JP2001098347A - Fe-Ni MATERIAL FOR SHADOW MASK - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an Fe-Ni material for shadow mask, excellent in etchability by etching and having clean hole shape in etching. SOLUTION: This material is an iron-nickel alloy material for shadow mask having a composition containing, by weight, 34-38% Ni and <=0.5% Si and also having 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 amount of segregation of Ni component in a plane parallel to a sheet plane obtained by grinding from the sheet surface to an arbitrary depth, CNis, is <=0.50%, and also the maximum amount of segregation, CNimax, is <=1.5%.

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, and for example, photoetching with an etching solution mainly containing a ferric chloride solution. At that time, we propose a low thermal expansion Fe-Ni-based shadow mask material that does not show any streaking or mottling (hereinafter referred to as streaking etc.).

[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 sheet is subjected to intermediate strain annealing by continuous annealing or batch annealing furnace, and after the intermediate cold rolling, the steel sheet is subjected to flaw removal if necessary, and then cold rolling and temper rolling for finishing are performed. (Including dull rolling). 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 attracting attention is that they are superior in terms of preventing color misregistration as compared with the low-carbon aluminum-killed steel sheet, and are particularly important materials for applications such as displays and large-sized televisions. It is one.

[0003] However, this Fe-Ni-based alloy has a problem in the piercing property at the time of photoetching. 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 the stripe unevenness is considered to be the effect of the presence of nonmetallic inclusions and the segregation of Ni. 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 stripes generated in the shadow mask material were caused by disorder of the orientation of individual crystal grains on the etched surface. And the disorder of the orientation occurred in the plane parallel to the plate surface, that is, the segregation of components such as Ni and Mn in the plane parallel to the plate surface polished to an arbitrary depth from the plate surface, nonmetallic inclusions, and during annealing. It was found that this was caused by the existence of a mixed grain structure due to coarse grains, the presence of a specific texture, and the like, and that these elements were complicatedly intertwined.
By the way, since the orientation of the crystal grains depends on the crystal orientation of the individual crystal grains, in order to prevent the occurrence of the above-described line unevenness and the like, inevitably control the texture and the component segregation. I learned that it is necessary. In addition, it has been recognized that control of the surface roughness of products and control of the number of inclusions are indispensable in order to excel in etching drilling property and to improve the hole shape after drilling. It was concluded that it was effective to control the surface roughness, the number of inclusions, etc. in conjunction with the control of.

The present invention is a material developed under such knowledge. That is, in the present invention, Ni: 34 to 38 wt%, Si: 0.5
wt.% or less, Mn: 1.0 wt.% or less, P: 0.1 wt.% or less, and if necessary, an iron-nickel alloy shadow mask material further containing 0.02 to 0.2 wt.% of Nb by a shultz reflection method ( 111) Cube orientation (1
00) <001> and its twin orientation (221) <2
12> and a Ni component in a plane parallel to the plate surface, that is, a plane at an arbitrary depth from the plate surface, having a texture in which the X-ray intensity ratio Ir with respect to 0.5 to 5: 1. Has an average segregation amount C _Ni s of 0.50% or less and a maximum segregation amount C _Ni max of 1.
We propose a Fe-Ni-based shadow mask material that is less than 5%.

In the present invention, in order to obtain a preferable texture, the X-ray intensity ratio Ir (X-ray count number ratio) between the cubic orientation and the twin orientation is set to 0.5 to 0.5 as described above.
5: 1 is the basis. The preferred lower limit of the X-ray intensity ratio Ir is 0.5 or more, more preferably 1 or more, and more preferably
1.5 or more. The preferable upper limit of the X-ray intensity ratio Ir is 5 or less, further preferably 4.5 or less, and more preferably 4.0 or less. Therefore, the actual X-ray intensity ratio Ir
Are, for example, 0.5 to 4.5: 1, 1 to 4.5: 1, 1 to 4.0
: 1, 1.5 to 4.0: 1, 2 to 3.5: 1.

