JP3293222B2 - Fe-Ni alloy sheet and Fe-Ni-Co alloy sheet having excellent magnetic properties for shadow mask and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
-Regarding Ni alloy thin plate and Fe-Ni-Co alloy thin plate, preferable Fe for shadow mask used for color cathode ray tube-
The present invention relates to a Ni alloy thin plate and a Fe—Ni—Co alloy thin plate and a method for producing them.

[0002]

2. Description of the Related Art In recent years, with the high quality of color televisions,
As an alloy for a shadow mask that can cope with the problem of color misregistration, an Fe-Ni-based alloy containing 34 to 38 wt% of Ni (hereinafter referred to as "conventional Fe-Ni-based alloy") is used. This conventional Fe-Ni alloy has a significantly lower coefficient of thermal expansion than low carbon steel conventionally used as a shadow mask material. Therefore, if a shadow mask is made of a conventional Fe-Ni alloy, even if the shadow mask is heated by an electron beam, the problem of color shift due to thermal expansion of the shadow mask hardly occurs.

[0003] An alloy sheet for a shadow mask is usually manufactured by the following steps. That is, an alloy ingot is prepared by a continuous casting method or an ingot-making method, and then, into the alloy ingot thus prepared, slab rolling, hot rolling, and cold rolling.
Annealing is performed to produce an alloy thin plate.

[0004] The alloy sheet for a shadow mask manufactured as described above is usually processed into a shadow mask by the following steps. That is, a hole for passing an electron beam (hereinafter, referred to as a hole) is formed on a thin alloy plate for shadow mask by photoetching.
(Hereinafter simply referred to as “holes”) (hereinafter, the thin alloy plate for a shadow mask that has been perforated by etching is referred to as a “flat mask”), and then the flat mask is annealed, and then the annealed flat mask is removed. Press-molding into a curved shape so as to conform to the shape of a cathode ray tube, assembling it into a shadow mask, and then subjecting the surface to blackening treatment.

However, when such a conventional general Fe-Ni alloy is used for a shadow mask, an electron beam is deflected by a stray magnetic field existing in an environment outside a color cathode-ray tube, and when the electron beam hits a predetermined pixel. "Color misregistration" due to disappearance often occurs, which is a problem in screen quality, and the following prior art is known for this problem. That is, JP-A-64-62421 discloses that a perforated mask (flat mask) is annealed at 900 to 1200 ° C. for 5 minutes or more, optionally in a reducing atmosphere, press-formed at 93.3 ° C., By annealing at 787.8 ° C. and in some cases a weakly oxidizing atmosphere, the DC coercive force is reduced to 1 Oersted or less, and the above-mentioned problem of “color shift” is solved.

[0006]

However, in the above-mentioned prior art, an effect was observed with respect to a DC stray magnetic field such as terrestrial magnetism, but in an actual external environment, it was 50 Hz.
There are many stray magnetic fields due to the alternating current at the above frequencies, and the effect cannot be sufficiently exerted on these stray magnetic fields. As a result, the electron beam is still deflected, and the color shift problem occurs. Remains.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been devised through repeated studies. The present invention has excellent magnetic characteristics, and particularly has excellent AC magnetic permeability of 50 Hz or more. Masks Fe-Ni alloy and Fe-, which can sufficiently shield the stray magnetic field in the region
The present invention has succeeded in providing a Ni-Co alloy thin plate and a method for producing the same, and is as follows.

(1) In wt%, Ni: 34-38%, Mn: 0.
35% or less, Si: 0.06% or less, Cr: 0.05% or less, T
i: 0.02% or less, Mo: 0.05% or less, W: 0.05% or less, Nb: 0.02% or less, V: 0.05% or less, Cu: 0.05
% Or less, and [Ti] + [Cr] + [Al] + [Si] +
Contains [Mo] + [W] + [Nb] + [V] + [Cu] ≤ 0.25%, and consists of the balance of unavoidable impurities and the composition of Fe, and to the surface of the alloy plate after blackening treatment {331},
Fe-Ni for a shadow mask excellent in magnetic properties, characterized in that the degree of integration of the {210} and {211} crystal planes satisfies the following table and the Vickers hardness (Hv) is 140 or less.
Alloy sheet.

