JP2002212759A - Sealing alloy member, panel pin for crt and its manufacturing method, and color crt using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve conventional problems in which a panel pin is prone to be deformed because its head comes into contact with a frame holder for supporting color selection electrodes and in which this deformation occasionally causes dislocation of the color selection electrodes. SOLUTION: The panel pin is provided with: a pin body which ahs a head for supporting the color selection electrodes and a leg to be sealed into a glass panel and which is made of an Fe-base alloy; a hard layer which is formed on the surface of at least the head of the panel pin body and which has a thickness of 10 μm or greater as well as a hardness of 250 Hv or higher in Vickers hardness; and a surface oxide film which is formed on the outermost surface of at least the leg of the panel pin body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sealing alloy member,
The present invention relates to a CRT panel pin, a method of manufacturing the same, and a color CRT using the same.

[0002]

2. Description of the Related Art In a color cathode ray tube having a color selection electrode, a fluorescent film formed on the inner surface of a glass panel is
A color selection electrode having a large number of pores and slits through which an electron beam passes is arranged facing each other with a predetermined gap. The color selection electrode is fixed to the glass panel by a frame holder disposed between a frame fixed to the outer periphery and a panel pin sealed to the glass panel. In the present invention, the term “color selection electrode” refers to an electrode generally called a shadow mask or an aperture grill.

Since the panel pins are directly fixed to the inner surface of the glass panel, those made of a so-called sealing alloy are used. 42% by mass Ni-6% by mass Cr as an alloy sealed to such glass or ceramics
-Fe alloys, 42-52 mass% Ni-Fe alloys, 16-20 mass% Cr-Fe alloys and the like are known.

[0004] Since the glass panel is generally made of soft glass, the panel pin has a thermal expansion coefficient of 16 to 20 which is close to that of soft glass among the above-mentioned sealing alloys.
Ferritic stainless steel such as a mass% Cr-Fe alloy is widely used.

When such a ferritic stainless steel is used as a panel pin, usually, a ferritic stainless steel material is processed into a desired panel pin shape, which is then heat-treated in, for example, a wet hydrogen atmosphere to form a glass with a glass surface. An oxide film having excellent wettability is formed, and in this state, it is sealed to a glass panel of a color CRT.

[0006]

The above-mentioned panel pin made of ferritic stainless steel has a characteristic that the thermal expansion coefficient is close to that of soft glass, but has the mechanical characteristics such as strength and deformation resistance. Is insufficient, there is a problem that deformation occurs when the color selection electrode is attached to the panel pin via the frame holder, and that the color selection electrode is displaced due to insufficient strength.

[0007] With respect to such a point, for example, Japanese Patent Laid-Open No. 11-7
No. 1653 discloses that ferrite stainless steel crystal grains are
It describes that the grain size is made smaller than 2 by the S grain number to improve the strength. However, such a method of refining the base material crystal grains has a limitation in improving the strength of the alloy, and also has a problem that the alloy is easily softened by heat treatment when forming a surface oxide film or sealing glass.

In particular, since the corners of the frame holder directly contact the heads of the panel pins, there is a problem that the heads are deformed and the color selection electrodes are shifted.

SUMMARY OF THE INVENTION The present invention has been made to address such problems, and maintains mechanical properties such as strength and deformation resistance, especially contact with other members, while maintaining sealing properties with soft glass or the like. It is an object of the present invention to provide a sealing alloy member, a CRT panel pin, and a method of manufacturing the same, which improve the strength of the part. Another object of the present invention is to provide a color cathode-ray tube in which the use of the panel pins for the cathode-ray tube suppresses the occurrence of an initial defect, a displacement of a color selection electrode, and the like.

[0010]

According to the present invention, there is provided a sealing alloy member having a metal part made of an Fe-based alloy and a metal part formed on at least a part of the surface of the metal part and having a thickness of 10 μm or more. And a surface oxide film formed on at least the hard layer.
The metal part may have an internally oxidized part, but in the present invention, the internal oxidized part is the metal part. In addition, the hard layer may indicate a portion having a higher hardness than the metal part, although the structure may be changed in a subsequent step.