Further, as described above, the present invention suppresses the segregation of Ni, Si, Mn, and P in an arbitrary plane parallel to the plate surface of the material to a range represented by the following formulas. Is preferred. A. For Ni: average segregation amount C _Ni s ≤ 0.50 (%); maximum segregation amount C _Ni max ≤ 1.5 (%); B. For Si: average segregation amount C _Si s ≤ 0.005 (%), Maximum segregation amount C _Si max ≦ 0.01 (%), C.I. The Mn; to satisfy the average segregation amount _{C Mn s ≦ 0.030 (%)} , satisfies the maximum segregation amount _{C Mn max ≦ 0.05 (%)} , D. For P; to satisfy the average segregation amount _{C P s ≦ 0.003 (%)} , satisfies the maximum segregation amount _{C P max ≦ 0.005 (%)} , is obtained.

As for the above segregation amount, when Ni is exemplified, C _Ni s and C _Ni max are values defined as follows (see FIG. 11 for detailed definition). Average segregation amount C _Ni s (%) = Ni component analysis value (%) x Ci _Ni s
(cps) / Ci _Ni ave. (cps) Maximum segregation amount C _Ni max (%) = Ni component analysis value (%) × Ci _Ni
max / Ci _Ni ave. Ci _Nis : Standard deviation of X-ray intensity (cps) Ci _Ni ave .: Average intensity of all X-ray intensities (cps) Ci _Ni max: Maximum X-ray intensity (cps) (= X-ray intensity Ci _Ni ave .: Average intensity of all X-ray intensities (cps) ・ Ni component analysis value (%) is the Ni content contained in the material, which is chemical (or physical). It is a value that is analyzed by a method or the like. This component segregation amount is defined as a plane polished from the plate surface to an arbitrary depth (a surface parallel to the plate surface) as a measurement surface for X-ray microanalyzer line analysis. The measurement direction of the line analysis is a direction perpendicular to the rolling direction. The measurement length is
10 mm. The segregation amount is calculated by the following equation based on the measured X-ray intensity (cps) of the line analysis.

(Equation 1)

Materials exhibiting the above-mentioned characteristics include, for example, Ni
A slab of an alloy containing 34 to 38% with the balance being substantially Fe is subjected to a homogenizing heat treatment at a high temperature of 1250 to 1400 ° C. for at least 40 hours, and the hot-rolled sheet is cold-rolled. Before annealing the rolled material, before the final rolling, the annealing temperature: 900 ~
It can be manufactured by performing intermediate annealing at 1150 ° C and soaking time: 5 to 60 seconds, and then performing final annealing at annealing temperature: 700 to 900 ° C and soaking time: 60 to 600 seconds. In the above manufacturing method, the respective annealing conditions are as shown in FIG.
It is desirable to perform the processing within the ranges shown in b, c and d.

In the present invention, the parameter Ra relating to the surface roughness is 0.2 μm ≦ Ra ≦ 0.
9 μm, the parameter Sm relating to the surface roughness is 20 μm ≦ Sm ≦ 250
μm, the parameter Rsk regarding the surface roughness is −0.5 ≦ Rsk, and the parameter Rθa regarding the surface roughness is 0.01 ≦ Rθa ≦ 0.
09, and the cross-sectional cleanliness defined by JIS G 0555 is 0.05
% Or less, 10μ at the position polished to an arbitrary depth from the plate surface
The number of inclusions not less than 65 m per unit area of 100 mm ² is not more than 65, and the number of inclusions not less than 10 μm
Grain size number 7 measured by the method according to JIS G0551 is not more than 80 per unit area of 0 mm ^2.
It is preferably 0 or more. The thickness of the shadow mask material is 0.01 to
Plates of 0.5 mm, preferably 0.05-0.5 mm, are common.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, streaks include irregularities in which relatively individual streaks appear to be caused by component segregation and relatively streaks considered to be caused by crystal orientation. Can be broadly classified into thin streaks (skin streaks) that look like a fine silk pattern, and there is also a form in which both are mixed with each other. It has been found that there are two types of streaks studied in the present invention, "streaches" caused by segregation of components such as Ni and Mn, and "streaches" depending on the crystal orientation. The streaks caused by these causes are:
When observed in a shadow mask product, if the degree is strong, it looks like a streak due to transmitted light, but is often observed in oblique light from the small hole side. It can be imagined that the light transmitted from the large holes to the small holes is scattered and diffracted, and the etched surface causing the stripes on the large holes is more emphasized.

