JP2003221651A - Fe-Ni-BASED AND Fe-Ni-Co-BASED ALLOY BAR FOR SHADOW MASK - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-strength Fe-Ni-based and Fe-Ni-Co-based alloy bars with high strength for a shadow mask capable of effectively preventing the occurrence of mask unevenness. <P>SOLUTION: In the Fe-Ni-based and Fe-Ni-Co-based alloys which contain Ni of 34-38 mass%, Mn of 0.1-1.0 mass%, C of 0.10 mass% or less and Al of 0.05 mass% or less, the average value αAVE of the ä100} integration degree distribution in the plate thickness direction on a plate surface is 60% or less and the ä100} integration degree α<SB>c</SB>on the plate surface after removing up to 50% of the plate thickness by etching is larger than the ä100} integration degree α<SB>s</SB>on the plate surface. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a strip for a shadow mask used for a color-selective electrode arranged in a cathode ray tube of a high-definition display for a color television or a personal computer.

[0002]

2. Description of the Related Art A strip used for a shadow mask is obtained by subjecting an ingot produced by melting and casting to hot forging and hot rolling, and then repeating cold rolling and annealing, followed by final cold rolling. It is applied and manufactured. This shadow mask strip is degreased and surface-treated by an etching maker, coated with photoresist on both sides, and then baked with a shadow mask pattern and developed, and then perforated by spraying ferric chloride solution from both sides. Then, a shadow mask is produced.

[0003]

In recent years, due to the finer pitch of holes accompanying the higher definition of personal computer displays, in the shadow mask strip, high etching piercing property, high strength, and low thermal expansion for suppressing the occurrence of mask unevenness are achieved. Characteristics are strongly demanded. In order to perforate fine pitch while suppressing the occurrence of mask unevenness, it is necessary to reduce the thickness of the material, but if the thickness is reduced, the rigidity becomes weaker, deformation during handling and impact resistance after assembling the cathode ray tube. There is a problem such as weakening. Therefore, the material for the shadow mask is desired to have excellent etching perforation properties and strength.

An etching factor (hereinafter referred to as EF) is one of the indexes for evaluating the etching perforation property. The EF is the ratio of the etching depth to the side etching amount (the size of the radius of the hole after etching minus the radius of the resist opening), and the larger this value, the better the etching piercing property. In order to increase this EF, the integration degree in the {100} direction on the plate surface (hereinafter, "{100}
It is known that a very good etching piercing property can be obtained especially when the {100} integration degree is 60% or more. However, in order to obtain a {100} integration degree of 60% or more on the plate surface, it is necessary to suppress the workability in the final cold rolling to be low. For this reason, since the degree of work hardening is limited, it is not possible to cope with high strength.

[0005]

The inventors of the present invention have conducted extensive studies on the relationship between the distribution of the degree of integration in the {100} direction with respect to the plate surface in the plate thickness direction and the etching piercing property. As a result, the mask unevenness is suppressed. In order to achieve this, it was found that it is more effective to improve the cross-sectional shape of the holes by optimizing the integration distribution in the {100} direction in the plate thickness direction rather than increasing the etching factor.

The Fe-Ni alloy strip for a shadow mask of the present invention was made on the basis of the above findings. Ni: 3
4-38 mass%, Mn: 0.1-1.0 mass%, C: 0.10 mass% or less, Si: 0.1 mass% or less, Al: 0.05 mass% or less, unavoidable It has a composition consisting of impurities and a substantial balance of Fe, and has a composition of {10
0} The average value α _{AVE in the} distribution in the plate thickness direction is 6
It is characterized in that it is 0% or less and the {100} integration degree α _{c on} the surface after removing up to 50% of the plate thickness by etching is larger than the {100} integration degree α _s on the plate surface.

FIG. 1 is a view for explaining the operation of the present invention, showing a cross section of a hole punched by etching. FIG. 1 (A) shows that when the average value α of the {100} integration degree in the plate thickness direction distribution on the strip plate surface is 60% or less,
(B) shows the cross-sectional shape of the hole when the average value α in the thickness direction distribution of the {100} integration degree on the strip plate surface exceeds 60%. From these figures, it can be seen that the case of FIG. 1B has a higher EF than the case of FIG. Further, in the case of FIG. 1 (A) where the EF is low, the boundary between the inner peripheral surface and the surface of the hole has a sharp cross-sectional shape, and as shown in FIG. 2 (A), the shape of the hole is not a perfect circle. The shape becomes distorted.
As a result, mask unevenness is likely to occur.