[0009]

[Table 4]

(2) In wt%, Ni: 34-38%, Mn: 0.
35% or less, Si: 0.06% or less, Cr: 0.05% or less, T
i: 0.02% or less, Mo: 0.05% or less, W: 0.05% or less, Nb: 0.02% or less, V: 0.05% or less, Cu: 0.05
%, Co: 1.0% or less, [Ti] + [Cr] +
[Al] + [Si] + [Mo] + [W] + [Nb] + [V] +
Contains [Cu] ≦ 0.25%, the balance being unavoidable impurities and Fe
And the degree of integration of {331}, {210}, and {211} crystal planes on the alloy plate surface after the blackening treatment satisfies the following table, and the Vickers hardness (Hv) is 14
An Fe—Ni—Co alloy sheet for a shadow mask having excellent magnetic properties, wherein the thickness is 0 or less.

[0011]

[Table 5]

(3) 30% to 38% of Ni and 0.3% of Mn in wt%.
35% or less, Si: 0.06% or less, Cr: 0.05% or less, T
i: 0.02% or less, Mo: 0.05% or less, W: 0.05% or less, Nb: 0.02% or less, V: 0.05% or less, Cu: 0.05
%, Co: 1.0% to 6%, and [Ti] +
[Cr] + [Al] + [Si] + [Mo] + [W] + [Nb] +
[V] + [Cu] ≦ 0.25%, the balance being composed of inevitable impurities and the composition of Fe, and {331}, {210}, {211} on the alloy plate surface after the blackening treatment. The degree of crystal plane integration satisfies the table below, and the Vickers hardness (H
v) Fe-Ni-Co alloy sheet for a shadow mask having excellent magnetic properties, characterized by having a value of 140 or less.

[0013]

[Table 6]

(4) The hot-rolled steel strip of the low-thermal-expansion alloy having the components described in the above items (1) to (3) is subjected to hot-rolled sheet annealing, and thereafter cold-rolling-recrystallization annealing-finish cold-rolling- After performing the strain relief annealing, performing the annealing before press molding, when manufacturing in the step of performing a blackening treatment after the subsequent press molding,
The hot-rolled sheet annealing temperature (T ₀ , ° C.) is 810-890 ° C.,
The annealing temperature (T ₁ , ° C.) before the press forming is 720 to 9
00 ° C, blackening temperature (T ₂ , ° C) 520-600 ° C
And [T ₂ ] ≧ − (4 [T ₁ ] / 9) +920 is satisfied, so that {33}
The Fe-Ni for a shadow mask having excellent magnetic properties, wherein the degree of integration of the crystal planes of {1}, {210}, and {211} and the Vickers hardness (Hv) are adjusted to the values described in claim 1. Method for producing alloy thin plate and Fe-Ni-Co alloy thin plate.

[0015]

The present invention as described above will be further described. From the viewpoint as described above, the present inventors have found that a Fe--Ni alloy thin plate for a shadow mask and a Fe--Ni alloy having excellent magnetic properties can be obtained.
-As a result of intensive research to develop a Co alloy thin plate, the following findings were obtained. That is, the present invention relates to Fe-Ni for shadow masks.
The required magnetic properties are obtained by adjusting the chemical composition of the alloy sheet and the Fe-Ni-Co alloy sheet, the Vickers hardness, and the degree of integration of a specific crystal plane on the alloy sheet surface within a predetermined range. . The required magnetic properties in the present invention are magnetic permeability at a frequency of 50 Hz or more, and it is intended in the present invention to increase the magnetic permeability.
By improving the magnetic permeability of 50 Hz or more, it is possible to sufficiently shield the stray magnetic field in the frequency range described above.

The present inventors have obtained the following findings. That is, in the production process of the present alloy, hot-rolled sheet annealing is performed at a predetermined temperature before cold-rolling the hot-rolled steel strip, and furthermore, by appropriately setting the annealing temperature and the blackening treatment temperature before press forming. By obtaining the Vickers hardness after the predetermined blackening treatment and the degree of integration of the crystal plane on the surface of the predetermined alloy thin plate, the magnetic properties can be improved.

