JP2590657B2 - Fe-Ni alloy excellent in adhesion seizure prevention and gas emission during annealing, and method for producing the same - Google Patents

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 excellent in adhesion seizure prevention during annealing and excellent gas emission, and a method for producing the same. The present invention relates to an alloy thin plate and a method for producing the same.

[0002] In recent years, as the quality of color televisions has increased, alloys for shadow masks that can deal with the problem of color misregistration have been developed.
34 to 38 wt. % Fe-Ni alloy (hereinafter referred to as "conventional Fe-Ni alloy") is used. This conventional Fe-Ni alloy has a significantly lower coefficient of thermal expansion than low carbon steel conventionally used as a shadow mask material. Therefore, if a shadow mask is made of a conventional Fe-Ni alloy, even if the shadow mask is heated by an electron beam, the problem of color shift due to thermal expansion of the shadow mask hardly occurs.

[0003] An alloy sheet for a shadow mask is usually manufactured by the following steps. That is, an alloy ingot is prepared by a continuous casting method or an ingot-forming method, and then the prepared alloy ingot is subjected to slab rolling, hot rolling and cold rolling to produce an alloy sheet.

[0004] The alloy sheet for a shadow mask manufactured as described above is usually processed into a shadow mask by the following steps. That is, a hole for passing an electron beam (hereinafter, referred to as a hole) is formed on a thin alloy plate for a shadow mask by photoetching.
(Hereinafter simply referred to as “holes”) (hereinafter, the thin alloy plate for a shadow mask that has been perforated by etching is referred to as a “flat mask”), and then the flat mask is annealed, and then the annealed flat mask is removed. Press into a curved shape to match the shape of the cathode ray tube, then assemble it into a shadow mask and then apply a blackening treatment on its surface.

However, the use of such a conventional Fe-Ni alloy has the following problems. That is, (1) Since the conventional Fe-Ni alloy contains a large amount of nickel, it has higher strength than low carbon steel. For this reason, in order to improve press formability, a flat mask made of a conventional Fe-Ni alloy needs to be annealed at a higher temperature than a flat mask made of a low carbon steel. There is. Therefore, in a flat mask made of a conventional Fe-Ni-based alloy, seizure easily occurs during the annealing. (2) Compared to shadow mask thin plates manufactured from low-carbon steel, the alloy thin plates for shadow masks manufactured by conventional Fe-Ni alloys have smaller holes formed by component segregation during photoetching. Irregularities easily occur in diameter and shape. When unevenness occurs in the hole diameter and hole shape,
The quality of the color cathode ray tube is significantly reduced. (3) In a conventional shadow mask made of an Fe-Ni-based alloy, when the shadow mask is heated by irradiating an electron beam during operation of the color cathode ray tube, gas is easily released from the surface of the shadow mask. When the gas is released from the surface of the shadow mask, the quality of the color cathode-ray tube is significantly reduced. (4) Conventional Fe-Ni alloys have remarkably low hot workability, so when performing slab rolling and hot rolling, flaws are likely to occur and a large amount of flaw removal is required. Manufacturing yield is extremely low.

In order to solve the above-mentioned problems, the following prior arts are known: (a) Japanese Patent Application Laid-Open No. 2-170,922 discloses 30-50 wt. %
Prior to hot rolling, a slab prepared by continuous casting of a nickel-containing Fe-Ni-based alloy of
At a temperature in the range of 00 to 1350 ° C., a soaking heat treatment is performed for 1 hour or more to reduce the segregation of components of Ni and Mn in the slab, thereby forming a streak-like pattern along the rolling direction generated by the segregation of components. It is disclosed that the occurrence of unevenness in the shape and diameter of the hole at the time of etching perforation is suppressed and the occurrence of sub-scale is suppressed to improve the yield at the time of manufacturing (hereinafter, "prior art 1"). ").

(B) Japanese Patent Application Laid-Open No. Hei 2-182,828 discloses that 30-
80 wt. % Nickel and 0.001-0.030 wt. %
90% boron-containing Fe-Ni alloy ingot,
A slab is prepared by heating to a temperature of 0 ° C. or more and forging with a cross-sectional reduction rate of 30% or more, and then a soaking treatment is performed on the slab thus prepared at a temperature of 1000 ° C. or more for 1 hour or more. Performing, thereby, due to the component segregation, due to the streak pattern along the rolling direction, to suppress the occurrence of unevenness of the shape and diameter of the hole at the time of etching drilling,
(Hereinafter referred to as “prior art 2”).

[0008]

However, the prior arts 1 and 2 described above can suppress the unevenness of the hole shape and the hole diameter at the time of the above-described etching drilling, but still have the following problems. ing. That is, at the time of etching drilling, the hole interface is significantly roughened, and another mist-like drilling defect occurs. Further, it is impossible to prevent the seizure occurring at the time of annealing the flat mask. That is, when the shadow mask is heated by the irradiation of the electron beam during the operation of the color cathode ray tube, gas is easily released from the surface of the shadow mask. Furthermore, the improvement in the production yield is insufficient.

That is, in the prior art 1, the slab is subjected to a soaking heat treatment to reduce the segregation of Ni and Mn components in the slab, thereby forming a streak-like line along the rolling direction generated by the segregation of Ni and Mn components. Although the occurrence of irregularities in the shape and diameter of the holes at the time of etching perforation due to the pattern is suppressed, the segregation of Si is not sufficiently reduced. This segregation of Si is more likely to remain in the final product of the Fe-Ni alloy than the segregation of Ni and Mn. That is, in the prior art 1, the slab is subjected to the soaking heat treatment to reduce the segregation of the Ni and Mn components. However, the soaking heat treatment is also used to reduce the segregation of the Si to a certain value or less. It is impossible to do. As a result, in Prior Art 1, seizure occurs during annealing of the flat mask due to large segregation of Si. Furthermore, when the segregation of Si described above is large, the hole interface is significantly roughened at the time of etching drilling, and a different mist-like drilling defect, which is different from the above-described etching drilling defect due to the segregation of Ni and Mn components, is generated. The quality of

In the prior art 1, 1200 to 1200
Since the soaking heat treatment is performed at a temperature in the range of 1350 ° C. for 1 hour or more, even if the oxygen concentration in the heating atmosphere is reduced, the production yield is low due to the generation of surface defects due to the sub-scale. Furthermore, in the prior art 1, since a fine crack (crack) exists in the alloy thin plate, a processing solution such as an etching solution remains in the above-described fine crack at the time of etching perforation. As a result, when the shadow mask is heated by the irradiation of the electron beam during the operation of the color cathode ray tube, gas is easily released from the surface of the shadow mask.

In the prior art 2, the addition of boron to the alloy suppresses the segregation of impurity elements such as C, Si, Mn, and Cr at the crystal grain boundaries, and reduces the segregation of components by forging. Thus, although the occurrence of unevenness in the shape and diameter of the holes at the time of etching drilling due to the streak pattern along the rolling direction, which is generated by the segregation of the Ni and Mn components, is suppressed, as in the prior art 1, Is not sufficiently reduced. That is, also in the prior art 2,
By adding boron and forging, Ni and
Although segregation of Mn components is reduced, it is impossible to reduce segregation of Si to a specific value or less.

As a result, similar to the prior art 1, due to the large segregation of Si, seizure occurs at the time of annealing of the flat mask, and the interface of the hole becomes extremely rough at the time of etching perforation. However, another perforation defect occurs. Furthermore, in the prior art 2, since forging is performed, the production yield is low. Further, in the prior art 2, as in the above-mentioned prior art 1, fine cracks (cracks) exist in the alloy thin plate, so that the shadow mask is heated by the irradiation of the electron beam during the operation of the color CRT. Thus, gas is easily released from the surface of the shadow mask. Further, in the prior art 2, since boron is added to the alloy, the grain boundary segregation of boron significantly increases,
At the time of etching drilling, the hole interface becomes extremely rough, and a drilling defect similar to the drilling defect caused by large Si segregation occurs. As a result, the quality of the color cathode ray tube is significantly reduced.

[0013] For this reason, the shadow mask which is excellent in etching perforation, can surely prevent seizure during annealing of the flat mask, suppresses gas emission during operation of the shadow mask, and has a high production yield. Fe-Ni for
Although there is a strong demand for a thin alloy plate and a method for producing the same,
Such an alloy sheet and a method for producing the same have not yet been obtained.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been devised through repeated studies. The present invention has excellent etching piercing properties and reliably prevents seizure during annealing of a flat mask. The present invention has succeeded in providing an Fe-Ni-based alloy thin plate for a shadow mask and a method for manufacturing the same, which suppresses the release of gas during the operation of the shadow mask and has a high production yield, as follows. It is.