In the sealing alloy member of the present invention, a hard layer having a thickness of 10 μm or more is provided, and a surface oxide film is formed on the hard layer to improve the strength of the sealing alloy member. Deformation and damage due to contact with the member can be suppressed.

The hard layer is preferably a nitrided or carbonized layer having a Vickers hardness specified in JIS Z2244 and a hardness of 250 Hv or more at a load of 9.8 N. at least
By providing a nitrided layer or a carbonized layer having a hardness of 250 Hv or more, deformation and damage due to contact with other members can be further suppressed.

A panel pin for a cathode ray tube according to the present invention has a head for supporting a color selection electrode, a leg sealed to a glass panel, and a panel pin main body made of an Fe-based alloy, and at least one of the panel pin main bodies. A hard layer formed on the surface of the head and having a thickness of 10 μm or more, and a surface oxide film formed on at least the outermost surface of the leg of the panel pin main body. .

Since the CRT panel pins support the color selection electrodes on the head, the head is highly likely to be deformed or damaged. Improving the strength by providing a hard layer having a thickness of 10 μm or more in at least such a portion,
Deformation and damage when supporting the color selection electrode can be suppressed.

In the CRT panel pin of the present invention, the hard layer preferably has a Vickers hardness of 250 Hv or more. By setting the hardness of the hard layer to 250 Hv or more, it is possible to further suppress deformation and damage when supporting the color selection electrode.

Preferably, the hard layer is a nitride layer or a carbon layer formed directly on the surface of the panel pin body. Such a nitrided or carbonized layer can be formed relatively easily by heat treatment or the like, and has excellent strength. Therefore, by adopting such a hard layer, the strength of the panel pin for a cathode ray tube can be improved and the manufacture thereof can be facilitated. Becomes possible.

When the hard layer is a nitride layer, it preferably contains at least one selected from the group consisting of Cr nitride, Fe nitride, Al nitride and Ti nitride. When the hard layer is a carbonized layer, it preferably contains at least one selected from Cr carbide, Fe carbide and Ti carbide.

Further, it is preferable that the surface oxide film is formed on the nitride layer or the carbonized layer. The surface oxide film is provided for improving the wettability with glass and ensuring the sealing, but by forming such a surface oxide film on a nitride layer or a carbonized layer, the strength is improved, and The sealing property can be improved.

Further, the hard layer may be composed of a coating layer. As such a coating layer, for example, a layer formed of a reactive sputtering film, an ion plating film, or a sprayed film can be mentioned. Since such a coating layer can be easily formed on an oxide film, the coating layer can be formed without removing the oxide film after oxidizing the entire panel pin, and the panel pin can be easily manufactured. Become.

The Fe-based alloy constituting the panel pin body for a cathode ray tube according to the present invention contains 17 to 28% by mass of Cr and 0.01 to 0.6% by mass.
Wt% Al, 0.1-0.6 wt% Ti, and 0.01-0.
Preferably, it contains 6% by mass of Si and the balance substantially consists of Fe. By employing an Fe-based alloy having such a composition, the coefficient of thermal expansion can be approximated to that of soft glass or the like, and the sealing property can be improved. Also,
By oxidizing the Fe-based alloy having such a composition, an oxide film having excellent wettability with glass can be formed.

In the method of manufacturing a panel pin for a cathode ray tube according to the present invention, for example, a surface oxide film is formed on the surface of the panel pin body, the surface oxide film on the head surface is removed, and then a hard layer is formed on at least a part of the head. Method. According to such a method, a nitride layer or a carbonized layer that cannot be formed on the oxide film can be formed on the head of the panel pin main body.

The hard layer can be formed before the formation of the surface oxide film. The hard layer may be formed only on the surface of the head that requires particularly high strength, or may be formed on a panel pin. It may be provided on the entire surface of the main body. In the method of forming the hard layer before the formation of the surface oxide film as described above, it is possible to employ a nitride layer and a carbonized layer which are relatively easily formed. Further, since an oxide film can be formed on the nitrided layer and the carbonized layer, the step of removing the oxide film as described above is not required, and the panel pins can be easily manufactured.

Further, a surface oxide film may be formed on the entire surface of the panel pin main body, and thereafter, a hard layer may be partially provided on the head region. In such a case, by a method such as reactive sputtering, ion plating or thermal spraying,
It is preferable to form a hard layer.

