JP3284732B2 - Fe-Ni-based alloy thin plate and Fe-Ni-Co-based alloy thin plate for a color picture tube having excellent magnetic properties and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to an e-Ni-based alloy thin plate and an Fe-Ni-Co-based alloy thin plate, which are preferably used for a color cathode ray tube.
The present invention relates to a thin alloy sheet and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, with the high quality of color televisions,
As an alloy for color picture tubes that can deal with the problem of color misregistration,
An Fe-Ni-based alloy containing 30 to 45 wt% of Ni (hereinafter referred to as "conventional Fe-Ni-based alloy") is used. This conventional Fe—Ni-based alloy has a significantly lower coefficient of thermal expansion than low carbon steel conventionally used as a shadow mask material or an aperture grill 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. In addition, even when the aperture grill is made of an Fe-Ni alloy, there is no decrease in the tension of the wires of the aperture grill due to the thermal expansion caused by the heating of the electron beam. Become.

The above-mentioned alloy thin plate for a color picture tube is usually manufactured by the following steps. That is, CC slab and alloy ingot are prepared by the continuous casting method or ingot making method, respectively, and then the alloy ingot thus prepared is subjected to slab rolling, and thereafter hot rolling, cold rolling and annealing. hand,
This is for producing alloy thin plates.

[0004] The alloy thin plate for a color picture tube 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, simply referred to as [hole]) is formed in the alloy thin plate for shadow mask by photoetching (hereinafter, the thin alloy plate for shadow mask as it is drilled by etching is referred to as [flat mask]. ) Then, the flat mask is annealed, and then the annealed flat mask is press-formed into a curved surface shape so as to conform to the shape of the cathode ray tube. Thereafter, this is assembled into a shadow mask and Is subjected to a blackening process.

However, such conventional Fe-N
When an i-based alloy is used for a color picture tube, a stray magnetic field existing in the environment outside the color cathode ray tube causes the electron beam to be deflected, and often causes "color shift" due to the fact that the electron beam does not hit a predetermined pixel. This is a problem in screen quality, and the following prior arts are known for this problem. That is, JP-A-64-62421 discloses that a perforated mask (flat mask) is used at 900 to 1200 ° C. for 5 minutes or more.
If necessary, anneal in a reducing atmosphere and press form 9
By annealing at 3.3 ° C. and then at 787.8 ° C., optionally in a weakly oxidizing atmosphere, to reduce the DC coercivity to 1
An Oersted or less is intended to solve the above-mentioned problem of "color shift".

[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, the effect was 50H.
There are many stray magnetic fields in alternating current with frequencies above z,
The effect cannot be sufficiently exerted on these stray magnetic fields, and as a result, the deviation of the electron beam still occurs, and the problem of color shift 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. Fe-Ni-based alloys and Fe-Ni-Co-based alloys for color picture tubes capable of sufficiently shielding (shielding) a stray magnetic field in a region, and a method of manufacturing the same have been successfully provided. The summary is as follows.

(1) In wt%, Ni: 30 to 45%, M
n: 0.001 to 0.70%, Si: 0.001 to 0.
In an Fe-Ni-based alloy containing 30%, Ti as an impurity is 0.10% or less, Mo is 0.10% or less,
W is 0.10% or less, Nb is 0.10% or less, and V is 0.1% or less.
10% or less, Cu is 0.30% or less, Sn is 0.10%
Hereinafter, the content of Al is set to 0.07% or less, and [Ti] + [A
l] + [Si] + [Mo] + [W] + [Nb] + [V]
+ [Cu] + [Sn] ≦ 0.70%, and {331}, {210},
The Fe-Ni alloy thin plate for a color picture tube having excellent magnetic properties, wherein the degree of integration of the crystal plane of {211] satisfies the following table and the Vickers hardness (Hv) is 150 or less.