(1) It is excellent in etching piercing property, prevents seizure during annealing, suppresses gas release, and is excellent in anti-adhesion seizure property and gas diffusion property during annealing, consisting essentially of: Fe-Ni alloy thin plate: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the remainder, iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P) as the unavoidable impurities, respectively Content of carbon: 0.0050 wt. % Or less, 1 ppm or less for hydrogen, and 0.0020 wt.% For nitrogen. % Or less, sulfur is 0.0020 wt. % Or less, oxygen is 0.0040 wt. % Or less, and about 0.0040 wt. % Or less, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045w
t +%, where Ca + Mg / 2 ≧ S + O / 5: The silicon (Si) segregation rate of the surface portion of the alloy thin plate represented by the following formula is 10% or less: Si segregation rate = [| segregation Si concentration in the region-average Si concentration | / average Si concentration] x 100

(2) It is excellent in etching piercing property, prevents seizure during annealing, suppresses gas release, and is excellent in adhesion seizure preventing property and gas diffusion property during annealing, consisting essentially of: Fe-Ni alloy thin plate: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the remainder, iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O), phosphorus (P) and The content of each of the metal inclusions is: for carbon, 0.0
05 wt. % Or less, 1.0 ppm or less for hydrogen, and 0.002 wt.% For nitrogen. % Or less, sulfur is 0.
002 wt. % Or less, 0.004 wt. % Or less, about 0.004 wt. % Or less, and for non-metallic inclusions, 0.004 wt. %
Hereinafter, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.00
45 wt.% Or less, provided that Ca + Mg / 2 ≧ S + O / 5: The non-metallic inclusions as unavoidable impurities are CaO—Al ₂ O ₃ —Mg
O 6 μm in the region of melting point above 1600 ° C. specified by the liquidus line at 1600 ° C. in the ternary phase diagram
It consists of a composition having the following particle size: and the silicon (Si) segregation rate, expressed by the following formula, of the surface part of the alloy sheet is less than 10%: Si segregation rate = [| segregation zone Concentration in silicon-average Si concentration | /
Si average concentration] x 100

(3) Fe which is excellent in etching piercing property, prevents seizure during annealing, suppresses gas release, and has excellent adhesion seizure preventing property and gas releasing property during annealing, comprising the following steps: -Method for producing Ni-based alloy thin plate: Prepared into an ingot or a continuously cast slab of Fe-Ni-based alloy essentially consisting of: Nickel (Ni): 34 to 38 wt.% Silicon (Si): 0.01 to 0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the remainder, iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P) as the unavoidable impurities, respectively Content of carbon: 0.0050 wt. %
Hereinafter, hydrogen is 1.0 ppm or less, and nitrogen is 0.0020 wt. % Or less, 0.002 for sulfur
0 wt. % Or less, oxygen is 0.0040 wt. % Or less, and 0.0040 wt.% Or less for phosphorus, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045 wt.%
The following, provided that Ca + Mg / 2 ≧ S + O / 5: the ingot or the continuously cast slab is subjected to at least one cooling with slab rolling, flaw removal, hot rolling, descaling / flaw removal, recrystallization annealing. Cold rolling, temper rolling and strain relief annealing are sequentially performed to prepare a Fe-Ni-based alloy sheet, and in the bulk rolling, the ingot or the continuous casting slab is subjected to 1
In a heating atmosphere with an H ₂ S concentration of 00 ppm or less,
Heating to a temperature T (° C.) in the range of 1300 ° C. for a time t (hr) represented by the following formula: 7.71−5.33 × 10 ⁻³ T ≦ logt ≦ 8.00−5.33 × 10 ⁻³ T, then slab-rolling at a cross-sectional reduction rate of 35% or more, and then slowly cooling to reduce the silicon (Si) segregation rate of the surface portion of the alloy thin plate represented by the following formula. Adjust to 10% or less: Si segregation rate = [| Si concentration in segregation area−Si average concentration | / Si average concentration] × 100

(4) A method for producing a Fe—Ni-based alloy sheet having excellent adhesion seizure prevention properties and gas diffusion properties during annealing according to the above item (3), characterized in that: The ingot or the continuously cast slab is
In a heating atmosphere having a H ₂ S concentration of 0 ppm or less, 1150 to 1
Heat to a temperature T (° C.) in the range of 300 ° C. for a time t (hr) represented by the following formula: 7.40−5.33 × 10 ⁻³ ≦ logt ≦ 7.71−5.33 × 10 ^-3 T, then primary slab rolling at a cross-sectional reduction rate in the range of 20 to 70%, and then in a heating atmosphere of H ₂ S concentration of 100 ppm or less, in a heating atmosphere of 1150 to 1300 ° C. Temperature T
(° C.) for a time t (hr) represented by the above formula,
Then, the secondary slab rolling is performed at a cross-sectional reduction rate in the range of 20 to 70%, and then gradually cooled, and silicon (Si) segregation of the surface portion of the alloy thin plate is represented by the following formula. The segregation rate is adjusted to 10% or less: Si segregation rate = [| Si concentration in segregation region−Si average concentration | /
Si average concentration] x 100

(5) Fe having excellent etching piercing properties, preventing seizure during annealing, and suppressing gas release, comprising: -Method for producing Ni-based alloy thin plate: Prepared into an ingot or a continuously cast slab of Fe-Ni-based alloy essentially consisting of: Nickel (Ni): 34 to 38 wt.% Silicon (Si): 0.01 to 0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg: 0.0003 to 0.0020 wt.%, But Ca + Mg / 2: 0.0005 to 0.0025 wt.%, And the balance: iron and unavoidable impurities; however, carbon (C ), Hydrogen (H), nitrogen (N), sulfur (S), oxygen (O), phosphorus (P) and non-metallic inclusions, respectively: for carbon: 0.0
05 wt. % Or less, 1.0 ppm or less for hydrogen, and 0.002 wt.% For nitrogen. % Or less, sulfur is 0.
002 wt. % Or less, 0.004 wt. % Or less, about 0.004 wt. % Or less, and for nonmetallic inclusions, 0.004 wt.% Or less in terms of oxygen, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.004
5 wt.% Or less, provided that Ca + Mg / 2 ≧ S + O / 5: The non-metallic inclusions as unavoidable impurities are CaO—Al ₂ O ₃ —Mg
O 6 μm in the region of melting point above 1600 ° C. specified by the liquidus line at 1600 ° C. in the ternary phase diagram
The composition having the following particle size, the ingot or the continuous cast slab is subjected to at least one time with slab rolling, flaw removal, hot rolling, descaling / flaw removal, recrystallization annealing. Cold rolling, temper rolling and strain relief annealing are sequentially performed to prepare a Fe-Ni-based alloy sheet, and in the bulk rolling, the ingot or the continuously cast slab is subjected to an H ₂ S concentration of 100 ppm or less. In a heating atmosphere, at a temperature T (° C.) within a range of 1150 to 1300 ° C.,
Heating time (hr) represented by the following formula: 7.71-5.33 × 10 ³ T ≦ logt ≦ 8.00-5.33 × 10 ³ T, and then with a cross-sectional reduction rate of 35% or more. , Mass-rolling, and then slow cooling to adjust the silicon (Si) segregation rate of the surface portion of the alloy thin plate to 10% or less, represented by the following formula: Si segregation rate = [| segregation zone Concentration in silicon-average Si concentration | /
Si average concentration] x 100

(6) A method for producing a Fe—Ni-based alloy sheet having excellent anti-adhesion seizure prevention property and gas diffusion property during annealing as described in the above item (5), characterized in that: , The ingot or the continuous cast slab is
In a heating atmosphere with a H ₂ S concentration of 00 ppm or less,
Heating to a temperature T (° C.) in the range of 1300 ° C. for a time t (hr) represented by the following formula: 7.40−5.33 × 10 ³ T ≦ logt ≦ 7.71−5.33 × 10 ³ T, then primary slab rolling at a cross-sectional reduction rate in the range of 20-70%, and then in a heating atmosphere with a H ₂ S concentration of 100 ppm or less, a temperature in the range of 1150-1300 ° C. T
(° C.) for a time t (hr) represented by the above formula,
Then, the secondary slab rolling is performed at a cross-sectional reduction rate in the range of 20 to 70%, and then gradually cooled, and silicon (Si) segregation of the surface portion of the alloy thin plate is represented by the following formula. The segregation rate is adjusted to 10% or less: Si segregation rate = [| Si concentration in segregation region−Si average concentration | /
Si average concentration] x 100

[0021]

The present invention as described above will be further described. From the above-mentioned viewpoint, the present inventors have excellent etching piercing properties, can reliably prevent seizure during annealing of a flat mask, and can prevent the flat mask from being burned during operation. For shadow masks, which suppresses outgassing at high temperatures and has a high production yield
The following findings were obtained as a result of intensive studies to develop Fe-Ni alloy thin plates. In other words, by adjusting the chemical composition of the Fe-Ni alloy thin plate for shadow mask and the segregation ratio of silicon within a predetermined range, it is excellent in etching piercing properties and reliably prevents seizure during annealing of the flat mask. Can reduce the emission of gas, but with a high production yield,
An Fe-Ni alloy thin plate for a shadow mask can be obtained.

