JP2000239802A - Fe-Ni-based alloy plate and shadow mask excellent in etching piercing property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-cost Fe-Ni-based alloy which has no defects at the time of etching perforation and can be used for a high-definition color television and a shadow mask for a personal computer. A board and a shadow mask are provided. SOLUTION: The total number of oxide inclusions contained in the Fe-Ni alloy plate is 1 × 10 ⁷ or less per 1 g of sample and the number of oxide inclusions having a particle size of 5 μm or more is 1 g of sample. 1 × 10 per
⁵ or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Fe--Ni alloy and a shadow mask having excellent etching characteristics.

[0002]

2. Description of the Related Art Conventionally, a cold rolled Fe—Ni alloy used for a shadow mask of a high-definition TV has been required to have a low coefficient of expansion and to be free from defects during etching perforation.

[0003] Since many of the defects generated at the time of etching perforation are caused by oxide-based inclusions, a method for controlling the composition, shape, size, and amount of oxide-based inclusions in a Fe-Ni-based alloy plate is disclosed. Have been.

Japanese Patent Application Laid-Open No. 63-231844 discloses that a cross section parallel to the rolling direction of a shadow mask and a surface thereof are JIS-compliant.
The width of A-type nonmetallic inclusions is 5.0 μm or less and the length is 50
μm or less, the width of the granular inclusion aggregate of B-type nonmetallic inclusions
5.0μm or less, length 50μm or less, single inclusion average diameter of C-based non-metallic inclusions 5.0μm or less, area ratio d (A + B + C) 60 × 4
It has been proposed to reduce the occurrence of defects at the time of etching perforation by using a plate manufactured from an Fe-Ni-based alloy plate having a cleanliness value of 00 or less of 0.01% or less.

In Japanese Patent Application Laid-Open No. Sho 62-161936, non-metallic inclusions contained in a cold rolled Fe—Ni alloy for a shadow mask are replaced with an Al ₂ O ₃ —MnO—SiO ₂ shown in FIG. In the ternary phase diagram, point 1: Al ₂ O ₃ : 4 wt% MnO: 58 wt% SiO ₂ : 38 wt% Point 2: Al ₂ O ₃ : 5 wt% MnO: 49 wt% SiO ₂ : 46 wt% Point 3: Al _{2 O 3: 23wt% MnO: 23wt} % SiO 2: 54wt% points _{4: Al 2 O 3: 27wt} % MnO: 31wt% SiO 2: 42wt% points _{5: Al 2 O 3: 17wt} % MnO: 54wt% SiO 2: A method has been proposed to reduce the occurrence of defects at the time of etching piercing by making the composition in the region surrounded by the line connecting successively 29 wt%.

[0006]

However, with the trend toward higher definition of color televisions and the increase in the use of shadow masks in personal computers, the demand for higher definition of shadow masks has been further increased. Fe applied
Even with a cold rolled Ni-based alloy sheet, it has become impossible to suppress defects at the time of etching perforation caused by inclusions. Therefore, Fe-Ni is free from defects at the time of etching drilling, which is a problem for the currently required high definition.
Based alloy cold rolled sheets have not yet been proposed.

[0007] It is naturally effective to reduce the amount of inclusions as much as possible in order to suppress the occurrence of defects at the time of etching perforation. However, further reduction of inclusions from the current level leads to a considerable increase in manufacturing cost. , Not realistic.

The present invention has been made in view of the above circumstances, and has no defect at the time of etching perforation, and can be used for a shadow mask for a high-definition color television and a personal computer. An object of the present invention is to provide a Fe-Ni-based alloy plate and a shadow mask having excellent properties.

[0009]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, between the hole shape abnormality and the linear defect generated at the time of etching and the total number and particle size of the oxide-type inclusions in the alloy plate, and the hole shape abnormality and the linear defect generated at the time of etching, It has been found that there is a very strong correlation between the amount and particle size of oxide-type inclusions in the alloy sheet.