[0009]

[Table 3]

(2) In wt%, Ni: 27-33%, C
o: 3 to 8%, Mn: 0.001 to 0.70%, Si:
In an Fe-Ni-Co alloy containing 0.001 to 0.30%, Ti as an impurity is 0.10% or less;
Mo is 0.10% or less, W is 0.10% or less, Nb is 0.10% or less, V is 0.10% or less, and Cu is 0.30%.
% Or less, Sn is 0.10% or less, Al is 0.07% or less, and [Ti] + [Al] + [Si] + [Mo] +
[W] + [Nb] + [V] + [Cu] + ≦ 0.70%, and moreover, ｛33 on the alloy plate surface after the blackening treatment
Fe-Ni for a color picture tube excellent in magnetic properties, characterized in that the degree of integration of crystal planes of {1}, {210}, and {211} satisfies the following table, and Vickers hardness (Hv) is 150 or less. -Co-based alloy sheet.

[0011]

[Table 4]

(3) The hot-rolled steel strip of the low-thermal-expansion alloy having the components described in (1) and (2) above is subjected to hot-rolled sheet annealing, and thereafter cold-rolling-recrystallization annealing-finish cold-rolling-strain After performing the strip annealing, the steel sheet is annealed before press forming, and in the process of performing a blackening treatment after the subsequent press forming, the hot-rolled sheet annealing temperature (T ₀ , ° C.) is set at 810 to 990.
° C, the annealing temperature before press molding (T ₁ , ° C) is 720
~ 900 ° C, blackening temperature (T ₂ , ° C) 520-600
C. and satisfying [T ₂ ] ≧ − (4 [T ₁ ] / 9) +920, a value of {33}
A color excellent in magnetic properties, wherein the degree of integration of crystal planes of {1}, {210}, and {211} and Vickers hardness (Hv) are adjusted to the values described in (1) and (2) above. Fe-Ni alloy thin plate for picture tube and Fe-N
A method for producing an i-Co alloy thin plate.

[0013]

The present invention as described above will be further described. From the above-mentioned viewpoints, the present inventors have found that Fe-Ni-based alloy thin plates and Fe-Ni-Co-based alloys for shadow masks having excellent magnetic properties. As a result of intensive research to develop a thin plate, the following findings were obtained. That is, the present invention adjusts the chemical composition, the Vickers hardness, and the degree of integration of a specific crystal plane on the surface of the alloy thin plate within a predetermined range for the Fe-Ni alloy thin plate for a color picture tube and the Fe-Ni-Co alloy thin plate. In some cases, required magnetic characteristics can be obtained. The required magnetic characteristics in the present invention are magnetic permeability at a frequency of 50 Hz or more, and it is the intention of the present invention to increase the magnetic permeability. By improving the magnetic permeability of 50 Hz or more, the stray magnetic field in the above-mentioned frequency range can be sufficiently shielded.

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-mentioned findings, and is based on the Fe for color picture tube of the present invention.
The reasons for limiting the chemical composition, Vickers hardness, and the degree of integration of crystal planes on the surface of the alloy thin plate regarding the -Ni-based alloy thin plate and the Fe-Ni-Co-based alloy thin plate are as follows.

(1) Nickel: The upper limit of the average thermal expansion coefficient required for a Fe—Ni alloy thin plate for a color picture tube in order to secure required screen quality is. 5.0 × 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 condition of the average thermal expansion coefficient is 30 to 45 wt.
% Range. Therefore, the nickel content is between 30 and 4
It should be limited to the range of 5 wt%. In addition, even within 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 amount that can further reduce the average thermal expansion coefficient is 35. 0.5-36.5%.

In the case of containing less than 3% of Co,
The amount of Ni satisfying the upper limit of the average thermal expansion coefficient is 3
The Ni content is 4 to 38%, and the preferable Ni content for lowering the average thermal expansion coefficient is 35 to 37%. Further, in the case of an Fe—Ni—Co-based alloy sheet containing 3% or more and 8% or more of cobalt, the range of the nickel content that satisfies the above condition of the average thermal expansion coefficient is 27 to 33%. 30 quantity
By setting the Co to 3 to 8% and the Co to 3 to 8%, the average coefficient of thermal expansion becomes lower and more excellent.

