JPH08167388A - Shadow mask and cathode ray tube using this shadow mask - Google Patents

Abstract

PURPOSE: To greatly improve the performance and reliability of a cathode-ray tube(CRT) by forming a specific amount of the metallic oxide in the grain inside and grain boundary on a side part of an electron beam passing hole of a shadow mask made of invar and the surface having an electron beam shielding surface. CONSTITUTION: The amount of the grain inside and grain boundary residual oxide after working a member made of invar is expressed by the generated amount of 0.05-17.0 units of Ni and Fe oxide, 0.01-3.9 units of Fe and Cr oxide, 0.04-5.5 units of Mn and Cr oxide, and 0.03-13.0 units of Mn and Fe oxide in terms of Cr oxide generated in the grain inside and grain boundary. The inver material is used where amorphous carbon (α-C) whose Raman park is detected at 1290-1310cm<-1> , 0.08-7.5 units of generated compound of each oxide and three or more kinds of chemical species of these compounds are formed. The performance and the reliability of a CRT 9 are greatly improved thereby.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron beam control shadow mask made of an amber material in which a certain amount of a metal oxide film is controlled and formed on the surface of a shadow mask, and a cathode ray tube provided with this shadow mask.

[0002]

2. Description of the Related Art Normally, in a color cathode ray tube, a shadow mask member for assembling a shadow mask made of an amber material is cleaned by removing press oil and the like remaining on the surface after molding parts with an organic solvent or a water-soluble cleaning agent. After assembling the product, the cleaned product which has been washed and removed with an organic solvent or a water-soluble cleaning agent is subjected to high temperature heat treatment.

That is, in order to secure the electrical characteristics required for a cathode ray tube, when a part of a shadow mask made of an amber material for controlling an electron beam is irradiated with an electron beam, a trace amount from an electron beam irradiation site is obtained. In order to prevent the deterioration of the electric characteristics due to the generation of the gas and to secure the desired electric characteristics and mechanical characteristics, various cleaning treatments and the above treatments are further subjected to high temperature heat treatment.

Conventionally, electrode parts, shadow masks and the like used in this type of cathode ray tube are washed with an organic solvent or a water-soluble cleaning agent after the press molding of the processed product to remove the press oil and the like, and further various products are further cleaned. As far as possible by the high temperature heat treatment cleaning method, it has been used as a highly cleaned product in which impurities on the surface of the above-mentioned various used metal parts or metal members are reduced.

In this cleaning treatment, the parts are washed a plurality of times with various organic solvents or water-soluble detergents and ion-exchanged pure water, and then subjected to various high-temperature heat treatments. It was

[0006] Since such conventional cleaning treatments for metal parts and metal members are well known, no reference is given thereto.

[0007]

In the cleaning process according to the prior art described above, carbon is reduced particularly in various impurities remaining on the surfaces of metal parts such as shadow masks and metal members. Used to secure the electrical characteristics required for cathode ray tubes by subjecting the product to various high-temperature heat treatments. Chemical species of oxide for which a metal oxide film is desired to be formed on each surface of metal parts and metal members in a controlled manner. It was difficult to control the film quality, the amount of oxide film formed, and the oxide film structure composed of the chemical species.

That is, in the past, since the washed product removed by washing with the organic solvent or the water-soluble cleaning agent was rinsed with the organic solvent or water for a long time in order to make it as clean as possible, it was necessary to wash the metal parts and metal members. Since a certain amount of carbon could not be left on the surface with good reproducibility, the metal oxide film is then subjected to various high-temperature heat treatments, so that the metal oxide film has a desired oxide chemical species and a film quality composed of the chemical species. However, it was difficult to control and form the oxide film formation amount and the oxide film structure with good reproducibility.