The present invention has been made on the basis of the above-described findings, and is based on the Fe for shadow mask of the present invention.
Reasons for limiting the chemical composition, Vickers hardness, and the degree of integration of crystal planes on the alloy sheet surface for the -Ni alloy sheet and Fe-Ni-Co alloy sheet are as follows.

(1) Nickel: In order to prevent the occurrence of color shift, the upper limit of the average thermal expansion coefficient in the temperature range of 30 to 100 ° C. required for the Fe—Ni alloy thin plate for the shadow mask is 2. 0 × 10 ⁻⁶ / ° C. The coefficient of thermal expansion depends on the nickel content of the alloy sheet. The range of the nickel content satisfying the above-mentioned condition of the average thermal expansion coefficient is in the range of 34 to 38 wt%. Therefore,
Nickel content should be limited to the range of 34-38 wt%. In addition, even in such a range of the Ni content, a preferable Ni amount that can reduce the average thermal expansion coefficient is 35 to 37.
%, And a more preferable Ni content that can further reduce the average coefficient of thermal expansion is 35.5 to 36.5%.

Even when Co is contained in an amount of 0.001 to 1.0%, the amount of Ni satisfying the upper limit of the average thermal expansion coefficient is 34 to 38%, and the preferable amount of Ni for lowering the average thermal expansion coefficient is Is 35-37%. In addition, more than 1.0% 6
% Of the Fe-Ni-Co alloy thin plate containing up to cobalt in the range of 30 to 38%, which satisfies the above-mentioned condition of the average thermal expansion coefficient, and the Ni content is 30 to 38%.
By setting the amount of Co to 33% and the amount of Co to 3 to 6%, the average coefficient of thermal expansion becomes lower and more excellent.

(2) Manganese: Mn improves hot workability in the present alloy.
The magnetic permeability at the above frequencies decreases. That is, the Mn content is 0.3
If it exceeds 5%, the above-mentioned deterioration of magnetic properties becomes remarkable, so 0.35% was made the upper limit. Note that the magnetic properties described above can be further improved by reducing the amount of Mn.

(3) Aluminum, silicon, chromium,
Titanium, molybdenum, tungsten, niobium, vanadium, copper: Al, Si, Cr, Ti, Mo, W, Nb, V, and Cu are one of the impurities unavoidably mixed into the present alloy. When the content of these elements increases, the magnetic permeability at a frequency of 50 Hz or more decreases. That is, when the above-mentioned elements exceed the following specific values, the magnetic properties are significantly deteriorated. Al: 0.02
0%, Si: 0.05%, Cr: 0.05%, Ti: 0.02%, M
o: 0.05%, W: 0.05%, Nb: 0.02%, V: 0.0
5%, Cu: 0.05%. Therefore, Al: 0.020% or less, S
i: 0.06% or less, Cr: 0.05% or less, Ti: 0.02% or less, Mo: 0.05% or less, W: 0.05%, Nb: 0.02% or less, V: 0 0.05% or less and Cu: 0.05% or less.

Furthermore, in order to obtain the magnetic properties intended in the present invention, it is important to define the total amount of the above-mentioned elements. That is, FIG. 1 shows that the amounts of Ti, Cr, Al, Si, Mo, W, Nb and V are within the range specified by the present invention, and the Vickers hardness (Hv) is also within the range specified by the present invention. [Ti] + [Cr] + [Al] + [Si] + [Mo] + [W] + in alloys having a degree of integration of the crystal planes of {210} and {211} respectively within the range specified in the present invention
It shows the relationship between the amount of [Nb] + [V] + [Cu] and the magnetic permeability. The method of measuring the magnetic permeability is as shown in Example 1 described later, and the manufacturing method is as shown in FIG.
[Ti] + [Cr] + [Al] + [Si] + [Mo] + [W] +
If the amount of [Nb] + [V] + [Cu] exceeds 0.25%, the magnetic permeability deteriorates remarkably, so the upper limit was set to 0.25%.
In addition, even if the total amount of these elements is within the scope of the present invention,
By reducing the total amount, the magnetic permeability can be further improved.

