JPH06279946A - Shadow mask material having excellent etching property, its intermediate material, its production, production of shadow mask, and cathode ray tube - Google Patents

Abstract

PURPOSE:To provide the process for production of the high-fineness shadow mask material having a good perforating property by etching. CONSTITUTION:The shadow mask material having >=85% {100} bearing integration degree and fibrous rolled structure under microscopic observation within the section perpendicular to the transverse direction of the material; the shadow mask having <=0.6mum Ra surface roughness of the etched surface by etching for the purpose of forming apertures for passage of electrons; the shadow mask material having the integration degree similar to the above, >=3 average aspect ratio of the crystal grains in the similar microscopic observation and >=130 Vickers hardness; the intermediate material for the shadow mask material of <=30% change in the {100} bearing integration degree before and after final annealing at <=850 deg.C; the process for production of the shadow mask material to execute >=85% cold rolling and annealing at >=700 deg.C and to execute cold rolling at a rolling rate of not exceeding the rolling rate of the cold rolling mentioned above and annealing at the temp. of not exceeding 850 deg.C and the cathode ray tube formed by using the materials mentioned above are provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to Fe-N for shadow masks.
The present invention relates to an i-based amber alloy, particularly to a shadow mask material having excellent etching properties, an intermediate material therefor, a method for producing the shadow mask material, a method for producing the shadow mask, and a cathode ray tube using these shadow masks or shadow mask materials. Is.

[0002]

2. Description of the Related Art Recently, aluminum-killed low-carbon iron materials (hereinafter referred to as AK
Material), Fe-Ni-based amber alloys with low thermal expansion characteristics are becoming popular for use in consumer televisions and cathode ray tubes for high-definition displays. However, it is known that the Fe-Ni alloy has a poorer etching piercing property than the AK material. Especially in recent ultra-high definition shadow masks, if there are subtle morphological differences in the etching holes (surface roughness of the etching surface, hole shape error), the appearance of the mask becomes uneven and the appearance of the electron beam is reduced when assembled into a cathode ray tube. This is one of the factors that induce scattering and deteriorate the image quality.

Regarding a shadow mask material requiring a precision etching process, as a compositional improvement, Japanese Patent Publication No. 2-5197
No. 3, JP-A-61-190023, etc., a proposal has been made to improve the quality of mask unevenness by reducing impurity elements such as C, O, and N that impede etching piercing properties. JP-A-61-39343 defines the size of crystal grains to improve the uniformity of etching holes, and Japanese Patent Publication No. 2-9655 discloses fine holes formed by photoetching by defining the crystal orientation of the material. It proposes that each of them is provided with high density, high precision and evenly.

[0004]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 2-51973
As described in JP-A-61-190023, reducing the impurity elements such as C, O, and N that compositionally hinder the etching perforation property is generally an ultra-high-definition shadow that requires precision etching. As a mask application, it is well known that the minimum requirement is to improve the etching rate or the quality of etching holes. However, the effect of improving the surface roughness of the etching surface and the hole shape error is not recognized by only reducing the impurities. In addition,
There are proposals for improving the structure to obtain fine and uniform etching holes by defining crystal grains or crystal orientations, such as 61-39343 and Japanese Examined Patent Publication No. 2-9655. Therefore, complicated cold working and annealing process adjustments are required.In the field where ultra-fine etching processing is required, there are still problems with the surface roughness and shape of the etched surface. At the present time when the quality of tubes is increasing, there is a demand for a shadow mask material that is more excellent in etching perforation properties.

Further, in recent years, there is a strong demand for cost reduction of shadow masks. For this reason, it is necessary to reduce the basic unit of the mask and to cope with the thinning of the plate due to the ease of etching. However, when the plate is made thin, the mask is deformed due to insufficient strength during the manufacturing and handling of the shadow mask itself and the manufacturing of the cathode ray tube, which causes a problem of a decrease in color purity.

With respect to the above points, the present invention relates to a high-definition or ultra-high-definition shadow mask material having a better etching perforation property, and an intermediate material in an intermediate step of manufacturing the shadow mask material (hereinafter simply referred to as an intermediate material). An object of the present invention is to provide a method for producing the shadow mask material, a method for producing a high-strength shadow mask, and a cathode ray tube having high definition.