More specifically, the segregation of silicon between dendrites is suppressed by the content of Si and S within a predetermined range and the segregation ratio of silicon within a predetermined range. In addition to preventing the shape of the hole from being etched, the seizure during annealing can be reliably prevented. In addition, C, N, S, within a predetermined range as described above.
The inclusion of O, P, Al, Mg, and Ca prevents unevenness in the shape and diameter of the holes during etching drilling, improves the hot workability of the alloy, and reduces the occurrence of surface defects during slab rolling. In addition to reducing the amount, it is possible to suppress minute internal cracks during slab rolling. That is, by reducing the occurrence of surface flaws during slab rolling, the production yield is improved, and by suppressing minute internal cracks during slab rolling, a processing solution such as an etching solution remains in the alloy sheet. Therefore, the release of gas can be suppressed. Further, as a gas to be released, hydrogen (H) existing in the alloy can be set to a specific value or less, and the emission of gas can be suppressed to a more excellent level. Further, by controlling the non-metallic inclusions to a predetermined composition, the etching piercing property can be improved.

Furthermore, we have obtained the following findings. That is, by heating at a temperature within a predetermined range and for a time within a predetermined range, and performing slab rolling at a cross-sectional reduction rate within a predetermined range, the segregation rate of silicon is adjusted within a predetermined range. Can be.

The present invention has been made based on the above findings. Below, the shadow mask Fe of the present invention
The reason for limiting the chemical composition of the Ni-based alloy thin plate to the above-described range will be described.

(1) Nickel: In order to prevent the occurrence of color shift, the upper limit of the average thermal expansion coefficient in the temperature range of 30 to 100 ° C., which is required for Fe—Ni alloy thin plates for shadow masks, is about 2.0 × 10 ⁻⁶ / ° C. The coefficient of thermal expansion depends on the nickel content of the alloy sheet. The range of the nickel content satisfying the above condition of the average thermal expansion coefficient is 34 to 38 wt. It is within the range of%. Therefore, the nickel content is 34-38 wt. It should be limited to the range of%. In addition, 0.01 to 6.00 wt. % Of cobalt, the range of the nickel content satisfying the above-mentioned condition of the average thermal expansion coefficient is 30 to 40 wt. %, The nickel content is 34-38 wt.
It may be within the range of%.

(2) Silicon: Silicon is an oxide film mainly composed of silicon, which is effective for preventing seizure during annealing of a flat mask made of an Fe-Ni alloy thin plate for a shadow mask, on the surface of the flat mask. It has an effect of preventing burning of the flat mask. However, when the silicon content is 0.01 wt. If it is less than%, desired effects cannot be obtained in the above-described operation. On the other hand, when the silicon content is 0.09 wt. %, The hole interface becomes extremely rough at the time of etching perforation of the Fe—Ni-based alloy thin plate, and the etching perforability deteriorates. Therefore, the silicon content is 0.01 to
0.09 wt. Should be limited to the% range.

Even when the silicon content is within the above-mentioned range, if the silicon segregation rate at the surface portion of the Fe—Ni-based alloy thin plate for a shadow mask is larger than a predetermined value,
Silicon is segregated between the dendrites, and locally a fog-like etching perforation defect is generated, and seizure occurs on a part of the surface of the flat mask during flat mask annealing. Therefore, in order to prevent the occurrence of the above-described haze-like etching piercing defects and prevent the seizure of the flat mask, in addition to the above limitation of the silicon content, Fe-
In the surface portion of the Ni-based alloy sheet, the silicon segregation rate represented by the following formula should be limited to 10% or less: Si segregation rate = [| Si concentration in segregation region−Si average concentration | /
Si average concentration] x 100

As described above, the silicon segregation rate is 10%
After limiting to the following, the minimum value of the silicon concentration at the unit surface portion of the Fe—Ni-based alloy thin plate was 0.01 wt. % Or more, and the maximum value of the silicon concentration is 0.09 wt. %, The local deterioration of the etching piercing property and the local occurrence of seizure during annealing can be prevented more reliably.

(3) Aluminum Aluminum is a component that affects the amount of nonmetallic inclusions and the size of the particle size in Fe—Ni-based alloy thin plates for shadow masks. The content of this aluminum is 0.002
~ 0.02wt. %, The particle size is small, and
Since a small amount of nonmetallic inclusions are generated in the alloy thin plate, defects are unlikely to occur during etching drilling. However, if the aluminum content is 0.002 wt. If it is less than%, the particle size is large, and a large amount of nonmetallic inclusions are formed in the alloy thin plate, and defects are likely to occur at the time of etching perforation. On the other hand, when the content of aluminum is 0.02 wt. %, A strong oxide film is formed on the alloy sheet surface,
The shape and diameter of the holes are uneven. Further, when the content of aluminum is 0.02 wt. %, The effect of improving the hot workability by adding a small amount of calcium does not appear, many surface flaws occur, the production yield decreases, and fine internal cracks occur in the alloy sheet, During the operation of the shadow mask, gas is easily released. Therefore, the content of aluminum is 0.002 to 0.020 wt. Should be limited to the% range.

(4) Calcium: Calcium has a function of precipitating sulfur and oxygen as stable and harmless precipitates and improving hot workability of the alloy. However, if this calcium content is 0.0002 wt. If it is less than%, desired effects cannot be obtained in such an operation, surface flaws are generated, and fine internal cracks occur in the alloy sheet. On the other hand, when the calcium content is 0.0020 wt. %, A strong oxide film mainly composed of calcium is formed on the surface of the alloy sheet, seizure occurs during annealing, and
When drilling by etching, haze-like drilling defects occur. Therefore, the calcium content is between 0.0002 and 0.0020 wt. %
Should be limited within the range.

(5) Magnesium: Magnesium, like calcium, has the effect of precipitating sulfur and oxygen as stable and harmless precipitates to improve the hot workability of the alloy. However, the magnesium content
0.0003 wt. If it is less than%, desired effects cannot be obtained in the above-described operation, surface flaws are generated, and fine internal cracks are generated in the alloy thin plate. On the other hand, when the magnesium content is 0.0020 wt. %, The surface of the alloy sheet becomes
A strong oxide film mainly composed of magnesium is formed,
Seizure occurs during annealing, and at the time of etching drilling,
Haze-like perforation defects occur. Therefore, the magnesium content is between 0.0003 and 0.0020 wt. Should be limited to the% range.

Since calcium differs from magnesium in a temperature range for forming precipitates of sulfur and oxygen, the addition of calcium and magnesium together causes the precipitation of sulfur and oxygen as stable and harmless precipitates. Thus, the hot workability of the alloy can be improved.

Incidentally, even when calcium and magnesium are contained within the scope of the present invention, the hot workability may not be sufficiently improved. This will be described with reference to FIG. That is, FIG.
Except for the contents of calcium and magnesium, in the slab and the alloy thin plate having the component composition within the scope of the present invention, when the contents of calcium and magnesium are respectively changed, the contents of calcium and magnesium, and the slab, The relationship between the amount of flaw removal, the etching piercing property of the alloy sheet, the seizure during flat mask annealing, and the release of gas during the operation of the shadow mask is shown.

As is clear from FIG. 1, the calcium content is 0.0002 wt. % And a magnesium content of 0.0003 wt. % Or more, the total content of Ca + Mg / 2 is 0.0005 wt. %, The hot workability of the alloy deteriorates, the amount of slab removal exceeds 5 mm per side, and gas is generated during the operation of the shadow mask due to the generation of minute internal cracks. I do. Furthermore, both calcium and magnesium contents are 0.0002 w
t. % Or less, the total content of Ca + Mg / 2 is 0.00
25 wt. %, A strong oxide film mainly composed of calcium and magnesium is formed on the surface of the alloy thin plate, and the interface of the holes becomes extremely rough at the time of etching drilling. Seizure occurs during annealing. Therefore, the total content of Ca + Mg / 2 is 0.0005 to 0.0025 wt. It should be limited to the range of%.

(6) Carbon: Carbon is one of the impurities unavoidably mixed into the Fe—Ni alloy, and the smaller the carbon content, the better. When the carbon content is 0.005 wt. %, Carbides are formed in the alloy in a large amount, deteriorating hot workability. As a result, surface flaws are remarkably generated at the time of bulk rolling, thereby lowering the production yield. At the same time, fine cracks are generated inside the alloy at the time of bulk rolling, and gas is released during the operation of the shadow mask. Furthermore, the carbon content is 0.00
5 wt. %, The etching piercing property is impaired.
Therefore, the carbon content is 0.005 wt. It should be limited to%.

(7) Nitrogen: Nitrogen is one of the impurities unavoidably mixed into the Fe-Ni alloy, and the nitrogen content is preferably as small as possible. The nitrogen content is 0.002 wt. %, Nitride precipitates at austenite grain boundaries in the alloy, deteriorating hot workability. As a result, surface flaws are remarkably generated at the time of bulk rolling, thereby lowering the production yield. At the same time, fine cracks are generated inside the alloy at the time of bulk rolling, and gas is released during operation of the shadow mask. Further, when the nitrogen content is 0.002 wt. %, The etching piercing property is impaired. Therefore, the nitrogen content is 0.002 wt.
It should be limited to%.

