JPH07243004A - Fe-ni alloy sheet and fe-ni-co alloy sheet for color picture tube, excellent in magnetic property, and their production - Google Patents

Abstract

PURPOSE:To obtain an Fe-Ni alloy sheet for color picture tube, excellent in magnetic properties, by limiting the impurities in an Fe-Ni alloy containing specific amounts of Ni, Mn, and Si and specifying crystal plane integration degree after blackening treatment and hardness, respectively. CONSTITUTION:In an Fe-Ni or Fe-Ni-Co alloy containing, by weight, 30-45% Ni or 27-33% Ni and 3-8% Co, 0.001-0.70% Mn, and 0.001-0.30% Si, the amounts of Ti, Mo, W, Nb, V, Cu, Sn, and Al as impurities are limited so that they satisfy <=0.10% Ti, <=0.10% Mo, <=0.10% W, <=0.10% Nb, <=0.10% V, <=0.30% Cu, <=0.10% Sn, and <=0.07% Al and also Ti+Al+Si+Mo+W+Nb+V+Cu+ Sn<=0.70% is satisfied. Further, the integration degrees of [331], [210], and [211] crystal planes to the surface of the alloy sheet after blackening treatment satisfy the table and also Vickers hardness Hv is regulated to <=150. In order to satisfy the above conditions, hot rolled plate annealing temp., annealing temp. before press forming, and blackening treatment temp. are regulated to 810-990 deg.C, 720-900 deg.C, and 520-600 deg.C, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an F magnetic film having excellent magnetic characteristics.
Regarding the e-Ni alloy thin plate and the Fe-Ni-Co alloy thin plate, a preferable Fe-Ni alloy thin plate and a Fe-Ni-Co alloy for a color picture tube used for a color cathode ray tube
TECHNICAL FIELD The present invention relates to a system alloy thin plate and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, with the increasing quality of color televisions,
As an alloy for color picture tubes that can deal with the problem of color misregistration,
An Fe-Ni alloy containing 30 to 45 wt% Ni (hereinafter referred to as "conventional Fe-Ni alloy") is used. This conventional Fe-Ni alloy has a remarkably small coefficient of thermal expansion as compared with the low carbon steel conventionally used as a material for a shadow mask or a material for an aperture grill. Therefore, if the shadow mask is made of the conventional Fe-Ni alloy, even if the shadow mask is heated by the electron beam, the problem of color shift due to thermal expansion of the shadow mask is unlikely to occur. Further, even when the aperture grill is made of the Fe-Ni alloy, the tension of the wire of the aperture grill does not decrease due to the thermal expansion caused by the heating of the electron beam, and the practically superior performance is provided. Become.

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

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, electron beam passage holes (hereinafter simply referred to as "holes") are formed in the shadow mask alloy thin plate by photoetching (hereinafter, the shadow mask alloy thin plate that has been perforated 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 shape to match the shape of the cathode ray tube, after which it is assembled into a shadow mask, and on the surface The blackening treatment is applied to.

However, such conventional general 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 deviated, which often causes a "color shift" because it does not hit a predetermined pixel, This is a problem in screen quality, and the following prior art is known for this problem. That is, Japanese Patent Laid-Open No. 64-62421 discloses a perforated mask (flat mask) at 900 to 1200 ° C. for 5 minutes or more,
In some cases, press forming is performed by annealing in a reducing atmosphere.
The coercive force of DC is set to 1 by performing annealing at 3.3 ° C. and then annealing at 787.8 ° C., if necessary, in a weakly oxidizing atmosphere.
It is intended to solve the above-mentioned problem of "color shift" by making it equal to or less than Oersted.

[0006]

However, in the above-mentioned prior art, the effect was seen against the DC stray magnetic field such as the earth magnetism, but in the actual external environment, 50H
There are many stray magnetic fields in alternating current at 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]

SUMMARY OF THE INVENTION The present invention has been devised through repeated studies in view of the above-mentioned circumstances, and has excellent magnetic characteristics, in particular, excellent magnetic permeability of alternating current of 50 Hz or higher. The present invention succeeds in providing an Fe-Ni-based alloy for a color picture tube and an Fe-Ni-Co-based alloy capable of sufficiently shielding a stray magnetic field in a region and a method for producing the same. The summary is as follows.