[0007]

Means for Solving the Problems As a result of extensive studies on the relationship between the structure and etching property of Fe-Ni-based amber alloy, the present invention has revealed that the optimum structure morphology and crystal orientation as a high-definition or ultra-high-definition shadow mask material. And the discovery of the manufacturing method thereof. Conventionally, all shadow mask materials have a recrystallized structure, and the crystal grain size is usually adjusted to a fine grain of JIS No. 8 to 11.
The reason for this is because of the difference in the etching rate for each crystal grain,
If the crystal grain size is too large, rough irregularities are formed on the etched surface, and the shape of the openings becomes jagged. Therefore, at present, the crystal grain size is made as small as possible to flatten the etching surface. In order to reduce the unevenness of the etched surface, the present inventors have conducted experiments on various cold rolling and annealing conditions, and examined grain refinement, but in the method disclosed in the above publication, the rolling step Therefore, even if the crystal grain size is finely adjusted to JIS No. 11 due to the material limitations of the Fe-Ni amber alloy, the unevenness of the etching surface due to the effect of crystal grains is sufficient. I found that it did not decline.

Therefore, the inventors of the present invention have made extensive studies by paying attention to the fact that the influence of the crystal grains can be prevented by forming a rolled structure having no clear crystal grain boundaries. The method consists of a speculum in a cross section perpendicular to the plate width direction, and in a shadow mask material having a fibrous rolled structure,
The present invention has been made based on the finding that a very excellent etching piercing property can be obtained. 1 and 2, the material of the present invention (a)
And conventional shadow mask material with recrystallized structure (b)
3A and 3B show the microstructure and the state of the etched perforated surface, respectively. Further, FIG. 3 shows respective surface roughness curves when the rolled surface is etched. The microstructure was obtained by observing with a 400X microscope after corrosion (about 10 seconds) with aqua regia saturated with cupric chloride. The material of the present invention has a fibrous rolling structure as shown in FIG. 1a under a microscope under the above conditions in a cross section perpendicular to the plate width direction, and has clear crystal grain boundaries as in Comparative Material b. The feature is that it is difficult. Therefore, it can be seen from the comparison of FIGS. 2 and 3 that the material of the present invention has significantly less irregularity on the etching surface due to the influence of the crystal grains, which is a problem with the comparative material (b), and has an extremely good shape.

Further, the present invention defines the degree of {100} orientation integration of the rolled surface at a high rate to prevent the etching property from deteriorating. Further, the present inventors have made the material having the above fibrous structure high strength by adding a specific element, and thereby, it becomes possible to make the material plate thin, so that the etching perforability is extremely improved. To be done, also
It was confirmed that by reducing the impurity elements of C, S, P, O and N, the uneven etching characteristics due to the fibrous structure were improved. Further, like the shadow mask material of the conventional recrystallized structure, the present invention, even in the material having the above-mentioned fibrous structure, by adding a specific element, blackening treatment during mask manufacturing or this blackening treatment This is based on the confirmation that the aging precipitation strengthening treatment inserted before or after the step can further strengthen the mask and thus facilitate thinning.

That is, the first invention of the present application is that Ni is used in% by weight.
F containing 30-40% with the balance Fe and unavoidable impurities
In the shadow mask material made of e-Ni amber alloy, the {100} orientation integration degree of the rolled surface is 85% or more, and it has a fibrous rolling structure in the cross section perpendicular to the strip width direction. It is a shadow mask material excellent in etching property, which is characterized by the following. In the present invention, the main constituent elements consist of Fe and Ni, and inevitable C and Mn in the production of steel are C ≦ 0.0.
5, applicable to steel containing Mn ≦ 0.1.