(8) Sulfur: Sulfur is one of the impurities unavoidably mixed into the Fe-Ni alloy, and the lower the sulfur content, the better. The sulfur content is 0.002 wt. %, Segregation occurs at austenite grain boundaries in the alloy, making the grain boundaries embrittled and deteriorating hot workability. As a result, surface flaws are remarkably generated at the time of bulk rolling, thereby lowering the production yield. At the same time, fine cracks are generated inside the alloy at the time of bulk rolling, and gas is released during operation of the shadow mask.
Further, when the sulfur content is 0.002 wt. %, The formation of an oxide film for effectively preventing seizure during annealing of the flat mask is hindered. Also, this sulfur content is 0.
002 wt. %, The etching piercing property is impaired. Therefore, the sulfur content is 0.002 wt. It should be limited to%.

In order to more effectively prevent seizure during annealing of the flat mask, the sulfur content is set to 0.0.
005 wt. %.

(9) Oxygen: Oxygen is one of the impurities unavoidably mixed into the Fe-Ni alloy. The smaller the oxygen content, the better. The oxygen content is 0.004 wt. If it exceeds 0.1%, it precipitates as a low-melting oxide at the austenite grain boundaries in the alloy, deteriorating hot workability. As a result, surface flaws are remarkably generated at the time of bulk rolling, thereby lowering the production yield. At the same time, fine cracks are generated inside the alloy at the time of bulk rolling, and gas is released during operation of the shadow mask.
Further, when the oxygen content is 0.004 wt. %, The etching piercing property is impaired. Therefore, the oxygen content is 0.0
04 wt. It should be limited to%.

(10) Phosphorus: Phosphorus is one of the impurities unavoidably mixed into the Fe—Ni alloy. The smaller the phosphorus content, the better. The phosphorus content is 0.004 wt. %, Segregation occurs at austenite grain boundaries in the alloy, making the grain boundaries embrittled and deteriorating hot workability. As a result, surface flaws are remarkably generated at the time of bulk rolling, thereby lowering the production yield. At the same time, fine cracks are generated inside the alloy at the time of bulk rolling, and gas is released during operation of the shadow mask.

Further, when the phosphorus content is 0.004 wt. %, Phosphorus segregates on the surface of the alloy thin plate, preventing formation of an oxide film for effectively preventing seizure during annealing of the flat mask. Further, when the phosphorus content is 0.004 wt. %, The etching piercing property is impaired. Therefore, the phosphorus content is 0.004 wt. It should be limited to%. In order to more effectively prevent seizure during annealing of the flat mask, the phosphorus content is 0.001 wt. %.

Even if the contents of carbon, nitrogen, sulfur, oxygen and phosphorus are within the scope of the present invention, C / 10 + N
/ 10 + S + O / 5 + P / 2 is 0.0045 wt.
If the content exceeds%, the austenite grain boundaries are significantly embrittled by the decrease in the strength of the austenite grain boundaries due to nitrogen, sulfur, oxygen and phosphorus, and the strengthening of the austenite grains by carbon. As a result, fine cracks occur at the triple point of the austenite grain boundary during slab rolling. Such fine cracks, even after hot rolling, subsequent to slab rolling,
It remains as crack in the alloy sheet without being pressed.

When an alloy thin plate having an internal crack as described above is subjected to etching perforation, the crack is exposed at the interface of the etching perforation, and the etching liquid enters the crack. As a result, when the temperature of the shadow mask rises due to electron beam irradiation during the operation of the shadow mask, the etching solution that has entered the cracks is vaporized and released as a gas. Therefore,
The total content of C / 10 + N / 10 + S + O / 5 + P / 2 is 0.0
045 wt. It should be limited to%.

(11) Hydrogen: Hydrogen is an impurity that is inevitably mixed during the production of an Fe—Ni alloy. In particular, Fe-3
Conventionally, in a 4 to 38% Ni invar alloy, CaO-based slag is used in the refining process at the time of its smelting, and this CaO easily absorbs moisture and becomes a supply source of hydrogen to the metal side.
Inevitably more than 1.0 ppm of hydrogen, possibly 4-5 pp
About m of hydrogen is mixed in, and this hydrogen gas degrades gas emission characteristics. In order to obtain the excellent outgassing characteristics intended in the present invention, it is necessary to make this hydrogen (H) less than 1.0 ppm.

In order to obtain the amount of hydrogen as defined in the present invention, it is essential to optimize the vacuum degassing method. That is, in order to reduce the apparent hydrogen partial pressure, in the Fe-Ni alloy intended in the present invention, the pressure at the time of degassing is set to 0.1 to
A method of achieving a high degree of vacuum at a pressure equal to or lower than rr, increasing the amount of diluted Ar gas at the bottom blow, and the like are employed.

(12) Non-metallic inclusions: Non-metallic inclusions are Fe
-One of the impurities unavoidably mixed into the Ni-based alloy. The nonmetallic inclusions are mainly composed of calcium oxide (CaO), aluminum oxide (Al ₂ O ₃ ), and magnesium oxide (MgO), and have a large effect on the etching piercing property of the Fe—Ni alloy thin plate. It is. The content of nonmetallic inclusions in the alloy sheet is 0.004 in terms of oxygen.
wt. %, The piercing property of the thin alloy sheet is hindered by etching, which causes puncturing defects. Therefore, the content of nonmetallic inclusions is 0.004 wt. Should be limited to%.

The non-metallic inclusions shown in FIG. 3 are CaO--Al ₂ O _3-
In the MgO ternary phase diagram, in the region other than the region surrounded by the line connecting points 1, 2, 3, 4, and 5 sequentially, that is, the liquidus line at 1600 ° C. (that is, the thick solid line in FIG. 3) The composition in the region having a melting point of 1600 ° C. or more specified by
The thickness becomes 6 μm or less, and the Fe—Ni-based alloy thin plate shows excellent etching piercing properties. In particular, the roughness of the pore interface is reduced,
Then, the contamination of the etching solution is reduced, and the etching work efficiency is improved. Therefore, the non-metallic inclusions
To indicate CaO - Al ₂ O ₃ - In ternary phase diagram MgO, should consist of a composition in the region other than the region surrounded by sequentially connecting line points 1, 2, 3, 4 and 5.

In order to control the nonmetallic inclusions in the alloy to the above-described composition, in the ladle refining after tapping, 20 to 20
40 wt. % Of the amount of use the MgO-CaO-based refractory steel ladle containing CaO within the range, then the Fe-Ni-based molten alloy in the ladle, comprising the following CaO - Al ₂ O ₃ - MgO
System slag: Sum of CaO and Al ₂ O ₃ : 57 wt. % Or more, provided that the ratio of CaO / (CaO + Al ₂ O ₃ ) is 0.45 or more and MgO:
25 wt. % Or less, SiO ₂ : 15 wt. % Or less, and an oxide of a metal having a lower oxygen affinity than silicon: 3 wt. % Or less. As a result, the amount of dissolved oxygen in the molten alloy is reduced by deoxidizing the Fe-Ni-based molten alloy, and the oxides generated in the molten alloy are absorbed by the slag. As a result, the total amount of non-metallic inclusions present in the Fe-Ni-based alloy sheet is 0.00 in terms of oxygen.
4 wt. % become. In other words, as the amount of dissolved oxygen in the molten alloy decreases, during solidification of the molten alloy, not only does the total amount of nonmetallic inclusions that precipitate decrease, but also a low-melting-point suspension that serves as precipitation nuclei. , The growth of the particle size of the nonmetallic inclusions is suppressed.

By adjusting the chemical composition of the nonmetallic inclusions as described above, the nonmetallic inclusions in the Fe—Ni-based alloy thin plate for a shadow mask are mainly composed of spherical nonmetallic inclusions of 3 μm or less. The amount of extensible linear nonmetallic inclusions extending in the rolling direction is extremely small. As a result, at the time of etching perforation, the formation of pits generated at the interface of the holes due to nonmetallic inclusions is suppressed, and the problem of contamination of the etching solution is extremely reduced.

Further, with respect to calcium, magnesium, sulfur and oxygen, the following conditions must be satisfied. That is, the lower limit of the total content of Ca + 1/2 Mg is S + O / 5 within the range of the total content of Ca + Mg / 2 described above.
Varies according to changes in the total content of This is illustrated in FIG.
FIG. 2 shows that, with the exception of the values of Ca + Mg / 2 and S + O / 5, in slabs and alloy sheets having a composition within the scope of the present invention, Ca + Mg / 2 and S +
When the value of + O / 5 was changed, the respective values of Ca + Mg / 2 and S + O / 5 and the removal amount of the slab,
4 shows the relationship between the etching piercing property of an alloy thin plate, seizure during flat mask annealing, and gas release during shadow mask operation.