A. When the cause of streaks is due to crystal orientation: Streaks are greatly affected by the crystal orientation, and the cubic orientation (100), which is the etching preferred orientation
It turned out that the accumulation of <001> must be secured to some extent. However, if this orientation is excessively accumulated, on the contrary, it becomes a structure with a fibrous directionality, and since the streak quality deteriorates, the secondary orientation (221) <212> that helps moderate dispersion of the texture We need to be present. A specific method for overcoming the cause of the line unevenness will be described later in detail.

B. When component segregation is the main cause of line unevenness: If component segregation is distributed on any plane parallel to the plate surface (horizontal cross-section position), the intensity and distribution of segregation distributed on the plate surface It is considered that the width controls the strength and shape of the stripes. Therefore, it is understood that the segregation distribution of each element can be accurately measured by performing line analysis by EPMA on segregation on a plane parallel to an arbitrary plate surface. The analysis result of the obtained data was represented by the average segregation amount and the maximum segregation amount defined in FIG. Here, what is considered as the maximum value of segregation at the measurement length is defined as the maximum segregation amount: Cmax, and the average segregation amount (standard deviation) at a plane parallel to the plate surface at an arbitrary depth is defined as Cs. By setting these values for Ni, Si, Mn, and P within a predetermined range, relatively thick uneven stripes caused by segregation are reduced. Table 1 shows specific measurement conditions by EPMA linear analysis.

[0015]

[Table 1]

Incidentally, the fact that segregation due to segregation of components such as Ni causes line unevenness has been described in Japanese Unexamined Patent Publication No.
This is disclosed in, for example, Japanese Patent No. 2725, Japanese Patent Application Laid-Open No. 2-117703, and Japanese Patent Application Laid-Open No. 9-136625. However, in these conventional techniques, only the manufacturing conditions, the amount of segregation at an arbitrary position, and the maximum amount of segregation in the thickness direction are specified. However, as in the present invention, there has been no publication focusing on both the average segregation amount and the maximum segregation amount in a plane at an arbitrary depth from the plate surface. That is, streaking caused by component segregation cannot be eliminated by controlling only the maximum segregation amount, and the average segregation amount (standard deviation) is also controlled on a plane having an arbitrary depth parallel to the plate surface. It is necessary. A method for overcoming the cause of the stripe unevenness will be described later in detail.

First, the reason for limiting the component composition of the Fe—Ni-based shadow mask material according to the present invention will be described. When C is contained in an amount of 0.1 wt% or more, not only carbides are precipitated to inhibit the etching property, but also adversely affect 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.

[0018] 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, C
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 the hot workability by being properly added to form MnS by combining with S which is harmful to the 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.
%.

Nb has an effect of lowering the blackening property and the coefficient of thermal expansion, so that 0.02 to 2.0 wt% can be added. For example, 36 wt% Ni-0.2 wt% Si-0.01 wt% C-0.
The effect has also been recognized for the 7 wt% Mn-0.05 wt% Nb material.

Next, in the present invention, as described above, first, the texture is controlled in order to suppress the streaks caused by the crystal orientation in order to realize the desired operation and effect (suppression of the streaks). . In the present invention, in order to suppress “striation unevenness” depending on the crystal orientation, (100) <0 of the cubic orientation is required.
By introducing the (221) <212> sub-orientation, which is the twin orientation of <01>, and dividing the cubic orientation (100) <001>, the disorder of the crystal grain orientation is eliminated, and the desired texture is thereby reduced. We decided to form it.

According to the study of the present inventors, the preferred texture for suppressing the occurrence of line unevenness is, in conclusion, a (100) cubic orientation in the (111) pole figure.
<001> and its twin orientation (221) <212>
Is expressed as the X-ray intensity ratio Ir, the preferable range is the X-ray intensity ratio (X-ray count number ratio Ir) of the (111) pole figure, which is 0.5 to 5: 1. . The preferred X-ray intensity ratio Ir is 1 to 4.5: 1, more preferably 1 to 4.0: 1, and still more preferably 1.5 to 4.0: 1.
It was also found that the optimum ratio for producing a shadow mask material excellent in streak quality was 2 to 3.5: 1.