A color CRT according to the present invention includes the above-described panel pin for a CRT according to the present invention. The color cathode ray tube of the present invention,
For example, an electron gun, a glass panel having a fluorescent film irradiated with an electron beam emitted from the electron gun, and a plurality of fine holes or a plurality of fine holes that are arranged to face the fluorescent film with a predetermined gap and pass the electron beam. The present invention includes a color selection electrode having a slit, and a CRT panel pin that is sealed on the inner surface side of the glass panel and supports the color selection electrode. Characterized by using a CRT panel pin.

In the present invention, it is possible to provide a color cathode-ray tube in which the initial failure and the displacement of the color selection electrode are suppressed by using the above-mentioned panel pin for the cathode-ray tube.

Embodiments of the present invention will be described below. FIG. 1 is a sectional view showing an embodiment of a panel pin for a cathode ray tube according to the present invention. The CRT panel pin 1 of the present invention includes a substantially cylindrical panel pin body 4 having a head 2 and legs 3, a hard layer 5 and a surface oxide film 6 formed on the panel pin body 4.

A panel pin 1 for a CRT shown in FIG.
In this embodiment, the hard layer 5 is formed on the outer surface of the head 2 and the leg 3
A surface oxide film is formed on the outer surface of the panel pin and the inner surface of the panel pin body.

The thickness of the hard layer 5 is at least 10 μm.
The reason for setting such a range is that when the thickness of the hard layer 5 is less than 10 μm, the head may be deformed by contact with the frame holder supporting the color selection electrode.
By providing the hard layer 5 having a thickness of 10 μm or more on at least the head 2, it is possible to suppress deformation and damage of the head 2 of the CRT panel pin 1 supporting the color selection electrode.

Preferably, the thickness of the hard layer 5 is 20 μm
It is preferable that the thickness be in the range from not less than to 500 μm. By setting the thickness to 20 μm or more, it is possible to suppress deformation and damage at the contact portion even when supporting a large color selection electrode. Further, when the hard layer is formed with a thickness exceeding 500 μm, there is a possibility of peeling. Therefore, it is preferable to provide the hard layer within a range of 500 μm or less.

The hardness of the hard layer 5 is preferably not less than 250 Hv in Vickers hardness. By setting the Vickers hardness at least to 250 Hv or more, it is possible to further suppress deformation and damage at a contact portion with the frame holder, and to suppress displacement or the like of the color selection electrode. Preferably it is 350 Hv or more. Three
By setting it to 50 Hv or more, it is possible to further improve the strength and suppress deformation in the head and the like.

Further, in the present invention, by providing a surface oxide film 6 on at least the outer surface and the inner surface of the leg 3 which is a sealing portion with glass, the wettability with glass is improved, and the sealing property is improved. Can be done.

FIG. 2 is a sectional view showing another embodiment of the panel pin 1 for a cathode ray tube according to the present invention. The CRT panel pin 1 shown in FIG. 2 has a hard layer 5 provided only on the outer surface of the head 2 of the panel pin body 4, and a surface oxide film 6 provided on all surfaces including the hard layer 5. .

In the panel pin 1 of the present invention, even if the oxide film 6 is formed on the hard layer 5, the hardness of the hard layer 5 is not affected at all, and deformation due to contact with other members is effectively suppressed. It is possible. Further, since the hard layer is provided directly on the panel pin main body 4, the hard layer can be a nitride layer or a carbonized layer.

The hard layer 5 is formed not only on the head 2 but also, for example, in FIG.
May be formed on the entire outer surface of the panel pin main body 1 as shown in FIG. Further, the hard layer 5 may be formed on the entire inner surface of the panel pin main body 1. In the panel pin 1 of the present invention, it is sufficient that the hard layer 5 is formed on at least the head 2. Preferably, the hard layer 5 is formed on the entire outer surface as shown in FIG. Can be further improved.

FIG. 4 shows an oxide film 6 formed on the surface of the panel pin body 4 and a hard layer 5 formed only on the oxide film 6 on the head 2. In the panel pin 1 of the present invention,
Even if the hard layer 5 is formed on the oxide film 6, the hardness of the hard layer 5 is not affected at all, and deformation due to contact with other members can be effectively suppressed. The hard layer 5 thus formed on the oxide film 6 is preferably a coating layer formed by, for example, reactive sputtering, ion plating, or thermal spraying. According to these methods, the hard layer can be easily formed on the oxide film.