As is apparent from FIG. 2, the contents of calcium, magnesium, sulfur and oxygen are respectively within the scope of the present invention, and the content of Ca + Mg / 2 is within the scope of the present invention. Also, when Ca + Mg / 2 <S + O / 5, sulfur and oxygen cannot be sufficiently precipitated as stable and harmless precipitates. Therefore, the slab flaw removal amount per one side exceeds 4 mm, and hot workability cannot be remarkably improved. Meanwhile, calcium, magnesium,
When the content of sulfur and oxygen is within the range of the present invention, and the content of Ca + Mg / 2 is within the range of the present invention, and Ca + Mg / 2 ≧ S + O / 5, And oxygen can be sufficiently precipitated as stable and harmless precipitates. As a result, hot workability can be significantly improved. Therefore, with respect to the content of calcium, magnesium, sulfur and oxygen, Ca + 1/2 Mg ≧ S
It should be limited to +1/5 O.

A method for reducing the silicon segregation rate to 10% or less will be described with reference to FIGS. 4 and 5. FIG. 4 shows an ingot or a continuously cast slab having a component composition within the scope of the present invention. Heat, then 35%
Heating temperature T at the time of slab rolling at the above section reduction rate
4 shows the relationship between (° C.) and heating time t (hr), the amount of slab flaw removal, and the Si segregation rate in the surface portion of the final sheet thickness (alloy sheet). As is clear from FIG. 4, the above-mentioned ingot or continuous cast slab was subjected to 1150 ° C. ≦ T ≦ 1300 ° C. log t ≦ 7.71−5.33 × 10 ⁻³ T log t ≦ 8.00−5.33. When heating is performed at a heating temperature and a heating time that satisfy the three formulas of × 10 ⁻³ T, then slab-rolling is performed at a cross-sectional reduction rate of 35% or more, and then slowly cooling, the slab removal amount becomes 5 mm or less, and The sicocon segregation rate in the surface portion of the prepared alloy thin plate becomes 10% or less.

On the other hand, when the heating temperature is lower than 1150 ° C. or when the log t <7.71−5.33 × 10 ⁻³ T, the silicon segregation ratio exceeds 10%. Further, when the heating temperature is 13
Exceeding 00 ° C or heating time log t> 8.00-5.
When it is within the range of 33 × 10 ⁻³ T, the slab flaw removal amount per one side exceeds 5 mm, and the yield decreases. Therefore, the heating temperature T (° C.) and the heating time t (hr) when the ingot or the continuously cast slab is subjected to slab rolling at a cross-sectional reduction rate of 35% or more are 1150 ° C. ≦ T ≦ 1300 ° C. and 7.71− 5.33 × 10 ⁻³ T ≦ logt ≦ 8.00−5.33 × 10 ⁻³ T

FIG. 5 illustrates heating an ingot or a continuously cast slab having a component composition within the scope of the present invention;
Next, the respective heating temperature T (° C.) in the heating and the reheating when the first and second sizing and rolling are performed at the section reduction rates of 20 to 70%, respectively, including the reheating. The relationship between the heating time t (hr) and the Si segregation rate and the slab flaw removal amount in the final plate thickness is shown.

As is clear from FIG. 5, the ingot or the continuously cast slab described above was subjected to 1150 ° C. ≦ T ≦ 1300 ° C. log t ≧ 7.40−5.33 × 10 ⁻³ T log t ≦ 7.71-5. .33 × 10 ^-3 T, heating at a heating temperature and a heating time satisfying the three formulas, then first primary slab rolling at a cross-sectional reduction rate of 20 to 70%, and a heating temperature and a temperature satisfying the above three formulas Heating again for the heating time, then secondary slab rolling at a cross-sectional reduction rate of 20 to 70%, and then slow cooling, the slab flaw removal amount becomes 5 mm or less, and the surface of the prepared alloy thin plate The silicon segregation rate in the portion becomes 10% or less. On the other hand, when one of the heating temperatures is lower than 1150 ° C. or one of the heating times is within the range of log t <7.40−5.33 × 10 ⁻³ T, the silicon segregation rate is 10%. Exceeds.

Further, one of the heating temperatures is 1300 ° C.
Or one of the heating times is log t> 7.
When it is in the range of 71-5.33 × 10 ⁻³ T, the slab flaw removal amount per one side exceeds 5 mm, and the yield is low. Therefore, heating and reheating when the ingot or the continuous cast slab is subjected to the first and second bulking with a reduction in area of 20 to 70%, respectively, including reheating. The respective heating temperature T (° C.) and heating time t (hr) in the heating are 1150 ° C. ≦ T ≦ 1300 ° C. and 7.40−5.33 × 10 ⁻³ T ≦ log t ≦ 7.71-5.33 Should be limited to × 10 ⁻³ T.

Ingots and continuous cast slabs within the scope of the invention may be heated at temperatures and times within the scope of the invention described above, and then subjected to slab rolling at a cross-sectional reduction rate within the scope of the invention. The concentration of H ₂ S in the heating atmosphere of the heating furnace is 1
If it exceeds 00 ppm, grain boundary embrittlement due to sulfur occurs during heating and at or near the surface of the ingot or continuous cast slab, and a large number of surface flaws are generated by slab rolling, and the amount of slab flaw removal per side is increased. Exceeds 5 mm. Therefore, the concentration of H ₂ S in the heating atmosphere of the heating furnace is 100 ppm
It should be limited to:

In order to lower the Si segregation rate,
After slab rolling, it is necessary to gradually cool.

Further, in order to lower the Si segregation rate,
In addition to the above, segregation prevention during ingot production, and
Rapid solidification by casting into a thin slab may be employed.
That is, electromagnetic stirring during casting, unidirectional solidification by light pressure casting, shortening of solidification time by adopting a flat ingot, and hot working, hot working under appropriate working conditions and heat treatment conditions in the strip manufacturing process. Cold working and cold working may be used in combination.

[0060]

Next, the present invention will be described in more detail with reference to specific examples.

(Example 1) By ladle refining, 7-ton ingots of Nos. 1 to 20 having the chemical composition shown in Table 1 were prepared.

[0062]

[Table 1]

The above Igot Nos. 1 to 5 and 7 to 20
The ladle used for ladle refining was 20 to 40 wt. %
Of MgO-CaO-based refractory containing CaO in the range of 0.45%, and the slag used is 0.45 or more (CaO).
/ {(CaO) + (Al ₂ O ₃ )} ratio and 25 wt. % MgO, 15 wt. % Or less of SiO ₂ or a metal having a lower oxygen affinity than Si. % Ca
O -Al was ₂ O ₃ -MgO slag.

The ladle used for refining the ladle of Igot No. 6 was 20 to 40 wt. % Of which consist of MgO -CaO based refractory containing CaO in the range, and,溶滓used had a CaO / SiO ₂ ratio in the range of 0.65 to 0.80, also, 3 wt . % Al ₂ O ₃ and 15 wt. % Was CaO -SiO ₂ -Al ₂ O ₃ slag containing the following MgO.

The thus prepared Nos. 1 to 18 and N
o. Care of each of the 20 ingots and 55 ppm H
Heating to a temperature of 1200 ° C. for 20 hours in a heating atmosphere of ₂ S concentration, followed by primary slab rolling with a reduction of area of 60%, and then in a heating atmosphere having a H ₂ S concentration of 55 ppm , Heated again to a temperature of 1200 ° C. for 20 hours,
Slab Nos. 1-18 and 20 were prepared by performing secondary slab rolling at a cross-sectional reduction rate of 45% and then gradually cooling. On the other hand, No. 1 prepared as described above was used. After cleaning the 19 iggots in a heating atmosphere of 55 ppm H ₂ S concentration at 1200 ° C.
The slab No. 19 was prepared by heating at 17 ° C. for 17 hours, followed by slab rolling with a reduction in area of 78%, and then slowly cooling. With respect to each of the slabs described above, the state of occurrence of surface flaws was investigated by observing the entire surface of the slab. The amount of surface flaw removal was determined by measuring the amount of reduction in the thickness and width of the slab after cutting with a cold scarf.
The results are shown in Table 2 below.

[0066]

[Table 2]

Next, each of the above-mentioned slab Nos. 1 to 20 was cared for, coated with an antioxidant, heated to a temperature of 1100 ° C., and then hot-rolled to obtain a hot-rolled coil no.
1-20 were prepared. The hot rolling conditions at this time were 10
The total draft at a temperature of 00 ° C. or more is 82%, 850
The total draft at 98 ° C. or higher was 98%, and the coiling temperature of the hot-rolled coil was 550 to 750 ° C.

Each of the thus prepared hot-rolled coils is descaled, repeatedly subjected to cold rolling and annealing, and then subjected to strain relief annealing to obtain a shadow mask Fe having a plate thickness of 0.25 mm. -Ni-based alloy sheets Nos. 1 to 20 were prepared (hereinafter referred to as "test materials" Nos. 1 to 20). For each of the cold-rolled coils obtained by cold rolling the hot-rolled coils described above, U
By examining ST defects, minute internal cracks were examined. The results are shown in Table 2.