Electrical characteristics required for a cathode ray tube by allowing a certain amount of a trace amount of carbon to remain on each surface of the cleaned metal parts or metal members with good reproducibility and subjecting the processed product to various high temperature heat treatments thereafter. The chemical species of the oxide that consumes the metal oxide film and the film quality of the chemical species that consumes the metal oxide, the amount of oxide film formed, and the oxide film structure are controlled and formed on each surface of the metal component or metal member As a result of conducting various studies on the above, as a result of removing and cleaning the press oil or the rust preventive agent of the metal parts and metal members after press molding, the cleaned product washed with the organic solvent or the water-soluble cleaning agent is further washed with the organic solvent or It is necessary to optimize the concentration of the organic solvent at the time of rinsing with water and perform a treatment to shorten the rinsing cleaning time by about 10% to 15%.

By the above-mentioned treatment, various kinds of high-temperature heat treatment are applied to the treated product in which a certain amount of carbon remains on the surface of the metal component or metal member, and the metal component or metal member is assembled and manufactured. As a result, the desired electron emission characteristics of the cathode ray tube can be obtained.

However, in a cathode ray tube assembled and manufactured by using the object to be treated in which a certain amount of carbon remains on the surface of the metal part or the metal member by the above-mentioned method, there are cases in which the electric characteristics vary. , Optimization of the rinse cleaning time and rinse with the organic solvent or water to rinse the removed product washed with an organic solvent or water-soluble cleaning agent to leave a certain amount of carbon on the surface of metal parts or metal members In the case of washed products that have been washed away with a mild detergent, difficult measures such as optimizing the concentration of the water-soluble detergent used have been required.

A first object of the present invention is to control the rinsing and cleaning time with an organic solvent or water when further cleaning the cleaning product which has been removed by cleaning with an organic solvent or a water-soluble cleaning agent, and apply it to the surface of the metal material. An object of the present invention is to provide a shadow mask made of an amber material for controlling an electron beam of a cathode ray tube, which can solve the problems of the above-mentioned conventional techniques by keeping a certain amount of carbon and can secure desired characteristics.

A second object of the present invention is to provide a cathode ray tube equipped with the above shadow mask.

[0014]

In order to achieve the first object, the first invention according to claim 1 is such that the constituent ratio of the contained elements is S: less than 0.005 wt%, P and C: 0.
Less than 015 wt%, Al: less than 0.07 wt%, Cr:
Less than 0.15 wt%, Si: less than 0.25 wt%, M
n: 0.20 to 0.45 wt%, Ni: 35.3 to 3
7.7 wt%, an amber material with the balance being Fe, after processing and molding, in the grains and on the surface of the grain boundaries and in the oxide distributed in the depth direction from the surface, inside the grains of the metal of the surface layer and grains of the metal Fe-based oxide (Fe ₂ O ₃ and / or Fe ₃ O ₄ ) generated in the boundary, Ni-based oxide (NiO), and M
Residual oxides formed after dissolution of n-type oxide (MnO ₂ ) by wet pretreatment using acid such as hydrochloric acid and / or dry pretreatment using Ar ⁺ ions are generated in the above-mentioned grains and grain boundaries. When the amount of the Cr-based oxide (Cr ₂ O ₃ ) is 1, the amount of Ni and Fe-based oxide (NiFe ₂ O ₄ ) produced is 0.05 to 17.0. The amount of oxide (FeCr ₂ O ₄ ) produced is 0.01 to 3.9, the amount of Mn and Cr oxide (MnCr ₂ O ₄ ) produced is 0.04 to 5.5, and Mn and Fe Compounds of oxide (MnFe ₂ O ₄ ) production amount of 0.03 to 13.0, amorphous carbon whose Raman peak is detected at 1290 cm ^{−1 to} 1310 cm ⁻¹ α-C) and each of the above oxides. The production amount of 0.08 to 7.5, and 3 or more chemical species of the above compounds are formed. And characterized by using the members material.