When the hard layer 5 is formed on the oxide film 6 as shown in FIG. 4, it is preferable to form the hard layer 5 except for at least a portion of the leg 2 to be sealed with glass. This is because, when the hard layer 5 is formed on the oxide film 6, the hard layer 5 has poor wettability with glass, so that the sealing property with glass is reduced.

As described above, examples of the hard layer 5 include a nitride layer, a carbonized layer and a coating layer. Examples of the nitride layer include those containing at least one selected from Cr nitride, Fe nitride, Al nitride and Ti nitride.

Such a nitride layer can be formed by nitriding the panel pin body. As the nitriding treatment, for example, a method of heat-treating the panel pin body at a temperature of 350 to 700 ° C. in a nitrogen gas or a compound atmosphere containing nitrogen such as ammonia, or ion nitriding by glow discharge in a vacuum atmosphere or a reduced pressure atmosphere Laws and the like can be applied.

Of these, in particular, according to the ion nitriding method, the surface compound layer (surface nitride layer) after the treatment can be a dense layer without voids, so that a better surface hardened layer can be obtained. Can be Also, because partial nitriding is easy,
A cured layer can be formed only on the surface where abrasion resistance is required according to the intended use.

As the carbonized layer, for example, Cr carbide, Fe
And those containing at least one selected from carbides and Ti carbides. Such a carbonized layer can be formed, for example, by carbonizing the panel pin body in an atmosphere containing carbon.

Examples of the coating layer include those formed of a reactive sputtering film, an ion plating film or a sprayed film, and specifically, titanium nitride (TiN), titanium carbonitride (TiCN), titanium carbide (TiC), Examples include at least one selected from zirconium nitride (ZrN), chromium nitride (CrN), and titanium aluminum nitride (TiAlN).

The panel pin body according to the present invention has a thickness of 17 to 28.
It is preferred that the alloy contains, by mass, Cr, 0.01 to 0.6 mass%, Al, 0.1 to 0.6 mass%, and 0.01 to 0.6 mass%, with the balance being substantially Fe.

Cr is a component that lowers the thermal expansion of the Fe-based alloy and makes the coefficient of thermal expansion approximate the coefficient of thermal expansion of the soft glass, and its content is preferably in the range of 17 to 28% by mass. If the Cr content is out of the above range, in any case, the difference in the coefficient of thermal expansion from the soft glass constituting the CRT panel becomes too large, and the properties as a sealing part for the soft glass deteriorate. . When the content of Cr exceeds 28% by mass, mechanical properties such as elongation also deteriorate. Cr is also a main component of the surface oxide film 6, whereby the surface oxide film 6 having excellent wettability to glass can be obtained.

Al is a component for improving the adhesion between the surface oxide film 6 and the panel pin main body (metal portion), and its content is preferably in the range of 0.01 to 0.6% by mass. A
When the content of l is less than 0.01% by mass, the effect of improving the adhesion of the surface oxide film is low. On the other hand, when the content exceeds 0.6% by mass, the thermal expansion coefficient of the panel pin body (metal portion) is changed, and sealing is performed. There is a possibility that distortion or the like may increase when worn. Al
Is more preferably in the range of 0.3 to 0.6% by mass.

Ti, like Al, has the function of improving the adhesion between the surface oxide film and the panel pin body (metal portion), and has the function of fixing harmful C and N. Is a component mainly composed of
It is preferable to be in the range of 1 to 0.6% by mass. When the content of Ti is less than 0.1% by mass, the effect of improving the adhesion of the surface oxide film 3 is low. On the other hand, when the content exceeds 0.6% by mass, workability may be reduced. Ti content is 0.3-0.6
More preferably, it is in the range of mass%.

In the oxidation treatment of Si, an oxide layer mainly composed of SiO ₂ is formed below the surface oxide film 6,
It is a component that enhances the adhesion between the surface oxide film and the panel pin body (metal portion), and its content is preferably in the range of 0.01 to 0.6% by mass. When the content of Si is less than 0.01% by mass, the effect of improving the adhesion of the surface oxide film is low. On the other hand, when the content exceeds 0.6% by mass, the coefficient of thermal expansion of the panel pin body (metal portion) is changed, and sealing is performed. There is a possibility that distortion or the like may increase when worn.