Next, for each of the above-mentioned test materials Nos. 1 to 20, the segregation ratio of Si on the surface portion of the alloy sheet, the etching piercing property, the seizure during flat mask annealing, and the gas release during the operation of the shadow mask investigated. The Si segregation rate at the surface part of the alloy sheet is EPMA
(Electron Probe Micro Analyzer) was examined by a mapping analyzer. The etching piercing property is to form a hole in each of the alloy thin plates by etching piercing, and to examine the haze-like piercing defects due to unevenness of the shape and size of the hole, and the roughness of the interface of the hole, and to examine the interface of the hole. Observation was made with a scanning electron microscope to check for pits.

Further, the contamination of the etching solution was evaluated by the amount of residue after the etching perforation. Seizure during flat mask annealing, stack 30 flat masks,
Annealing was performed at a temperature of 950 ° C., and the occurrence of seizure of the flat mask was examined. Outgassing during the operation of the shadow mask is performed by annealing the flat mask at a temperature of 950 ° C., and then holding the flat mask at a temperature of 850 ° C. and a reduced pressure for 5 minutes. It was evaluated by: Table 2 shows the results. Further, the results of investigating the composition and distribution of nonmetallic inclusions in the alloy sheet are shown in Table 3 below and FIG.

[0071]

[Table 3]

As is clear from Table 2, the test materials Nos. 1 and 2 having a component composition within the range of the present invention and having a Si segregation ratio within the range of the present invention were the same as those of the test materials No. The generation was extremely small, the etching perforation was excellent, the seizure during flat mask annealing did not occur, and the release of gas was extremely low.

On the other hand, the test material No. No. 3 contains carbon outside the scope of the present invention, and 4
Contained nitrogen outside the scope of the present invention. as a result,
Test material No. In Nos. 3 and 4, many surface flaws were generated, and a large amount of gas was released.

The test material No. Sample No. 5 contains sulfur outside the scope of the present invention. No. 6 contains oxygen outside the scope of the present invention. And the test material No. 7 contained phosphorus outside the scope of the present invention. As a result, the test material No. 5,6
In Nos. 7 and 7, a large number of surface defects were generated, and a large amount of gas was released. Further, the test material No. In Nos. 5 and 7, seizure occurred during flat mask annealing.

The test material No. No. 8 contained silicon exceeding the upper limit of the range of the present invention, and as a result, the interface of the holes was significantly roughened at the time of etching drilling, and a mist-like drilling defect occurred. Test material No. No. 9 contained silicon below the lower limit of the range of the present invention, and as a result, seizure occurred during flat mask annealing.

The test material No. Sample No. 10 contains calcium exceeding the upper limit of the range of the present invention. 12
Contains magnesium exceeding the upper limit of the range of the present invention. And the test material No. No. 14 contains (Ca + Mg / 2) exceeding the upper limit of the range of the present invention. In Nos. 10, 12, and 14, haze-like perforation defects occurred during etching perforation, and seizure occurred during flat mask annealing.

The test material No. Sample No. 11 contains calcium less than the lower limit of the range of the present invention. 13 is
It contains magnesium less than the lower limit of the range of the present invention. No. 15 contained (Ca + Mg / 2) less than the lower limit of the range of the present invention. As a result, the test material No. 1
In Nos. 1, 13 and 15, many surface flaws were generated, and the release of gas was large.

Test material No. No. 16 contained (C / 10 + N / 10 + S + O / 5 + P / 2) exceeding the upper limit of the range of the present invention. As a result, many surface flaws were generated and gas was released more.

The test material No. 17 is ([Ca] + [Mg] / 2) /
([S] + [O] / 5) was less than the lower limit of the range of the present invention, and some surface flaws occurred.

The test material No. 19 has a component composition within the scope of the present invention, but has a Si segregation rate outside the scope of the present invention. As a result, at the time of etching perforation, a haze-like perforation defect occurs, Seizure occurred during flat mask annealing.

The test material No. 18 contains aluminum outside the scope of the present invention, and as a result, a small number of surface flaws occur, and when drilling by etching, haze-like drilling defects occur,
Also, there was much gas release.

The test material No. No. 20 contained hydrogen outside the range of the present invention, and as a result, released gas was extremely high.

As is apparent from the above description, the slab having no surface flaws, the fine internal cracks were not generated, and the etching perforation was not caused by the component composition within the scope of the present invention and the Si segregation rate within the scope of the present invention. Excellent in seizure, no seizure during flat mask annealing, and low gas emission
It can be seen that an Fe-Ni alloy thin plate for a shadow mask can be obtained.

Further, as is apparent from the above description, there is a correlation between the large amount of gas release and the generation of fine internal cracks in the alloy.

The distribution of nonmetallic inclusions in the test material shown in Table 3 was evaluated according to the following method. That is, the cross section of the alloy thin plate along the rolling direction was magnified 800 times with a microscope, and the thickness in the plate thickness direction and the length in the rolling direction of all nonmetallic inclusions in the visual field were measured. The area of the measurement cross section was 60 mm ² in total. Then, the thicknesses of the spherical nonmetallic inclusions and the linear nonmetallic inclusions in the plate thickness direction were classified by size, and the above distribution was evaluated based on the number of nonmetallic inclusions per 1 mm ² .

The above-mentioned spherical nonmetallic inclusions have a ratio of the length to the thickness of the nonmetallic inclusions of 3 or less: that is, (length / thickness) ≦
3 and the linear non-metallic inclusions are:
Non-metallic inclusions having a ratio of length to thickness of more than 3: that is, (length / thickness)> 3.

As is clear from Table 3 and FIG. Non-metallic inclusions in 1-4 and 7-20 are
Spherical nonmetallic inclusions having a melting point of 1600 ° C. or more and a thickness of 3 μm or less were mainly used. Therefore, at the time of etching perforation, the formation of pits generated at the interface of the holes due to the nonmetallic inclusions is suppressed, and the contamination of the etching solution due to the mixing of the linear nonmetallic inclusions into the etching solution. Very few.

On the other hand, the test material No. Sample No. 5 contains sulfur outside the scope of the present invention. The nonmetallic inclusions in 5 are mostly linear nonmetallic inclusions. As a result, pits were generated at the interface of the etching perforation, and a little stain of the etching solution was generated.

The test material No. The nonmetallic inclusions in 6 are 1
5 wt. % Al ₂ O ₃ , 45 wt. % MnO and 40 wt. %
Of which consists of SiO _2, not shown, MnO -SiO ₂ -Al ₂ O
_{3 In the} ternary phase diagram, called spacer tight,
Since it is composed of the composition in the region surrounded by the liquidus temperature line of 1200 ° C., the nonmetallic inclusion has a low melting point, a large deformation, and a large total amount. As a result, when the ingot is hot-rolled, the nonmetallic inclusions in the alloy sheet are deformed linearly long in the rolling direction. As is clear from Table 3, the test material No. The nonmetallic inclusions in 6 are mostly linear nonmetallic inclusions. As a result, pits were formed at the etching perforation interface, and the etchant was stained.

As is apparent from the above description, in the Fe—Ni-based alloy sheet within the scope of the present invention, by controlling the nonmetallic inclusions in the alloy sheet to a composition within the scope of the present invention, Excellent etching piercing properties can be provided.

Example 2 A 7-ton ingot No. 1 shown in Table 1 was used. Each of 1 and 2 was maintained, slab-rolled under the conditions shown in Table 4 described below, and then slowly cooled to prepare a slab. Further, each of the slabs thus prepared was cared for, an antioxidant was applied, and 1100
C., and hot-rolled to prepare a hot-rolled coil. The hot rolling conditions at this time are 1000
The total draft at a temperature of 850 ° C. or higher was 82%, the total draft at a temperature of 850 ° C. or higher was 98%, and the winding temperature of the hot-rolled coil was 550 to 750 ° C. Each of the thus prepared hot-rolled coils is descaled, repeatedly subjected to cold rolling and annealing, and then subjected to strain relief annealing to obtain 0.2.
Fe-Ni alloy thin plate for shadow mask with a thickness of 5mm
Nos. 21 to 34 were prepared (hereinafter referred to as "test materials" No. 21).
~ 34).

[0092]

[Table 4]

With respect to each of the slabs described above, the occurrence of surface flaws was examined. In addition, for each of the cold-rolled coils obtained by performing cold rolling on the above-described hot-rolled coils, minute internal cracks were examined. Next, the test material No. Regarding each of 21-34, the segregation rate of Si in the surface portion of the alloy thin plate, the etching piercing property, the seizure during flat mask annealing, and the gas release during the operation of the shadow mask were investigated. Each of the above-described investigations was performed by the same method as described in Example 1. The results are shown in Table 5 below.
Shown in

[0094]

[Table 5]

As is clear from Table 5, the test material No. 2
Each of 1, 22, 26 and 27 is subjected to slab rolling with an H ₂ S concentration, a heating temperature, a heating time and a cross-sectional reduction rate within the range of the present invention, and has a Si segregation rate within the range of the present invention. Since it has, there is little occurrence of surface flaws, at the time of etching perforation, due to roughening of the interface of the hole, no haze-like perforation defect occurs, no seizure occurs during flat mask annealing, and
Outgassing was low.