In order to achieve the first object,
A second invention described in claim 2 is the first invention,
The generation amount of the chemical species formed in the grain and the grain boundary of the shadow mask which is subjected to the high temperature heat treatment after the processing is 0.4 to 0.9 in the grain with respect to the grain boundary 1, respectively. The above-mentioned production amount is 1.05 to 5.
0, the above-mentioned production amount is 1.04 to 1.0 in the grain with respect to the grain boundary 1.
3.9, the above-mentioned production amount is 1.0 inside the grain with respect to 1 grain boundary
2 to 3.6, the amount of generation is 1.01 to 2.9 in the grain with respect to the grain boundary 1, the amount of generation is 0.3 to 1.9 in the grain with respect to the grain boundary 1, Is characterized in that.

Further, in order to achieve the above first object, the third invention according to claim 3 is such that the irregularities inside the grains of the metal oxide or the like are 0.05 to μm, and the irregularities at the grain boundary portion are Is 0.
It is characterized in that it is 05 to 1.5 μm.

In order to achieve the above-mentioned second object, a fourth aspect of the present invention provides a panel portion which is an image screen, a neck portion which houses an electron gun, and a panel portion and a neck portion. Fluorescence is formed by coating the inner surface of the panel section through the electron beam passing holes of the shadow mask made of an amber material for controlling the electron beam, which is composed of a funnel section connected to each other and which is emitted from an electron gun on the funnel section. A cathode ray tube having a deflection yoke for scanning the surface thereof, wherein the shadow mask is used as the shadow mask.
The shadow mask described in 2 or 3 is used.

[0018]

In order to stabilize and improve the variation in the electron emission characteristics of the cathode ray tube, the temperature of the Ni cap constituting the cathode by energizing the cathode ray tube is 730 ± 5.
During operation at ° C, a certain amount of magnesium (Mg) added as an activator in the Ni cap must be stably diffused and evaporated through the grain boundaries of the Ni cap for a long time, and at the same time, the operation of the cathode ray tube. When the surface of the shadow mask made of amber material for controlling the electron beam and the side surface of the electron beam passage hole are irradiated with the electron beam, a small amount of gas is emitted from the electron beam irradiation surface, which causes electron emission. There is a case where the characteristics deteriorate, and the electron beam passage hole is mechanically deformed due to the prevention of the deterioration of the electron emission characteristics and the temperature rise of the surface of the shadow mask made of amber material irradiated with an electron beam, thereby causing a color change. Prevention of slippage deterioration is essential.

That is, when the cathode ray tube is operated under the above conditions, a slight amount of gas is not emitted from the electron beam irradiation surface during operation, and mechanical deformation is prevented even though the electron beam passage hole increases in temperature. In order to do so, it is necessary to form a metal oxide film of controlled film quality on the surface of the shadow mask made of amber material, which can eliminate the above-mentioned drawbacks.

As a countermeasure, for example, among various components for forming an electron beam control unit for a color cathode ray tube,
For the electron beam controlling shadow mask portion having electron beam passage holes, (1) after the press oil used in the organic solvent or the water-soluble cleaning agent for the shadow mask made of amber material after press molding is removed by washing, After cleaning the amber material shadow mask after cleaning, the rinse cleaning time with an organic solvent or water is made shorter than that in the conventional case, and then the amber material shadow mask is subjected to, for example, in H ₂ . Alternatively, after annealing heat treatment at a high temperature of 900 ° C. in vacuum, N ₂
Heat treatment again at a high temperature of 700 ° C. in a medium atmosphere.