In the present invention, the method and conditions for measuring the X-ray intensity ratio Ir are as follows. First, the measurement method of the X-ray intensity ratio Ir is such that, after covering one surface of a plate with a Teflon seal, the other surface is chemically polished with a commercially available chemical polishing solution (CPE1000 manufactured by Mitsubishi Gas Chemical Co., Ltd.) to obtain a plate thickness of 70%. The measurement surface was obtained by reducing the thickness to 30%. As the measurement surface, it is desirable to measure the vicinity of the center of the plate thickness. The thus-obtained sample surface after chemical polishing was subjected to the (111) pole measurement by the Schulz reflection method under the measurement conditions shown in Table 2 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> / twin orientation (221) <
X-ray intensity of 212>

[0025]

[Table 2]

Next, an example of a texture conforming to the present invention and an example of a non-conforming texture will be described based on a pole figure.
FIGS. 2 to 6 show Fe-Ni-based materials having the component compositions shown in Table 3 and Nos. 1 and 2 of the present invention manufactured under the conditions shown in Tables 4 and 5.
The pole figures of Nos. 3 and 4 and Comparative materials Nos. 6 and 17 are shown. FIG.
The pole figure of the comparative material No. 17 in Tables 4 and 5 is shown.
00) <001> cube orientation is more developed,
(221) <212> X-ray intensity ratio Ir with twin orientation is 1
It is 3.9. Regarding the etching property of this sample (comparative material 11), as shown in Table 5, although the mottling was good due to the high etching rate, streaking was clearly recognized, and as an actual shadow mask product. Is not suitable.

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

3 (No. 3), FIG. 4 (No. 1), and FIG. 5 (No.
4) shows pole figures of the present invention materials Nos. 3, 1 and 4 in Tables 4 and 5, respectively, which are pole figures of materials conforming to the present invention. 3 and 4 show the upper limit Ir = 4.66 and the lower limit Ir = 0.93 of the present invention, respectively, and FIG. 5 shows the optimum condition Ir = 2.79 of the present invention. On the other hand, FIG. 6 shows a pole figure of comparative material No. 6,
(100) <001> The cubic orientation is very weak, and the normalized intensity ratio is 0.36: 1. This comparison material
Regarding the etching property of No. 6, the quality of the mottling was poor, which was also unsuitable as a shadow mask product.

In Tables 4 and 5, with respect to Nos. 10, 11, and 15, the X-ray intensity ratio Ir of the pole figure falls within an appropriate range, but homogenization by slab soaking is insufficient. Therefore, component segregation in a plane at an arbitrary depth from the plate surface is out of the applicable range of the present invention. From this,
Relatively thick and non-uniform stripes caused by component segregation are observed, which is unsuitable as a shadow mask product. No. Regarding 12, 13, and 14, the most major Ni segregation during the component segregation satisfies the range of the present invention, but the segregation of impurity components such as Si, Mn, and P is out of the preferred range of the invention. Some line unevenness tends to be observed. Nos. 16 and 17 are examples in which all the conditions of the present invention are deviated.

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.

According to the present invention, in order to obtain a preferable texture, an appropriate range of the azimuth component by the above-described pole figure is defined, and thereby, a streak unevenness at the time of etching generated in the material for the shadow mask and an entirety called mottling are generated. It is a material that prevents generation of unevenness.

Next, in order to suppress the occurrence of stripe unevenness due to component segregation, the material according to the present invention further controls the texture indicated by the above-mentioned X-ray intensity ratio Ir, and furthermore, further controls the surface of the sheet from the surface. Controls segregation of Ni, Si, Mn and P components on the surface polished to the depth. FIG. 12 shows a method of measuring the segregation of components as an example of measuring Ni segregation. 1. Regarding Ni component segregation in a plane at an arbitrary depth from the plate surface; the average segregation amount C _Ni s is 0.50% or less. Preferably
0.40% or less, more preferably 0.20% or less. The maximum segregation amount C _Ni max is set to 1.5% or less. It is preferably at most 1.0%, more preferably at most 0.5%. The reason for this is that Ni is a main component, and the segregation of Ni is likely to cause line unevenness. 2. Since the Si component segregation on a plane having an arbitrary depth from the plate surface causes stripe unevenness similarly to Ni, it is preferably controlled to the following numerical value. The average segregation amount C _Si s is set to 0.005% or less. It is preferably at most 0.004%, more preferably at most 0.002%. The maximum segregation amount C _Si max is set to 0.01% or less. Preferably it is 0.07% or less, more preferably 0.05% or less. 3. Regarding Mn component segregation on a plane at an arbitrary depth from the plate surface, similar to Ni and Si, it causes stripe unevenness,
It is preferable to control to the following numerical values. Average segregation C _Mn s is set to 0.030% or less. It is preferably at most 0.020%, more preferably at most 0.010%. The maximum segregation amount C _Mn max is set to 0.05% or less. It is preferably at most 0.025%, more preferably at most 0.020%. 4. P component segregation on a plane at an arbitrary depth from the plate surface causes line unevenness as in the case of Ni, Si, and Mn. Average segregation C _P s is less 0.003%. Preferably
It is 0.002% or less, more preferably 0.001% or less. Maximum segregation C _P max is not more than 0.005%. It is preferably at most 0.003%, more preferably at most 0.002%. In order to prevent the above-described segregation of components such as Ni segregation, it is effective to perform a homogenizing heat treatment on the slab after casting or forging. For example, cast slabs at temperatures above 1250 ° C
This can be achieved by performing heat treatment for 40 hours or more.