That is, it is applied to a shadow mask or the like.
Fe-Ni alloy sheets are usually refined in an electric furnace,
(Vacuum-arc degassing method), VOD (vacuum-oxygen decarburization method), obtained by subjecting steel ingots to slab rolling, hot rolling, cold rolling, or after exiting a converter. The molten steel obtained by adjusting the components in the secondary refining is cast into a mold to form an ingot, or is continuously cast into a slab, and is obtained by slab rolling, hot rolling and cold rolling. By controlling the total number and grain size of oxide-based inclusions or the amount and grain size of oxide-based inclusions contained in the Fe-Ni-based alloy plate obtained at the same time, defects that occur during etching drilling can be prevented. I found what I could do.

The present invention has been made based on such knowledge, and the first invention is that the total number of oxide inclusions contained in the Fe—Ni alloy plate is 1 × 10 ⁷ per 1 g of the sample. Or less, and the number of oxide-based inclusions having a particle size of 5 μm or more is 1 g of the sample.
An object of the present invention is to provide a Fe-Ni-based alloy sheet excellent in etching piercing property, wherein the number of Fe-Ni-based alloy sheets is 1 × 10 ⁵ or less.

The second invention is characterized in that, in the first invention, the number of oxide-based inclusions having a particle size of 5 μm or more contained in the Fe—Ni-based alloy plate is 1 × 10 ³ or less per 1 g of the sample. An object of the present invention is to provide an Fe-Ni-based alloy plate having excellent etching piercing properties.

[0013] The third invention is that the total amount of the oxide-based inclusions contained in the Fe-Ni-based alloy sheet is 50 ppm or less and the amount of the oxide-based inclusions having a particle size of 5 µm or more is 20 ppm or less by weight. An object of the present invention is to provide a Fe-Ni-based alloy sheet having excellent etching piercing properties, characterized by the following.

The fourth invention is the third invention, wherein the weight ratio is
Fe with excellent etching piercing property, characterized in that the total amount of oxide inclusions contained in the Fe-Ni alloy plate is 30 ppm or less
-Ni-based alloy plates are provided.

A fifth invention is the third or fourth invention, wherein
Fe, excellent in etching piercing property, characterized in that the amount of oxide-based inclusions having a particle size of 5 μm or more is 10 ppm or less by weight.
-Ni-based alloy plates are provided.

According to a sixth aspect of the present invention, in the first to fifth aspects, the particle size, the number, and the amount of the inclusions of the oxide-based inclusions are determined by extracting only the oxide-based inclusions by dissolving the sample, and determining the particle size of the extract. Fe-N obtained by measuring the distribution by a light diffraction scattering method or a centrifugal sedimentation-light transmission method.
An i-type alloy plate is provided.

A seventh invention provides a shadow mask manufactured using the Fe—Ni-based alloy plate according to the first to sixth inventions as a raw material.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the actual state of abnormal hole shapes and linear defects generated during etching was investigated. Inclusions at this site
Most of them were oxide inclusions mainly composed of Al ₂ O ₃ , and had a size of about several μm to several tens μm.

The present inventors have conducted a study based on the above findings, focusing on the relationship between the number, particle size and amount of oxide-based inclusions contained in the material and the defect rate.

First, etching drilling was performed in a laboratory using Fe-Ni-based alloy cold-rolled plates for shadow masks manufactured under various conditions. In the case of etching perforation in a laboratory, if the defective etching rate is 1% or less, there is no problem in an actual etching line.

Next, a sample of about 50 g was sampled from the cold rolled plate subjected to the etching perforation, dissolved in a 10% Br ₂ -methanol solution to extract oxide inclusions, and the particle size of the inclusions after the extraction was extracted. The distribution was measured by the light diffraction scattering method.

Originally, in steel, in addition to oxide-based inclusions,
Includes sulfide-based inclusions, carbide-based inclusions, and nitride-based inclusions.
There are a halogen-organic solvent dissolving method, an electrolytic extraction method and the like. However, in order to selectively extract only oxide-based inclusions in the Fe-Ni-based alloy and to determine the number and amount of the inclusions, acid-soluble extraction or halogen-organic solvent extraction is suitable.
If there is no need to consider the presence of sulfide-based inclusions, carbide-based inclusions, or nitride-based inclusions, or if there is only a trace amount, an electrolytic extraction method using a non-aqueous solvent-based electrolyte can also be applied. .