Further, the second to sixth inventions are shadow mask materials comprising Fe-Ni based amber alloys whose chemical components each contain 30 to 40% by weight of Ni, and the second invention: Mo, V, W. , Any one or more of Si, 0.001% to 3% in total, consisting of the balance Fe and unavoidable impurities. Third invention: Of the impurities, C 0.005% or less, S 0.005% or less, P 0.005% Below, O 0.005% or less and N 0.005% or less, respectively, with the balance Fe and unavoidable impurities. Fourth invention: Any one or more of Mo, V, W, and Si 0.001% to 3% in total Containing the balance Fe and unavoidable impurities, of the above impurities, C 0.005% or less, S 0.005% or less,
P 0.005% or less, O 0.005% or less, N 0.005% or less, respectively. Fifth invention: a part of Ni of any one of claims 1 to 4 is used as a component of Co of 10% or less and Co of 5% or less. 6th invention: In addition to the component of any one of claims 1 to 5, B, Mg
And one or more of Ca in total of 0.0001 to 0.0010
%, With the balance Fe and unavoidable impurities,

The seventh aspect of the present invention is that the chemical composition is% by weight,
Ni or one or two of Co and Cr as Ni + Co + Cr
In a shadow mask material made of Fe-Ni amber alloy containing 30 to 45%, one or more of Nb, Ti, Zr, Be, Al and Ta is contained in a total amount of 0.1 to 5.0%. , Balance Fe
And unavoidable impurities, which is the same as in claim 1 below.
A shadow mask material with excellent etching properties characterized by having a {100} orientation integration degree of 85% or more on the rolled surface and having a fibrous rolled structure in a cross section perpendicular to the sheet width direction. Is.

Also, in any of the first to seventh inventions of the present application, as an embodiment, the same speculum as described above does not include a non-fibrous tissue, or the area ratio is limited to 50% or less. FeCl ₃ solution (42 Baume, 60
Roughness of etched surface by spraying is 0.6 μm
The following can be listed. Further, the eighth invention of the present application is the same in an amber alloy having the same composition.
{100} orientation degree of integration is 85% or more, with the same speculum, average aspect ratio of crystal grains is 3 or more, and Vickers hardness is HV130
A shadow mask material having excellent etching properties as described above,
The ninth invention is a cold-rolled material made of an amber alloy having the same composition as any of the above, and the change in the {100} orientation integration degree of the rolled surface before and after annealing at 850 ° C or less is 30% or less. It is an intermediate material for a shadow mask material which is characterized by having excellent etching properties.

In a tenth aspect of the invention, after melting the Fe-Ni-based amber alloy and hot working, cold rolling at 85% or more and annealing at 700 ° C or more are performed at least once in this order, and then the cold rolling ratio is set. A method for producing a shadow mask material having excellent etching properties, which comprises performing cold rolling at a rolling rate not exceeding 850 ° C. and annealing at a temperature not exceeding 850 ° C. in this order,
The first invention is characterized in that the shadow mask material of the seventh invention is used to undergo aging strengthening by performing heat treatment at a temperature of 550 to 800 ° C. after each step of etching perforation, mask annealing and press molding. A method for producing a high-strength shadow mask, and a twelfth aspect of the present invention are a cathode ray tube which realizes a high to ultra-high definition image by using a shadow mask material having excellent etching properties among the above-mentioned materials.

[0015]

Next, the reasons for limiting the numerical values of the present invention will be described. Of rolling surface
If the {100} orientation integration degree is less than 85%, a difference between the orientations causes a step between the crystal grains during etching to impair the flatness of the etching surface, resulting in mask unevenness, so that the rolling surface has a {100} orientation integration degree of 85%. Limited to at least%. This definition is a very important requirement in the present invention. If the Ni content is less than 30%, the austenite structure becomes unstable, while if it exceeds 40%, the coefficient of thermal expansion increases, and the original low thermal expansion characteristics are not satisfied, so Ni% is limited to 30-40%. . However, when the precipitation treatment is performed by adding the precipitation strengthening element described below, a part of Ni is
Since an intermetallic compound is formed, effective Ni is reduced. In this case, the upper limit of Ni is 45%.

Mo, V, W and Si are added as solid solution strengthening elements, but if the addition amount is less than 0.001%, there is no effect, and if added over 3%, carbides and intermetallic compounds are added. Is easily generated, and it is exposed on the wall surface of the etching hole,
There is a problem such as causing an abnormal hole shape. Further, the surface oxidation is promoted, the surface oxide film cannot be easily removed by the surface conditioning treatment before etching, and the etching property is significantly impaired due to the decrease in the resist adhesiveness, so the amount is limited to 0.001 to 3%. Nb,
Ti, Zr, Be, Al, Ta also act as a solid solution strengthening element in the shadow mask material state, but by forming a fine intermetallic compound with Ni by blackening treatment or precipitation strengthening heat treatment, It produces a precipitation hardening effect. This effect is insufficient if it is less than 0.1%, but if it exceeds 5.0%, the coefficient of thermal expansion becomes large and the characteristics as an amber are deteriorated. Therefore, their addition is 0.1 to 5.0%.