It should be noted that the Fe—
Ni and Fe-Ni-Co alloy, as described above, the basic composition of Fe-Ni and Fe-Ni-Co, a specific amount of Mn, Al, Si, Cr,
Ti, Mo, W, Nb, V, and Cu, and as described later, {331}, {210},
It is characterized in that the degree of integration of the {211} crystal plane is not more than a specific value and the Vickers hardness (Hv) is not more than 140. In addition to the above composition, C: 0.0001 to 0.0050
%, N: 0.0001-0.0020%, S: 0.0001-
0.0020%, P: 0.0001 to 0.0050%, O: 0.000%
It is preferably 0001 to 0.0030% or less.

In order to obtain excellent magnetic properties in the present invention, it is important to control the degree of integration of specific crystal planes on the surface of the alloy plate after the blackening treatment and the control of Vickers hardness in addition to the above-mentioned components. It is.

That is, the degree of integration of {331}, {210}, and {211} crystal planes on the alloy plate surface after the blackening treatment (hereinafter simply referred to as the degree of integration of the {331} crystal plane, {21}
0% crystal plane and {211} crystal plane) exceed 35%, 16% and 20%, respectively.
Even when the above-mentioned component requirements are satisfied, required magnetic properties cannot be obtained.

From the above technical circumstances, {331}
The degree of integration of the crystal plane is set to 35% or less, the degree of integration of the {210} crystal plane is set to 16% or less, and the degree of integration of the {211} crystal plane is set to 20% or less.

In the present alloy, (1) was obtained by X-ray diffraction.
11), (200), (220), (311), (33)
The X-ray diffraction intensities of the diffraction planes 1), (420) and (422) are obtained, and the degree of integration of the crystal orientation can be measured based on these. That is, the degree of integration of the {331} crystal plane is (331) and the relative X-ray intensity ratio of the diffraction plane is (111).
(200), (220), (311), (331),
It was obtained by dividing by the sum of the relative X-ray intensity ratios of the diffraction planes of (420) and (422).

Here, the relative X-ray diffraction intensity ratio is obtained by dividing the X-ray diffraction intensity measured on each diffraction surface by the theoretical X-ray intensity of the diffraction surface. For example, the relative X-ray diffraction intensity ratio of the (111) diffraction surface is obtained by dividing the X-ray diffraction intensity of the (111) diffraction surface by the theoretical X-ray diffraction intensity of the (111) diffraction surface. Also, the degree of integration of each of the crystal planes {210} and {211} is (420), (42)
The relative X-ray diffraction intensity ratio of the diffraction surface of (2) is as described above (11).
It is obtained by dividing by the sum of the relative X-ray diffraction intensity ratios of the seven diffraction planes from 1) to (422).

In order to obtain the required magnetic properties intended in the present invention, it is important to control the Vickers hardness in addition to the above-described component definition and crystal orientation control. That is, FIG.
Shows the relationship between the magnetic permeability of the alloy plate and the Vickers hardness of the alloy plate, in which the degree of integration of the components, {331}, {210}, and {211} crystal planes, is within the range of the present invention. If the Vickers hardness (Hv) exceeds 140, the magnetic permeability decreases and the required magnetic properties intended in the present invention cannot be obtained. As described above, in the present invention, the Vickers hardness (Hv) after the blackening treatment is 14
It was determined to be 0 or less. Even when Hv is 140 or less, the magnetic permeability of the alloy plate can be set to a higher level by lowering Hv.

As described above, Mn, A of the alloy of the present invention
l, Si, Cr, Ti, Mo, W, Nb, V, Cu, [Ti] + [Cr]
+ [Al] + [Si] + [Mo] + [W] + [Nb] + [V] +
[Cu], {331}, {210},
By defining the degree of integration of the {211} crystal plane and defining the Vickers hardness, the magnetic properties intended in the present invention can be improved.