In the present invention, if necessary, Mn
Or a small amount of Ni or the like. These elements contribute to improving the workability of the sealed part, adjusting the thermal expansion characteristics, and the like. Further, since C and N may decrease the workability of the Fe-Cr-based alloy, the content of each of them is preferably less than 0.02% by mass.

Next, a method of manufacturing a panel pin for a cathode ray tube according to the present invention will be described. As a method of manufacturing a CRT panel pin of the present invention, a CRT panel pin shown in FIG. 1 will be described as an example.

The panel pin body 4 (metal portion) is, for example,
17-28% by mass of Cr, 0.01-0.6% by mass of Al, 0.1-0.
It can be obtained by using an alloy plate containing 6% by mass of Ti and 0.01 to 0.6% by mass of Si, the balance being substantially composed of Fe, and forming this by drawing or the like. The shape of the panel pin body 4 is a substantially cylindrical shape with one end sealed, and has, for example, a cross-sectional shape as shown in FIG.

Next, a surface oxide film 6 is formed on the entire surface of the panel pin body 4. The surface oxide film 6 is applied to the panel pin body 4 at, for example, 900 to 1400 ° C. in a wet hydrogen atmosphere.
Is formed by performing a heat treatment, that is, an oxidation treatment, at a temperature in the range described above. According to such an oxidizing treatment, a surface oxide film 6 containing Cr oxide as a main component on the surface of the panel pin main body 4 and having excellent wettability to glass can be obtained.

Further, of the surface oxide film 6 formed on the panel pin main body 4, only the surface oxide film 6 formed on the head 2 is removed and then nitrided to obtain a head as shown in FIG. A panel pin for a cathode ray tube in which the hard layer 5 (nitrided layer) is formed only in the portion 2 is manufactured. This hard layer 6
Include Cr nitride, Fe nitride, Al nitride and Ti
At least one selected from nitrides is contained.

The removal of the surface oxide film by the above-mentioned manufacturing method is difficult even if the surface oxide film is subjected to a nitriding treatment, so that the surface oxide film is removed and the panel pin body 4 is removed. This is for exposing the bullion portion.

As the nitriding treatment, for example, a method of heat-treating the panel pin body 4 at a temperature of 350 to 700 ° C. in a nitrogen gas or a compound atmosphere containing nitrogen such as ammonia, or in a vacuum atmosphere or a reduced pressure atmosphere For example, an ion nitriding method using a glow discharge can be applied. Among them, in particular, according to the ion nitriding method, the surface compound layer (surface nitride layer) after the treatment has no voids and can be a dense layer, so that a better surface hardened layer can be obtained. Further, since partial nitriding is easy, a hardened layer can be formed only on the surface where abrasion resistance is required depending on the intended use.

Note that a carbonized layer may be formed by performing a carbonizing process instead of the nitriding process. In this case C
A carbide layer containing at least one selected from r carbide, Fe carbide and Ti carbide is formed.

Next, a method of manufacturing the CRT panel pin 1 shown in FIG. 2 will be described. First, a panel pin main body 4 (metal portion) having a cross-sectional shape as shown in FIG. 5 is manufactured. The composition and the like are the same as those of the CRT panel pin 1 shown in FIG.

The hard layer 5 is provided on the head 2 of the panel pin body 4.
To form a nitrided layer, a carbonized layer, or a coating layer. The coating layer can be formed using, for example, a method such as reactive sputtering, ion plating, or thermal spraying. Specifically, titanium nitride (TiN), titanium carbonitride (TiCN), titanium carbide (TiC), Examples include zirconium (ZrN), chromium nitride (CrN), and titanium aluminum nitride (TiAlN). When the hard layer is formed by thermal spraying, for example, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Y ₂ O ₃
And WC can be used. The hard layer 5
May be formed on the entire outer surface of the panel pin main body 4 as shown in FIG. 3, for example.