A small amount of C, P, O, N impurities causes etching,
In particular, strict regulation has a remarkable effect because it inhibits the uneven characteristics of the etching mask. C 0.005% or less, S 0.005%
Below, if P is 0.005 or less, O is 0.005% or less, and N is 0.005% or less, it becomes possible to deal with ultra-high definition shadow masks. B,
Mg and Ca are hot workability improving elements. As you know, F
e-Ni alloys are inferior in hot workability.
It is recommended to add a trace amount of B, Mg, Ca, etc. If the addition amount is less than 0.0001%, there is no effect, and if it exceeds 0.001%, it is excessively segregated in the crystal grain boundaries to strengthen the grain boundaries, the corrosion resistance is improved, and the etching property is impaired, so the content is limited to 0.001% or less.

When Co is replaced with an equal amount of Ni, even lower thermal expansion characteristics can be obtained. However, if it exceeds 10%, it becomes expensive in terms of price. Therefore, if it is added, it is limited to 10% or less. To do. It is preferably 5% or less. Cr is an effective element when it is necessary to lower the yield strength of the material, but if added in excess of 5%, the oxidation resistance is improved and the oxide film growth during blackening is suppressed, so it is added. In the case, it is limited to 5% or less.
If the etching surface roughness Ra on the rolled surface exceeds 0.6 μm, the electron beam is easily scattered by the etching holes and the image quality is deteriorated. Therefore, the etching roughness on the rolled surface is limited to 0.6 μm or less Ra. Good. Each of the inventive materials of the present invention can sufficiently satisfy this limitation.

When the non-fibrous structure exceeds 50% by microscopic examination in a cross section perpendicular to the plate width direction, unevenness due to the difference in etching rate between the structure and the fibrous rolled structure which is the matrix is high. The non-fibrous structure is preferably 50% or less because it occurs frequently and a flat etched surface due to the fibrous rolled structure, which is an important constituent feature of the present invention, cannot be obtained. More preferably, it is 30% or less. The non-fibrous tissue means
In a cross section perpendicular to the width direction of the plate, as shown in FIGS. 4a and 4b, it means a structure formed in a fibrous matrix in the form of islands, which are as shown in FIG. 1b.
The shape is different from the polygonal recrystallized structure usually found in austenite. This non-fibrous structure is probably in the initial state of recrystallization, but is referred to as a non-fibrous structure in the present application for the sake of accuracy. The ratio of the non-fibrous structure was calculated by the following formula. Ratio of non-fibrous tissue = (area of non-fibrous tissue / unit area)
× 100 (%)

If the average aspect ratio of the crystal grains is less than 3, good etching properties cannot be obtained, and the average aspect ratio of the crystal grains is set to 3 or more, preferably 10 or more, and a rolling structure having a sufficient fibrous elongation is preferable. Incidentally, the average aspect ratio of the crystal grains, with a mirror in a cross section perpendicular to the plate width direction, the ratio of the maximum dimension in the rolling direction of the crystal grains and the direction perpendicular thereto is obtained for each crystal grain, and it is averaged. It was done. Practically, a straight line is drawn in the plate thickness direction on the photograph of the appropriate magnification in the above cross-section, and the crystal grain (the both ends are within the photograph) that the straight line traverses has a large area visually. In order from 1
0 pieces are selected, and the ratio of the above dimensions is arithmetically averaged. If the Vickers hardness of the material is less than HV130, the material is likely to be bent or bent during handling during the etching process or the like, and the Vickers hardness is preferably limited to HV130 or more.