{331}, {210},
The degree of integration of {211} crystal planes is 35% or less and 16
% And 20% or less, in order to minimize the {331}, {210}, and {211} crystal planes in the subsequent cold rolling and annealing processes from solidification to hot working in the production of alloy thin plates. Is achieved by adopting manufacturing conditions that do not accumulate.
For example, when the present alloy is manufactured from a hot-rolled steel strip obtained by subjecting an ingot or a continuously cast slab to slab-rolling and hot rolling, the hot-rolled steel strip is used as a material, and thereafter, hot-rolled sheet annealing-cooling is performed. Cold rolling-Recrystallization annealing-Finish cold rolling-Strain relief annealing, then annealing before press forming, When manufacturing in the step of performing blackening treatment after press forming, first, appropriate after hot rolling Hot rolled sheet annealing, {331},
This is effective for preventing the {210} and {211} crystal planes from being accumulated. At this time, the temperature of the hot-rolled sheet annealing is 810-89.
By selecting an appropriate temperature within the range of 0 ° C.,
The degree of integration of the {1}, {210}, and {211} crystal planes can each be equal to or less than the specified value of the present invention. From the above,
The hot rolled sheet annealing conditions for keeping the degree of integration of the {331}, {210}, and {211} crystal planes within the range of the present invention are 810.
８890 ° C. was determined.

In the present invention, such hot-rolled sheet annealing is performed when the hot-rolled steel strip of the present alloy is sufficiently recrystallized before hot-rolled sheet annealing. In order to obtain the degree of integration of {331}, {210}, and {211} crystal planes, which is intended in the present invention, the slab homogenizing heat treatment after slab rolling is not preferable in producing the present alloy. For example, when the above-mentioned homogenizing heat treatment is performed under the condition of 1200 ° C. or more and 10 hours or more, {331}, {210}, and {211}, the degree of integration of crystal planes exceeds the specified value of the present invention. Such processing must be avoided.

In the case of manufacturing from the above-mentioned hot-rolled steel strip, in the above-mentioned series of steps, the pre-press annealing conditions and the blackening conditions are also optimized in {331}, {210}, and {21}.
1｝ The degree of integration of crystal planes is set to the value specified in the present invention or less,
Further, it is necessary to keep the Vickers hardness after the blackening treatment within the range specified in the present invention.

FIG. 3 shows the magnetic permeability of an alloy sheet prepared by manufacturing a hot-rolled steel strip of the alloy according to the present invention as shown at the top of the figure, the annealing temperature before press (T ₁ , ° C.) and the blackening. It shows the results of investigations and examinations by changing the processing temperature (T ₂ , ° C.). That is, from FIG. 3, T ₁ : 720 to 90
0 ° C., T ₂ : 520 to 600 ° C., and [T ₂ ] ≧ −
By setting (4 [T ₁ ] / 9) +920, it becomes 33
The degree of integration of 1｝, {210｝, and {211} crystal planes is 35% or less, 16% or less, and 20% or less, the Vickers hardness (Hv) is 140 or less, and the magnetic permeability at 50 Hz is 1000.
As described above, required magnetic characteristics are obtained.

On the other hand, when T ₁ exceeds 900 ° C.,
One or more of the degree of integration of the {31}, {210}, and {211} crystal planes exceeds the definition of the present invention, and the magnetic permeability falls below the level intended in the present invention. When T ₁ is less than 720 ° C. and / or [T ₂ ] <− (4 [T ₁ ] / 9) +920, the Vickers hardness (Hv) exceeds 140, and the magnetic permeability falls below the level intended in the present invention. Falls below. Furthermore, T ₂ is 600
When the temperature exceeds ℃, the adhesion of the blackened film is deteriorated.

According to the above study, the degree of integration of the {331}, {210}, and {211} crystal planes after the blackening treatment is 35% or less, 16% or less, and 20% or less, respectively, and the Vickers hardness (Hv ) Is set to 140 or less, and T ₁ : 720 to 90
0 ° C., T ₂ : 520 to 600 ° C., [T ₂ ] ≧ − (4 [T
₁ ] / 9) +920. The blackening time is 2mi
When the value is n or more and less than 10 minutes, the effects intended in the present invention can be achieved under the above-described control of T ₁ and T ₂ within the range of the present invention. If the pre-press annealing time is not less than 20 min and less than 60 min, the effects intended in the present invention are the above-mentioned T ₁ , T ₂
Under control within the scope of the present invention.

The alloy thin plate after the blackening treatment was # 33
In addition to the methods described above, the method of controlling the degree of integration of 1｝, {210}, and {211} crystal planes within the range of the present invention employs a food-cooling solidification method, texture control by controlling recrystallization in hot working, and the like. There is. In addition, the method of setting the Vickers hardness after the blackening treatment within the range of the present invention also includes the cold rolling conditions other than those described above,
It can also be achieved by properly combining the annealing conditions.