FIG. 1 shows the relationship between the number of oxide-based inclusions and the etching failure rate. From this figure, it is confirmed that there is a very strong correlation between the number of oxide-based inclusions and the etching failure rate.

That is, in a region where the total number of oxide-based inclusions contained in the Fe—Ni-based alloy cold-rolled sheet is 1 × 10 ⁷ or less per 1 g of the sample, the oxide-based inclusions having a particle size of 5 μm or more are used. The defect rate is suppressed to 1% or less when the number is 1 × 10 ⁵ or less per 1 g of the sample, and it is completely defective when the number of oxide-based inclusions with a particle size of 5 μm or more is 1 × 10 ³ or less per 1 g of the sample. Has not occurred.

On the other hand, when the total number of oxide inclusions contained in the Fe—Ni alloy cold-rolled sheet exceeds 1 × 10 ⁷ per 1 g of the sample, the etching failure rate exceeds 1%. Also, Fe
If the number of oxide-based inclusions with a grain size of 5μm or more contained in the -Ni-based alloy cold-rolled sheet exceeds 1 × 10 ⁵ per 1g of sample, even if it is contained in the Fe-Ni-based alloy cold-rolled sheet Even if the total number of oxide-based inclusions is 1 × 10 ⁷ or less per 1 g of sample, the etching failure rate exceeds 1%.

Based on these results, in the present invention, the total number of oxide-based inclusions is set to 1 × 10 ⁷ or less per 1 g of a sample from the viewpoint of suppressing the etching failure rate to a level having no problem in an actual etching line. And, in that region, the number of oxide-based inclusions having a particle size of 5 μm or more is 1
× 10 ⁵ or less. Further, when the number of oxide-based inclusions having a particle size of 5 μm or more is 1 × 10 ³ or less per 1 g of a sample, no etching failure occurs at all. × 10 ³ or less.

FIG. 2 shows the relationship between the amount of oxide-based inclusions and the etching failure rate. From this figure, it is confirmed that there is a very strong correlation between the amount of the oxide-based inclusions and the etching failure rate.

That is, in a region where the amount of oxide-based inclusions contained in a cold-rolled Fe—Ni alloy sheet is 50 ppm or less,
When the amount of the oxide-based inclusions having a particle diameter of 5 μm or more is 20 ppm or less, the defect rate is suppressed to 1% or less, and further, in this region, the total amount of the oxide-based inclusions becomes 30 ppm or less or the particle size is 5 ppm or less.
The defect rate is suppressed to 0.5% or less in a region where the amount of oxide-based inclusions of μm or more is 10 ppm or less. Furthermore, in the region where the total amount of the oxide-based inclusions is 30 ppm or less and the amount of the oxide-based inclusions having a particle size of 5 μm or more is 10 ppm or less, no defect occurs.

On the other hand, when the total amount of oxide inclusions contained in the Fe—Ni alloy cold rolled sheet exceeds 50 ppm, the etching failure rate exceeds 1%. In addition, the amount of oxide-based inclusions having a particle size of 5 μm or more contained in the Fe-Ni alloy cold-rolled sheet was 20 ppm.
If the total amount exceeds 50%, the etching failure rate exceeds 1% even if the total amount of the oxide-based inclusions contained in the cold-rolled Fe-Ni alloy plate is 50 ppm or less.

Based on these results, according to the present invention, the total amount of oxide-based inclusions is reduced from the viewpoint of suppressing the etching failure rate to a level having no problem in an actual etching line.
The content was set to 50 ppm or less, and the amount of oxide-based inclusions having a particle size of 5 μm or more in that region was set to 20 ppm or less. Further, it is more preferable that the total amount of the oxide-based inclusions in this region is 30 ppm or less or the amount of the oxide-based inclusions having a particle size of 5 μm or more is 10 ppm or less, because the etching failure rate can be further suppressed. Further, when the total amount of the oxide-based inclusions is 30 ppm or less and the amount of the oxide-based inclusions having a particle size of 5 μm or more is 10 ppm or less, no etching failure occurs, and therefore, it is most preferable.