(2) Manganese: Mn is contained in the present alloy.
Although the hot workability is improved, when the content is increased, 50
The magnetic permeability at a frequency higher than Hz is reduced. That is, when the amount of Mn exceeds 0.70%, the above-mentioned deterioration of the magnetic characteristics becomes remarkable, so the upper limit is set to 0.70%. Note that this Mn
The magnetic properties described above can be further improved by reducing the amount. However, if the amount is less than 0.001%, the hot workability deteriorates. Therefore, the lower limit of the amount of Mn is set to 0.001%.

(3) Silicon: Si acts as a deoxidizing element in the present alloy.
The magnetic permeability at a frequency higher than Hz is reduced. That is, when the amount of Si exceeds 0.30%, the above-described deterioration of the magnetic characteristics becomes remarkable, so the upper limit is set to 0.30%. Note that this S
The magnetic properties described above can be further improved by reducing the amount of i, but if it is less than 0.001%, deoxidation cannot be sufficiently performed, so the lower limit of the amount of Si is made 0.001%.

(4) Aluminum, titanium, molybdenum, tungsten, niobium, vanadium, copper, tin: A
l, Ti, Mo, W, Nb, V, Cu, and Sn 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: 0.07%, Ti: 0.10%, M
o: 0.10%, W: 0.10%, Nb: 0.10%,
V: 0.10%, Cu: 0.30%, Sn: 0.10%
Therefore, Al: 0.07% or less, Ti: 0.10% or less, Mo: 0.10% or less, W: 0.10%, Nb:
0.10% or less, V: 0.10% or less, Cu: 0.30
%, Sn: 0.10% 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 Al, Ti, Si, Mo, W, Nb, V, C
The amounts of u and Sn are within the range specified by the present invention, and the Vickers hardness (Hv) is also within the range specified by the present invention. {311}, {2}
[Al] + [Ti] + [Si] in an alloy whose degree of integration of the {10} and {211} crystal planes is within the range specified in the present invention.
+ [Mo] + [W] + [Nb] + [V] + [Cu] +
It shows the relationship between the [Sn] amount 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. 1, but [Al] + [T
i] + [Si] + [Mo] + [W] + [Nb] + [V]
When the amount of + [Cu] + [Sn] exceeds 0.70%, the magnetic permeability is significantly deteriorated. Therefore, the upper limit is set to 0.70%. Even if the total amount of these elements falls within the range of the present invention, the magnetic permeability can be further improved by reducing the total amount.

It should be noted that the present invention relates to a color picture tube Fe-
As described above, the Ni-based and Fe-Ni-Co-based alloys contain a specific amount of Mn, Sn, Al, Si, Ti, Mo, in the basic composition of the Fe-Ni-based and Fe-Ni-Co-based alloys.
W, Nb, V, and Cu, and, as described later, {331}, {210}, and {21}
It is characterized in that the degree of integration of 1｝ crystal planes is not more than a specific value and the Vickers hardness (Hv) is not more than 150. In addition to the above composition, C: 0.050% or less, N:
0.0030% or less, S: 0.0050% or less, P:
0.010% or less, O: 0.0050% or less, H: 3p
pm 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%, 20% and 20%, respectively.
Even when the above-mentioned component requirements are satisfied, required magnetic properties cannot be obtained.

From the above technical circumstances, the degree of integration of the {331} crystal plane is 35% or less, the degree of integration of the {210} crystal plane is 20% or less, and the degree of integration of the {211} crystal plane is 20% or less. Each was determined.

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 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 (11)
1) Divided by the theoretical intensity of X-ray diffraction on the diffraction surface. The degree of integration of each of the crystal planes {210} and {211} is azimuthally the same as this crystal plane (420), and the relative X-ray diffraction intensity ratios of the diffraction planes of (422) are (111) to (111). 422) by dividing by the sum of the relative X-ray diffraction intensity ratios of the seven diffraction planes up 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 150, 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 set to 150 or less. Even when Hv is 150 or less, the magnetic permeability of the alloy plate can be made higher by lowering Hv.

