JPS61224246A - Color picture tube - Google Patents

Abstract

PURPOSE:To obtain a bright and flat picture image by forming at least one part in tube with alloy mainly composed of Fe containing 25-45 wt% of Ni, 0.2-10 wt% of Co, 0.3-10 wt% of Cr or partially replacing Mn and unavoidable impurities applied with black film. CONSTITUTION:The composition of Ni is set to 25-45 wt% for the purpose to lower the thermal expansion factor below 90X10<-7>/ deg.C and deviation over this range will disable production of in-tube parts material having low thermal expansion factor. In other word, clear picture image having low PD level can not be obtained. Upon exceeding over 45 wt%, 0.2% withstandability for indicat ing the moldability will increase to degrade the moldability considerably. Cr will contribute to increase the thermal expansion factor of Fe-Ni alloy while to reduce 0.2% withstandability thus to contribute considerably for improvement of moldability. Cr contained in the material has important roll for considerably reducing 0.2% withstandability of material in annealing process.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention is directed to improving display image quality by using tube parts such as shadow masks, frames, inner shields, and bimetals that have good moldability and excellent thermal characteristics. Concerning high color picture tubes.

[Technical development of the invention and its problems]

A color picture tube generally has the configuration 7 shown in FIG.

That is, the neck portion 2 constituting one end of the glass envelope 1 is provided with, for example, an in-line array of emitter guns 3, and the face of the other end of the glass envelope 1 facing the emitter gun 3 is provided. In part 4, there is a fluorescent surface 5 in which red, positive, and green phosphors are arranged in sections.
I'm begging you.

A shadow mask 6 having a large number of beam apertures is disposed close to and facing the fluorescent surface 5. This shadow mask 6 is housed via a frame 71: a locking tool 8, and an inner shield 9 is housed in the frame 7 to block the influence of earth's magnetic field.

However, in the color picture tube configured in this way, the pupil beam 11 emitted from the pupil gun 3 is deflected by a deflection device provided at the base of the neck part 2. The light is deflected by the light, passes through the aperture yxm of the shadow mask 6, and strikes the front 5 of the fluorescent light to generate fluorescent light to form a color image.

Incidentally, the shadow mask 6, the frame 7, and the inner shield 9 have better etching and formability than conventional ones, and are made of rimmed steel or rimmed steel. AJ Killed steel is formed as a composite material. However, in recent years, in order to correspond to new media in each building, color picture tubes have been made into flat-shaped tubes,
In other words, the so-called visibility and ultra-fineness of the displayed image are required, and the shadow mask 6, frame 7, and inner shield 9 made of the above-mentioned rimmed steel or AJ killed steel? Il′
Used (- means a problem has occurred.

That is, during operation of the color picture tube, the temperature of each of the above-mentioned sections rises to 30 to 100 DEG C., and so-called doming occurs due to distortion in the shape of the shadow mask due to thermal expansion, for example. As a result, a gap occurs in the relative positional relationship between the striped mask and the front of the fluorescent light, and a color shift called purity drift (PD) occurs. In particular, in germ-quality color picture tubes, the aperture diameter and aperture pitch of the M shadow mask are very small, so the relative deviation ratio becomes large.
Pipe internal parts made of n-killed @'4 material are not practical. In particular, the above-mentioned problems occurred particularly with the high curvature type color picture tube C2 which reduced image distortion and reflected external light by 7.

Therefore, conventionally, as a material for the pipe parts of this building,
N1-Fe alloys with a small coefficient of thermal expansion, such as amber (
35Ni-Fe)
-25446, JP-A No. 50-58977, JP-A-5
0-68650 etc. However,
This company's N1-Fe alloy has poor thermalization properties, and not only does it tend to accumulate heat, but it also tends to cause so-called springback, which is denting from the normal shadow mask spherical surface toward the tK subgun side. Furthermore, when the holes in the shadow mask are formed by etching, there are disadvantages in terms of etching properties and moldability, such as the fact that the diameter of the holes tends to be uneven. For this reason, there was a limit to the ability to improve the quality of color picture tubes.