In the present invention, in order to determine the particle size and the number of the oxide-based inclusions, or the amount and the particle size of the inclusions, the sample is dissolved, and only the oxide-based inclusions are extracted. It is preferable to measure the distribution to determine the particle size and the number, or the amount of inclusions and the particle size. It is also possible to measure the particle size and number, or the amount and size of inclusions from optical microscopy or scanning electron microscope observations, but it is better to dissolve the sample and extract oxide-based inclusions in this way. Is high. In this case, the amount of the sample is preferably several tens g or more. As a method for extracting oxide-based inclusions, the above-described acid dissolution extraction or halogen-organic solvent extraction is suitable, and any of these methods is preferably used. The particle size distribution is preferably measured by a method such as a light diffraction scattering method or a centrifugal sedimentation transmission method that can measure the distribution as a whole.

In the present invention, the total number of oxide-based inclusions and the number of oxide-based inclusions having a particle size of 5 μm or more, or the total amount of oxide-based inclusions and the amount of oxide-based inclusions having a particle size of 5 μm or more, There is no particular limitation on the alloy composition of Fe-N of a composition usually used for shadow masks and the like.
Any alloy may be used as long as it is an i-based alloy. For example, C: 0.005% or less, Si: 0.4% or less, Mn: 0.1% to 1%, Ni: 30% to 45%, Cr:
0.1% or less, O: 0.003% or less, S: 0.005% or less, N: 0.005%
Hereinafter, an Fe-Ni-based alloy containing 0.002 to 0.03% of Al and the balance of Fe and inevitable impurities can be used. In addition, the addition of alloying elements such as Ca and Mg as required does not impair the function and effect of the present invention.

[0033] Regarding the production method, steel that has been adjusted to a predetermined composition by a converter and secondary refining or the like may be converted into a slab by continuous casting or ingot making and slab rolling.
Refining in an electric furnace, VAD (vacuum-arc degassing method), V
It is also possible to form a slab by subjecting steel refined by OD (vacuum-oxygen decarburization method) to ingot slab rolling after ingot making.

The slab thus obtained is subjected to hot rolling, cold rolling, etc., according to a conventional method, to obtain a slab having a predetermined thickness.
-It is a Ni-based alloy plate. Specifically, for example, a slab is hot-rolled, pickled, cold-rolled, annealed, and cold-finished rolled to obtain a product.

Further, when a shadow mask is manufactured by using the alloy plate obtained as described above as a raw material and performing perforation by etching in a conventional manner, a shadow mask with high definition can be obtained.

[0036]

The present invention will be described below with reference to examples. (Example 1) Electric furnace, VAD (vacuum-arc degassing method) and V
Using OD (vacuum-oxygen decarburization method), C: 0.005% or less, Si:
0.4% or less, Mn: 0.1% to 1%, Ni: 30% to 45%, Cr: 0.1% or less, O: 0.003% or less, S: 0.005% or less, N: 0.005% or less, A
l: 0.002 to 0.03%, balance of Fe and Fe-
The Ni-based alloy was melted to adjust the components and cast to obtain a steel ingot. This steel ingot was subjected to hot rolling, pickling, cold rolling, annealing, and cold finish rolling to obtain a 0.13 mm-thick steel sheet for a shadow mask. At this time, the number of oxide-based inclusions was variously changed by adjusting the amount of deoxidizer, slag composition, refining conditions, and the like.

A sample for inclusion measurement was taken from this steel sheet,
Approximately 50 g is dissolved in a 10% Br ₂ -methanol solution to extract inclusions, and the particle size distribution of the extracted inclusions is determined by the light diffraction scattering method according to the procedure of FIG. 3 (Materia Vol. 35, No. 4 ( 1996)] to determine the particle size and number of oxide-based inclusions. At the same time, this steel plate is etched through a shadow mask to investigate the defect rate such as abnormal hole shape and linear defect, and evaluated according to the total number of oxide-based inclusions and the number of oxide-based inclusions of 5 μm or more. Was done. Table 1 shows the results.