(1) wt%, Ni: 30-45%, M
n: 0.001 to 0.70%, Si: 0.001 to 0.
In an Fe-Ni 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.
10% or less, Cu 0.30% or less, Sn 0.10%
Below, Al is 0.07% or less, and [Ti] + [A
l] + [Si] + [Mo] + [W] + [Nb] + [V]
+ [Cu] + [Sn] ≦ 0.70%, and moreover, {331}, {210} on the alloy plate surface after blackening treatment,
A Fe-Ni alloy thin plate for a color picture tube excellent in magnetic properties, characterized in that the degree of integration of {211] crystal planes satisfies the following table and that the Vickers hardness (Hv) is 150 or less.

[0009]

[Table 3]

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

[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 annealed by hot-rolling, and thereafter cold rolling-recrystallization annealing-finishing cold rolling-strain. After performing pre-annealing, annealing before press forming is performed, and in the step of producing the blackening treatment after the subsequent press forming, the hot-rolled sheet annealing temperature (T ₀ , ° C) is set to 810 to 990.
℃, the annealing temperature before the press molding (T ₁ , ℃) is 720
~ 900 ° C, blackening treatment temperature (T ₂ , ° C) 520-600
By satisfying [T ₂ ] ≧ − (4 [T ₁ ] / 9) +920 at 0 ° C., {33
1}, {210}, {211} crystal plane integration and Vickers hardness (Hv) are adjusted to the values described in (1) and (2) above, and a color having excellent magnetic properties. Fe-Ni alloy thin plate for picture tube and Fe-N
A manufacturing method of an i-Co alloy thin plate.

[0013]

The present invention as described above will be further described. From the viewpoint as described above, the present inventors have found that the Fe-Ni-based alloy thin plate for a shadow mask and the Fe-Ni-Co-based alloy excellent in magnetic properties are excellent. As a result of intensive studies 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 an alloy sheet within a predetermined range for the Fe-Ni alloy sheet and the Fe-Ni-Co alloy sheet for color picture tubes. By doing so, the desired magnetic characteristics can be obtained. The required magnetic property in the present invention is the magnetic permeability at a frequency of 50 Hz or higher, and the present invention intends to increase this magnetic permeability. By improving the magnetic permeability of 50 Hz or more, the stray magnetic field in the frequency range described above can be sufficiently shielded.

Further, the present inventors have obtained the following findings. That is, in the manufacturing process of the present alloy, hot-rolled steel strip is annealed at a predetermined temperature before cold rolling the hot-rolled steel strip, and further, by appropriately adjusting the annealing temperature and the blackening treatment temperature before press forming. The magnetic properties can be made excellent 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 present invention was made on the basis of the above-mentioned findings, and Fe for a color picture tube of the present invention is provided.
The reasons for limiting the chemical composition, the Vickers hardness, and the degree of integration of crystal planes on the surface of the alloy thin plate are as follows for the -Ni alloy thin plate and the Fe-Ni-Co alloy thin plate.

(1) Nickel: The upper limit of the average coefficient of thermal expansion required for the Fe-Ni alloy thin plate for a color picture tube in order to secure the required screen quality is. 5.0 x 10 ^-6 /
℃. The coefficient of thermal expansion depends on the nickel content of the alloy sheet. Then, the range of the nickel content that satisfies the above-described average thermal expansion coefficient is 30 to 45 wt.
% Range. Therefore, the nickel content is 30 to 4
It should be limited to the range of 5 wt%. Even within such a range of Ni content, the preferable Ni amount that can lower the average thermal expansion coefficient is 35 to 37%, and the further preferable Ni amount that can further lower the average thermal expansion coefficient is 35. It is 0.5 to 36.5%.

When Co is contained in an amount of less than 3%,
The amount of Ni satisfying the upper limit of the above average thermal expansion coefficient is 3
It is 4 to 38%, and the preferable amount of Ni that lowers the average thermal expansion coefficient is 35 to 37%. Further, in the case of the Fe-Ni-Co alloy thin plate containing 3% or more and 8% or less of cobalt, the range of the nickel content satisfying the condition of the above-mentioned average thermal expansion coefficient is 27 to 33%. Quantity 30
By setting the content of Co to 33% and Co to 3 to 8%, the average coefficient of thermal expansion becomes even lower and excellent.

(2) Manganese: Mn is
Improves hot workability, but if the content increases, it will be 50
Permeability decreases at frequencies above Hz. That is, when the Mn content exceeds 0.70%, the above-mentioned deterioration of magnetic properties becomes remarkable, so 0.70% was made the upper limit. In addition, this Mn
The magnetic properties described above can be further improved by reducing the amount, but if it is less than 0.001%, the hot workability deteriorates, so the lower limit of the amount of Mn is made 0.001%.