As described above, Mn,
Al, Sn, Si, Ti, Mo, W, Nb, V, Cu,
Sn, [Al] + [Ti] + [Si] + [Mo] +
[W] + [Nb] + [V] + [Cu] + [Sn], {331}, {210}, {211} after blackening
The definition of the degree of integration of crystal planes and the definition of Vickers hardness can improve the magnetic properties intended in the present invention.

{331}, {210},
The degree of integration of {211} crystal planes is 35% or less and 20
% 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 used to manufacture a slab or continuous cast slab by ingot-bulking rolling or a hot-rolled steel strip obtained by hot rolling, the hot-rolled steel strip is used as a material, and thereafter, hot-rolled sheet annealing is performed. -Cold rolling-recrystallization annealing-finishing cold rolling-performing strain relief annealing, then performing annealing before press forming, and performing blackening treatment after press forming, first, after hot rolling The proper hot-rolled sheet annealing at
This is effective for preventing the crystal planes of {31}, {210}, and {211} from being accumulated.
By selecting an appropriate temperature within the range of 0 to 990 ° C., the degree of integration of the {331}, {210}, and {211} crystal planes can each be equal to or less than the value specified in the present invention. From the above, 810 to 990 ° C. was determined as the hot-rolled sheet annealing condition for keeping the degree of integration of the {331}, {210}, and {211} crystal planes within the range of the present invention.

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, if the above homogenization heat treatment is performed at a temperature of 1200 ° C. or more and 10 hours or more, {311}, {210}, and {211}, the degree of integration of crystal planes exceeds the prescribed 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, 20% or less, 20% or less, respectively, the Vickers hardness (Hv) is 150 or less, and the magnetic permeability at 50 Hz is 10%.
With a value of 00 or more, 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. or [T ₂ ] <− (4 [T ₁ ] / 9) +920, the Vickers hardness (Hv) exceeds 150, and the magnetic permeability falls below the level intended in the present invention. Go around. Further, when T ₂ exceeds 600 ° C., the adhesion of the blackened film deteriorates.

Based on the above examination, the degree of integration of the {331}, {210}, and {211} crystal planes after the blackening treatment is 35% or less, 20% or less, 20% or less, respectively, and the Vickers hardness (Hv ) Is set to 150 or less, and T ₁ : 720 to 9
00 ° C., T ₂ : 520 to 600 ° C., [T ₂ ] ≧ − (4
[T ₁ ] / 9) +920 was determined. If the blackening processing time is 2 minutes 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. Annealing time before press is 1 min or more 6
If it is less than 0 min, the effects intended in the present invention can be achieved under the control of T ₁ and T ₂ within the range of the present invention.

The alloy thin plate after the blackening treatment was # 33
The method for controlling the degree of integration of 1｝, {210｝, and {211} crystal planes within the scope of the present invention includes, besides the above, adoption of a rapid solidification method, texture control by controlling recrystallization in hot working, and the like. is there. 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 higher than 50 Hz is 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.

[0040]

The present invention will be described below in more detail with reference to specific examples. Example 1 A steel ingot consisting of No. 1 to No. 20 having the chemical components shown in the following Tables 5 to 6 was formed by ladle refining by an ingot making method and made of No. 21 to No. 26. Each CC slab was prepared by a continuous casting method. The H content of each alloy was 1 ppm or less.

[0041]

[Table 5]

[0042]

[Table 6]

After each of the ingots and CC slabs obtained as described above were cared for, the ingots were subjected to slab rolling, while the CC slabs were not subjected to slab rolling, and surface defects were removed.
The hot-rolled sheet was annealed under the conditions shown in the following Table 7 using the hot-rolled coil obtained by hot rolling (heating at 1100 ° C. for 3 hours) and flaw removal. 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 Nos. 1-26 correspond to material Nos. 1-2, respectively).
6 or less). Note that these alloys were sufficiently recrystallized after hot rolling.