[0038]

【table 1】

Comparative Examples 1 and 2 are examples in which defective etching perforation occurred because the total number of oxide-based inclusions exceeded 1 × 10 ⁷ per 1 g of the sample.

In Comparative Examples 3 and 4, the total number of oxide-based inclusions was 1 × 10 ⁷ or less per gram of the sample, but the number of oxide-based inclusions having a particle size of 5 μm or more was 1 × 10 ⁵ per gram of the sample. This is an example in which defective etching perforation has occurred because the number exceeds the number.

Further, in Comparative Examples 5 and 6, both the total number of oxide-based inclusions and the number of oxide-based inclusions having a particle size of 5 μm or more are out of the range of the present invention, and particularly, the etching failure rate is high. .

On the other hand, examples of the invention which are within the scope of the present invention
All of Nos. 1 to 11 have an etching failure rate of 1% or less, which indicates that good etching piercing properties are obtained. Above all, Invention Examples 1 to 6 in which the number of oxide-based inclusions having a particle size of 5 μm or more was 1 × 10 ³ or less had an etching failure rate of 0.

Example 2 Using an electric furnace and VAD (vacuum-arc degassing method) and VOD (vacuum-oxygen decarburizing method), C: 0.00
5% or less, Si: 0.4% or less, Mn: 0.1% to 1%, Ni: 30% to 45%,
Cr: 0.1% or less, O: 0.003% or less, S: 0.005% or less, N: 0.0
A Fe-Ni-based alloy consisting of 0.05% or less, Al: 0.002 to 0.03%, balance Fe and unavoidable impurities was melted to adjust the components, and cast to obtain a steel ingot. This steel ingot is subjected to hot rolling, pickling, cold rolling, annealing, and cold finishing rolling to a thickness of 0.13 mm.
Steel plate for shadow masks. At this time, the amount of the oxide-based inclusions was variously changed by adjusting the amount of the deoxidizer, the slag composition, the refining conditions, and the like.

A sample for inclusion measurement was taken from this steel sheet,
Approximately 50 g is dissolved in a 10% Br ₂ -methanol solution to extract inclusions, and the particle size distribution of the extracted inclusions is determined by the light diffraction scattering method according to the procedure of FIG. 3 (Materia Vol. 35, No. 4 ( 1996)] to determine the particle size and amount of oxide-based inclusions. At the same time, this steel plate was etched and drilled in a shadow mask to investigate the defect rate such as abnormal hole shape and linear defect, and evaluated according to the total amount of oxide-based inclusions and the amount of oxide-based inclusions of 5 μm or more. Was. Table 2 shows the results.

[0045]

[Table 2]

In Comparative Examples 1 and 2, the total amount of oxide inclusions was 50 ppm.
This is an example in which etching perforation failure occurs due to the above.

In Comparative Examples 3 and 4, the total amount of oxide inclusions was 50 ppm.
Below, but the amount of oxide-based inclusions with a particle size of 5 μm or more is 20p
This is an example in which etching perforation failure occurs due to exceeding pm.

Further, in Comparative Examples 5 and 6, both the total amount of the oxide-based inclusions and the amount of the oxide-based inclusions having a particle size of 5 μm or more are out of the range of the present invention, and the etching failure rate is particularly high.

On the other hand, examples of the invention which fall within the scope of the present invention
In all of the samples Nos. 1 to 20, the defective etching rate was 1% or less, indicating that good etching piercing properties were obtained.