(2) Alternatively, when cleaning the amber material shadow mask after press molding with a water-soluble cleaning agent, the concentration of the water-soluble cleaning agent in the water-soluble cleaning liquid used is higher than the conventional concentration. After rinsing with the above liquid, the shadow mask made of amber material is washed with H.
After heat treatment at 900 ° C in an atmosphere of ₂ or vacuum at a high temperature of 900 ° C, heat treatment is performed again at a high temperature of 700 ° C in an atmosphere such as N ₂ to adhere and remain on the surface of the shadow mask made of amber material. Among the trace amount of impurities, carbon is present on the metal surface of the above-mentioned metal component, inside the grain on the side surface of the electron beam passage hole, and at grain boundaries.
For example, the shadow mask made of amber material in which carbon in an amount of 0 ⁻⁴ g / 2 μm ² to 10 ⁻⁹ g / 2 μm ² is left is
After annealing heat treatment at a high temperature of 900 ° C in ₂ or in vacuum, and then heat treatment again at a high temperature of 700 ° C in an atmosphere such as N ₂ , the surface of the shadow mask made of amber and the electron beam passage holes It is possible to obtain a shadow mask made of amber material having a film quality and having various oxide shapes and chemical species formed to obtain desired characteristics on the side grain boundaries and inside the grains.

The shadow masks of the first to third inventions are film-type shadow masks having the above-mentioned various oxide shapes and chemical species. By using this shadow mask to construct a cathode ray tube, It is possible to secure desired electrical characteristics.

[0023]

Embodiments of the present invention will now be described in detail with reference to the drawings.

FIG. 1 is a sectional view for explaining the structure of a color cathode ray tube for explaining one embodiment of the cathode ray tube according to the present invention, in which 1 is a panel portion, 2 is a neck portion, 3 is a funnel portion, 4 is a phosphor screen, 5 is an amber material shadow mask, 6 is a mask frame, 7 is a magnetic shield, 8 is a suspension spring, 9 is an electron gun, 10 is a deflection yoke, and 11 is an external magnetic device.

In FIG. 1, the color cathode ray tube comprises a panel portion 1 which is an image screen, a neck portion 2 for accommodating an electron gun, and a funnel portion 3 connecting the panel portion and the neck portion. Have an electron gun 9
A deflection yoke 10 for scanning the three electron beams B emitted from the electron beam B through a hole (electron beam passage hole) of a shadow mask 5 made of an amber material for electron beam control and onto a fluorescent screen 4 formed by coating on the inner surface of the panel portion 1. Is installed.

The electron gun housed in the neck 2 is
It is composed of a cathode structure, a control electrode, a focusing electrode, an accelerating electrode and the like. The cathode structure uses a cathode cap, and an electron beam from an electron emitting substance composed of an alkaline earth salt applied to the cathode cap is modulated by a signal applied to a control electrode, and a desired cross section is passed through a focusing electrode and an accelerating electrode. The shape and energy are applied to the fluorescent surface 4 to cause it to strike the fluorescent surface 4 to emit light.

The shadow mask 5 is made of an amber material, and an electron beam from an electron emitting substance composed of an alkaline earth salt applied to the cathode cap is projected onto the phosphor screen 4 through the holes of the shadow mask 5 made of an amber material. To make it emit light.

On the way to reach the phosphor screen 4, the electron beam is deflected in the horizontal and vertical directions by a deflection yoke 10 attached to the transition portion of the neck portion 2 and the funnel portion 3, and passes through a shadow mask 5 serving as a color selection electrode to cause fluorescence. The surface 4 is reached and a two-dimensional image is formed on the fluorescent surface 4.

FIG. 2 is an explanatory view of a configuration example of an in-line type color electron gun and a shadow mask used in the color cathode ray tube described in FIG. 1 and its operation. FIG. 2 (a) is a side view showing a partially broken electron gun. (B) is a schematic view of the operation of the electron gun and the shadow mask.

As shown in FIG. 3A, this electron gun has a cathode, a control electrode, a focusing electrode, and an accelerating electrode arranged in a predetermined order and position. It comprises a stem portion 12 in which pins are planted, a shield cup 13, a getter 14, a contact spring 15 and the like, and is housed in the neck portion 2 of FIG.
The cathode and each electrode part of the electron gun surrounded by the dotted line A in (a) are the cathode assembly 30 and the first electrode assembly as shown in (b).
Grid G ₁ , second grid G ₂ , third grid G ₃ ,
4th grid G ₄ , 5th grid G ₅ , 6th grid G
_The cathode structure 30 and the first grid G ₁
The second grid G ₂ constitutes a so-called three-pole portion, and the second grid G ₂ , the third grid G ₃ , the fourth grid G ₄ , the fifth grid G ₅ , and the sixth grid G ₆ constitute a focusing accelerating portion. To do.