As described above, the main object of the present invention is to improve the magnetic properties. However, to improve the adhesion of the blackened film during the blackening process, one of the constituent requirements of the present invention is to improve the adhesion.
One. FIG. 3 described above shows the magnetic permeability at 50 Hz. However, the magnetic permeability in a frequency range exceeding this is also excellent if T ₁ and T ₂ are within the above-described conditions of the present invention as described above. Level.

Further, the annealing before press molding in the present invention may be performed before the photoetching. In this case, if the annealing conditions before press forming are within the provisions of the present invention,
The required photo-etching quality can be ensured.

The present invention described above will now be described by way of specific examples.
This will be described in more detail as follows. Example 1 Ingots No. 1 to No. 26 having the chemical components shown in the following Tables 2 to 4 were prepared by ladle refining. The H content of each alloy was 1.0 ppm or less.

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

After each of the ingots obtained as described above was groomed, it was subjected to slab rolling, surface flaw removal, hot rolling (hot rolling at 1100 ° C. × 3 hours), and hot rolling obtained by flaw removal. Hot rolled sheet annealing was performed using the coil under the conditions shown in Table 5 below. Thereafter, cold rolling-annealing-finish cold rolling-strain relief annealing was performed to obtain an alloy plate having a thickness of 0.25 mm (alloy No. 1).
To 26 are hereinafter referred to as material Nos. 1 to 26, respectively). Note that these alloys were sufficiently recrystallized after hot rolling.

[0045]

[Table 10]

After these materials are converted into flat masks by etching, the flat masks are heated at 860 ° C. × 2.
At 0 min, annealing before press molding was performed, and after press molding, blackening treatment was performed at 600 ° C. × 2 minutes. {331}, {210},
Table 4 shows the result of the degree of integration of the {211} crystal plane obtained by the method based on the X-ray diffraction described above. Also, the adhesion of the blackened film was measured by placing a tape on the blackened film, bending it 180 °, peeling off the tape, and evaluating the adhesion of the blackened film on the tape. Those having no blackened film were determined to have good adhesion of the blackened film, and those having the blackened film adhered to the tape were determined to have poor adhesion of the blackened film.

The adhesion of the blackened film of each of the materials No. 1 to No. 26 in this example was all good. In the present invention, such excellent adhesion of the blackened film is one of the important components.

It should be noted that the alloy plate (material) which has been subjected to the annealing before press forming, the subsequent press forming, and the blackening treatment described above.
From No. 1 to No. 26), the ring test piece was processed, and 50Hz, 0.
The AC permeability at 3 KHz, 3 KHz and 30 KHz was also examined. The applied magnetic field is 5 m Oersted. In addition, Vickers hardness (H
v) was measured on the cross section of the alloy plate, and the results are also shown in Table 10 above.

As is evident from the results shown in Tables 7 to 9, the component compositions and Vickers hardness (Hv) within the range of the present invention, and {331} and {2} within the range of the present invention.
Material No. 16 having a degree of integration of {10} and {211} crystal planes
The magnetic permeability of No. 26 to No. 26 at 50 Hz or higher is higher than that of a comparative example described later, indicating an excellent level. Material No. 17
, No.18, No.20, No.23, No.24, No.25, No.26
In the examples of the present invention, Hv was reduced to a more preferable level, and No. 17, No. 18, No. 20, No. 23, N
The magnetic permeability above 50 Hz of o.24 shows a higher value. Further, among these materials, Material No. 20 is M
n, Al, Si, Cr, Ti, Mo, W, Nb, V, Cu, and [T
i] + [Cr] + [Al] + [Si] + [Mo] + [W] + [N
b] + [V] + [Cu] amount was reduced to a more preferable level, and the magnetic permeability above 50 Hz shows a higher value. Materials No. 25 and No. 26 containing Co also show excellent characteristics.

On the other hand, materials No. 1 to No. 11 are respectively Mn, Al, Si, Cr, Ti, Mo, W,
Nb, V, Cu, [Ti] + [Cr] + [Al] + [Si] + [Mo]
+ [W] + [Nb] + [V] + [Cu], and the permeability at 50 Hz or more is inferior to that of the examples of the present invention.