In general, the Fe-Ni-based amber alloy forms a cubic structure (two {100} faces of each {100} face are parallel to the rolling face and the plane in the rolling direction and the plate thickness direction) in the recrystallization process. , Cold rolling ratio is less than 85% or subsequent annealing is 70
If it is less than 0 ° C, a sufficient cubic structure cannot be obtained. Therefore, in the method for producing the material of the present invention, it is very important to recrystallize at least once in the process before finish rolling to obtain a cubic structure, in order to obtain an optimum fibrous rolling structure. The manufacturing method of the present invention, first, cold rolling of 85% or more and 7
Annealing at a temperature of 00 ° C. or higher is performed at least once in this order to obtain a precursor material having a cubic structure developed.

FIGS. 5 and 6 show the precursor material of the present invention having a sufficiently cubic structure prepared by rolling and annealing under the conditions shown in the figures, respectively, and the cold rolling ratio of less than 85% or the annealing temperature of 700. Precursor material for comparative materials prepared at temperatures below ° C and having inadequate cubic texture
(Indicated as-annealed (FIG. 6 only)), relationship between hardness when cold rolling with a rolling ratio of 80% and further annealing at each temperature thereafter, and {100} orientation integration degree of rolling surface ( %).

As shown in FIG. 5, the recrystallization temperature of the precursor material of the present invention is shifted to the high temperature side, and the Vickers hardness is about HV130 or more even at the annealing temperature of 875 ° C. or less, which is higher than that of the comparative material. The strength is very high, and therefore it is structurally stable, and from FIG. 6, cold rolling of 80%, that is, the reduction rate during preparation of the precursor material, and annealing up to an annealing temperature of 850 ° C. Then there is almost no change in the {100} orientation integration (10
It can be seen that the change in the degree of orientation integration is about 25% or less at an annealing temperature of 875 ° C. Therefore, it can be seen that the precursor material of the present invention is very little affected by the change in crystal orientation even by cold rolling or annealing. Therefore, the material of the present invention maintains a high fibrous rolling structure and a high degree of {100} orientation integration even after annealing, and thus exhibits a high etching property. That is, the production method of the present invention does not destroy the cubic orientation of the precursor material obtained as described above, and therefore, as a subsequent process, cold rolling at a rolling rate not exceeding the cold rolling rate and annealing subsequently performed are
It is performed at 850 ° C or lower.

The final treatment in the production method of the present invention, that is, for the purpose of making a dull surface after adjusting the plate shape after annealing at a temperature not exceeding 850 ° C.
Since the structure of the material of the present invention does not change even if cold rolling by reduction of about 20% or less and subsequent strain relief annealing (850 ° C. or less) are added, its high etching property is maintained. Further, like the comparative material of FIG. 6, a material whose {100} orientation integration degree has decreased to less than 85% by cold rolling is
In order to increase this to 85% or more, high temperature annealing of about 750 ° C or higher is required after rolling.
As shown in Fig. 5, the Vickers hardness is less than HV130 and the strength is insufficient, and the non-fibrous structure area ratio is 50%.
As described above, the etching property is deteriorated. As an intermediate material of the material of the present invention, in the rolled state, the change in the degree of {100} orientation integration before and after subsequent annealing is 30%.
As below, the amount of recrystallization can be limited. As can be seen from FIG. 6, when the annealing temperature is set to 850 ° C. or lower, the material of the present invention can sufficiently attain the orientation integration degree of 85% or higher.

As described above, the material of the present invention is hot-rolled, then a precursor material having a sufficient cubic structure is obtained under specific rolling and annealing conditions, and further rolled into a fibrous rolled structure. The post-annealing is a shadow mask material having excellent etching properties in which irregularities on the etching surface due to recrystallized grains are highly reduced. Further, in the above-described shadow mask material having excellent etching properties, when one or more of Nb, Ti, Zr, Be, Al, and Ta are contained as a strengthening element in a total amount of 0.1 to 5%, 550 to 800 ° C during, before, or after blackening treatment in the mask manufacturing process
It is possible to further increase the strength of the mask by heat-treating at. If the temperature is lower than 550 ° C, the precipitation of the Ni-based intermetallic compound is insufficient and the alloy is not strengthened. If it exceeds 800 ° C or the precipitation of the intermetallic compound may occur, the precipitate becomes coarse and does not contribute to strengthening. Therefore, 550 to 800 ° C is suitable as the aging temperature.