Electron beam B generated at cathode assembly 30
Is taken in by the three-pole part, and given the required cross-sectional shape and energy in the focusing acceleration part, and is directed in the direction of the phosphor screen 4.

The electron beam B is color-selected by a shadow mask 5 arranged immediately in front of the phosphor screen 4, and is landed on a predetermined phosphor mosaic constituting the phosphor screen to emit light.
Play the video.

In the schematic structure of the cathode structure shown in FIG. 3B, 31 is an electron emission layer, 32 is a cathode cap, 33 is a heater sleeve, and 34 is a heater.

In the figure, a heater 34 is inserted and installed in the heater sleeve 33.
Cathode cap 3 made of nickel (Ni) at one end of
2 are fitted and fixed to form an emitter.

On the surface of the cathode cap 32, an electron emitting material (Ba, Ca, S) mainly composed of alkaline earth salt is formed.
r) O is applied to form an electron emission layer (emitter) 31.

The electron emission layer 31 generates thermoelectrons by the heating of the heater 34, is taken into the electrode of the electron gun, and is focused and accelerated to emit light from the phosphor screen.

The shadow mask 5 is arranged close to the phosphor screen 4, and its electron beam passage hole 5a is used to select the color so that the three electron beams B impinge on a predetermined phosphor.

FIG. 3 shows a shadow mask obtained by performing a high temperature heat treatment after depositing a certain amount of a trace amount of carbon on the grain boundaries and inside the grain of the metal material after cleaning, and a cathode ray tube assembled using this shadow mask. FIG. 4 is a process diagram for explaining the outline of the manufacturing process of 1., 100 is a primary cleaning process, 200 is a secondary cleaning process, 300 is a drying process, and 400 is an annealing / blackening process (high temperature heating annealing process → high temperature heating blackening process). , 500
Is an inspection process (dimension measurement → surface shape measurement process → measurement confirmation of chemical species of generated oxide and its generation amount on the surface of high temperature heating annealed product / high temperature heating blackened product) 600 is a shadow mask assembly Process 700 is a cathode ray tube manufacturing process,
Reference numeral 800 is a process for inspecting the electrical characteristics of the cathode ray tube.

In the figure, step 100 to step 500
Is a pretreatment for cleaning when the pressed product of the shadow mask made of amber material according to the present invention is washed with a water-soluble cleaning agent, dried, and then annealed / blackened by high temperature heat treatment and the above-mentioned treatment. This is an example of the inspection process such as the measurement of the surface shape of the product and the measurement confirmation of the chemical species of the produced oxide and the amount of the produced oxide on the surface of the product subjected to the high temperature heat annealing treatment and the high temperature heat blackening treatment.

In the primary cleaning step 100, the pressed product of the shadow mask made of amber material shown in FIG. 5 at 5 is filled with a cleaning solution containing 1% of a water-soluble detergent in two cleaning tanks in order, After spray cleaning for 6 minutes in each of the first tank to the second tank, each tank is spray rinse cleaned for 6 minutes in an ion exchange pure water cleaning tank composed of two tanks of the third tank to the fourth tank.

Further, in the secondary cleaning step 200, the cleaning solution containing 1% of the aqueous cleaning agent containing the primary cleaning treatment product cleaned in the primary cleaning step 100 is put into two cleaning tanks in order, and After spray cleaning for 6 minutes for each of the 5th tank to the 6th tank, each tank is spray rinsed for 6 minutes in an ion exchange pure water cleaning tank consisting of 2 tanks of the 7th tank to the 8th tank, and in the drying step 300 dry.