Materials No. 12 to No. 15 have Vickers hardness (Hv), {331} crystal plane density, {210} crystal plane density, and {211} crystal, respectively, which are outside the scope of the present invention. In each case, the magnetic permeability above 50 Hz is inferior to that of the present invention.

As is clear from the above description, the component composition within the scope of the present invention and the Vickers hardness (Hv) within the scope of the present invention, {331}, {210}, {211}.
It can be seen that by setting the degree of integration of the crystal planes, an Fe—Ni alloy sheet and an Fe—Ni─Co alloy sheet for a shadow mask having an excellent level of magnetic permeability of 50 Hz or more can be obtained.

Example 2 Using the hot-rolled steel strips of alloys No. 16 to No. 22, 25, and 26 used in Example 1 described above,
After the hot-rolled sheet annealing was performed under the conditions shown in Table 6 below, cold rolling-recrystallization annealing-finish cold rolling-
A strain relief annealing was performed to obtain an alloy plate having a thickness of 0.25 mm.

[0054]

[Table 11]

Each alloy plate as shown in Table 6 was annealed before press forming under the conditions as shown in Table 7 to form a flat mask by subsequent etching.
This flat mask was press-molded and subjected to a blackening treatment to obtain material Nos. 25 to 43 as shown in Tables 7 and 8. Further, using these materials, the adhesion of the blackened film was investigated in the same manner as in Example 1. Further, together with the adhesion of the blackened film, the magnetic permeability and Vickers hardness (Hv) after the blackening treatment were examined in the same manner as in Example 1, and the results are shown in Table 8.

[0056]

[Table 12]

[0057]

[Table 13]

As is clear from the results shown in Table 13 above, the component composition and Vickers hardness (H
v), materials No. 25 to No. 34 and No. 42, No. 43 having a degree of integration of {331}, {210}, {211} crystal planes
The magnetic permeability of 50 Hz or higher is higher than that of a comparative example described later, and shows an excellent level.

On the other hand, the materials No. 35 and No. 39 have the Vickers hardness (Hv) of the case where the annealing temperature and the blackening treatment temperature before press molding exceed the upper limit of the present invention, respectively. Exceeding the requirements of the present invention, the magnetic permeability of 50 Hz or more is inferior to the examples of the present invention. Material No.3
In No. 6, the blackening treatment temperature exceeds the upper limit specified in the present invention, and the adhesion of the blackened film is poor.

Material No. 39 has a blackening temperature lower than that specified in the present invention, and materials No. 40 to No. 41 have [T ₂ ] ≧ − (4 [T ₁ ] / 9). It does not satisfy +920, the Vickers hardness (Hv) after the blackening treatment exceeds the specified value of the present invention, and the magnetic permeability at 50 Hz or more is clearly lower than that of the examples of the present invention. Furthermore, material No. 37 to No. 38
The pre-press annealing temperature exceeds the upper limit of the present invention, {331}, {210}, one or more of the degree of integration of the {211} crystal plane exceeds the upper limit of the present invention, Magnetic permeability above 50 Hz is clearly lower than in the examples of the present invention.

As described above, Vickers hardness (Hv),
In order to keep the degree of integration of the {331}, {210}, and {211} crystal planes within the range of the present invention and to achieve an excellent level of adhesion of the blackened film, the annealing temperature before pressing and the blackening treatment conditions (temperature , Time) within the scope of the present invention.

[0062]

According to the present invention as described above, the magnetic properties are excellent, and particularly the magnetic permeability in the frequency band of 50 Hz or more is excellent. It is possible to provide an Fe-Ni alloy thin plate and an Fe-Ni-Co alloy thin plate for a shadow mask capable of sufficiently performing (shielding), and as an effect thereof, a color shift caused by an electron beam bias caused by the stray magnetic field is reduced. This is an invention that is industrially highly effective, such as obtaining favorable results, such as exercising.

[Brief description of the drawings]

FIG. 1 Magnetic permeability and Mn content, [Ti] + [Cr] + [Al] + [S
It is a table | surface which summarized and showed the relationship of [i] + [Mo] + [W] + [Nb] + [V] + [Cu] amount (the value in the parenthesis shows the value of magnetic permeability at 50 Hz).