(3) Silicon: Si acts as a deoxidizing element in the present alloy, but when the content increases, it becomes 50
Permeability decreases at frequencies above Hz. That is, if the Si content exceeds 0.30%, the above-mentioned deterioration of the magnetic properties becomes remarkable, so the upper limit was made 0.30%. In addition, 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
1, Ti, Mo, W, Nb, V, Cu, and Sn are one of the impurities that are inevitably mixed in the present alloy. When the contents of these elements increase, the magnetic permeability at a frequency of 50 Hz or higher 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.

Further, in order to obtain the magnetic characteristics 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.
Each amount of u and Sn is within the range specified by the present invention, and Vickers hardness (Hv) is also within the range specified by the present invention. {311}, {2
[Al] + [Ti] + [Si] in alloys having 10} and {211} crystal plane integration degrees within the ranges specified by the present invention.
+ [Mo] + [W] + [Nb] + [V] + [Cu] +
It shows the relationship between [Sn] amount and 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.
i] + [Si] + [Mo] + [W] + [Nb] + [V]
When the amount of + [Cu] + [Sn] exceeds 0.70%, the magnetic permeability is significantly deteriorated, so 0.70% is set as the upper limit. Even if the total amount of these elements is within the range of the present invention, the magnetic permeability can be further improved by reducing the total amount.

Fe- for a color picture tube according to the present invention
As described above, the Ni-based and Fe-Ni-Co-based alloys have a specific amount of Mn, Sn, Al, Si, Ti, Mo, in addition to the basic composition of the Fe-Ni-based and Fe-Ni-Co-based alloys.
W, Nb, V, Cu, and as will be described later, {331}, {210}, {21 on the surface of the alloy plate after the blackening treatment.
1} is characterized in that the degree of integration of crystal faces is set to a specific value or less and the Vickers hardness (Hv) is set to 150 or less. However, 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
It is preferably pm or less.

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

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

From the above technical circumstances, the degree of integration of the {331} crystal face is 35% or less, the degree of integration of the {210} crystal face is 20% or less, and the integration degree of the {211} crystal face is 20% or less. Specified respectively.

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

Here, the relative X-ray diffraction intensity ratio is the X-ray intensity measured on each diffraction surface divided by the theoretical X-ray intensity of that diffraction surface. For example, the relative X-ray diffraction intensity ratio of the (111) diffraction plane is (11)
1) Divided by the theoretical X-ray diffraction intensity of the diffractive surface. Further, the degree of integration of each of the {210} and {211} crystal planes is azimuthally the same as that of this crystal plane (420), and the relative X-ray diffraction intensity ratio of the (422) diffraction plane is (111) to ( It is obtained by dividing by the sum of the relative X-ray diffraction intensity ratios of the seven diffraction surfaces up to 422).

In order to obtain the required magnetic characteristics intended by the present invention, it is important to control the Vickers hardness in addition to the above-mentioned 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, falls within the scope of the present invention. If the Vickers hardness (Hv) exceeds 150, the magnetic permeability decreases and the desired magnetic properties intended by the present invention cannot be obtained. From the 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 explained above, Mn of the alloy of the present invention,
Al, Sn, Si, Ti, Mo, W, Nb, V, Cu,
Sn, [Al] + [Ti] + [Si] + [Mo] +
Specification of [W] + [Nb] + [V] + [Cu] + [Sn], {331}, {210}, {211} after blackening treatment
By prescribing the degree of integration of crystal planes and prescribing Vickers hardness, the magnetic properties intended in the present invention can be made excellent.

{331}, {210} after blackening,
The degree of integration of {211} crystal planes is 35% or less, 20
% Or 20% or less, solidification to hot working in the production of alloy thin plates, cold rolling / annealing process thereafter, {331}, {210}, {211} crystal planes as much as possible. This is achieved by adopting manufacturing conditions that do not integrate
For example, when the present alloy is manufactured from a hot-rolled steel strip obtained by hot rolling a slab or a continuously cast slab by ingot-making / slab-rolling, the hot-rolled steel strip is used as a raw material, and thereafter hot-rolled sheet annealing -Cold rolling-Recrystallization annealing-Finishing cold rolling-Strain relief annealing is performed, then annealing before press molding is performed, and when manufacturing in the step of performing blackening treatment after press molding, first, after hot rolling Appropriate hot-rolled sheet annealing with {3
31}, {210}, {211} is effective for preventing the crystal planes from being integrated. At this time, the temperature of hot-rolled sheet annealing is 81
By selecting an appropriate temperature within the range of 0 to 990 ° C., the degree of integration of {331}, {210}, and {211} crystal planes can be made equal to or less than the specified value of 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 {331}, {210}, and {211} crystal faces within the scope of the present invention.

