the encapsulating side was removed by applying a high voltage between internal electrodes to ionize the encapsulated gas and using the ion radiation to remove the oxide film, so a thick oxide film could not be removed; It was necessary to provide an oxide film, which resulted in a decrease in sealing strength, but with this invention, a thick oxide film can be provided, the sealing strength is significantly improved, and the thickness of the oxide film can also be adjusted. .

Examples Example 1 Cr18wt%- with plate thickness 0.1mm x width 100mm dimensions
Both main surfaces of the Fe sealing alloy are cold welded to a thickness of 0.
An alloy layer of NL42Wi%-F@ having dimensions of 0.05 mm x width of 100 mm was formed to obtain a composite alloy for sealing according to the present invention.

Next, this arrived composite alloy plate is made into a lead length of 70 mm.
, lead part width 2.0+nm, lead part pitch 3.0mm
.

10 lead parts - processed into a shape with 30 mm wide lead connecting parts at all ends, roughly etched partially using photo etching method, and coated with 1 thread of Cr18Wi%-Fe sealing alloy on each side of the material. An exposed surface was provided.

Next, in a humid H2 atmosphere with a dew point of +30°C, 1150
A preliminary oxide film treatment was performed at 11 hours at °C, and an oxide film mainly composed of Cr oxide with a thickness of 3A511 was provided on the exposed surface.

Roughly, the processed material was immersed in a ferric chloride solution to dissolve and remove the alloy layer on the surface to obtain an electrode material for a display tube with an oxide film provided only at required locations.

Bottle dust ■2 Plate thickness 0.15mm NL42Wj%-Cr 6wt%-
Both main surfaces of the Fe sealing alloy are cold welded to a thickness of 0.
A 05 mm thick NL alloy layer was formed to obtain a composite alloy for sealing according to the present invention.

Next, partial etching was performed using a photoetching method, and Nj layers with a width of 5 mm were removed at positions 10 mm from the ends on both main surfaces of the material by pickling, and two strips of NL 42 wt%--C were removed.
An exposed surface of r swt%-Fe sealing alloy was provided. After that, as shown in Figure 2, it is processed into the required shape and roughened.
In a humid H2 atmosphere with a dew point of +30°C, at 1100°C and 0.
A preliminary oxide coating treatment was performed for 5 hours. As a result, an oxide film mainly composed of Cr oxide with a thickness of 2 was formed only on the surface of the Cr-containing sealing alloy plate.

Apply a low-melting glass paste to the oxide film, sandwich the material from both sides in a glass container, and heat it for 50 minutes in a nitrogen gas atmosphere.
Sealing was completed by heating at 0° C. for 10 minutes.

Since there is no oxide film on the enclosing side, in this invention, a thick oxide film can be provided only on the sealing portion, and the sealing strength is significantly improved.

[Brief explanation of the drawing]

FIGS. 1 and 2 are explanatory diagrams showing a method of manufacturing an electrode for a display tube using the composite alloy for sealing according to the present invention.・ 1. Cr-containing sealing alloy plate, 2... Metal layer or alloy layer, 3... Oxide film, 4... Glass, 5... Glass container. Figure 1 (α) (b) (d) (f) Figure 2 (a) (b) (C)

Claims (1)

[Claims] 1. A composite alloy for sealing, characterized in that a metal layer or an alloy layer that does not form an oxide film by preliminary oxidation film treatment is provided on both main surfaces of a Cr-containing sealing alloy plate.