JP2001247939A - Thin alloy sheet for shadow mask, excellent in blackening treatability, and shadow mask using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin alloy sheet for shadow mask, excellent in blackening treatability, by removing nonuniformity in blackening treatment. SOLUTION: The thin alloy sheet for shadow mask excellent in blackening treatability is composed of a shadow mask material having a composition consisting of, by mass, 29-45% Ni and the balance essentially Fe. Further, when the outermost surface of this shadow mask material is measured by the use of a device for photoelectron spectroscopic analysis, Si, Mn, B and N satisfy, by atom, Si>=1.0%, Mn>=0.5%, B<=25% and N<=35%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alloy thin plate for a shadow mask and a shadow mask used for a picture tube of a color television or a computer display.

[0002]

2. Description of the Related Art Alloy thin plates for shadow masks used for picture tubes of color televisions and computer displays are known as:
In order to promote thermal diffusion and prevent rust, it is necessary to form a black oxide film on the surface. This process of forming a black oxide film is generally called a blackening process. As a shadow mask material alloy thin plate having excellent blackening processability, for example, Fe- Oxide-forming elements such as Mn, Al, Si, Cr and Ti, such as Ni alloy, and M
Each element in the Fe-Ni alloy such as o, W, Nb, V, Cu, As, Sb, and other elements that control the blackening film growth rate, B, H, and rare earth elements that determine the characteristics of the blackening film It has been proposed to obtain an excellent blackening film treatment property by adjusting the content of an appropriate amount.

[0003]

As described above, in order to improve the blackening properties, only control of the composition of the alloy thin plate for a shadow mask has been attempted so far. According to the study of the present inventors, in fact, the element on the outermost surface on which the direct blackening film is formed directly governs the direct blackening property, and among them, particularly oxides of Si and Mn and compounds thereof. Is present in a specific amount in the grain boundaries and in the grains,
It has been found that it is highly possible to suppress the diffusion of B and N, or their compounds, which cover the crystal grain boundaries on the outermost surface and impair the blackening film properties, and further, those compounds on the outermost surface. Therefore, analyze the outermost surface of the shadow mask alloy thin plate with a photoelectron spectrometer or Auger spectrometer called ESCA or XPS to know the elements present on the measurement surface, the amount of the elements, and the bonding state of the elements. Is important.

According to the study of the present inventors, as a result of a detailed study of the relationship between the outermost layer portion of the alloy thin plate for a shadow mask and the blackening property, it has been found that a compound singly or in a combined state,
Or a single or compound compound + metal
There were B, N, Mn, Si, and the like, and it was found that these elements existed on the outermost surface. Therefore, the present inventors conducted a detailed analysis of the outermost surface of the shadow mask alloy thin plate before the blackening treatment and the shadow mask alloy thin plate after the blackening treatment where the blackening film was not formed uniformly. On the outermost surface, a thin black alloy film after the blackening treatment is non-uniform in a thin alloy sheet in which a specific amount of the above-mentioned specific element is present alone or in a compound, or a specific amount of an element showing the combined state of compound and metal is present. It has been found that various oxidation spots occur.

Further, the present inventors have further studied the state of the outermost surface, and as a result, those having the above-described elements on the outermost surface are the main constituent elements of the blackened film after the treatment. It was also found that C and O were locally concentrated, resulting in uneven blackness. An object of the present invention is to provide an alloy thin plate for a shadow mask excellent in blackening processability by eliminating non-uniformity of blackness and a shadow mask using the same.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and the most important features of the present invention are as follows.
The object of the present invention is to adjust the amount of an element showing the bonding state of a compound or a compound or a compound or a metal on the outermost surface. That is, the present invention, Ni: 29 to 45% by mass%
In a shadow mask material substantially consisting of Fe, the balance is as follows: when the outermost surface of the shadow mask material is measured by a photoelectron spectrometer, Si: 1.0% or more in atomic%;
5% or more, B: 25% or less (including 0%), and N: 35% or less. This is an alloy thin plate for a shadow mask having excellent blackening properties.

In the present invention, a shadow mask material containing 29 to 45% of Ni by mass% and the balance substantially consisting of Fe was used, and the outermost surface of the shadow mask material was measured by an Auger electron spectrometer. In this case, B is a thin alloy sheet for a shadow mask having excellent blackening properties, in which the crystal grains segregated on the surface are 30% or less (including 0%) in view area ratio. Preferably, when the outermost surface of the shadow mask material is observed with a scanning electron microscope, a hemispherical oxide is 12% or more in view area ratio and is a thin alloy plate for a shadow mask excellent in blackening treatment.

The preferred chemical composition of the shadow mask alloy sheet of the present invention is as follows: Ni: 29 to 45% by mass, Si: 0.03% by mass.
% Or less, Mn: 0.3% or less, B: 0.003% or less (including 0%), N:
0.005% or less, the balance being an unavoidable impurity and substantially Fe, which is an alloy thin plate for a shadow mask excellent in blackening processability. Fe may be partially substituted with 7% or less of Co.