First cleaning step 100 to second cleaning step 2
For the cleaning in each cleaning step of No. 00, the detergent concentration and the cleaning time for each tank were washed at a value of one half of the known condition that is conventionally used, In the drying step 300, a very small amount of the water-soluble detergent is left on the surface of the shadow mask.

In the high temperature heat treatment step 400, annealing and blackening treatment (high temperature heating annealing step → high temperature heating blackening step) are performed, and then, in the measuring step 500, the grain boundaries and the inside of the shadow mask surface of the amber material of the treated product And confirm the measurement of the chemical species of oxides produced on the surface of the high temperature heat annealed products and the high temperature heat blackened products and the amount of the oxides produced.

The shadow mask made of amber material is assembled into a shadow mask structure made of amber material in a cathode ray tube member assembling step 600, and then a cathode ray tube manufacturing step 70.
At 0, it is installed in a cathode ray tube. The electrical characteristics of the assembled cathode ray tube are measured in the shipping inspection process 800.

From the measurement / inspection results, the electron emission characteristics of the cathode ray tube satisfy the desired initial characteristics, and are defined even if the cathode ray tube extracted from the cathode ray tube for which the characteristic measurement / inspection has been completed is operated for a long time. It was confirmed that it could operate for a time and showed good electron emission characteristics.

FIG. 4 shows the grain boundaries and the grain boundaries of the metal oxide formed on the surface of the pressed amber material of the shadow mask according to the present invention, which is subjected to degreasing cleaning, rinse cleaning, and then high temperature heat treatment before hydrochloric acid treatment. FIG. 6 is a copy of an electron micrograph for explaining an example of measuring the surface shape of FIG.

In the figure, (a) is the surface shape inside the grain,
(B) shows an electron micrograph of the surface shape of the grain boundary at each 20,000 times.

FIG. 5 is a diagram of a shadow mask according to the present invention.
It is explanatory drawing of an example of the laser Raman measurement result for confirming the chemical species of the metal oxide formed in the surface in the grain shown in (a) before hydrochloric acid treatment.

FIG. 6 is a diagram of a shadow mask according to the present invention.
It is explanatory drawing of an example of a laser Raman measurement result for confirming the chemical species before the hydrochloric acid treatment of the metal oxide formed on the surface of the grain boundary shown in (b).

FIG. 7 is a diagram of a shadow mask according to the present invention.
4A and 4B are explanatory views of an example of measurement results for confirming the chemical species of the metal oxide formed in the grains after the hydrochloric acid treatment shown in FIG. 3, in which (a) is a copy of a micrograph and (b) is a laser. It is explanatory drawing of a Raman measurement result. FIG. 8 is an explanatory view of an example of measurement results for confirming the chemical species of the metal oxide formed at the grain boundaries shown in FIG. 6 of the shadow mask according to the present invention after the hydrochloric acid treatment. A copy of a micrograph,
(B) is an explanatory view of a laser Raman measurement result. Figure 9
Of the shadow mask according to the present invention shown in FIGS. 5 and 6, which is formed in the grain and at the grain boundary in the example of the result of the microscopic laser Raman measurement for confirming the chemical species of various metal oxides before the hydrochloric acid treatment of the metal oxide. an illustration of an example of the in which Cr ₂ O ₃ of the amount of the confirmation measurement results are.

FIG. 10 shows the inside of an example of the result of microscopic laser Raman measurement for confirming the chemical species of various metal oxides after the hydrochloric acid treatment of the metal oxides shown in FIGS. 8 and 9 of the shadow mask according to the present invention. an example of the amount of check measurements of formed MnFe ₂ O ₄ is an explanatory view of.

FIG. 11 shows the time from turning on the power of the color cathode ray tube using the shadow mask according to the present invention to the time when an image is displayed on the image display screen and the formation inside and inside the grain boundary of the shadow mask. of the metal oxide is an explanatory view of the relationship between the Fe ₃ O ₄ formed thickness.