Next, the material according to the present invention can be used in addition to controlling texture and component segregation represented by the X-ray intensity ratio Ir.
In addition, the cross-sectional cleanliness defined by JIS G 0555
0.05% or less, preferably 0.03% or less, more preferably 0.1% or less.
02% or less, more 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 section is based on 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.
The observation 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
The thickness becomes 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.

Next, for the material according to the present invention, it is preferable to further appropriately control the roughness of the material surface represented by Ra, Rsk, and Sm. Regarding the surface roughness of the product, the center line average roughness Ra is a parameter indicating the average size of the roughness.If this value is too large, the scattering at the time of exposure becomes strong and the difference between the drilling start time at the time of etching. And the shape of the hole becomes worse.
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. The lower limit of the center line average roughness Ra is preferably 0.25 μm or more, more preferably 0.3 μm or more, and further preferably 0.35 μm or more. On the other hand, the upper limit is preferably 0.85 μm or less, more preferably 0.8 μm or less, and still more preferably 0.
7 μm or less.

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 expressed numerically according to the following equation. It is a representation. Rsk = 1 / σ ³ ∫Z ³ P (z) dz Here, σ indicates the root mean square value, and ∫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.

For the average mountain gap expressed by Sm,
It is a parameter indicating the size of the pitch of the peaks and valleys of roughness,
It can be said that such roughness simply indicates a partial evacuation defect that occurs when the unevenness is too large, and a defect in the hole shape due to increased scattering during exposure that occurs when the unevenness is too small. In the present invention, this Sm is set to 20 μm ≦ Sm ≦ 250 μm. The preferred lower limit of Sm is 40 μm or more, more preferably 50 μm or more, and further preferably 80 μm or more.
On the other hand, the preferred upper limit is 200 μm or less, more preferably 1 μm or less.
60 μm or less, more preferably 150 μm or less, 130 μm
m or less is an optimal example.

The root-mean-square gradient represented by Rθa represents the average gradient of roughness, and the larger the value of this parameter, the greater the steepness of each roughness. This value can be determined by the following equation.

(Equation 2) (However, L represents the measurement length, and f (x) represents the cross-sectional curve of the roughness.) When this value is large, scattering at the time of exposure is generally increased, and the hole shape is likely to be defective, and the pore size is too small. In this case, poor adhesion between the pattern and the substrate is likely to occur during evacuation. In the present invention, this Rθa is 0.01 ≦ Rθa ≦
The range is 0.09. The preferred lower limit of Rθa is 0.015
Or more, more preferably 0.020 or more, even more preferably 0.
025 or more. On the other hand, the preferred upper limit is 0.07 or less, more preferably 0.06 or less, further preferably 0.05 or less 0.04.
The following is an optimal example.

The surface roughness Ra, Rsk,
Sm and Rθa can be easily realized by using a dull roll when cold rolling a shadow mask material to the final size on the above alloy. The dull roll is a roll having a predetermined surface roughness. By using the dull roll to roll a shadow mask material made of the above alloy, the inverted pattern can be stamped at an appropriate transfer rate. In order to obtain such a dull roll, it can be easily obtained by processing by electric discharge machining, laser machining, shot blasting or the like. For example, it can be performed by using a steel grid of # 120 as a roll processing condition by the shot blast method.