[Purpose of the invention]

The present invention was made in consideration of these circumstances, and its purpose is to provide a color system that has a nearly flat screen, has little color shift, and can obtain extremely fine, bright, high-quality images. The goal is to provide picture tube video.

[Summary of the invention]

The present invention provides at least one inner part of a color picture tube, such as a shadow mask, an inner shield, a frame, and a bimetal, containing Fe containing 25 to 45 wt% of N1v.
'lz main component, 0.2~l0wt% Co, 0.3
~IQ wt% Cr, or Mn partially or totally substituted
A black film is formed on the surface of the alloy containing unavoidable impurities, thereby improving the etching formability and heat dissipation properties of shadow masks, inner shields, frames, bimetal parts, etc.! Gain,
Using this, you can get a bright, flat, and easy-to-see image with a low PD value! This is a color picture tube that can be obtained.

Here, the reason why the Ni composition amount Y is set to 25 to 45 wt% is to make the thermal expansion coefficient v90xlo'/°C as expected. It is no longer possible to obtain a material for pipe internal parts that has a low coefficient of thermal expansion. In other words, a clear image with a low PD value cannot be obtained. Furthermore, when the amount of Nj added exceeds 45 wt%, the 02% yield strength, which is a measure of the quality of the moldability, increases.
Its moldability deteriorates significantly.

For example, in the case of a shadow mask, springback occurs, and a clear image becomes difficult to obtain. At the same time, due to its poor oxidation resistance, it becomes extremely difficult to carry out the blackening treatment that is normally applied to its surface.

Regarding etching properties, when the amount of Nl increases, fine etching becomes difficult, and the inner wall of the etching hole becomes a so-called rough hole, or a large amount of N1 enters the etching solution.
The melt penetration causes problems such as a decrease in the etching rate.

Further, Cr increases the thermal expansion coefficient of the Fe-Ni alloy by 1, but on the other hand, it reduces the above-mentioned 0.2% can resistance and greatly contributes to improving its formability. Because it is kneaded, its PD value does not become worse than that of conventional amber due to the addition of Cr. This plays an important role in improving moldability, especially when obtaining a shadow mask with a high curvature.

In other words, in general, when Cr is added to a 35NI-Fe alloy and it is not annealed at temperatures above the town crystallization temperature, the crystal grains are fine, resulting in an increase in yield strength of 0.2% at room temperature, and it is difficult to maintain the curvature as a shadow mask, for example. This makes it difficult to increase the strength of the material by adding Cr. However, as in the present invention (Cr7 added 'ft: (6N
When a specific annealing treatment is applied to l-F e alloy, the amount of decrease in its 02% yield strength is the same as that of 35Nl-F without Cr addition.
The amount is significantly higher than that of e-alloy (amber). In other words, the Cr contained in the material is reduced to zero in the material during the annealing process.
．． It exhibits an important effect in greatly reducing the 2% proof stress.

Figure 2 shows the annealing temperature j versus 0,
The change in 2% proof stress is shown as characteristic A, and characteristic B is the change in 0 and 2% proof stress with respect to annealing temperature in a Cr-free 36NI-Fe alloy shown for comparison. As shown in this figure, the material for pipe internal parts according to the present invention has a higher 0.2% proof stress at room temperature, but at 500°C
When annealed with the above conditions, the 0.2% yield strength becomes sufficiently lower than that of the conventional one. For example, when annealing is carried out at 1000 to 12oO℃, the 02% proof stress of the pipe internal parts according to the present invention is 12 -, but in the case of conventional Cr-free products, 02% It has a high yield strength of about 22 Kt/xrd. Therefore, from this fact as well, it can be seen that the addition of Cr greatly contributes to the reduction of the 0.2% proof stress at annealing IL'7:16. Incidentally, there is un, which exhibits the same effect as this Cr. Therefore, part of Cr F<
It is also possible to substitute with Mn.