From the results shown in FIGS. 4 to 11, the pretreatment for cleaning the shadow mask made of amber material for controlling the electron beam for the color cathode ray tube in steps 100 to 400 of FIG. By subjecting the treated product to a heat treatment at a high temperature, it is possible to confirm that a desired metal oxide film quality is formed in the grain boundaries and within the grains of the shadow mask surface made of amber material. According to the method, a desired metal oxide is formed in the grain boundaries and inside the grain of the surface of the shadow mask made of amber material.

According to the present embodiment, the amber material is heat-treated after treating the content concentration of the water-soluble detergent in the cleaning liquid and the cleaning time at the time of 1.5 times or 2 times that of the conventional method, respectively, as described above. The initial electron emission characteristics of the cathode ray tube can be maintained within the required characteristic range even if the shadow mask made of the electron beam is irradiated with an electron beam, and the required life characteristics are satisfied even if it is operated for a long time. In addition, it is possible to manufacture high-quality cathode ray tubes in large quantities.

[0055]

As described above, among the metal electrode parts constituting the color cathode ray tube, the shadow mask made of amber material for electron beam control has the structure of the present invention. It is possible to form a certain amount of metal oxide in the grain boundary and grain boundary of the surface of the electron beam passage hole and the electron beam shielding surface of the cathode ray tube, and to greatly improve the performance and reliability of the cathode ray tube. Can be achieved.

[Brief description of drawings]

FIG. 1 is a sectional view illustrating a structure of a color cathode ray tube for explaining an embodiment of a cathode ray tube according to the present invention.

FIG. 2 is an explanatory diagram of a configuration example of an in-line type color electron gun and a shadow mask used in the color cathode ray tube described in FIG. 1 and its operation.

FIG. 3 is a schematic process diagram illustrating an example of a pretreatment method for cleaning a shadow mask made of amber material using a water-soluble cleaning agent.

FIG. 4 is a grain boundary and a surface inside a grain of a metal oxide formed on the surface of the pressed amber material forming the shadow mask according to the present invention, which is subjected to degreasing cleaning, further rinse cleaning, and then high temperature heat treatment before hydrochloric acid treatment. It is a mimicking figure of the electron micrograph explaining an example which measured the shape.

FIG. 5 is an explanatory view of an example of a laser Raman measurement result for confirming the chemical species before the hydrochloric acid treatment of the metal oxide formed on the intragranular surface shown in FIG. 4 (a) of the shadow mask according to the present invention. Is.

FIG. 6 is an explanatory diagram of an example of a laser Raman measurement result for confirming the chemical species of the metal oxide formed on the surface of the grain boundary shown in FIG. 4B of the shadow mask according to the present invention before the hydrochloric acid treatment. Is.

7 is an explanatory view of an example of measurement results for confirming the chemical species after the hydrochloric acid treatment of the metal oxide formed in the grains shown in FIG. 5 of the shadow mask according to the present invention, FIG. Is a copy of a micrograph, and (b) is an explanatory diagram of a laser Raman measurement result.

8 is an explanatory view of an example of measurement results for confirming the chemical species of the metal oxide formed on the grain boundaries shown in FIG. 6 of the shadow mask according to the present invention after the treatment with hydrochloric acid, FIG. Is a copy of a micrograph, and (b) is an explanatory diagram of a laser Raman measurement result.

FIG. 9 shows an example of the results of microscopic laser Raman measurement for confirming the chemical species of various metal oxides before the hydrochloric acid treatment of the metal oxides shown in FIGS. 5 and 6 of the shadow mask according to the present invention. an example of the amount of check measurements of Cr ₂ O ₃ formed on the field is an explanatory view of.

10 is a diagram of a shadow mask according to the present invention, which is formed in an inner grain of an example of a microscopic laser Raman measurement result for confirming chemical species of various metal oxides after hydrochloric acid treatment of the metal oxides shown in FIGS. 8 and 9. FIG. and is an explanatory diagram showing an example of the MnFe ₂ O ₄ of the amount of check measurements.