FIG. 2 is a table showing the relationship between magnetic permeability and Vickers hardness (Hv).

FIG. 3 is a table summarizing the relationship among magnetic permeability, blackening temperature and annealing temperature before pressing.

Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI H01J29 / 07 H01J29 / 07Z (56) References JP-A-6-41688 (JP, A) JP-A-5-209254 (JP, A JP-A-5-195160 (JP, A) JP-A-5-86441 (JP, A) JP-A-3-267320 (JP, A) JP-A-1-52024 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C22C 38/00-38/60 H01J 9/14 H01J 29/07

Claims (4)

(57) [Claims] (1) In wt%, Ni: 34-38%, Mn: 0.35
% Or less, Si: 0.06% or less, Cr: 0.05% or less, Ti: 0.
02% or less, Mo: 0.05% or less, W: 0.05% or less, N
b: 0.02% or less, V: 0.05% or less, Cu: 0.05% or less, [Ti] + [Cr] + [Al] + [Si] + [Mo]
+ [W] + [Nb] + [V] + [Cu] ≦ 0.25%, the balance is composed of unavoidable impurities and the composition of Fe. ｝, ｛21
An Fe-Ni alloy sheet for a shadow mask having excellent magnetic properties, wherein the degree of integration of the crystal planes of 0% and {211} satisfies the following table and the Vickers hardness (Hv) is 140 or less. [Table 1] 2. In wt%, Ni: 34-38%, Mn: 0.35
% Or less, Si: 0.06% or less, Cr: 0.05% or less, Ti: 0.
02% or less, Mo: 0.05% or less, W: 0.05% or less, N
b: 0.02% or less, V: 0.05% or less, Cu: 0.05% or less, Co: 1.0% or less, [Ti] + [Cr] + [Al]
+ [Si] + [Mo] + [W] + [Nb] + [V] + [Cu] ≦
0.25%, the balance consists of the composition of unavoidable impurities and Fe.
Fe-Ni for a shadow mask having excellent magnetic properties, wherein the degree of integration of the crystal planes of 31%, {210}, and {211} satisfies the following table, and the Vickers hardness (Hv) is 140 or less. -Co alloy sheet. [Table 2] 3. In wt%, Ni: 30-38%, Mn: 0.35
% Or less, Si: 0.06% or less, Cr: 0.05% or less, Ti: 0.
02% or less, Mo: 0.05% or less, W: 0.05% or less, N
b: 0.02% or less, V: 0.05% or less, Cu: 0.05% or less, Co: more than 1.0% to 6%, and [Ti] + [Cr]
+ [Al] + [Si] + [Mo] + [W] + [Nb] + [V] +
Contains [Cu] ≦ 0.25%, the balance being unavoidable impurities and Fe
And the degree of integration of {331}, {210}, and {211} crystal planes on the alloy plate surface after the blackening treatment satisfies the following table, and the Vickers hardness (Hv) is 14
An Fe—Ni—Co alloy sheet for a shadow mask having excellent magnetic properties, wherein the thickness is 0 or less. [Table 3] 4. A hot-rolled steel strip of a low-thermal-expansion alloy having the components according to claim 1 is subjected to hot-rolled sheet annealing, and thereafter, cold rolling, recrystallization annealing, finish cold rolling, and strain relief annealing are performed. After that, annealing is performed before press forming, and in the process of performing blackening after the subsequent press forming, the hot-rolled sheet annealing temperature (T ₀ , ° C.) is set to 810 to 890 ° C., and the press forming is performed. The previous annealing temperature (T ₁ , ° C.) is 720-900 ° C., the blackening temperature (T ₂ , ° C.) is 520-600 ° C., and [T ₂ ] ≧ − (4 [T ₁ ] / 9) +920. By satisfying {331}, {2} on the alloy plate surface after the blackening treatment
The Fe-Ni alloy sheet and Fe for a shadow mask having excellent magnetic properties, wherein the degree of integration of the crystal plane of {10} and {211} and the Vickers hardness (Hv) are adjusted to the values described in claim 1. -A method for producing a Ni-Co alloy sheet.