By the way, a color picture tube was set up using a Nyadou mask, which was formed by hydrogen annealing at 800°C and oxidized with steam to form a black oxide film on the surface of the flat mask shown in the above characteristics. When the PD value was measured for 3 minutes, it showed a small value of 95 μm. This T1
．． When similar measurements were carried out using a conventional shadow mask using Amber 7, which had been subjected to the same heat treatment, the spring puncture of the shadow mask was significant, and the color unevenness was severe. could not.

By the way, if the amount of Cr added is Q, less than 3 wt%,
As with the 35Ni-Fe alloy without the addition of Cr, the annealing temperature was set to 1.
Even if it is as high as 200℃, its 0.2% yield strength is 20K5
It will never be less than J/-. Also, the amount added is lQ
wt%, the thermal expansion coefficient is 90 x 10'
/°C and causes color shift, making it unsuitable for use in high-definition color picture tubes. In addition, if the amount of Cr added exceeds 1Qwt%, the surface (:Cr2O3
A protective film is likely to be formed, which causes disadvantages in the blackening process, such as a decrease in the surface blackening rate.

That is, Fig. 3 (2) shows the change characteristic C of 0.2% yield strength when a plant mask formed using the material for pipe internal parts according to the present invention is annealed at 1000°C in water and its coefficient of thermal expansion. The change characteristics of C and Cr are shown as parameters, using the amount of Cr added as a parameter.
%, the annealing increases the yield strength to 0.2% to 22?
It can be seen that springback can be prevented by suppressing the springback to below /-1d. Furthermore, when the amount of Cr added exceeds 1Qwt%, not only does the yield strength increase by 0.2%, but also the coefficient of thermal expansion increases, causing a drift in the PD value. Therefore, as mentioned above, it is necessary to limit the amount of Cr added to 0.3 to 10 wt%.

In addition, conventionally, 36
As an example of adding Crf to Ni-Fe alloy, JP-A-59-
There are issues such as No. 59861. However, no effort has been made to reduce the yield strength; the material is simply high-strength, and no attempt has been made to reduce the yield strength by 0.2%. Furthermore, as explained next, no blackening film is formed on the surface,
Considering all these points, it can be said that the material for pipe internal parts according to the present invention is completely different.

CO has the effect of improving etching properties and reducing the coefficient of thermal expansion. As the CTa degree increases, etching becomes difficult unless the crystal grain size is specified as No. 8 to 12 shown in JI8GO551, but if C(l) is added, etching is possible even if the grain size does not necessarily meet the grain size specifications. Furthermore, etching is possible even if the crystal orientation 2 of the rolled surface does not necessarily align with (100).Also, the coefficient of thermal expansion decreases due to the increase in CO2.
The minimum value is taken at wt% addition. Furthermore, the content of CO'&
The reason why it is set at 0.2 to 1Qwt% is that the above effects cannot be obtained outside this range.

The blackened film formed on the surface of the material described above plays an important role in improving its heat dissipation property Z, and plays a major role in lowering the FD value of the color picture tube. This heat dissipation property is determined by the degree of blackness and the roughness of the surface, and the blackened film according to the present invention is excellent in the following points.

That is, Crx1Nix2Cox, Fe, -x, -x2-
The blackening film consisting of x, 04 (0<xl, x2゜x3<3) differs from the blackening film formed on conventional Al guild steel and rimmed steel. Department fc
It has a spinel type oxide structure in which o% of Cr or Nl is substituted.

This Crx, N1x2 CoxB Fe5-x, -X,
-xsO, is less likely to contain voids due to gas or protrusions inside the film, and has excellent adhesion to the material. Furthermore, because of its high hardness, it is also effective in preventing howling caused by vibration.