By this treatment, a high-strength shadow mask is obtained, and it is possible to cope with thinning, and to suppress deformation in handling such as temporary attachment and detachment to a panel for exposure of each color of fluorescent substance. It will be possible. The cathode ray tube of the present invention is
Since the mask material used has high shape accuracy due to high etching property, smooth surface roughness, and electron beam passage hole with high uniformity without mask unevenness, high three-primary color reproducibility, high saturation, and images without color unevenness can be realized. it can.

[0027]

EXAMPLES As shown in Table 1 collectively, A, B1 to B1
6, C1-C7, D1-D5, E1-E5 various Fe-N
i-based amber alloy is vacuum induction melted, cast, then 110
Forging and hot rolling were performed at 0 to 1150 ° C to obtain a hot rolled coil having a predetermined thickness. Then, the surface is pickled and polished, and then, Table 2
Further, cold rolling shown in each of the precursor material columns in Table 3 and subsequent annealing were performed to prepare the precursor materials.
Here, each material of F1 to F6 in Table 3 uses the same material as A. Subsequently, cold rolling was performed at the rolling ratios shown in the respective finishing material columns to a thickness of 0.15 mm, and then the annealing shown in the finishing material column was performed. After each treatment, while measuring the degree of {100} orientation integration of the rolled surface, the material after the annealing, as shown in the shadow mask evaluation column, hardness, non-fiber by a micrograph in a cross section perpendicular to the plate width direction The area ratio of the textured structure and the aspect ratio were measured, the etching surface roughness (Ra) by the etching test, and the mask unevenness (quality) of the mask after etching were determined.

{100} orientation integration is {111}, {100}, {11
It was determined from the relative intensity I in X-ray diffraction in the main directions of 0} and {311} by the following formula. D _{100} % = I _{100} x 100 / (I _{111} + I _{100} + I
_{110} + I _{311} ) The etching quality is 0.15mm thick finish material is degreased with hot alkali, and the photoresist of the specified pattern is masked, then spray-etched with FeCl ₃ solution (42 Baume, 60 ° C) for shadowing. The mask was obtained and the quality of the unevenness of the mask was visually evaluated. The roughness of the etched surface was measured in the plate width direction on the spray-etched surface. However, there was almost no difference from the rolling direction.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

The materials A1 to E5 according to the present invention are 85% in the material after hot rolling as shown in the precursor materials column of Tables 2 and 3.
The above cold rolling and annealing at 700 ° C. or more are performed respectively, so that the cubic structure is developed, so that the subsequent cold rolling not exceeding the above-mentioned cold rolling rate and the subsequent 850
After annealing not exceeding ℃, the recrystallization temperature shifts to the high temperature side as described in Figs.
The degree of {100} orientation integration is high and the variation is small ({100} orientation integration after annealing 88 to 100%).

As a result, due to the action due to the high degree of {100} orientation integration and the recrystallization retardation effect, the fiber structure remains highly developed (non-fibrous structure area ratio ≤13%, average aspect ratio ≥30). By the action of the fibrous rolling structure that does not have clear crystal grain boundaries such as conventional materials, the surface roughness Ra value (≦ 0.6 μm) of the etching surface and the excellent etching property can be seen from the mask quality. have. Among these, A1 to C7 are suitable for etching and ultra-high-definition shadow masks, because the impurities are regulated to be sufficiently low and the mask quality is uniform. Also, D1
~ E5 is insufficient in the regulation of impurities and the mask quality is
It is slightly uneven. However, as shown by the etching surface roughness value, the fibrous structure of the present invention maintains a high etching property and has a sufficiently high quality as a high-definition shadow mask material. The {100} orientation change column in the finishing material column in Tables 2 and 3 shows the {100} orientation change before and after the annealing in the same column, and it shows that the intermediate material of the present invention is annealed at 850 ° C or lower. The change in the degree of {100} orientation integration of the rolled surface before and after fully satisfies the regulation of 30% or less.