Of these, the total amount of oxide inclusions is 30 ppm or less and the amount of oxide inclusions having a particle size of 5 μm or more is 20 ppm.
pm or less, invention examples 6 to 10, and the total amount of oxide diameter inclusions was 5
Inventive Examples 11 to 15 in which the content of oxide-based inclusions having a particle diameter of 5 μm or more was 0 ppm or less and the amount of oxide inclusions was 10 ppm or less, the etching failure rate was suppressed to 0.5% or less. Further, inventive examples 16 to 20 in which the total amount of oxide inclusions was 30 ppm or less and the amount of oxide inclusions having a particle diameter of 5 μm or more was 10 ppm or less, the etching failure rate was 0.

[0051]

As described above, according to the present invention,
Number of oxide-based inclusions with a particle size of 5 μm or more and total number of oxide-based inclusions, or total amount of oxide-based inclusions and particle size of 5 μm
By defining the amount of the oxide-based inclusions described above, it is possible to reduce etching defects such as abnormal hole shapes and linear defects caused by the oxide-based inclusions without extremely reducing the amount of the oxide-based inclusions. Fe-Ni with excellent etching piercing properties
A system alloy plate can be obtained at low cost.

The shadow mask manufactured using the Fe-Ni alloy plate of the present invention as a raw material has few etching defects such as abnormal hole shapes and linear defects, and thus is used for a shadow mask for a high-definition color television and a personal computer. can do.

[Brief description of the drawings]

FIG. 1 shows the number of oxide inclusions obtained by dissolving with a 10% Br ₂ -methanol solution to extract inclusions, measuring the particle size distribution of the inclusions after extraction by a light diffraction scattering method, The figure which shows the relationship with an etching defect rate.

FIG. 2 Dissolved in 10% Br ₂ -methanol solution to extract inclusions, and measured the particle size distribution of the extracted inclusions by light diffraction scattering method, the amount of oxide inclusions obtained, and poor etching The figure which shows the relationship with a rate.

FIG. 3 is a diagram illustrating an operation procedure of a light diffraction scattering method.

FIG. 4 is an Al ₂ O ₃ —MnO—SiO ₂ ternary phase diagram showing a region of the composition of oxide-based inclusions present in a conventional Fe—Ni-based alloy plate.

Continuing from the front page (72) Inventor Shinichi Okimoto 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Inventor Tomohiko Uchino 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Stock F term in the company (reference) 4K057 WA10 WB02 WB03 WB17 WN03 5C031 EE05

Claims (7)

[Claims] 1. The total number of oxide-based inclusions contained in a Fe—Ni-based alloy plate is 1 × 10 ⁷ or less per 1 g of a sample and the number of oxide-based inclusions having a particle size of 5 μm or more is a sample. 1 × 10 per g
Fe-Ni alloy plate excellent in etching piercing property, characterized in that the number is ⁵ or less. 2. The etching perforation according to claim 1, wherein the number of oxide inclusions having a particle size of 5 μm or more contained in the Fe—Ni alloy plate is 1 × 10 ³ or less per 1 g of the sample. Fe-Ni alloy plate with excellent properties. 3. The method according to claim 1, wherein the total amount of the oxide-based inclusions contained in the Fe-Ni-based alloy sheet is 50 ppm or less, and the amount of the oxide-based inclusions having a particle size of 5 μm or more is 20 ppm or less. Fe-Ni alloy sheet with excellent etching piercing properties. 4. The Fe-Ni-based alloy excellent in etching piercing property according to claim 3, wherein the total amount of oxide-based inclusions contained in the Fe-Ni-based alloy plate is 30 ppm or less by weight. Alloy plate. 5. The Fe—Ni-based alloy sheet excellent in etching piercing property according to claim 3, wherein the amount of oxide-based inclusions having a particle size of 5 μm or more is 10 ppm or less in weight ratio. 6. The particle size, the number and the amount of inclusions of the oxide-based inclusions are determined by dissolving the sample and extracting only the oxide-based inclusions.
The Fe-Ni-based alloy plate according to any one of claims 1 to 5, wherein the particle size distribution of the extract is determined by measuring the particle size distribution by a light diffraction scattering method or a centrifugal sedimentation-light transmission method. 7. A shadow mask manufactured using the Fe—Ni-based alloy plate according to claim 1 as a raw material.