Moreover, inside the color picture tube, the blackened film is difficult to peel off because Cr condenses on the metal/oxide interface, and there is a risk that it may be damaged by flakes removed by the heat of the electron gun. Furthermore, since acicular crystals are easily formed perpendicular to the mask, the surface area of the surface oxide increases, further improving its thermal emissivity. Further, Co is uniformly dissolved as a solid solution in the blackened film and is useful for increasing the hardness of the blackened film.

If the material is one in which a part of C [f is replaced with Mn, the blackening film is Cr x, Mnx, N 1x3cox4P
e3-X, -N2-X, -x, 0° (0<XI, N2.
N3. A spinel structure is obtained (N4<3), and even in such a case, the same effect is exhibited.

However, unlike Cr, Mn is often uniformly dispersed in the oxide film. In addition, when forming this blackened film,
When grass oxidation or steam oxidation methods are used, α
-Pe20B is formed, but since the film thickness is thin, it does not pose a problem.

By the way, when comparing the PD values of two color picture tubes assembled using a shadow mask made of the above-mentioned material formed on the surface of the blackened film 2 having the composition Z and a shadow mask Z that does not form a blackened film, In contrast to C2, which had a 3-minute PD value of 120 to 130 μm without a blackened film,
Blackened film! Formed one: If so, its PD value is 80μ
It was confirmed that it was as small as m. In other words, this blackened film enhances the heat dissipation effect and has a great effect in suppressing PDg. In particular, the effect of this blackening film is remarkable when forming a flattened shadow mask with a curvature of 900 m or more.

[Effects of the Invention] Thus, according to the present invention, Crf is added to a predetermined N1-re series alloy to reduce its 0.2% proof stress and improve its formability. Since the color picture tube is formed by using the sound of parts inside the tube, such as a shadow mask with improved etching properties and a black oxide film formed on its surface, it is possible to produce a bright, ultra-fine, madder quality image. can. Moreover, its moldability is good, so
It is possible to effectively obtain an image with little color shift even at the four corners of the screen, and it is possible to suppress color change even for a long-time white image. In particular, since it is possible to form a flat screen, it is possible to suppress the curvature of straight-line images, which is effective in displaying bright, high-contrast images. On the other hand, because its strength is high, it does not cause vibrations caused by low-frequency sound waves from speakers placed close to each other, and can withstand mechanical shocks etc., so that images without fluctuation can be obtained. The effect is produced.

[Embodiments of the invention]

Next, a first embodiment of the present invention will be explained.

[Example-1 First, 32% Nl and Fey were used as main components, Coy 5%, C
Contains 2 wt% r, and removes C and sI as additive components. Ro, 01 wt%, P and 82 are each 30.0
An ingot of an alloy containing 0.05 wt% was prepared, and the ingot was completely repeatedly annealed and cold-worked to produce a plate with a thickness of Q and 13 m. Thereafter, a photoresist was applied to this plate material, and after drying, a film having a reference pattern in the form of slots or dots was adhered to both sides of the plate, and the photoresist was exposed and developed. This development dissolves and removes the unexposed portions of the photoresist. After that, the remaining photoresist was hardened by Y-burning, and then etched with a ferric chloride solution.
Thereafter, the remaining resist was removed with hot alkali to produce a flat mask that would serve as a shadow mask original plate.

Thereafter, the flat mask was cleaned, sheared, and then vacuum annealed at 10' torr and 1150''C.

The thermal expansion coefficient at this time is 22x 10'/'C10,
The 2% yield strength was 21 Kp/-. Thereafter, a formed mask with a curved radius of 1000 m was obtained by pressing.

After this formed mask was subjected to acid treatment, trichlene cleaning, and water washing treatment, it was heated and oxidized in a 30% 0□-N, humid atmosphere of 670° C. for 30 minutes.

By using the shadow mask t-spot welding produced in this way, a frame produced by a similar method (
Second installation, this unit was attached to the panel via bimetal. After that, add red to match the hole in the shadow mask above.
After applying blue and green phosphors, AJ vapor deposition, and DAG coating, the inner shield was installed, and the funnel at the rear of the envelope with the cylindrical gun was fully connected to this panel, and its internal gate was installed. A color picture tube was manufactured by evacuating the air. The above inner shield was also manufactured using the same material.