On the other hand, the comparative materials of F1 to F6 are A
It is the same material as the material, and there is no problem in composition,
Inappropriate cold rolling conditions (F
1, F5, F6) or inappropriate annealing conditions (F2,
F5, F6) results in insufficient cubic structure development, or inappropriate cold rolling conditions (F1, F3, F5, F6) as shown in the finishing material column, or in the finishing material column. The cubic texture is destroyed by such inappropriate annealing conditions (F4, F6), and as a result, the final shadow mask material has a recrystallized texture similar to the conventional one,
Or an insufficient fibrous rolling structure (non-fibrous or recrystallized structure area ratio 100%, average aspect ratio
1 to 1.5), the surface roughness value Ra of the etched surface is 0.63 to 0.75
It is as rough as μm and has mask unevenness.

Also, the change in the {100} orientation of the comparative material (%)
Is the annealing temperature of 870 ° C, except for F4 and F6,
All exceeded 30%, and did not satisfy the ninth invention of the present application. Further, as can be seen from the high recrystallization temperature described in FIG. 5, the material of the present invention has a high hardness, which makes it convenient to handle and can be thinned as a shadow mask. In this case, there is an advantage that etching becomes easier.

Next, Table 4 shows the finish materials of A1 and B1 to B16 in Table 2 after annealing at 900 ° C. for 10 minutes (mask annealing), and subsequently after aging precipitation at 500 to 850 ° C. for 1 hour, respectively. The hardness (measurement yield strength for 600 ° C. treatment) is shown. From now on, Nb, Ti, Zr, Be, Al, Ta
In the material added with the strengthening element of No. 3, precipitation strengthening occurs in the temperature range of 600 to 700 ° C, and A1 and B4 to 6,8,1 of the additive-free material
It can be seen that the hardness is improved as compared with Nos. 5 and 16, and therefore, the resistance to deformation due to thinning and handling during the manufacturing process of the cathode ray tube is high.

[0037]

[Table 4]

[0038]

As described above, the shadow mask material of the present invention has a fibrous rolling structure which is completely different from that of the conventional material having a recrystallized structure. It is an extremely high-quality, high-definition or ultra-high-definition shadow mask material that has excellent surface roughness of the etched surface and small hole shape error and can obtain high-quality mask with no unevenness. In addition, the method of the present invention does not require complicated cold working and annealing adjustment for optimizing the structure as in the prior art,
It is possible to produce a high-definition shadow mask material having a good etching piercing property by a relatively simple process. Further, this material can be subjected to an aging treatment to obtain a shadow mask having higher strength, which can be applied to thinning and has high resistance to deformation. Therefore, according to the present invention, it is possible to manufacture a high-definition or ultra-high-definition cathode ray tube by using a shadow mask material or the like having an etching property that has not been hitherto available, for TV or display applications which are becoming more sophisticated in recent years. Therefore, the industrial effect is extremely large.

[Brief description of drawings]

FIG. 1 is a cross-sectional metallographic photograph of a material of the present invention and a comparative material.

FIG. 2 is a scanning electron micrograph of metal structures of etched surfaces of the material of the present invention and the comparative material.

FIG. 3 is a diagram showing the surface roughness of the etching surface of the material of the present invention and the comparative material.

FIG. 4 is a photograph of a non-fibrous cross-section metallographic structure.

FIG. 5 is a correlation diagram between final annealing temperature and hardness.

FIG. 6 is a correlation diagram between final annealing temperature and {100} orientation integration degree.

Front page continued (72) Inventor Ryoji Inoue 2107-2 Yasugi-cho, Yasugi-shi, Shimane Prefecture 2 Hitachi Metals Co., Ltd. Yasugi Plant

Claims (14)