Such hot-rolled sheet annealing in the present invention is exhibited when the hot-rolled steel strip of the present alloy is sufficiently recrystallized before the hot-rolled sheet annealing. Further, in order to obtain the degree of integration of {331}, {210}, and {211} crystal planes intended in the present invention, the slab homogenization heat treatment after slabbing is not preferable in producing the present alloy. For example, when the homogenizing heat treatment is performed at 1200 ° C. or higher for 10 hours or longer, {311}, {210}, {211}, the degree of crystal plane integration exceeds the specified value of the present invention. Such processing must be avoided.

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

FIG. 3 shows the magnetic permeability of an alloy sheet produced by the method as shown in the upper part of the hot-rolled steel strip of the alloy according to the present invention, the annealing temperature before press (T ₁ , ° C.) and the blackening. The results of investigations and examinations while changing the processing temperature (T ₂ , ° C) are shown. 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, {33
1}, {210}, and {211} crystal planes have integration degrees of 35% or less, 20% or less, and 20% or less, respectively, Vickers hardness (Hv) of 150 or less, and magnetic permeability of 10 at 50 Hz.
The required magnetic characteristics of not less than 00 are obtained.

On the other hand, when T ₁ exceeds 900 ° C., {3
One or more of the degree of integration of 31}, {210}, and {211} crystal planes exceeds the definition of the present invention, and the magnetic permeability falls below the level intended by the present invention. When T ₁ is lower 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 by the present invention. Turn around. Furthermore, when T ₂ exceeds 600 ° C., the adhesion of the blackened film deteriorates.

From the above examination, the degree of integration of the {331}, {210}, and {211} crystal planes after the blackening treatment was made 35% or less, 20% or less, and 20% or less, respectively, and the Vickers hardness (Hv ) was 150 or less, as a condition to exhibit superior required magnetic properties, T _1: seven hundred twenty to nine
00 ° C., T ₂ : 520 to 600 ° C., [T ₂ ] ≧ − (4
[T ₁ ] / 9) +920 was set. If the blackening treatment time is 2 minutes or more and less than 10 minutes, the effect intended by the present invention is achieved under the control of T ₁ and T ₂ within the scope of the present invention. Annealing time before pressing is 1 min or more 6
If it is less than 0 min, the effect intended in the present invention is achieved under the control of T ₁ and T ₂ described above within the range of the present invention.

The alloy thin plate after the blackening treatment was {33
1), {210}, {211} The degree of integration of crystal planes is within the scope of the present invention. In addition to the above, the rapid solidification method is adopted, texture control by controlling recrystallization in hot working, etc. is there. In addition, cold rolling conditions other than the above method for keeping the Vickers hardness after blackening treatment within the scope of the present invention,
It can also be achieved by properly combining the annealing conditions.

As described above, the main purpose of the present invention is to improve the magnetic properties, but it is also one of the constituent features of the present invention that the adhesion of the blackening film during the blackening treatment is excellent.
Is one. Further, the above-mentioned FIG. 3 shows the magnetic permeability at 50 Hz, but the magnetic permeability in the frequency range exceeding 50 Hz is excellent as long as T ₁ and T ₂ are within the above-specified conditions of the present invention. Indicates the level.

Further, the annealing before press forming in the present invention may be carried out before photoetching. In this case, if the annealing conditions before press forming are within the scope of the present invention,
The required photoetching quality can be ensured.

[0040]

EXAMPLES The present invention described above will be described in more detail with reference to specific examples as follows. [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 produced by ladle refining by an ingot making method, and consisting of No. 21 to No. 26. Each CC slab was prepared by continuous casting. The H content of each alloy was 1 ppm or less.