[Example-21 30%N2 and Fei main components, Co f 5 wt%
, Crf' 1wt%, C and sIin as incidental components, oiwt%, respectively, and P and S, respectively.
．． A flat mask was manufactured in the same manner as [Example-1] using an ingot of an alloy containing 0.005 wt%. Then, this flat mask Y was hydrogen annealed at 1150°C. At that time, the thermal expansion coefficient was 41.0xlO'/°C, and the 0.2% proof stress was 20.49/-. A flat mask having this characteristic was molded and obtained as a shadow mask, and this was used to complete a color picture tube.

[Example-3 32% Fe'i and Co'Q 5 wt%
Contains 14wt% of Cr, and as incidental components, C and 81y<0.01wt% each, and P and 8y<0.01wt% each.
A flat mask was manufactured in the same manner as [Example 1] using an alloy ingot containing 1% of 005w. and,
This flat masker was hydrogen annealed at 900°C. At this time, the thermal expansion coefficient was 3s x 10'/°C, and the 0.2% proof stress was 16.0KP/-. A flat mask with these characteristics was molded to obtain a shadow mask 7, which was used to complete a color picture tube.

As a result of examining the color picture tubes of Examples 1 to 3 obtained in this manner by examining two FD lines at the four corners, it was found that the distance between the mouth and the mouth of the conventional one was about 120 to 130 μm. It showed a small value. Also PD
The time it takes to return to the original normal state after this occurs is about half (about 2 minutes and 30 seconds) compared to the conventional 22. Also that II! Ultra-fine, high-quality images with no color shift were obtained over the entire 11 sides. Furthermore, since the etching holes were not rough holes, there was no uneven color on the screen.

In addition, although the formation of a shadow mask was explained here as an example,
It is also possible to obtain a color picture tube by similarly manufacturing the inner shield, frame, bimetal, etc. others,
The present invention can be modified and implemented in various ways without departing from the spirit thereof.

[Brief explanation of drawings]

Figure 1 is a diagram showing the schematic structure of a color picture tube Z (not shown), Figure 2 is a diagram showing changes in 0 and 2% proof stress with respect to annealing temperature, and Figure 3 is a diagram showing the coefficient of thermal expansion for the addition needle of C' and 0.2%. It is a diagram showing changes in % proof stress. 1... Envelope, 3... Ishigun, 6...
・Shadow mask, 7...Frame, 9...Inner shield. Agent Patent attorney Kensuke Chika (and 1 other person) Figure 1 Electricity 1 degree (°C) Figure 2

Claims (5)

[Claims] (1) The main component is Fe containing 25 to 45 wt% Ni,
0.2-10wt% Co, 0.3-10wt% Cr
1. A color picture tube characterized in that it is made of an alloy containing Mn, or Mn replacing a part thereof, and unavoidable impurities, and has an inner tube part whose surface is coated with a black film. (2) The color picture tube according to claim 1, wherein the tube internal components include a shadow mask, an inner shield, a frame, and a bimetal. (3) The color picture tube according to claim 1, wherein the black film is formed as an oxide of an alloy. (4) The oxide forming the black film is Crx_1Nix_2
Cox_3Fe_3-x_1-x_2-x_3O_4(
0<x1, x2, x3<3) or Mnx_1Ni
x_2Cox_3Fe_3-x_1-x_2-x_3O
_4 (0<x_1, x_2, x_3<3) or C
rx_1Mnx_1Nix_3Cox_1Fe_3-x
_1-x_2-x_3-x_4O_4(0<x1, x2
, X3, x4<3). (5) The shadow mask, which is an internal part of the pipe, has a curvature of 9
Claim 1, which is molded to a size of 00 mm or more
Color picture tube as described in section.