[Claims] 1. By weight percent, containing 30-40% Ni, balance Fe
In a shadow mask material made of Fe-Ni amber alloy consisting of unavoidable impurities, the degree of {100} orientation integration of the rolled surface is 85% or more, and fibers are observed by microscopy in a cross section perpendicular to the strip width direction. A mask material having an excellent etching property, which has a roll-shaped structure. 2. A shadow mask material composed of a Fe—Ni-based amber alloy containing 30 to 40% by weight of Ni, wherein Mo,
Any one or more of V, W and Si is 0.001% to 3% in total
Contains the balance Fe and unavoidable impurities.
A shadow mask material having an excellent etching property, which has a {100} orientation integration degree of 85% or more and has a fibrous rolling structure in a cross section perpendicular to the plate width direction. 3. By weight percent, containing 30-40% Ni, balance Fe
In the Fe-Ni amber alloy consisting of and unavoidable impurities, among the above impurities, C 0.005% or less, S 0.005% or less, P 0.005% or less, O 0.005% or less, N 0.005% or less, respectively, of the rolling surface A shadow mask material having an excellent etching property, which has a {100} orientation integration degree of 85% or more and has a fibrous rolling structure in a cross section perpendicular to the plate width direction. 4. A shadow mask material comprising an Fe-Ni-based amber alloy containing 30 to 40% by weight of Ni, wherein Mo,
Any one or more of V, W and Si is contained in a total amount of 0.001% to 3%, and the balance is Fe and inevitable impurities. Of the above impurities, C 0.005% or less, S 0.005% or less, P 0.005% Less than,
O is limited to 0.005% or less and N is 0.005% or less, the {100} orientation integration degree of the rolled surface is 85% or more, and the fibrous rolling structure is observed by microscopy in the cross section perpendicular to the strip width direction. A shadow mask material having excellent etching properties, which comprises: 5. A component obtained by substituting a part of Ni of the component according to any one of claims 1 to 4 with an equal amount of one or two kinds of Co of 10% or less and Cr of 5% or less, A shadow mask material with excellent etching properties characterized by having a {100} orientation integration degree of 85% or more on the rolled surface and having a fibrous rolled structure in a cross section perpendicular to the sheet width direction. . 6. In addition to the component according to any one of claims 1 to 5,
One or two or more of B, Mg and Ca in total 0.0001-0.
Fe- containing 0010% and the balance Fe and unavoidable impurities
In the shadow mask material made of Ni-based amber alloy,
A shadow mask material with excellent etching properties characterized by having a {100} orientation integration degree of 85% or more on the rolled surface and having a fibrous rolled structure in a cross section perpendicular to the sheet width direction. . 7. A shadow mask material comprising a Fe-Ni-based amber alloy containing 30 to 45% by weight of Ni or one or two of Co and Cr (Ni + Co + Cr) in an amount of Nb. , T
Any one or more of i, Zr, Be, Al, Ta in total
Containing 0.1-5.0%, balance Fe and unavoidable impurities, the {100} orientation integration of the rolling surface is 85%, and the fibrous rolling structure is observed by microscopy in the cross section perpendicular to the strip width direction. A shadow mask material having excellent etching property, which is characterized by having. 8. The shadow mask material excellent in etching properties according to claim 1, which does not contain a non-fibrous structure in a cross section perpendicular to the plate width direction or contains 50% or less in area ratio. 9. A FeCl ₃ solution (42 Baume, 60
The shadow mask material according to claim 1, which has a surface roughness Ra in the plate width direction of 0.6 μm or less when etched by a spray of (° C.). 10. Fe-N as a component according to claim 1.
In the shadow mask material made of i-based amber alloy,
The degree of integration of {100} orientation of the rolled surface is 85% or more, the average aspect ratio of crystal grains in the cross section perpendicular to the sheet width direction is 3 or more, and the Vickers hardness is HV130 or more. Characteristic shadow mask material with excellent etching properties. 11. Fe-N as a component according to claim 1.
A cold rolled material made of i-based amber alloy,
An intermediate material for a shadow mask material having excellent etching properties, characterized in that the degree of integration of {100} orientation on the rolled surface changes by 30% or less before and after annealing at 50 ° C or less. 12. The alloy of any one of claims 1 to 7 is melted and hot worked, followed by cold rolling at 85% or more and annealing at 700 ° C. or more at least once in this order, and then the cold cooling. A method for producing a shadow mask material having excellent etching properties, which comprises performing cold rolling at a rolling rate not exceeding the hot rolling rate and annealing at a temperature not exceeding 850 ° C in this order. 13. The shadow mask material according to claim 7, which is subjected to etching perforation, mask annealing and press molding, and then heat-treated at a temperature of 550 to 800 ° C. to enhance aging. Method for manufacturing high strength shadow mask. 14. A cathode ray tube equipped with a shadow mask produced by using the material according to claim 1.