Further, the panel pin main body 4 having the hard layer 5 formed on the head 2 is placed in a wet hydrogen atmosphere, for example, at 900 to 1 mm.
By performing a heat treatment (oxidation treatment) at a temperature in the range of 400 ° C., a CRT panel pin 1 in which an oxide film 6 is formed on the hard layer 5 and the panel pin body 1 as shown in FIG. be able to.

Next, a method of manufacturing the CRT panel pin 1 shown in FIG. 4 will be described. First, a panel pin main body 4 (metal portion) having a cross-sectional shape as shown in FIG. 5 is manufactured. The composition and the like are the same as those of the CRT panel pin 1 shown in FIG.

The surface oxide film 6 is formed on the panel pin body 4 by performing a heat treatment, that is, an oxidation treatment, at a temperature in the range of 900 to 1400 ° C. in a wet hydrogen atmosphere, for example. Further, by forming the hard layer 5 on the surface oxide film 6 of the head 2, the CRT panel pin 1 shown in FIG. 4 is manufactured.

The hard layer 5 is formed, for example, by reactive sputtering,
Examples include a coating layer formed by a method such as ion plating or thermal spraying.
N), titanium carbonitride (TiCN), titanium carbide (Ti
C), zirconium nitride (ZrN), chromium nitride (Cr
N), and titanium aluminum nitride (TiAlN)
Etc. are included.

In the panel pin 1 for a cathode ray tube shown in FIG. 4, the hard layer 5 is provided only on the head 2, but in the present invention, at least a portion of the leg 3 related to sealing with glass is surface oxidized. As long as the film is exposed, the range in which the hard layer 5 is formed is not limited to only the head 2. Next, the color cathode ray tube of the present invention will be described. FIG.
1 is a sectional view schematically showing a color cathode ray tube of the present invention. In the color cathode ray tube 7 of the present invention, a phosphor screen 9 composed of a three-color phosphor layer that emits blue, green, and red light is disposed on the inner surface of a panel 8. 10 are arranged. The phosphor screen 9 is scanned with an electron beam emitted from an electron gun 11 via the color selection electrode 10 to form a structure for displaying a color image.

The color selection electrode 10 has a large number of electron beam passage holes formed in a predetermined arrangement on the surface facing the inner surface of the panel 8, and the electron beam passage holes are formed around the effective surface where the electron beam passage holes are formed. The frame 12 is provided via an ineffective portion where no is formed. Furthermore, this frame 1
One end of a frame holder 13 is fixed to 2, and the other end is fixed to a panel pin 1 for a cathode ray tube of the present invention sealed on the inner surface of a panel 8.

In the color cathode ray tube of the present invention, the panel pins for the cathode ray tube of the present invention as described above are used as the panel pins sealed in the panel for fixing the color selection electrodes, thereby sealing the panel pins with the panel. This can be performed reliably, and the displacement of the color selection electrode can be suppressed.

[0063]

EXAMPLES Examples 1, 3, 5, 8, 11, 12 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
An Fe-based alloy having a composition of Fe (mass ratio) was press-formed to produce a plurality of panel pin bodies 4 as shown in FIG. After an oxidation process was performed on each of these panel pin bodies 4 to form a surface oxide film, only the surface oxide film on the head 2 was removed.

Thereafter, in Examples 1 and 3, 550
C. and 720.degree. C., gas nitriding was performed at 550.degree. C. and 720.degree. C. in Examples 5 and 8, respectively.
Gas carburizing was performed at 0 ° C., and gas carbonitriding was performed at 650 ° C. in Example 12, to produce a CRT panel pin 1 as shown in FIG.

Examples 2, 4, 6, 9 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
An Fe-based alloy having a composition of Fe (mass ratio) was press-formed to produce a plurality of panel pin bodies 4 as shown in FIG.

In Examples 2 and 4, the temperature was 550 ° C. and 720 ° C., respectively.
After gas-nitriding, an oxidation treatment was performed. In Examples 6 and 9, ion nitriding was performed at 550 ° C. and 720 ° C., respectively, and then an oxidation treatment was performed to produce a CRT panel pin 1 as shown in FIG.

Examples 7, 10, 17, 18 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
An Fe-based alloy having a composition of Fe (mass ratio) was press-formed to produce a plurality of panel pin bodies 4 as shown in FIG.