On the other hand, in order to increase the {100} integration degree, as described above, it is necessary to suppress the workability in the final cold rolling to be low, and it is not possible to cope with the high strength. The present invention is
The average value α in the thickness direction distribution of {100} integration is 6
The hole as shown in FIG. 1 (B) and FIG. 2 (B) is obtained while the content is 0% or less. That is, in the Fe—Ni-based alloy strip for shadow masks of the present invention, the {100} integration degree of the plate thickness surface layer portion is lower than the inside (the EF is small). 1 (B) because the horizontal etching rate is increased.
As shown in, a smooth cross-sectional shape of the edge of the hole is obtained,
As shown in FIG. 2 (B), a hole close to a perfect circle can be obtained. As described above, when the holes are formed by spray injection, the distribution of the {100} integration degree in the plate thickness direction is small near the surface layer, and the higher the inside, the better the hole cross-sectional shape. Further, since the {100} integration degree is high on the inner side in the plate thickness direction, the EF is high and a good etching piercing property can be obtained.

Further, in the present invention, since the average value α _{AVE in the} distribution in the plate thickness direction of the {100} integration degree on the plate surface is 60% or less, the degree of work hardening in the final rolling is high,
Therefore, the strength can be increased. Where {1
00} degree of integration is calculated by the following mathematical expression 1. Further, the integrated intensity I (hkl) of each crystal plane is determined by X-ray diffraction (hereinafter referred to as XRD), and the azimuth peak position (2) is obtained.
θ) is the intensity obtained by subtracting the background from the integrated intensity in the range of ± 3 °.

[0010]

## EQU1 ## {100} Accumulation degree (%) α = I (200) /
{I (111) + I (200) + I (220) + I (3
11)} × 100

Further, the average value α _{AVE in the} distribution in the plate thickness direction of the {100} integration degree on the plate surface is defined by the following _expression 2. Further, FIG. 3 is a diagram showing the distribution of the {100} integration degree in the present invention.

[0012]

[Equation 2]

In practice, the average value α _AVE can be approximately calculated as shown in FIG. 12 μm from the surface of each alloy and one side by spray etching (plate thickness 10
%), 36 μm (30% of plate thickness), 60 μm
The measured surface (corresponding to 50% of the plate thickness) was measured using XRD.

In order to surely obtain the above-described action and effect of the present invention, {100} of the plate surface having {100} integration degree α _{c on} the surface after removing up to 50% of the plate thickness by etching {100}. } The ratio to the integration degree α _s is preferably 1.2 or more.

Further, the above-mentioned Fe-N for shadow mask is used.
i-type alloy strips fall into the category of amber alloys,
The Fe-Ni-Co alloy strip has a lower thermal expansion than the Fe-Ni alloy strip, and also has high strength and is excellent for a shadow mask, which is one of the features of the present invention. That is, Fe-Ni- for the shadow mask of the present invention
The Co-based alloy strip has Ni: 28 to 34 mass% and Co: 2 to
7% by mass, Mn: 0.1 to 1.0% by mass, and C:
0.10 mass% or less, Si: 0.1 mass% or less, Al:
0.05 mass% or less, inevitable impurities and substantial Fe
It has a composition consisting of the balance, the average value α _AVE in the thickness direction distribution of the {100} integration degree on the plate surface is 60% or less, and {100} after removing up to 50% of the plate thickness by etching. } The degree of integration α _c is {100} the degree of integration α of the plate surface
It is characterized by being larger than _s . In addition, since Co having a similar action to Ni is added to the above alloy strip, the content of Ni is reduced to 28 to 34 mass%.

The above-mentioned alloy strip for shadow masks can also obtain the same actions and effects as those described above. Further, in order to surely obtain the action and effect of the present invention, {100} integration on the plate surface having {100} integration degree α _{c on} the surface after removing up to 50% of the plate thickness by etching is performed. Degree α
_The ratio to _s is preferably 1.2 or more.
Further, the above-mentioned Fe-Ni system for shadow mask and Fe
In the —Ni—Co alloy strip, “substantially Fe balance” means that other than Fe, any element that does not change the properties of the alloy strip of the present invention can be contained.

The strips used for the shadow mask are provided with a concavo-convex pattern called a dull on the rolling surface for the purpose of preventing the shadow masks from adhering (burning) to each other in the heat treatment process after etching. This dull pattern can be obtained by rolling with a rolling roll (hereinafter referred to as a dull roll) whose surface is appropriately roughened by shot processing or the like. In the rolling process, a deformation amount difference occurs between the surface layer portion and the inside as the workability is increased, and this tendency is particularly remarkable in the dull roll because the friction force with the material surface is higher than that in the bright roll. In the alloy strip for shadow masks of the present invention, such a dull roll is used to control the final rolling degree and the diameter of the dull roll, and thus the {100} integration degree of the surface layer portion is controlled to be the optimum {100}. An integration degree distribution can be obtained. In addition,
Although the present invention defines the components as described above, the added element is not limited to such components,
Any component can be contained as long as the functions of Ni, Mn, etc. are not impaired. Further, although claim 1 is an Fe-Ni-based alloy, a trace amount (0.02% or less) of Co is contained with the addition of Ni. Therefore, Co is 0.02%
When included below, it is included in the category of Fe-Ni based alloys.

[0018]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Alloys A and B having the compositions shown in Table 1 were melted by vacuum melting, and then the ingot was hot forged and hot rolled. In this case, alloy A has the composition defined in claims 1 and 2, and alloy B has the composition defined in claims 3 and 4. Then, after removing the oxide scale on the surface, cold rolling and annealing were repeated, and finally cold rolling was performed to manufacture an alloy strip having a thickness of 0.12 mm. Table 2 shows the final cold workability and the diameter of the dull roll used in the cold rolling. Further, the 0.2% proof stress of each alloy strip was measured, and the results are also shown in Table 2. Furthermore, the surface of each alloy and 12 μm from one side by spray etching (corresponding to 10% of the plate thickness), 36 μm
(Equivalent to 30% of plate thickness), 60 μm (Equivalent to 50% of plate thickness)
The removed surface was measured using XRD.

[0019]

[Table 1]

The obtained degree of integration is also shown in Table 2. Also,
The average value in the distribution in the plate thickness direction was approximately calculated from the degree of accumulation in the depth ratio of 0 to 50% of the thickness as shown in FIG. 4, and the average value α _AVE is also shown in Table 2. Further, the ratio of the {100} integration degree α _c at the center of the plate thickness to the {100} integration degree α _s of the surface was determined, and the results are also shown in Table 2.

[0021]

[Table 2]

Next, a photoresist is applied to both sides of these alloy strips by a known photoetching method, and after a pattern is baked and developed, a ferric chloride solution is sprayed from both sides to perforate a shadow mask. Was produced. The obtained shadow mask was observed in a dark room with transmitted light or reflected light to confirm the presence or absence of mask unevenness. The results are shown in Table 2 as "X" when the mask unevenness occurs, "O" when the mask unevenness does not occur, and "Δ" when the mask unevenness occurs but there is no problem in use. Further, the mask strength was evaluated from the measured 0.2% proof stress, and when the mask strength was insufficient, it was shown as "x", and when it was sufficient, it was shown in Table 2 together.

As can be seen from Table 2, in the embodiment, 40%
Since the final processing was performed, the work hardening of the alloy strip was sufficiently performed and sufficient mask strength was obtained. Further, since the workability was high, the average value α _{AVE in the} distribution in the plate thickness direction of the {100} integration degree was 60% or less. Further, in the example, since the dull roll having a diameter of 50 to 60 mm was used,
The work strain of the surface layer of the alloy strip becomes large, and the surface {10
0} The degree of integration α _s decreased, and α _c / α _s exceeded 1. In Examples 5 to 6 with a diameter of 60 mm, mask unevenness occurred, but there was no problem in use, and Example 1 with a diameter of 50 mm was used.
In Nos. 4 to 4, no mask unevenness occurred. In addition, the mask strength was sufficient in all cases.

On the other hand, in Comparative Examples 7 to 10, the final workability was as low as 30%, and the {100} integration degree α in the plate thickness direction was obtained.
Distribution of more than 60%, no mask unevenness occurred regardless of the diameter of the roll. However, since the final workability was low, the mask strength was insufficient. The mask strengths of the B alloys of Comparative Examples 8 and 10 are the same as those of the A alloy of Example 1,
Although it is higher than 2, it is insufficient as a B alloy which may require high mask strength. On the other hand, in Comparative Examples 11 and 12 in which the final workability was increased, the mask strength was sufficient, but the mask diameter was large, so that mask unevenness occurred. If the diameter of the dull roll in the final processing is large, the processing strained layer becomes deeper, so that α _c / α _s becomes smaller, and as a result,
Mask unevenness occurs.

[0025]

As described above, according to the present invention, the average value α _AVE in the thickness direction distribution of the {100} integration degree on the plate surface is 60% or less, and up to 50% of the plate thickness. Since the {100} integration degree α _{c on} the surface after removal by etching is larger than the {100} integration degree α _s on the plate surface, it is possible to effectively prevent generation of mask unevenness with high strength. can get.

[Brief description of drawings]

FIG. 1 is a diagram showing a cross-sectional shape of a hole punched by etching.

FIG. 2 is a diagram showing a planar shape of holes punched by etching.

FIG. 3 is a diagram showing a distribution of {100} integration degree in the present invention.

FIG. 4 is a diagram showing a method of approximately obtaining an average value α _{AV E} in a plate thickness direction distribution of {100} integration degree on a plate surface.

Claims (4)

[Claims] 1. Ni: 34 to 38 mass%, Mn: 0.1
To 1.0% by mass, C: 0.10% by mass or less, S
i: 0.1 mass% or less, Al: 0.05 mass% or less, not
It has a composition consisting of inevitable impurities and the substantial balance of Fe.
However, in the distribution in the thickness direction of the {100} integration degree on the plate surface
Average value α_AVEIs 60% or less and 50% of the plate thickness
Up to {100} on the surface after removal by etching
Degree of accumulation α _cIs the {100} integration degree α of the plate surface_sGreater than
Fe-Ni compound for shadow masks characterized by a threshold
Gold strip. 2. Ni: 34 to 38 mass%, Mn: 0.1
To 1.0% by mass, C: 0.10% by mass or less, S
i: 0.1 mass% or less, Al: 0.05 mass% or less, not
It has a composition consisting of inevitable impurities and the substantial balance of Fe.
However, in the distribution in the thickness direction of the {100} integration degree on the plate surface
Average value α_AVEIs 60% or less and 50% of the plate thickness
Up to {100} on the surface after removal by etching
Degree of accumulation α _c{100} accumulation degree α of the plate surface of_sAgainst
Shadow mass characterized by a ratio of 1.2 or more
Fe-Ni alloy strips for steel. 3. Ni: 28 to 34% by mass, Co: 2 to 7
% By weight, Mn: 0.1-1.0% by weight, C:
0.10 mass% or less, Si: 0.1 mass% or less, Al:
0.05 mass% or less, inevitable impurities and substantial Fe
It has a composition consisting of the balance, the average value α _AVE in the thickness direction distribution of the {100} integration degree on the plate surface is 60% or less, and {100} after removing up to 50% of the plate thickness by etching. } The degree of integration α _c is {100} the degree of integration α of the plate surface
Fe for shadow mask characterized by being larger than _s
-Ni-Co alloy strip. 4. Ni: 28 to 34% by mass, Co: 2 to 7
% By weight, Mn: 0.1-1.0% by weight, C:
0.10 mass% or less, Si: 0.1 mass% or less, Al:
0.05 mass% or less, inevitable impurities and substantial Fe
It has a composition consisting of the balance, the average value α _AVE in the thickness direction distribution of the {100} integration degree on the plate surface is 60% or less, and {100} after removing up to 50% of the plate thickness by etching. } {100} degree of integration α of the plate surface with degree of integration α _c
A Fe-Ni-Co alloy strip for a shadow mask, characterized in that the ratio to _s is 1.2 or more.