[0041]

[Table 5]

[0042]

[Table 6]

After servicing each of the ingot and CC slab obtained as described above, the ingot was subjected to slabbing, while the CC slab was not slabbing and surface flaw removal,
Hot-rolled sheet annealing was performed under the conditions shown in the following Table 7 using the hot-rolled coil obtained by hot rolling (1100 ° C. × 3 hours for hot rolling heating) and flaw removal. After that, cold rolling-annealing-finishing cold rolling-strain relief annealing was performed to obtain an alloy plate having a plate thickness of 0.25 mm (alloy Nos. 1-26 are material Nos. 1-2, respectively).
6). Note that these alloys were sufficiently recrystallized after hot rolling.

[0044]

[Table 7]

A flat mask is formed from these materials by etching, and then the flat mask is set at 860 ° C. × 2.
Annealing before press molding was performed for 0 min, press molding was performed, and then blackening treatment was performed under the condition of 600 ° C. × 2 minutes. {331}, {210} of the surface of the alloy plate after the blackening treatment,
The degree of integration of the {211} crystal plane was determined by the above-mentioned method using X-ray diffraction. The results are shown in Table 8. The adhesion of the blackening film was evaluated by the adhesion of the blackening film on the tape after putting the tape on the blackening film, bending the tape 180 °, and peeling off the tape. The adhesiveness of the blackened film was determined to be good when the blackened film was not attached, and the adhesiveness of the blackened film was determined to be poor when the blackened film was attached to the tape.

[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 constituent requirements.

It should be noted that the alloy sheet (material which has been subjected to the above-mentioned annealing before press forming, subsequent press forming, and blackening treatment)
From No.1 to No.26), ring test pieces are processed to 50H
The AC permeability at z, 0.3 KHz, 3 KHz and 30 KHz was also investigated. 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, and the results are also shown in Table 8 above.

As is clear from the results shown in Tables 5 to 8 above, {331}, which has a component composition and Vickers hardness (Hv) within the range of the present invention and within the range of the present invention,
Material N with {210} and {211} crystal plane integration
The magnetic permeability of 50 to 50 Hz of No. 16 to No. 26 is higher than that of the comparative example described later, which is an excellent level. Also,
Materials No. 17, No. 18, No. 20, No. 23, and No. 25 have Hv reduced to a more preferable level among the examples of the present invention, and No. 17, No. 18, No. 20. , No. 2
The magnetic permeability of 50 and above of No. 3, No. 25 shows a higher value. Furthermore, among these materials, the 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]
The amount of + [Sn] is reduced to a more preferable level, and the magnetic permeability at 50 Hz or higher shows a higher value. The Co-containing materials No. 25 and No. 26 also show excellent characteristics.

On the other hand, each of the materials No. 1 to No. 11 is out of the scope of the present invention, Mn, Al, Si, Sn, T.
i, Mo, W, Nb, V, Cu, Sn, [Al] + [T
i] + [Si] + [Mo] + [W] + [Nb] + [V]
Since each of them contains + [Cu] + [Sn], the magnetic permeability at 50 Hz or higher is inferior to the examples of the present invention.

Material Nos. 12 to 15 are respectively
Vickers hardness (Hv) outside the scope of the present invention, {331}
Crystal plane integration, {210} Crystal plane integration, {21
1) The degree of integration of crystal planes, and the magnetic permeability at 50 Hz or more is inferior to the examples 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}, {21.
1} Fe-for a color picture tube having a high level of magnetic permeability at 50 Hz or more by having a degree of integration of crystal planes.
It can be seen that the Ni-based alloy thin plate and the Fe-Ni-Co-based alloy thin plate can be obtained.

[Example 2] Using the hot-rolled steel strips of alloy Nos. 16 to 22, 25, and 26 used in Example 1 described above,
After that, about what was hot-rolled board annealing was performed on the conditions shown in the following Table 9, cold rolling-recrystallization annealing-finishing cold rolling-strain relief annealing was performed, and the alloy sheet with a plate thickness of 0.25 mm. Got

[0054]

[Table 9]

Each of the alloy plates described above 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 shown in Table 11 were obtained. Further, using these materials, the adhesion of the blackened film was investigated by the same method as in Example 1. Further, the magnetic permeability and Vickers hardness (Hv) after the blackening treatment as well as the adhesion of the blackened film were examined by the same method as in Example 1, and the results are shown in Table 11.

[0056]

[Table 10]

[0057]

[Table 11]

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

On the other hand, materials No. 35 and No. 39
Shows the case where the annealing temperature before press molding and the blackening treatment temperature are lower than the lower limit of the present invention, respectively, but the Vickers hardness (Hv) exceeds the present invention, and the magnetic permeability of 50 Hz or more is 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.