In Examples 7, 10, 17, and 18, only the head 2 was partially ion-nitrided at 550 ° C., 720 ° C., 450 ° C., and 430 ° C., respectively, and then oxidized as a whole, as shown in FIG. The panel pin 1 for such a cathode ray tube was manufactured.

Examples 13 to 16 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
An Fe-based alloy having a composition of Fe (mass ratio) was press-molded to produce a plurality of panel pin bodies 4 as shown in FIG. 5, and these panel pin bodies 4 were oxidized to form surface oxide films.

In Examples 13 and 14, TiN and TiC were coated by ion plating, and in Examples 15 and 16, WC and Al ₂ O ₃ were coated by thermal spraying. Panel pin 1 was produced.

Comparative Example 1 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
After press-forming an Fe-based alloy having a composition of Fe (mass ratio) into a shape as shown in FIG. 5, it was subjected to an oxidation treatment to produce a CRT panel pin.

Comparative Example 2 18% Cr-0.35% Al-0.35% Ti-0.3% Si-bal.
An Fe-based alloy having a composition of Fe (mass ratio) was press-formed to produce a panel pin main body 4 as shown in FIG. After oxidizing the panel pin body 4 to form a surface oxide film, only the surface oxide film on the head was removed. Further, gas nitriding was performed at 430 ° C. to produce a CRT panel pin as shown in FIG.

Next, the hardness of the hard layer and the buckling strength of the panel pins for cathode ray tubes of the respective examples and comparative examples were measured. Table 1 shows the results together with the components and thickness of the hard layer.
Shown in

[Table 1]

As is clear from Table 1, it was confirmed that all of the examples of the present invention had excellent buckling strength. In contrast, in Comparative Example 1 in which the hard layer was not formed only by the oxidation treatment, and in Comparative Example 2 in which the hard layer was formed but the thickness was less than 10 μm, it was recognized that sufficient buckling strength could not be obtained. Was.

[0075]

According to the present invention, there is provided a sealing alloy member comprising: a metal part made of an Fe-based alloy; and a hard layer formed on at least a part of the surface of the metal part and having a thickness of 10 μm or more. And at least a surface oxide film formed on the hard layer, which has excellent strength and can suppress deformation and damage due to contact with other members.

The CRT panel pin of the present invention has a hard layer having a thickness of 10 μm or more formed at least on the head supporting the color selection electrode, and has a surface oxidation layer on the outermost surface of the leg portion sealed to the glass panel. By providing the film, it is possible to have excellent sealing properties with glass and to suppress deformation and damage due to contact with a frame holder or the like that supports the color selection electrode.

The color cathode-ray tube of the present invention has excellent quality by supporting the color selection electrode using the CRT panel pin, thereby suppressing the deformation or damage of the CRT panel pin and the displacement of the color selection electrode. can do.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a CRT panel pin of the present invention in which a hard layer is formed only on the head of a panel pin main body.

FIG. 2 is a cross-sectional view showing a panel pin for a cathode ray tube of the present invention in which a hard layer is formed on a head portion of a panel pin main body and an oxide film is entirely formed including the hard layer on the head portion.

FIG. 3 is a cross-sectional view showing a CRT panel pin of the present invention in which a hard layer is formed on the entire outer surface of a panel pin main body and an oxide film is formed on the entire surface including the hard layer.

FIG. 4 is a sectional view showing a panel pin for a cathode ray tube of the present invention in which an oxide film is formed on the entire panel pin main body and a hard layer is formed on the oxide film on the head.

FIG. 5 is a sectional view showing a panel pin main body.

FIG. 6 is a sectional view schematically showing a color cathode ray tube of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Panel pin for cathode ray tubes 2 ... Head 3 ... Leg part 4 ... Panel pin main body 5 ... Hard layer 6 ... Surface oxide film 7 ... Color cathode ray tube 8 ... Panel 9 ... Phosphor screen 10 ... Color selection electrode 11 ... Electron gun 12 ... Frame 13 ... Frame holder