[0044]

[Table 7]

After these materials are made into a flat mask by etching, this flat mask is heated at 860 ° C. × 2.
Annealing before press molding was performed at 0 min, and after press molding, blackening treatment was performed at 600 ° C. × 2 minutes. {331}, {210},
The degree of integration of the {211} crystal plane was determined by the above-described method using X-ray diffraction. The results are shown in Table 8. Also, the adhesion of the blackened film was measured by placing a tape on the blackened film, bending the tape 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.

[0046]

[Table 8]

The adhesion of the blackened film of each of the materials Nos. 1 to 26 in this example was 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), process the ring test piece and
The AC permeability at z, 0.3 KHz, 3 KHz and 30 KHz was also examined. The applied magnetic field is 5 m Oersted. The Vickers hardness (Hv) of these alloy plates after the blackening treatment was measured on the cross section of the alloy plates. The results are also shown in Table 8 above.

As is evident from the results shown in Tables 5 to 8, the component composition and Vickers hardness (Hv) within the scope of the present invention and {331},
Material N with {210}, {211} crystal plane integration
The magnetic permeability of 50 Hz or more of o.16 to No.26 is higher than that of a comparative example described later, and shows an excellent level. Also,
Materials No. 17, No. 18, No. 20, No. 23 and No. 25 are those in which Hv was reduced to a more preferable level among the examples of the present invention, and No. 17, No. 18, No. 20 , No.2
3. The magnetic permeability of 50 Hz or more of No. 25 shows a higher value. Furthermore, among these materials, material No.
20 is Mn, Al, Si, Cr, Ti, Mo, W, N
b, V, Cu, Sn and [Al] + [Ti] + [S
i] + [Mo] + [W] + [Nb] + [V] + [Cu]
+ [Sn] is 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, the materials No. 1 to No. 11 respectively contain Mn, Al, Si, Sn, T
i, Mo, W, Nb, V, Cu, Sn, [Al] + [T
i] + [Si] + [Mo] + [W] + [Nb] + [V]
+ [Cu] + [Sn], and the magnetic permeability at 50 Hz or more is inferior to that of the present invention.

The materials No. 12 to No. 15 are respectively
Vickers hardness (Hv) out of the range of the present invention, {331}
Crystal plane integration degree, {210} crystal plane integration degree, {21
It has a degree of integration of 1｝ crystal plane, and the permeability at 50 Hz or more is inferior to that of the present invention.

As is apparent from the above description, the component composition within the scope of the present invention and Vickers hardness (Hv) within the scope of the present invention, {331}, {210}, {21}
By setting the degree of integration of the 1｝ crystal plane, Fe-Fe for a color picture tube having an excellent level of magnetic permeability at 50 Hz or more.
It can be seen that a Ni-based alloy thin plate and a Fe-Ni-Co-based alloy thin plate 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,
Thereafter, for those subjected to hot-rolled sheet annealing under the conditions shown in Table 9 below, cold rolling-recrystallization annealing-finish cold rolling-strain relief annealing was performed, and an alloy sheet having a sheet thickness of 0.25 mm was obtained. I got

[0054]

[Table 9]

Each of the above alloy plates was annealed before press forming under the conditions shown in Table 10 below to form a flat mask by subsequent etching, and then the flat mask was press-formed and blackened. Material Nos. 25 to 43 as shown in Table 11 were obtained. 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 11.

[0056]

[Table 10]

[0057]

[Table 11]

As is evident from the results shown in Table 11 above, the component composition and Vickers hardness (H
v), {331}, {210}, and {211} materials having a crystal plane density No. 25 to No. 34 and No. 42, No. 42
The magnetic permeability of No. 43 at 50 Hz or higher is higher than that of a comparative example described later, indicating an excellent level.

On the other hand, materials No. 35 and No. 39
Are the cases of the annealing temperature and the blackening treatment temperature before press forming, respectively, which are less than the lower limit of the present invention. The Vickers hardness (Hv) exceeds the present invention, and the magnetic permeability of 50 Hz or more is higher than that of the present invention. It is inferior to the invention examples. Also the material
In No. 36, the blackening treatment temperature exceeded the upper limit specified in the present invention, and the adhesion of the blackened film was poor.