On the other hand, the test material No. No. 23 was slab-rolled in a single slab-rolling with a cross-sectional reduction rate less than the lower limit of the range of the present invention. Test material No. No. 24 was heated in a single bulk rolling at a heating temperature below the lower limit of the range of the present invention. Test material No. No. 28 was heated in the first bulk rolling for a heating time shorter than the lower limit of the range of the present invention. Test material No. Sample No. 29 was subjected to the second bulk-rolling at a cross-sectional reduction ratio less than the lower limit of the range of the present invention. Test material No. 33 is
In the first bulk rolling and the second bulk rolling, each was heated at a heating temperature lower than the lower limit of the range of the present invention. Test material No. No. 34 was first bulk-rolled at a cross-sectional reduction rate less than the lower limit of the range of the present invention. As a result, these test materials N
o. Each of 23, 24, 28, 29, 33 and 34 has a silicon segregation rate of more than 10% at its surface portion. As a result, as is clear from Table 5, the test material No. 23, 24, 28, 29, 3
3 and 34, at the time of etching drilling,
The interface of the holes was rough, and a mist-like perforation defect occurred, and seizure occurred during flat mask annealing.

The test material No. No. 25 was heated in a single slab rolling with a heating time exceeding the upper limit of the range of the present invention. Test material No. No. 30 was heated in the second bulk rolling for a heating time exceeding the upper limit of the range of the present invention. Test material
No. No. 32 was heated in a single slab rolling at a heating temperature exceeding the upper limit of the range of the present invention. As a result, the test material No. In 25, 30 and 32, the number of surface flaws was large.

The test material No. In No. 31, since the H ₂ S concentration in the heating atmosphere of the heating furnace exceeded the upper limit of the range of the present invention, surface flaws were extremely large.

As is clear from the above description, the ingot or the continuously cast slab having the component composition of the present invention is used in a heating furnace in a heating furnace within the scope of the present invention.
Concentration of H ₂ S, the heating temperature, the heating time and reduction of area by rolling blooming, reduced generation of surface flaws, there is no irregularity in the shape and size of the perforations at the time of etching the perforations,
In addition, there is no haze-like perforation defect due to roughening of the surface of the hole or generation of a strong oxide film, no seizure during flat mask annealing does not occur, and little gas is released.
Ni-based alloy sheets can be obtained.

Example 3 A 7-ton ingot No. shown in Table 1 was used. 13 at a temperature of 1200 ° C. for 5
The slab was heated for an hour and then slab-rolled at a 78% reduction in area. The slab thus prepared was subjected to care, and then subjected to a soaking treatment of heating at a temperature of 1300 ° C. for 10 hours in a heating atmosphere having an O ₂ concentration of 0.02 vol%, and then subjected to surface grinding. .02vol
% In an atmosphere of O ₂ , and then hot-rolled at a hot-rolling end temperature of 950 ° C. to prepare a hot-rolled coil. Each of the thus prepared hot-rolled coils was descaled, then repeatedly subjected to cold rolling and annealing, and then subjected to strain relief annealing at a temperature of 700 ° C. for 10 seconds to reduce the thickness to 0.20 mm. Fe- for shadow mask
Ni-based alloy sheet No. 13 (hereinafter referred to as “test material” N
o. 13).

With respect to the slab described above, the occurrence of surface flaws was examined. Further, with respect to the cold-rolled coil obtained by subjecting the above-described hot-rolled coil to cold rolling, minute internal cracks were examined. Next, the test material No. Regarding No. 13, the segregation rate of Si in the surface portion of the alloy thin plate, etching piercing property, seizure during flat mask annealing, and gas release during operation of the shadow mask were investigated. That is, each of these investigations was performed by the same method as described in Example 1 above. The results are shown in Table 6 below.

[0102]

[Table 6]

As apparent from Table 6, the test material No.
No. 13 had a component composition within the scope of the present invention, except that it contained manganese not contained in the present invention. Further, the test material No. No. 13 had a segregation ratio of silicon out of the range of the present invention. As a result, a large amount of surface flaws were removed, the interface of the holes was roughened at the time of etching drilling, and a mist-like drilling defect was generated, seizure occurred during flat mask annealing, and gas was released.

The test material No. described above was used. Reference numeral 13 denotes an alloy having the same composition as that of the prior art 1 manufactured by the same method as that of the prior art 1. As is clear from the above description, the superior effect of the present invention cannot be obtained by the prior art 1.

Example 4 35.7 wt. % Nickel, 0.
005 wt. % Boron, hydrogen 1.0 ppm, 0.05 wt. % Silicon, 0.005 wt. % Aluminum, 0.004w
t. % Carbon, 0.0018 wt. % Nitrogen, 0.002 wt. %
Of sulfur, 0.0026 wt. % Oxygen, 0.003 wt. % Phosphorus and the ingot of the invar alloy consisting of the balance iron is then groomed and then heated to a temperature of 1250 ° C.
Hot forging with a reduction of area of 78%, and
A slab was prepared by performing soaking at a temperature of 00 ° C. for 5 hours. The slab prepared in this manner was subjected to the above-described Example 1
By performing the same steps as above, a Fe-Ni-based alloy thin plate for a shadow mask having a plate thickness of 0.20 mm was prepared.

In the same manner as in the above embodiment, the state of occurrence of surface flaws, minute internal cracks,
The segregation rate, etching perforation, seizure during flat mask annealing, and outgassing during shadow mask operation were investigated. The results are shown in Table 7 below.

[0107]

[Table 7]

As is evident from Table 7, the above-mentioned alloy sheet had a composition different from that of the present invention. Furthermore, the above-mentioned alloy sheet had a silicon segregation rate outside the range of the present invention. As a result, the surface flaw removal amount was large, the interface of the holes was roughened at the time of etching perforation, and a mist-like perforation defect was generated, seizure occurred during flat mask annealing, and gas was released.

The above-mentioned alloy thin plate is an alloy having the same composition as that of the prior art 2 manufactured by the same method as that of the prior art 2. As is clear from the above description, the superior effect of the present invention cannot be obtained by the prior art 2.

[0110]

According to the present invention as described in detail above,
Low generation of surface flaws, no unevenness in shape and size of perforation at the time of etching perforation, no haze-like perforation defects due to rough interface of perforations, and seizure during flat mask annealing In addition, since it is possible to provide an Fe-Ni-based alloy thin plate for a shadow mask and a preferable method for producing the same, which emit less gas, an industrially advantageous effect is brought about. It is a great invention.

[Brief description of the drawings]

FIG. 1 shows the contents of calcium and magnesium in a slab and an alloy sheet having a composition within the scope of the present invention except for the contents of calcium and magnesium, when the contents of calcium and magnesium are respectively changed. 5 is a graph showing the relationship between the amount and the slab flaw removal amount, the etching piercing property of the alloy sheet, the seizure during flat mask annealing, and the release of gas during the operation of the shadow mask.

FIG. 2 shows the results when the respective values of Ca + Mg / 2 and S + O / 5 are changed in a slab and an alloy sheet having a composition within the range of the present invention except for the values of Ca + Mg / 2 and S + O / 5. The respective values of Ca + Mg / 2 and S + O / 5,
4 is a graph showing a relationship between a slab flaw removal amount, an etching piercing property of an alloy thin plate, burn-in during flat mask annealing, and gas release during shadow mask operation.

FIG. 3 is a ternary phase diagram of CaO—Al ₂ O ₃ —MgO showing the composition range of nonmetallic inclusions present in the Fe—Ni-based alloy thin plate of the present invention.

FIG. 4 shows a heating temperature (T) ° C. when an ingot or a continuously cast slab having a component composition within the scope of the present invention is heated and then subjected to slab rolling at a cross-sectional reduction rate of 35% or more.
4 is a graph showing a relationship between heating time (t) h and a Si segregation rate and a slab flaw removal amount in a final sheet thickness (alloy sheet).

FIG. 5: Heat an ingot or continuous cast slab having a component composition within the scope of the present invention, and then
Each primary heating temperature T () at the time of primary slab rolling at a cross-sectional reduction rate of 0%, then heating again, and then at a secondary slab rolling at a cross-sectional reduction rate of 20 to 70%. FIG. 6 is a graph showing a relationship between the temperature (° C.) and the heating time t (hr), the Si segregation rate in the final sheet thickness (alloy sheet), and the slab flaw removal amount.