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 having a size of 10 μm or more is controlled to 65 or less per unit area of 100 mm ² . In this case, preferably 35 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 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. The above-mentioned control of cleanliness and inclusions can be controlled by floating and separating inclusions with a ladle in the refining process.

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 size of the crystal grains can be controlled by setting the conditions of cold rolling reduction and annealing. In general, fine crystal grains are formed by increasing the cold rolling ratio, accumulating distortion, increasing the driving force of recrystallization, and repeating annealing at a relatively low temperature (a temperature slightly higher than the recrystallization temperature) one or more times. can get.

The method of measuring the crystal grain size described above is such that the plate cross section in the direction perpendicular to the rolling direction is taken as a microscope surface, buffed, etched with aqua regia, and observed at a magnification of 200 times with an austenite structure standard described in JIS G 0551. The grain size number is determined in comparison with the grain size diagram. The standard grain size diagram is 1
Since the observation magnification of 00 was used as a reference, the crystal grain number in the standard drawing was corrected by +2.0. (Measure the grain size number in increments of 0.5)

Next, in the present invention, it is desirable to employ the following method for controlling the texture and controlling the component segregation described above. For example, an alloy containing Ni34 to 38 wt% and the balance substantially consisting of Fe is refined, and the slab after forging or forging after casting is subjected to a homogenizing heat treatment of 40 hours or more in a temperature range of 1250 to 1400 ° C. Subsequently, hot rolling is performed to obtain a hot-rolled plate of about several mm. The homogenization treatment of the slab is effective for reducing segregation in the plane of the plate and eliminating streaking caused by segregation. The hot-rolled sheet thus obtained is subjected to, for example, recrystallization annealing or pickling, if necessary, followed by, for example, intermediate cold rolling, and thereafter, intermediate annealing before final rolling.

In the above-mentioned intermediate annealing, the cubic orientation (100) <
001> is controlled in order to control the development. 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 individual etching holes is reduced during pattern etching of the shadow mask, which is called mottling. The whole unevenness occurs.

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.

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

[0051]

Example 1 An ingot of an alloy having a composition shown in Table 3 above and conforming to the present invention was refined and melted by a vacuum degassing process, and the slab was subjected to the conditions shown in Table 4 below. Heat treatment of
Subsequently, a hot-rolled sheet of 5 mm was formed by hot rolling, and the hot-rolled sheet was repeatedly cold-rolled and annealed under the conditions shown in Table 4 to produce a hot-rolled sheet.
After being adjusted to a product thickness of, the product was evaluated as an actual shadow mask product shown in Table 5 through a photoetching process. The etching was carried out using a 0.26 mm pitch mask pattern at 46 Baume of the ferric chloride solution, at a liquid temperature of 50 ° C., and a spray pressure of 2.5 kgf / cm ² . No. 1-4, 12-1 in the table
4 is a sample obtained under the production conditions of the present invention,
11, 15 to 17 are comparative examples. 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 Ir, the intensity distribution of Ni segregation on a plane having an arbitrary depth parallel to the plate surface, and the cross-sectional cleanliness are within appropriate ranges, the conventional shadow mask is used. The shadow mask material is more satisfactory in terms of quality and product yield than the material, but the combination with various factors was examined in order to further improve the yield and the like. Table 6 shows the results. Table 6 shows section cleanliness and surface roughness (Ra, Rs
2 shows the relationship among the number of inclusions and the grain size number of 10 μm or more in the plane and cross section, the presence or absence of seizure at the time of annealing before press, and the percentage of defective holes. The surface roughness meter used was Tokyo Seimitsu Surfcom 1500A.
As a result, the following became clear. When the cross-sectional cleanliness exceeds 0.05%, the hole defect rate increases slightly (No. 21). 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. 2).
9, 30). 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.31). 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, Sm, and Rθa, blackening unevenness was caused by the hole defect rate due to etching and seizure (adhesion between the plates during annealing before press) (No. .22, 23, 24, 25, 26, 27, 28). In addition, the above-mentioned effect of the present invention example showed almost the same tendency for the Nb-containing material.

[0053]

[Table 6]

[0054]

As described above, according to the present invention, an Fe-Ni alloy having excellent etching characteristics, particularly, a Fe-Ni alloy having low thermal expansion which does not cause unevenness or mottling during etching.
A material for a system 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 a relationship between an appropriate range of an intermediate annealing condition and a final annealing condition 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 diagram showing a method of measuring the cleanliness of the cross section of an alloy plate.