All the materials No. 40 to No. 41 are [T
₂ ] ≧ − (4 [T ₁ ] / 9) +920 is not satisfied, the Vickers hardness (Hv) after blackening exceeds the specified value of the present invention, and the magnetic permeability at 50 Hz or more, the present invention. Obviously lower than the example. Furthermore, materials No.37 to No.38
Indicates that the pre-press annealing temperature exceeds the upper limit specified in the present invention, and one or more of {331}, {210}, and {211} crystal plane integration degrees exceed the upper limit specified in the present invention. The magnetic permeability above 50 Hz is obviously lower than that of the present invention.

As described above, the Vickers hardness (Hv),
In order to make the degree of integration of {331}, {210}, and {211} crystal planes within the scope of the present invention and to bring the adhesion of the blackened film to an excellent level, the pre-press annealing temperature and the blackening treatment condition (temperature , Time) within the scope of the present invention is important.

[0062]

According to the present invention as described above, the magnetic properties are excellent, and the magnetic permeability in the frequency band of 50 Hz or more is also excellent, which makes it possible to shield the stray magnetic field in the frequency band described above. Fe-Ni alloy thin plate for color picture tube capable of sufficiently performing (shielding) and Fe-Ni
-Co-based alloy thin plate is provided, and as a result, it is possible to obtain favorable results such as reduction of color shift caused by deviation of the electron beam caused by the stray magnetic field Is.

[Brief description of drawings]

FIG. 1 Magnetic permeability and Mn amount, [Al] + [Ti] + [S
i] + [Mo] + [W] + [Nb] + [V] + [Cu]
4 is a table summarizing the relationship of + [Sn] amount (the values in parentheses indicate the value of magnetic permeability at 50 Hz).

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

FIG. 3 is a chart summarizing the relationship between magnetic permeability, blackening treatment temperature and pre-press annealing temperature.

Front page continuation (72) Inventor Hiroshi Wakasa 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd.

Claims (3)

[Claims] 1. Ni: 30 to 45% and Mn: wt%
0.001-0.70%, Si: 0.001-0.30
%, Fe 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 0.10%. 10
%, Cu 0.30% or less, Sn 0.10% or less, Al 0.07% or less, and [Ti] + [A
l] + [Si] + [Mo] + [W] + [Nb] + [V]
+ [Cu] + [Sn] ≦ 0.70%, and moreover, {331}, {210} on the alloy plate surface after blackening treatment,
A Fe-Ni alloy thin plate for a color picture tube excellent in magnetic properties, characterized in that the degree of integration of {211] crystal planes satisfies the following table and that the Vickers hardness (Hv) is 150 or less. [Table 1] 2. Ni: 27-33%, Co:
3-8%, Mn: 0.001-0.70%, Si: 0.
In an Fe-Ni-Co based alloy containing 001 to 0.30%, Ti as an impurity is 0.10% or less, Mo
0.10% or less, W 0.10% or less, Nb 0.1
0% or less, V 0.10% or less, Cu 0.30% or less, Sn 0.10% or less, Al 0.07% or less, and [Ti] + [Al] + [Si] + [Mo] +
[W] + [Nb] + [V] + [Cu] + ≦ 0.70%, and {33
Fe-Ni for color picture tube excellent in magnetic characteristics, characterized in that the degree of integration of crystal planes of 1}, {210}, and {211} satisfy the following table and Vickers hardness (Hv) is 150 or less. -Co-based alloy thin plate. [Table 2] 3. A hot-rolled steel strip of a low-thermal expansion alloy having the components according to claims 1 and 2 is annealed by hot-rolled sheet and thereafter cold-rolled-recrystallization annealed-finish cold-rolled-strain relief annealed. After the annealing, the hot-rolled sheet annealing temperature (T ₀ , ° C) is 810 to 990 ° C, and the press forming is performed in a step of performing annealing before press forming, and subsequently performing blackening treatment after press forming. The previous annealing temperature (T ₁ , ° C) was 720-900 ° C, the blackening treatment temperature (T ₂ , ° C) was 520-600 ° C, and [T ₂ ] ≧-(4 [T ₁ ] / 9) +920. By satisfying the condition, {331}, {2} on the surface of the alloy plate after the blackening treatment
10}, {211} crystal plane integration and Vickers hardness (Hv) are adjusted to the values described in claims 1 and 2, which are excellent in magnetic properties. Method for manufacturing thin plate and Fe-Ni-Co alloy thin plate.