Further, all of the materials No. 40 to No. 41 [T
₂ ] ≧ − (4 [T ₁ ] / 9) +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. Clearly lower than in the example. Further, 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, The permeability above 50 Hz is clearly lower than in 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 characteristics are excellent, and the magnetic permeability in the frequency band of 50 Hz or more is particularly excellent. Fe-Ni alloy thin plate for color picture tube and Fe-Ni capable of sufficiently performing (shielding)
-Co-based alloy thin plate, and has an industrially significant effect, such as obtaining favorable results such as reduction of color shift caused by electron beam deviation caused by the stray magnetic field. It is.

[Brief description of the drawings]

FIG. 1 shows magnetic permeability and Mn content, [Al] + [Ti] + [S
i] + [Mo] + [W] + [Nb] + [V] + [Cu]
5 is a table summarizing the relationship between the amounts of + [Sn] (the values in the parentheses indicate the values of the 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 (72) Inventor Hiroshi Wakasa 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (56) References JP-A-7-62496 (JP, A) JP-A-7-34201 ( JP, A) JP-A-6-57384 (JP, A) JP-A-6-57383 (JP, A) JP-A-6-41688 (JP, A) JP-A-5-209254 (JP, A) JP JP-A-5-195160 (JP, A) JP-A-5-86441 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C22C 38/00-38/60 H01J 29/07

Claims (3)

(57) [Claims] 1. In wt%, Ni: 30 to 45%, Mn:
0.001 to 0.70%, Si: 0.001 to 0.30
% Of an Fe—Ni-based alloy containing 0.1% or less of Ti, 0.10% or less of Mo, 0.10% or less of W, 0.10% or less of Nb, and 0.1% or less of V as impurities. 10
%, Cu is 0.30% or less, Sn is 0.10% or less, Al is 0.07% or less, and [Ti] + [A
l] + [Si] + [Mo] + [W] + [Nb] + [V]
+ [Cu] + [Sn] ≦ 0.70%, and {331}, {210},
{211] Fe-Ni alloy thin plate for a color picture tube having excellent magnetic properties, wherein the degree of integration of crystal planes satisfies the following table and the Vickers hardness (Hv) is 150 or less. [Table 1] 2. In wt%, Ni: 27-33%, Co:
3-8%, Mn: 0.001-0.70%, Si: 0.
In an Fe—Ni—Co alloy containing 001 to 0.30%, Ti as an impurity is 0.10% or less,
0.10% or less, W is 0.10% or less, and Nb is 0.1% or less.
0% or less, V is 0.10% or less, Cu is 0.30% or less, Sn is 0.10% or less, Al is 0.07% or less, and [Ti] + [Al] + [Si] + [Mo] +
[W] + [Nb] + [V] + [Cu] + ≦ 0.70%, and moreover, ｛33 on the alloy plate surface after the blackening treatment
Fe-Ni for a color picture tube excellent in magnetic properties, characterized in that the degree of integration of crystal planes of {1}, {210}, and {211} satisfies the following table, and Vickers hardness (Hv) is 150 or less. -Co-based alloy sheet. [Table 2] 3. A hot-rolled steel strip of a low-thermal-expansion alloy having the components described in 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, the steel sheet is annealed before press forming, and then subjected to a blackening treatment after the subsequent press forming. In the production, the hot-rolled sheet annealing temperature (T ₀ , ° C.) is 810 to 990 ° C., and the press forming is performed. before annealing temperature (T _1, ° C.) to 720 to 900 ° C., the blackening treatment temperature (T _2, ° C.) was a five hundred twenty to six hundred ° C., and [T _2] ≧ - (4 [T _1] / 9) Tasu920 Satisfying {331} and {2} on the surface of the alloy plate after the blackening treatment.
3. A Fe-Ni alloy for a color picture tube having excellent magnetic properties, wherein the degree of integration of crystal planes of {10} and {211} and Vickers hardness (Hv) are adjusted to the values described in claim 1 or 2. A method for producing a thin plate and an Fe—Ni—Co alloy thin plate.