FIG. 11 is a diagram illustrating a definition of a component segregation amount on a plate plane.

FIG. 12 is a diagram showing an example of measuring the amount of Ni segregation by an X-ray microanalyzer.

[Procedure amendment]

[Submission date] December 6, 2000 (200.12.
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

The present invention is a material developed under such knowledge. That is, in the present invention, Ni: 34 to 38 wt%, Si: 0.5 w
t% or less, Mn: 1.0% by weight or less, P: 0.1% by weight or less, and if necessary, further, 0.02 to 2.0 % by weight of Nb. 111) Cube orientation (1
00) <001> and its twin orientation (221) <2
12> and the Ni component in a plane parallel to the plate surface, that is, a plane at an arbitrary depth from the plate surface, having a texture in which the X-ray intensity ratio Ir with respect to 0.5 to 5: 1. The present invention proposes an Fe—Ni-based shadow mask material having an average segregation amount C _Ni s of 0.50% or less and a maximum segregation amount C _Ni max of 1.5% or less.

Claims (13)

[Claims] 1. Ni: 34-38 wt%, Si: 0.5 wt% or less, Mn:
In a material for an iron-nickel alloy shadow mask containing 1.0 wt% or less and P: 0.1 wt% or less, the cubic orientation (100) <001> and its twin orientation (221) <212 in the (111) pole figure. X-ray intensity ratio Ir
In a plane parallel to the plate surface having a texture in the range of 0.5 to 5: 1 and polished to an arbitrary depth from the plate surface
Average segregation amount of Ni component C _Ni s is 0.50% or less, maximum segregation amount
Fe—Ni characterized in that C _Ni max is 1.5% or less.
Materials for shadow masks. 2. The Fe-Ni-based shadow mask material according to claim 1, further comprising 0.02 to 0.2 wt% of Nb in addition to the above components. 3. The average segregation amount C _Si s of Si component on a plane parallel to the plate surface polished to an arbitrary depth from the plate surface is 0.005.
% Or less, the maximum segregation amount C _Si max is Fe-Ni based material for shadow mask according to claim 1 or 2, characterized in that 0.01% or less. 4. An average segregation amount _Mn s of Mn component on a plane parallel to the plate surface polished to an arbitrary depth from the plate surface is 0.030.
% Or less, and the maximum segregation amount C _Mn max is 0.05% or less, Fe- according to any one of claims 1 to 3 characterized by the above-mentioned.
Ni-based shadow mask material. 5. An average segregation amount _{P P} s of P component in a plane parallel to the plate surface polished to an arbitrary depth from the plate surface is 0.003.
% Or less, the maximum segregation amount C _P max is according to any one of claims 1 to 4, characterized in that not more than 0.005% Fe
-Materials for Ni-based shadow masks. 6. The Fe-Ni-based shadow mask material according to claim 1, wherein a parameter Ra relating to surface roughness satisfies 0.2 μm ≦ Ra ≦ 0.9 μm. 7. The Fe-Ni-based shadow mask material according to claim 1, wherein a parameter Sm relating to surface roughness satisfies 20 μm ≦ Sm ≦ 250 μm. 8. The Fe-Ni-based shadow mask material according to claim 1, wherein a parameter Rsk relating to surface roughness satisfies -0.5 ≦ Rsk. 9. The Fe-Ni-based shadow mask material according to claim 1, wherein a parameter Rθa relating to surface roughness satisfies 0.01 ≦ Rθa ≦ 0.09. 10. The cross-section cleanliness defined by JIS G 0555 is 0.05% or less.
The material for a Fe-Ni-based shadow mask according to any one of the above items. 11. 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 .
11. The material for an Fe-Ni-based shadow mask according to any one of items 10 to 10. 12. The Fe—Ni alloy according to claim 1, wherein the number of inclusions having a size of 10 μm or more measured in a cross section of the plate is 80 or less per unit area of 100 mm ^2. Materials for shadow masks. 13. The Fe particle according to any one of claims 1 to 12, wherein a crystal grain size number measured by a method according to JIS G 0551 indicates a size of 7.0 or more.
-Materials for Ni-based shadow masks.