FIG. 6 shows a thin Fe—Ni alloy sheet for a shadow mask used in an example of the present invention. CaO showing the component composition of the nonmetallic inclusions contained in each of 1 to 5 and 7 to 19,
FIG. 3 is a ternary phase diagram of Al ₂ O ₃ —MgO.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomoyoshi Ohkita 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (72) Shinichi Okimoto 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Japan (56) References JP-A-4-168248 (JP, A) JP-A-2-170922 (JP, A) JP-A-61-113746 (JP, A) JP-B-59-38302 (JP, A) , B2)

Claims (6)

(57) [Claims] The present invention is excellent in etching piercing property, prevents seizure during annealing, suppresses gas release, and is excellent in adhesion seizure preventing property and gas releasing property during annealing, essentially consisting of: Fe-Ni alloy thin plate: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the balance, substantially iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P) )): For carbon, 0.0050 wt. % Or less, 1 ppm or less for hydrogen, and 0.0020 wt.% For nitrogen. % Or less, sulfur is 0.0020 wt. % Or less, oxygen is 0.0040 wt. % Or less, and about 0.0040 wt. % Or less, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045w
t +%, where Ca + Mg / 2 ≧ S + O / 5: The silicon (Si) segregation rate of the surface portion of the alloy thin plate represented by the following formula is 10% or less: Si segregation rate = [| segregation Si concentration in the region-average Si concentration | / average Si concentration] x 100 2. It is excellent in etching piercing property, prevents seizure during annealing, suppresses gas release, and is excellent in adhesion seizure preventing property and gas releasing property during annealing. Fe-Ni alloy thin plate: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0.09 wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the balance, substantially iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O), phosphorus (P) ) And non-metallic inclusions are: 0.005 wt. % Or less, 1 ppm or less for hydrogen, and 0.002 wt.% For nitrogen. % Or less, 0.002 wt. % Or less, 0.004 wt. % Or less, 0.004 wt. % Or less, and for nonmetallic inclusions, 0.004w
t. % Or less, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045w
t.% or less, where Ca + Mg / 2 ≧ S + O / 5: The non-metallic inclusions as unavoidable impurities are CaO −
In the Al ₂ O ₃ -MgO ternary phase diagram, consisting of a composition having a particle size of 6 μm or less in a region having a melting point of 1600 ° C. or more specified by a liquidus line of 1600 ° C .:
The silicon (Si) segregation rate of the surface portion of the alloy thin plate represented by the following equation is 10% or less: Si segregation rate = [| Si concentration in segregation region−Si average concentration | / Si average concentration] × 100 3. The method according to claim 1, comprising the following steps: Fe—excellent in etching piercing property, preventing seizure during annealing, and suppressing gas release; Production method of Ni-based alloy sheet: Prepared into ingot or continuous cast slab of Fe-Ni-based alloy essentially consisting of: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0 .09wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg): 0.0003-0.0020 wt. % However, Ca + Mg / 2: 0.0005 to 0.0025 wt. % And the balance, substantially iron and unavoidable impurities, provided that carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P) )): For carbon, 0.0050 wt. % Or less, 1 ppm or less for hydrogen, and 0.0020 wt.% For nitrogen. % Or less, sulfur is 0.0020 wt. % Or less, oxygen is 0.0040 wt. % Or less and 0.0040 wt.% Or less for phosphorus, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045 w
t.% or less, provided that Ca + Mg / 2 ≧ S + O / 5: the ingot or the continuously cast slab is subjected to at least one of the following steps: Cold rolling, temper rolling and strain relief annealing are sequentially performed to prepare a Fe-Ni-based alloy thin plate, and in the slab rolling, the ingot or the continuously cast slab is subjected to 100 ppm or less of H ₂ S. Temperature T in the range of 1150-1300 ° C.
(° C.) and heated for a time t (hr) represented by the following formula: 7.71−5.33 × 10 ⁻³ T ≦ logt ≦ 8.00−5.33 × 10 ⁻³ T, then 35 The agglomerate is rolled at a cross-sectional reduction ratio of not less than 10%, and then gradually cooled to adjust the segregation ratio of silicon (Si) of the surface portion of the alloy thin plate to 10% or less represented by the following formula: Si Segregation rate = [| Si concentration in segregation area−Si average concentration | / Si average concentration] × 100 4. The Fe-Ni alloy according to claim 3, which has excellent anti-seizure property and gas emission property during annealing.
Production method of thin alloy sheet: In the slab rolling, the ingot or the continuously cast slab is heated at a temperature T (° C.) in a range of 1150 to 1300 ° C. in a heating atmosphere having an H ₂ S concentration of 100 ppm or less.
Is heated for a time t (hr) represented by the following formula: 7.40-5.33 × 10 ⁻³ ≦ logt ≦ 7.71−5.33 × 10 ⁻³ T, and then 20-70% Primary slab rolling at a cross-sectional reduction rate within the range, and then, in a heating atmosphere having an H ₂ S concentration of 100 ppm or less, a temperature T within a range of 1150 to 1300 ° C.
(° C.) for a time t (hr) represented by the above formula,
Then, the secondary slab rolling is performed at a cross-sectional reduction rate in the range of 20 to 70%, and then gradually cooled, and silicon (Si) segregation of the surface portion of the alloy thin plate is represented by the following formula. The segregation rate is adjusted to 10% or less: Si segregation rate = [| Si concentration in segregation area−Si average concentration | / Si average concentration] × 100 5. The method according to claim 1, which comprises the following steps: Fe—excellent in etching piercing property, preventing seizure during annealing, and suppressing gas release, and excellent in anti-adhesion seizure during annealing and excellent gas diffusion property. Production method of Ni-based alloy sheet: Prepared into ingot or continuous cast slab of Fe-Ni-based alloy essentially consisting of: Nickel (Ni): 34-38 wt.% Silicon (Si): 0.01-0 .09wt. % Aluminum (Al): 0.002 to 0.020 wt. % Calcium (Ca): 0.0002 to 0.0020 wt. % Magnesium (Mg: 0.0003 to 0.0020 wt.%, But Ca + Mg / 2: 0.0005 to 0.0025 wt.%, And the balance substantially iron and unavoidable impurities; The respective contents of carbon (C), hydrogen (H), nitrogen (N), sulfur (S), oxygen (O), phosphorus (P) and non-metallic inclusions are: 0.005 wt.% For carbon Hereinafter, 1 ppm or less for hydrogen, 0.002 wt.% Or less for nitrogen, 0.002 wt.% Or less for sulfur, 0.004 wt.% Or less for oxygen, and 0.004 wt.% For phosphorus. % Or less, and for non-metallic inclusions, 0.004 w
t.% or less, provided that C / 10 + N / 10 + S + O / 5 + P / 2: 0.0045w
t.% or less, where Ca + Mg / 2 ≧ S + O / 5: The non-metallic inclusions as unavoidable impurities are CaO −
In the Al ₂ O ₃ -MgO ternary phase diagram, in a region having a melting point of 1600 ° C. or more, which is specified by a liquidus line of 1600 ° C., comprising a composition having a particle size of 6 μm or less; The ingot or the continuous cast slab is subjected to at least one cold rolling, temper rolling, and strain relief annealing, accompanied by block rolling, scratch removal, hot rolling, descaling / scratch removal, and recrystallization annealing. Then, an Fe-Ni-based alloy thin plate is prepared. In the slab rolling, the ingot or the continuous casting slab is heated at a temperature T in a range of 1150 to 1300 ° C. in a heating atmosphere having an H ₂ S concentration of 100 ppm or less. (℃)
Then, heating is performed for a time t (hr) represented by the following formula: 7.71−5.33 × 10 ³ T ≦ logt ≦ 8.00−5.33 × 10 ³ T, and then a cross-sectional reduction of 35% or more And then gradually cooled to adjust the segregation rate of silicon (Si) of the surface portion of the alloy sheet to 10% or less represented by the following formula: Si segregation rate = [| Si concentration in segregation region−Si average concentration | / Si average concentration] × 100 6. Excellent in adhesion seizure prevention property and gas emission property during annealing as described in claim 5, characterized in that:
Method of manufacturing a Fe-Ni alloy sheet: In the blooming rolling, the ingot or the continuous casting slabs, in a heated atmosphere in the following concentration of H ₂ S 100 ppm, the temperature T in the range of 1150 to 1300 ° C. (° C. )
Is heated for a time t (hr) represented by the following formula: 7.40-5.33 × 10 ³ T ≦ logt ≦ 7.71-5.33 × 10 ³ T, then in the range of 20-70% Primary slab rolling at a cross-sectional reduction rate within a range of 1250 to 1300 ° C. in a heating atmosphere having a H ₂ S concentration of 100 ppm or less.
(° C.) for a time t (hr) represented by the above formula,
Then, the secondary slab rolling is performed at a cross-sectional reduction rate in the range of 20 to 70%, and then gradually cooled, and silicon (Si) segregation of the surface portion of the alloy thin plate is represented by the following formula. The segregation rate is adjusted to 10% or less: Si segregation rate = [| Si concentration in segregation area−Si average concentration | / Si average concentration] × 100