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 8/16 C23C 8/16 8/26 8/26 H01J 9/14 H01J 9/14 G 29/02 29 / 02 B (72) Inventor Kiyoshi Nagasaki 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Inside the Toshiba Yokohama Office (72) Inventor Hiroshi Shimozawa 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Toshiba Yokohama Business In-house (72) Inventor Mitsuhiro Matsunaga 8F Shin-Sugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4K028 AA02 AB01 AB06 4K031 AA06 BA05 CB42 CB43 CB45 FA07 4K044 AA03 AB05 BA12 BA18 BB01 BB03 CA12 CA13 5C027 HH30 5C031 BB03 BB14

Claims (17)

[Claims] 1. A metal part made of an Fe-based alloy, and formed on at least a part of a surface of the metal part, and
An alloy member for sealing, comprising: a hard layer having a thickness of 10 μm or more; and at least a surface oxide film formed on the hard layer. 2. The sealing alloy member according to claim 1, wherein said hard layer comprises a nitrided layer or a carbonized layer having a Vickers hardness of 250 Hv or more. 3. A panel pin main body having a head for supporting a color selection electrode, a leg portion sealed to a glass panel, and made of an Fe-based alloy, and at least a surface of the head of the panel pin main body. A panel pin for a cathode ray tube, comprising: a hard layer formed and having a thickness of 10 μm or more; and a surface oxide film formed on at least the outermost surface of the leg portion of the panel pin body. 4. The CRT panel pin according to claim 3, wherein the hard layer has a Vickers hardness of 250 Hv or more. 5. The panel pin for a cathode ray tube according to claim 3, wherein the hard layer is a nitride layer or a carbonized layer formed directly on a surface portion of the panel pin body. 6. The CRT panel pin according to claim 5, wherein the nitride layer contains at least one selected from the group consisting of Cr nitride, Fe nitride, Al nitride and Ti nitride. . 7. The CRT panel pin according to claim 5, wherein the carbonized layer contains at least one selected from the group consisting of Cr carbide, Fe carbide and Ti carbide. 8. The cathode ray tube panel pin according to claim 5, wherein said surface oxide film is formed on said nitrided layer or said carbonized layer. . 9. The panel pin for a cathode ray tube according to claim 3, wherein the hard layer comprises a coating layer formed directly on the surface of the panel pin main body or on the surface oxide film. Panel pin for CRT. 10. The CRT panel pin according to claim 9, wherein the coating layer is made of a reactive sputtering film, an ion plating film, or a sprayed film. 11. The panel pin for a cathode ray tube according to any one of claims 3 to 10, wherein the Fe-based alloy constituting the panel pin body comprises 17 to 28% by mass of Cr and 0.01 to 0.6% by mass of Al. , 0.1-0.6% by mass
Characterized by containing Ti and 0.01 to 0.6% by mass of Si, and the balance substantially consisting of Fe. 12. A step of forming a panel pin main body having a head for supporting a color selection electrode and a leg portion sealed to a glass panel and made of an Fe-based alloy; A method for manufacturing a panel pin for a cathode ray tube, comprising forming a film, removing the surface oxide film on the surface of the head, and then forming a hard layer on at least a part of the head. 13. A step of forming a panel pin main body having a head for supporting a color selection electrode and a leg sealed to a glass panel and made of an Fe-based alloy; And forming a surface oxide film only on the surface of the leg portion or on the entire surface of the panel pin body including the hard layer. 14. A step of forming a panel pin main body having a head supporting a color selection electrode and a leg portion sealed to a glass panel and made of an Fe-based alloy; A method of manufacturing a panel pin for a cathode ray tube, comprising forming a surface oxide film including the hard layer after forming the layer. 15. A step of forming a panel pin main body having a head for supporting a color selection electrode and a leg portion sealed to a glass panel and made of an Fe-based alloy; A method of manufacturing a panel pin for a cathode ray tube, comprising forming a hard layer on at least a part of the head region on the surface oxide film after forming the surface oxide film. 16. A color cathode ray tube comprising the cathode ray tube panel pin according to claim 3. Description: 17. An electron gun, a glass panel having a fluorescent film to be irradiated with an electron beam emitted from the electron gun, and a plurality of glass panels opposed to the fluorescent film with a predetermined gap and passing the electron beam. A CRT panel pin according to any one of claims 3 to 11, wherein the color selection electrode has pores or slits, and is sealed on the inner surface side of the glass panel and supports the color selection electrode. A color CRT comprising: