JP2001059140A - Fe-Ni SHADOW MASK MATERIAL - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an Fe-Ni shadow mask material free from the occurrence of striped irregularity and mottling (overall irregularity) resultant from inferior etching. SOLUTION: This material is an iron-nickel alloy shadow mask material containing 34-38 wt.% Ni. The material has a texture where the X-ray intensity ratio Ir between the cubic orientation (100)<001> in the (111) pole figure and its twin orientation (221) <212> is (0.5 to 5):1. Further, the cleanliness of cross section defined by JIS G 0555 is <=0.05%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for an Fe-Ni-based shadow mask used as a material for a color television CRT or the like. We propose a low thermal expansion Fe-Ni-based shadow mask material that does not show any stripes or mottling (hereinafter referred to as stripes) during etching.

[0002]

2. Description of the Related Art Conventionally, a low carbon aluminum killed steel plate has been used as a shadow mask material. This steel plate
The steel sheet after the intermediate cold rolling is subjected to an appropriate strain relief by a continuous annealing or batch annealing furnace, and is subjected to a flaw removal if necessary. Then, the cold rolling and the temper rolling (final rolling) are performed. (Including). On the other hand, in recent years, low-thermal-expansion Fe-Ni-based alloy plates have attracted attention as materials for high-quality color television CRTs and displays. This Fe-Ni-based alloy plate has been developed as a substitute for a low-carbon aluminum-killed steel plate previously used as a shadow mask material. The reason why such Fe-Ni-based alloys are receiving attention is that
Compared to the low-carbon aluminum-killed steel sheet, it is superior in terms of preventing color misregistration, and is one of the indispensable materials especially for applications such as displays and large-sized televisions.

[0003] However, this Fe-Ni alloy has a problem in photo-etching properties. That is, it has been pointed out that the Fe-Ni-based alloy has a poor perforation shape at the time of photoetching and is more likely to cause a defect called stripe unevenness, as compared with aluminum killed steel. In particular, it has been found that this defect called streaking causes streaky contrast unevenness in a white portion of an image in a color cathode-ray tube, and significantly lowers the quality of a display.
The cause of this stripe unevenness is the presence of non-metallic inclusions and
The effect of Ni segregation is considered. Therefore, it is effective to eliminate these causes in order to reduce streaking. However, even if all of these causes were removed, unresolved streaks still remain, so the inventors assumed that there was another factor and continued their research.

It is a primary object of the present invention to provide a material for an Fe-Ni-based shadow mask which finds the true cause of streak unevenness and mottling (whole unevenness) caused by poor etching and does not cause these. It is another object of the present invention to provide an Fe-Ni-based shadow mask material having good etching piercing properties and a clear hole shape at the time of the piercing. It is still another object of the present invention to provide a low-cost and reliable material for a color cathode ray tube or display with a clear image.

[0005]

Means for Solving the Problems The inventors obtained the following knowledge as a result of intensive studies on the problems, such as streaking, remaining in the prior art as a problem to be solved. That is,
It was found that the stripe unevenness or the like generated in the shadow mask material was caused by disorder of the orientation of individual crystal grains on the etched surface. The disorder of the orientation is caused by Ni segregation, non-metallic inclusions, residual mixed grain structure due to coarse grains generated during annealing, orientation of a specific texture, etc., and these elements are entangled with each other. Was found to occur. Further, since the orientation of such crystal grains depends on the crystal orientation of each crystal grain, it is concluded that it is absolutely necessary to control the texture in order to prevent the occurrence of the above-mentioned line unevenness and the like. Reached. Also,
In order to excel in etching drilling properties and to improve the hole shape after drilling, it was further recognized that control of product roughness and control of the number of inclusions were indispensable. It was concluded that control of surface roughness and the number of inclusions was also required.

The present invention is a material developed under such knowledge. That is, the present invention relates to a material for an iron nickel alloy shadow mask containing 34 to 38 wt% of Ni: (11
1) It has a texture in which the X-ray intensity ratio Ir of the cubic orientation (100) <001> and its twin orientation (221) <212> in the pole figure is in the range of 0.5 to 5: 1, and Cross section cleanliness as defined by JIS G 0555 is 0.05
% Or less, which is a Fe-Ni-based shadow mask material.

Further, the present invention provides a method for producing a semiconductor device comprising: C: 0.1 wt% or less;
0.5% by weight or less, Mn: 1.0% by weight or less, Ni: 34 to 38% by weight, and the balance is substantially composed of Fe,
(111) Cube orientation in pole figure (100) <00
X of (1) and its twin orientation (221) <212>
A material for an Fe-Ni-based shadow mask, having a texture having a linear intensity ratio Ir in the range of 0.5 to 5: 1 and having a cross-sectional cleanliness of 0.05% or less as defined by JIS G 0555. It is.

Further, the present invention relates to a method for producing Ni: 23 to 38 wt%, Co: 10
In a material for an iron-nickel-cobalt-based alloy shadow mask containing not more than wt%, the cubic orientation (100) <001> in the (111) pole figure and its twin orientation (2)
21) It has a texture in which the X-ray intensity ratio Ir with respect to <212> is in the range of 0.5 to 5: 1, and the cross-sectional cleanliness defined by JIS G 0555 is 0.05% or less. A material for an Fe-Ni-Co-based shadow mask.

In the present invention, the above X-ray intensity ratio
(X-ray count number ratio) is 0.5 to 5: 1 as described above.
The lower limit of the strength ratio is preferably 0.5 or more, more preferably 1 or more, and even more preferably 1.5 or more. Further, a preferred lower limit of the intensity ratio is 5 or less, further preferably 4.5 or less, and more preferably 4.0 or less. Therefore, for example, the X-ray intensity ratio (X-ray count number ratio) is basically 0.5 to 5: 1 as described above,
0.5-4.5: 1,1-4.5: 1,1-4.0: 1,1.5-
It is preferable to narrow the range such as 4.0: 1, and it is more preferable to adjust the range to a range of 2 to 3.5: 1.

[0010] The above-mentioned material is used, for example, for annealing a cold-rolled material obtained by processing an alloy containing 34 to 38 wt% of Ni and substantially the balance of Fe according to a conventional method, and before the final rolling. Annealing temperature: 900 to 1150 ° C, soaking time: 5 to 60 seconds, and then intermediate annealing, then annealing temperature: 700 to 900 ° C, soaking time: 60 to 600 seconds. Can be. In the above-described manufacturing method, it is preferable that each annealing condition is performed within a range illustrated in FIGS. 1A, 1B, 1C, and 1D.

Further, in the present invention, the surface roughness is 0.2 μm ≦ Ra ≦ 0.9 μm, the surface roughness is 20 μm ≦ Sm ≦ 250 μm, and the surface roughness is It is effective that −0.5 ≦ Rsk.

Further, in the present invention, the surface roughness is 0.2 μm ≦ Ra ≦ 0.9 μm and −0.2.
5 ≤ Rsk, surface roughness 0.2 μm ≤ Ra ≤ 0.9 μm, -0.5 ≤
It is recommended that Rsk and 20 μm ≦ Sm ≦ 250 μm.

[0013] In the present invention, at a position polished from the plate surface to an arbitrary depth,
The number of inclusions of 10 μm or more per unit area of 100 mm ²
65 or less, the number of inclusions of 10 μm or more measured in the cross section of the plate is 80 or less per unit area of 100 mm ² , and the crystal grain size number measured by the method according to JIS G 0551 is 7.0 or more It is preferable to indicate the size of

[0014] The thickness of the shadow mask material is 0.
A plate thickness of from 01 to 0.5 mm, preferably from 0.1 to 0.5 mm, is common.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, streaks appear to be relatively wide in the width of individual streaks, unevenness caused by so-called segregation, and relatively streaks appearing in a thin silk pattern,
They can be classified as so-called streak irregularities (silk-like streaks) caused by crystal orientation, and there is also a form in which both are mixed with each other. The present invention seeks to improve the latter of these non-uniformities, namely, the non-uniformity depending on the crystal orientation. For this reason, in the present invention, the disorder of crystal grain orientation is controlled by dividing the twin crystal orientation by introducing the (100) plane twin orientation of the cubic orientation. Hereinafter, the method of crystal grain orientation of the present invention will be described.

First, an alloy material having a predetermined component composition is hot-rolled according to a conventional method and, if necessary, is subjected to recrystallization annealing, pickling, or the like, and then, for example, is subjected to intermediate cold rolling. Is subjected to intermediate annealing. This intermediate annealing is performed to control the development of the cubic orientation (100) <001>. This intermediate annealing is performed at a temperature of 900 to 1150 ° C. When the temperature is low (<900 ° C.), the cubic orientation in the final product is excessively developed, and the ratio of twin orientation (221) <212> becomes low, so that the line streak quality deteriorates. The reason why the streak quality deteriorates due to the decrease in the twin orientation ratio is that the alignment of the preferred orientation <001> in the rolling direction is slightly disturbed in each crystal grain unit due to the accumulation of the cubic orientation, and this becomes a stripe shape. It is considered visible. Conversely, when the temperature of the intermediate annealing is high (> 1150 ° C),
The cubic orientation is poorly developed, the etching rate is reduced, and the coherence of the individual etching holes is reduced during pattern etching of the shadow mask, resulting in the occurrence of overall unevenness called mottling.

The soaking time in the intermediate annealing is as follows:
The range of 5 to 60 seconds is preferable. If the time is shorter than 5 seconds, the recovery and recrystallization are not sufficiently performed, and the structure of a mixed particle state is maintained, thereby deteriorating the etching quality. On the other hand, if this time is longer than 60 seconds, the grains become coarse, the development of the cubic orientation is reduced, and a mixed grain structure is also formed, resulting in a decrease in etching properties.

Next, in the present invention, it is effective to regulate not only the conditions of the intermediate annealing described above but also the conditions of the final annealing. That is, the final annealing is performed in order to finely and uniformly arrange the crystal grains of the product and to prevent roughness of the hole wall after etching which causes mottling, and is performed at an annealing temperature of 700 to 900 ° C. , 60
It is effective to process with a soaking time of ~ 600 seconds. The reason is that if the annealing temperature is lower than 700 ° C. in the final annealing, recrystallization becomes insufficient, while if it is higher than 900 ° C., the recrystallization becomes coarse and the etching quality deteriorates.

The soaking time for this annealing depends on the degree of growth of individual crystal grains and development of crystal orientation.
It is preferably within the range of ~ 600 seconds. For example, if the soaking time is short (<60 seconds), the cubic orientation will be insufficiently developed, and the etching rate will decrease and mottling will occur. On the other hand, if the soaking time is long (> 60 seconds), the crystal grains become coarse, and the twin orientation is excessively developed with respect to the cubic orientation, resulting in a decrease in streak quality.

There is an appropriate range for these annealing conditions, and a region surrounded by a, b, c, and d in FIG. 1 is preferable.

Next, the reasons for limiting the component composition of the Fe—Ni-based shadow mask material according to the present invention will be described. C is
If it is contained in an amount of 0.1 wt% or more, not only does carbide precipitate and inhibits the etching property, but also adversely affects the shape freezing property after the shadow mask forming process. In addition, when the amount of C is large, the proof stress increases, the springback increases, and the adaptation to the mold during the molding process is deteriorated. Therefore, in the present invention,
The C content is preferably 0.1 wt% or less.

[0022] Si is one of the deoxidizing components. If the amount is too large, the hardness of the material itself increases, and at the same time, the C content increases.
In the same manner as described above, the moldability is adversely affected, and as the amount increases, the yield strength increases, and the springback increases. In addition, the influence on the stripe unevenness at the time of etching is produced.
Therefore, in the present invention, the amount of Si is preferably 0.5 wt% or less.

Mn is one of the deoxidizing components, and improves hot workability by being appropriately added to form MnS by combining with S which is harmful to hot workability. However, if the addition amount is too large, the thermal expansion coefficient is increased and the Curie point is displaced to a higher temperature side. Therefore, in the present invention, the amount of Mn is preferably 1.0 wt% or less.

Ni is the most important element in the present invention. If the Ni content is less than 34% by weight, the thermal expansion coefficient increases, and martensitic transformation may occur to cause uneven etching. On the other hand, when the amount of Ni is more than 38% by weight, there is a problem that a similar thermal expansion coefficient becomes large and color unevenness occurs when applied to a color CRT or the like. Therefore, in order to improve the good etching property and the color unevenness of the color cathode ray tube, the Ni content is 34 to 38 wt.
%.

The present invention also relates to a so-called Fe-32wt% Ni-Fe alloy in addition to the above-mentioned invar material represented by the 36wt% Ni-Fe alloy.
The present invention can be similarly applied to an Fe-Ni-Co-based alloy called super amber containing -5 wt% Co as a typical component. In this alloy system, the low thermal expansion characteristic is further excellent, and the cathode ray tube using the same is further sharpened. this
In the case of a Fe-Ni-Co alloy, the content of Ni is preferably 23 to 38 wt%. Preferably, the lower limit of Ni is 25 wt% or more, more preferably 27 wt%.
%, More preferably 30% by weight or more. The preferred upper limit of Ni is 36% by weight or less, and more preferably 35% by weight.
wt% or less. Co is preferably 10% by weight or less. If it is more than this, the coefficient of thermal expansion increases, and the etching property is remarkably reduced. It is preferably at most 8 wt%, more preferably at most 7 wt%, even more preferably at most 6 wt%. When considering the lower limit of Co, 0.5
wt% or more, preferably 1 wt% or more, more preferably 1.5 wt%
wt% or more, more preferably 2 wt% or more, even more preferably 2.5 wt% or more, and most preferably 3 wt% or more. It is also effective to regulate the total content of Ni and Co to 32 to 38 wt%.

In the present invention, in order to achieve the desired effects, it is necessary to control the texture in addition to the alloy design relating to the above-mentioned composition. The inventors have confirmed by an experiment that the morphology of the texture needs to satisfy the following conditions as an element for obtaining good stripe unevenness. That is, as a preferred texture as a material for a shadow mask according to the present invention, a cubic orientation (1
00) <001> and its twin orientation (221) <2
12>, there is an optimum range for the X-ray intensity ratio Ir (X-ray count number ratio I in the (111) pole figure).
r), from 0.5 to 5: 1, preferably from 1 to 4.5: 1, more preferably from 1 to 4.0: 1, even more preferably from 1.5 to 4.0: 1.
: 1 and the optimum ratio for producing a shadow mask material having excellent stripe quality was found to be 2 to 3.5: 1.

In the present invention, the X-ray intensity ratio I
The measuring method and measuring conditions of r are as follows.
First, a method of measuring the X-ray intensity ratio Ir is such that one surface of a plate is covered with a Teflon seal, and the other surface is a commercially available chemical polishing solution.
(CPE1000 manufactured by Mitsubishi Gas Chemical Co., Ltd.)
The thickness was reduced to 0 to 30% to obtain a measurement surface. As the measurement surface, it is desirable to measure the vicinity of the center of the plate thickness. The (111) pole measurement by the Schulz reflection method was performed on the sample surface thus obtained after the chemical polishing under the measurement conditions shown in Table 1 below, and the (100) pole figure was obtained based on the pole figure obtained thereby. <001> azimuth X-ray intensity and (22
1) The ratio of the <212> orientation to the X-ray intensity was determined. Each X-ray intensity is the maximum X-ray intensity (maximum X-ray count)
, The intensity is divided into 15 equal parts, the contour line intensity corresponding to the intensity corresponding to (100) <001> and (221) <212> is read from the obtained pole figure, and the intensity is calculated for each X-ray intensity. Defined. Then, the (100) <001> direction and (22)
1) The respective ratios of the <212> directions were obtained and defined as the X-ray intensity ratio Ir. Note that the X-ray intensity ratio Ir is defined as follows. Ir = X-ray intensity of cubic orientation (001) <001> / X-ray intensity of twin orientation (221) <212>

[0028]

[Table 1]

Next, pole figures which conform to the present invention and which do not conform will be described. 2 to 6 show the pole figures of the inventive materials Nos. 1, 3, and 4 and the comparative materials Nos. 6 and 11 manufactured under the conditions shown in Table 3 for the Fe-Ni-based materials having the component compositions shown in Table 2. Show. FIG. 2 shows a pole figure of Comparative Material No. 11 in Table 3, in which the (100) <001> cubic orientation is more developed and the X-ray with (221) <212> twin orientation is shown. The intensity ratio Ir is 13.91. This sample (comparative material 11)
As shown in Table 2, the etching rate was high, and the mottling was good because of the high etching rate. However, the unevenness was clearly recognized, indicating that it was not suitable as an actual shadow mask product. .

[0030]

[Table 2]

[0031]

[Table 3]

FIGS. 3, 4 and 5 show Table 2 respectively.
The pole figures of the present invention material Nos. 3, 1, and 4 are shown, and are the pole figures of the materials conforming to the present invention. 3 and 4 show the upper limit of the present invention, Ir = 4.6.
6, the lower limit Ir = 0.93, and FIG. 5 shows the optimum condition Ir = 2.79 of the present invention. On the other hand, FIG.
The pole figure of No. 6 is shown, in which the (100) <001> cubic orientation is very weak and the normalized intensity ratio is 0.36: 1. With respect to the etching property of this comparative material No. 6, the quality of the mottling was poor, which was also unsuitable as a shadow mask product.

FIG. 7 summarizes the above relationship. In this figure, the horizontal axis represents the logarithm of the X-ray intensity ratio Ir,
The vertical axis shows the etching factor (the value obtained by dividing the etching amount in the depth direction when pattern etching was performed by the etching amount in the width direction (side etch)). As shown in the figure, as the X-ray intensity ratio Ir increases (as the ratio of twins decreases).
It is recognized that the etching factor (etching rate in the thickness direction) increases. On the other hand,
If the line intensity ratio Ir is too large or too small, it becomes worse. As can be seen from the results shown, the proper range of the X-ray intensity ratio Ir is in the range of 0.5 to 5. It should be noted that with respect to motoling, it is advantageous that the etching rate is higher, but as can be seen from the figure, when Ir exceeds approximately 1.0, there is no large change and there is no difference.

The present invention is directed to a material which defines an appropriate range of the azimuth component by such a pole figure, thereby preventing the occurrence of stripe unevenness at the time of etching which occurs in a shadow mask material and overall unevenness called motoling. is there.

The material according to the present invention also has an X-ray intensity ratio I
r in addition to the limited texture shown by r
The cleanliness of the cross section according to the definition of 5 is set to 0.05% or less, preferably 0.03% or less, more preferably 0.02% or less, and further preferably 0.017% or less. The reason for this is that if the cross-sectional cleanliness d exceeds the above value, the etching accuracy is reduced and the product defect rate is reduced.

The measured value of the cleanness d of the cross section is in accordance with JIS.
Perform according to G 0555. Specifically, the product was cut to a length of 30 mm in the rolling direction, and after polishing the cross section, a grid having 20 grid lines each in the vertical and horizontal directions was mounted on a microscope,
While moving the field of view in a zigzag as shown in FIG.
This was performed by observing 60 visual fields at 400 times. Therefore, the measurement surface is a cross section parallel to the rolling direction, and the measurement area is a plate thickness × 30 mm. When the number of lattice points is P, the number of visual fields is f, and the number of total lattice point centers in f visual fields is n, the cross-sectional cleanliness d is expressed by the following formula: d (%) = (n / P × f) × 100.

The material according to the present invention also comprises Ra, Rsk, Sm
It is preferable to appropriately control the roughness of the material surface represented by First, in the product surface roughness, the center line average roughness Ra
Is a parameter indicating the average size of the roughness. If this value is too large, scattering at the time of exposure is increased, and a difference occurs in the drilling start time at the time of etching, so that the shape of the hole is deteriorated. On the other hand, if it is too small, exhaust is not sufficiently performed at the time of evacuation, and poor adhesion between the pattern and the material is likely to occur. Therefore, in the present invention, 0.2 ≦ Ra ≦ 0.9. A preferred lower limit of the center line average roughness Ra is 0.25 μm or more,
More preferably 0.3 μm or more, still more preferably 0.35 μm
m or more is preferable. On the other hand, the upper limit is preferably 0.85 μm or less, more preferably 0.8 μm or less, and even more preferably 0.7 μm or less.

Next, Rsk, which indicates the relativity of the surface roughness, is a parameter that simply indicates whether the pattern is convex or concave. The symmetry with respect to the center line of the amplitude distribution curve (ADF) distribution is calculated according to the following equation Is a numerical value. Rs
k = 1 / σ ³ ∫Z ³ P (z) dz where σ is a root mean square value,
∫Z ³ P (z) dz indicates the third moment of the amplitude distribution curve. When the value of Rsk is negative and large, scattering at the time of exposure is increased, and the shape of the hole is deteriorated. On the other hand, if it is too large, the evacuation is not sufficiently performed, and poor adhesion between the pattern and the material is likely to occur. Therefore, in the present invention,
-0.5 ≤ Rsk. A preferred lower limit is 0 or more, and a more preferred lower limit is 0.1 or more. On the other hand, the upper limit is preferably 1.3 or less, more preferably 1.1 or less, and 1.0 or less as an optimal example.

Next, the average peak gap represented by Sm indicates the size of the pitch of the peaks and valleys of the roughness, and such a roughness is caused by partial evacuation that occurs when the unevenness is too large. It can be said that this clearly indicates a defect in the hole shape due to the strong scattering at the time of exposure which occurs when the defect is too small. In the present invention, this Sm is set to 20 μm ≦ Sm ≦ 250 μm. This Sm
Is preferably at least 40 μm, more preferably at least 50 μm, even more preferably at least 80 μm. On the other hand, a preferred upper limit is 200 μm or less, more preferably 160 μm or less,
More preferably, it is 150 μm or less, and the optimal example is 130 μm or less.

The method for adjusting the surface roughness as described above can be easily realized by using a dull roll when cold rolling a shadow mask material to a final size, for example. Such a dull roll is a roll having a predetermined surface roughness, and by rolling the shadow mask material using this roll, it is possible to stamp the inverted pattern at an appropriate transfer rate. Such a dull roll can be easily obtained by processing by electric discharge machining, laser machining, shot blasting, or the like. For example, as a roll processing condition by the shot blast method,
This is possible by using a # 120 steel grid.

In the present invention, in addition to the above characteristics, it is preferable to control the number of inclusions. That is, polishing is performed to an arbitrary depth from the plate surface, and the number of the measured inclusions of 10 μm or more is controlled to 65 or less per unit area of 100 mm ² . In this case, preferably 40 or less, more preferably
30 or less, more preferably 25 or less, and most preferably 20 or less. The reason for this limitation is that, in general, a shadow mask requires a fine etching technique, so that it is better that the inclusions in the material be as small as possible. Although the number of inclusions and the cross-sectional cleanliness are similar concepts, the cross-sectional cleanliness d alone merely defines the area of the foreign matter. It is also effective to limit the size of. The method for measuring the number of inclusions was as follows: the plate surface was polished, and finally finished by buffing, and the surface parallel to the plate surface was observed with a microscope to measure the number. Measurement is 10mm x 10
mm surface was observed. FIG. 8 shows a photograph of a large inclusion causing a defect.

According to the present invention, in addition to the control of the number of inclusions on the surface of the plate, 10 μm
It is effective to control the number of the above inclusions to 80 or less per unit area of 100 mm ² . This number is preferably
70 or less, more preferably 50 or less, still more preferably
The optimal example is 40 or less, 30 or less, and further 20 or less. This is because the defect rate cannot be reduced to 0 only by controlling the cross-sectional cleanliness d described above, and the defect rate is further reduced by limiting the size of the inclusions. Because it can be. The number of inclusions in the plate cross section was measured by polishing a cross section parallel to the rolling direction, finishing by buffing, and observing with a microscope. The measurement was performed by measuring about three cross sections having a thickness of 25 mm and a length of 100 mm ² . FIG. 9 shows a photograph of a large inclusion causing a defect. In the present invention, as a method of controlling the cleanliness and the number of inclusions described above, in the refining process,
This is possible by floating the inclusions in a ladle.

In the present invention, the grain size of the alloy is further determined by the grain size number measured by the method according to JIS G 0551.
It is preferable to use a particle size that indicates a size of 7.0 or more (more fine control). Preferably 8.0 or more, more preferably
It is 8.5 or more, more preferably 9.5 or more. The reason for limiting in this way is that it is necessary to make the crystal having a crystal grain size number of 7.0 or more.First, if the crystal grain is large, the diameter of the hole at the time of etching differs in the etching rate of each crystal orientation, Variation and unevenness of transmitted light due to unevenness of etching holes occur, and eventually, a phenomenon called motoling occurs, and hole defects occur, thereby lowering the yield. Also, the crystal grains become too large during the press working, which causes a press failure. The method of measuring the crystal grain size is such that the plate cross section in the direction perpendicular to the rolling direction is a microscopic surface, etched with aqua regia after buffing, and the austenite structure standard crystal grain size described in JIS G 0551 at an observation magnification of 200 times. The grain size number is determined by comparison with the figure. Since the standard grain size diagram is based on an observation magnification of 100 times, the grain size number in the standard diagram was corrected by +2.0. (Measure the grain size number in increments of 0.5)

[0044]

Example 1 An ingot of an alloy having a composition shown in Table 2 above and conforming to the present invention was melted by a vacuum degassing process, and then hot-rolled to form a hot-rolled sheet of 5 mm. This was repeatedly manufactured by repeatedly performing cold rolling and annealing under the conditions shown in Table 3 to obtain 0.13 t
After being adjusted to the product thickness of, the product was evaluated as an actual shadow mask product through an actual photo-etching process. Etching was performed using a ferrite chloride solution of 46 Baume using a 0.26 mm pitch mask pattern, a liquid temperature of 50 ° C., and a spray pressure of 2.
The test was performed at 5 kgf / cm ² . Sample Nos. 1 to 5 in Table 2 are examples manufactured according to the present invention, and Sample Nos. 6 to 11 are examples of comparative materials. When the properties of the obtained shadow mask products after etching were evaluated, all of the materials of the present invention exhibited good mold conformability to a mold in press moldability and good tensile rigidity, and also exhibited blackening properties. Also, it was confirmed that a blackened film having good adhesiveness and sufficient radiation characteristics was formed, and it was found that the film exhibited excellent characteristics as a shadow mask product.

Embodiment 2 In this embodiment, if the X-ray intensity ratio and the cross-sectional cleanliness d are within the appropriate ranges, the shadow mask material is compared with the conventional shadow mask material.
Although it is a shadow mask material that is sufficiently satisfactory in terms of quality and product yield, a combination with various factors was examined in order to further improve the yield and the like. Table 4 shows the results. Table 4 shows section cleanliness and surface roughness (Ra, Rsk, S
m), the number of inclusions and grain size number of 10μm or more of the plane and cross section and the presence or absence of seizure during annealing before press,
It shows the relationship between the hole defect rates. Surface roughness meter
Tokyo Seimitsu Surfcom 1500A was used. As a result, the following became clear. When the cross-sectional cleanliness exceeds 0.05%, the percentage of defective holes increases slightly (No. 44). When the number of inclusions of 10 μm or more observed in a plane and a cross section exceeded 65 per unit area and 80, respectively, it was confirmed that the occurrence of hole defects slightly increased (No. 5).
0, 51). When the crystal grain size number becomes 7.0 or less, the hole defect rate slightly increases.However, since the individual crystal grains are large, the hole shape depends on the crystal orientation, and it is relatively difficult to form uniform holes. (No.52). As described above, proper surface roughness has the role of improving the adhesion of the resist in the resist coating and etching processes before etching, improving the vacuum evacuation, preventing halation due to exposure, and preventing shadowing during annealing before pressing. Prevents close contact between masks, and thus prevents unevenness of the blackened (oxidized) film due to close contact. In order to support these points, it was confirmed that depending on the combination of Ra, Rsk, and Sm, unevenness of blackening due to the hole defect rate due to etching and seizure (adhesion between the plates during annealing before press) was caused.
(No. 45, 46, 47, 48, 49).

[0046]

[Table 4]

Example 3 The same experiment as in Example 1 was carried out for the Fe—Ni—Co alloy shadow mask materials shown in Table 5. The results are shown in Table 6, and the same results as in the case of the Fe-Ni-based shadow mask material were obtained.

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

As described above, according to the present invention, a Fe-Ni-based alloy having excellent etching characteristics, especially a Fe-Ni alloy having a low thermal expansion which does not cause uneven stripes or mottling during etching.
A material for a Ni-based shadow mask can be provided. Therefore, it is possible to reliably provide a high-yield material for a color CRT or a display having a beautiful image.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing the relationship between the appropriate ranges of intermediate annealing conditions and final annealing conditions according to the present invention.

FIG. 2 is a (111) pole figure of a comparative material 11;

FIG. 3 is a (111) pole figure of a material 3 of the present invention.

FIG. 4 is a (111) pole figure of the material 1 of the present invention.

FIG. 5 is a (111) pole figure of the material 4 of the present invention.

FIG. 6 is a (111) pole figure of Comparative Material 6.

FIG. 7 shows Ir, etching factor, and stripe irregularity;
It is explanatory drawing which shows the relationship with the quality of moto ring.

FIG. 8 is a photograph showing an example of large inclusions on the surface of an alloy plate.

FIG. 9 is a photograph showing an example of a large inclusion in a cross section of an alloy plate.

FIG. 10 is a view showing a method for measuring the cleanness of the cross section of an alloy plate.

Claims (9)

[Claims] 1. An iron-nickel alloy shadow mask material containing 34 to 38 wt% of Ni: (111) cubic orientation (100) <001> and its twin orientation (221) <212> in a pole figure. X-ray intensity ratio Ir of 0.5
Has a texture in the range of ５5: 1 and JIS G 055
5. A material for an Fe-Ni-based shadow mask, which has a cross-sectional cleanliness of 0.05% or less as defined in 5. 2. C: 0.1 wt% or less, Si: 0.5 wt% or less,
Mn: 1.0 wt% or less, Ni: 34 to 38 wt%, and the balance is substantially composed of Fe, and the cubic orientation (100) <001> and its twin in the (111) pole figure The X-ray intensity ratio Ir with (221) <212> which is the azimuth is
Has a texture in the range of 0.5 to 5: 1 and JIS G
A material for an Fe-Ni-based shadow mask, wherein the cross-sectional cleanliness as defined in Article 0555 is 0.05% or less. 3. An iron-nickel-cobalt alloy shadow mask material containing 23 to 38% by weight of Ni and 10% by weight or less of Co, the cubic orientation (10%) in the (111) pole figure.
0) <001> and its twin orientation (221) <21
2> and Fe-Ni having a texture of Ir in the range of 0.5 to 5: 1 and a cross-sectional cleanliness of 0.05% or less as defined by JIS G 0555.
-Co-based shadow mask material. 4. The material for a Fe—Ni-based shadow mask according to claim 1, wherein the surface roughness is 0.2 μm ≦ Ra ≦ 0.9 μm. 5. The material for a Fe—Ni-based shadow mask according to claim 1, wherein the surface has a roughness of 20 μm ≦ Sm ≦ 250 μm. 6. The Fe-Ni-based shadow mask material according to claim 1, wherein the surface roughness satisfies -0.5 ≦ Rsk. 7. The method according to claim 1, wherein the number of inclusions of 10 μm or more at a position polished from the plate surface to an arbitrary depth is 65 or less per unit area of 100 mm ^2. 13. The material for an Fe-Ni-based shadow mask according to the above item. 8. The Fe—Ni alloy according to claim 1, wherein the number of inclusions having a size of 10 μm or more measured in a section of the plate is 80 or less per unit area of 100 mm ^2. Materials for shadow masks. 9. The Fe-particle according to claim 1, wherein a crystal grain size number measured by a method according to JIS G 0551 indicates a size of 7.0 or more.
Ni-based shadow mask material.