FIG. 11 is a diagram illustrating the time from when the color cathode ray tube using the shadow mask according to the present invention is turned on to the time when an image is displayed on the image display screen, the metal formed in the grains and the grain boundaries on the surface of the shadow mask. FIG. ₄ is an explanatory diagram of a relationship with the film thickness of Fe ₃ O ₄ formed among oxides.

[Explanation of symbols]

 1 panel part 2 neck part 3 funnel part 4 phosphor screen 5 shadow mask made of amber material 6 mask frame 7 magnetic shield 8 suspension spring 9 electron gun. 10 Deflection yoke 11 External magnetic device.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kyomi Mori 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd. Electronic Device Division (72) Inventor Toshikazu Morishita 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd. Electronic Devices Within the business unit

Claims (4)

[Claims] 1. The composition ratio of contained elements is S: 0.005 wt.
%, P and C: less than 0.015 wt%, Al:
Less than 0.07 wt%, Cr: less than 0.15 wt%, S
i: less than 0.25 wt%, Mn: 0.20 to 0.45 w
t%, Ni: 35.3 to 37.7 wt% with the balance being Fe
Of a Fe material formed in the surface of the metal grains and in the grain boundaries of the metal in the surface of the grain boundaries and the oxides distributed in the depth direction from the surface after processing and shaping the amber material consisting of Wet pretreatment of oxides (Fe ₂ O ₃ and / or Fe ₃ O ₄ ), Ni-based oxides (NiO), and Mn-based oxides (MnO ₂ ) with an acid such as hydrochloric acid and / or Ar ⁺
When the residual oxide after dissolution in the dry pretreatment using ions etc. is set to 1 for the Cr-based oxide (Cr ₂ O ₃ ) generated in the above-mentioned grains and grain boundaries, Ni and Fe-based The amount of oxide (NiFe ₂ O ₄ ) produced is 0.05 to 17.0, the amount of Fe and Cr oxide (FeCr ₂ O ₄ ) produced is 0.01 to 3.9, and Mn and Cr The amount of oxide (MnCr ₂ O ₄ ) produced is 0.04 to 5.5, the amount of Mn and Fe-based oxide (MnFe ₂ O ₄ ) produced is 0.03 to 13.0, 1290 cm ^{−1 to} 1310 cm. -A Raman peak is detected at ^{-1. The amount} of amorphous carbon) α-C) and each of the above-mentioned oxide compounds produced is 0.08 to 7.5, and three or more chemical species of the above-mentioned compound are formed. A shadow mask using the above-mentioned amber material. 2. The generation amount of the chemical species formed in the grain and in the grain boundary of the shadow mask which has been subjected to the high temperature heat treatment after the processing according to claim 1, respectively. Intragranular 0.4-0.
9. The above-mentioned production amount is 1.05 to 5.
0, the above-mentioned production amount is 1.04 to 3.
9. The above-mentioned generation amount is 1.02 to 3.
6. The above-mentioned generation amount is 1.01-2.
9. The above-mentioned production amount is 0.3-1.
9. A shadow mask characterized by: 3. The unevenness in the grain of the metal oxide or the like is 0.05 to μm, and the unevenness in the grain boundary portion is 0.05 to 1.5 μm. Shadow mask. 4. A panel unit, which is an image screen, a neck unit for accommodating an electron gun, and a funnel unit connecting the panel unit and the neck unit, and three electrons emitted from the electron gun to the funnel unit. A cathode ray tube equipped with a deflection yoke for scanning a beam onto a phosphor screen coated and formed on an inner surface of a panel section through an electron beam passage hole of an electron beam controlling amber material shadow mask, wherein the shadow mask is used as the shadow mask. Alternatively, a cathode ray tube using the shadow mask described in 3.