Further, according to the present invention, a shadow mask material containing 29 to 45% of Ni by mass% and the balance substantially consisting of Fe is subjected to a blackening treatment, and the shadow mask material after the blackening treatment is subjected to a blackening treatment. When the surface is measured with a photoelectron spectrometer, C: 30% in atomic%
Hereinafter, it is an alloy thin plate for a shadow mask having O: 50% or less. Further, the present invention is a shadow mask using the above-mentioned alloy thin plate for a shadow mask.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the most important feature of the present invention is that, as described above,
In the shadow mask material containing 29-45% of Ni and the balance being substantially Fe, it was found that the element on the outermost surface on which the direct blackening film is formed directly controls the blackening property. The purpose of the present invention is to adjust the amount of a specific element showing the bonding state of a compound or a compound + metal on the outermost surface. Therefore, in the present invention, the bonding state and the amount of the element measured on the outermost surface of the surface to be measured obtained by the photoelectron spectrometer (not sputtered by dry etching), or the distribution of the element using an Auger electron spectrometer The area ratio becomes important.

At this time, in order to obtain high-accuracy information with a small error in the measurement area, it is good to take in a large amount of signal. For this purpose, the larger the measurement area, the better. In the case of observation and analysis, it is desirable to perform analysis under conditions that enable high magnification observation. Therefore, it is desirable to analyze and average at least 5 fields of view in a photoelectron spectrometer over a wide range of about 10 mm × 2 mm and auger electron spectrometer at 1500 times the field of view, and if these measurement areas cannot be secured, at least about 20 The measurement magnification is used so that the crystal grains can be seen. When the measurement surface for performing these measurements is extremely contaminated with oil or the like, the reliability of the measurement results is lacking, so that the measurement results may be washed with an organic solvent.

Next, the reason why the amount of the element on the outermost surface specified in the present invention is limited will be described as follows. First, B (boron) detected on the outermost surface is mainly boron nitride or boron oxide, or further a composite compound thereof,
And boron as a metal are detected, but these are subjected to softening annealing heat treatment at about 800 ° C., for example, which is performed prior to the blackening treatment, so that the outermost surface oozes from the inside through the grain boundary diffusion from the crystal grain boundary to the surface. Diffusion, and further diffusion spreads the surface so as to cover the crystal grains observed on the surface, which inhibits the adhesion of the blackened film and causes the blackened film to cause uneven oxidation spots Therefore, it is specified to 25 atomic% or less.

In the present invention, B is preferably measured in the range of a binding energy of 185 to 196 eV. If measured in this range, boron nitride, which is present on the outermost surface and inhibits the blackening property, may be measured. , Boron oxide, or their composite compounds, and boron as a metal. Although the mechanism is unknown, it is compared with the case where, for example, boron oxide is detected in a large amount in boron nitride, boron oxide, or a composite compound thereof, and boron as a metal, which are measured within the above range. Therefore, when boron nitride or boron which is a complex compound with boron oxide is detected in a large amount, there is a phenomenon that the blackened film is more likely to cause uneven oxidation spots.

In order to measure B with an Auger electron spectrometer, a KLL peak of 140 to 190 eV is employed in the integrated spectrum, and elemental mapping of B is performed using this peak, so that B at the surface is determined by Auger electron intensity. By looking at the density, two-dimensional B distribution information can be obtained. At this time, the segregated crystal grains that determine the viewing area ratio have a threshold value of luminance 32 when the maximum detection intensity of the element is luminance 256, and 1
When 80% or more of individual crystal grains are covered with B, the crystal grains are regarded as segregated crystal grains, and the visual field area ratio is the ratio of the sum of the areas of these crystal grains to the total visual field. . When the surface area ratio of the crystal grains in which B segregates on the surface exceeds 30%, oxidation spots occur when a blackened film is formed. Therefore, the crystal grains in which B segregates on the surface include 0% in the visual area ratio. At 30%
It must be: Preferably it is 25% or less.

The above-mentioned B (boron) is an element that is easily linked to N (nitrogen). If N is present, it has a property of easily forming a compound of N and B. It promotes exudation and further promotes concentration up to a depth of about 1 nm from the outermost surface. In most cases, N combines with boron nitride or other elements to form a nitride. For example, the bonding state of N detected within this range of the binding energy of 395 to 403 eV indicates that many of the compounds bonded to B described above and the surface layer has B
It can be confirmed that N (boron nitride) is formed. In addition to BN, nitrides associated with other elements are mainly formed near grain boundaries, but when these nitrides are present in excess, they are formed to cover the entire outermost surface of the thin plate by surface diffusion In other words, since not only the adhesion of the blackened film is reduced but also the blackened film causes uneven oxidation spots, N is set to 35 atomic% or less.

As described above, it is preferable to measure the N within the range of the binding energy of 395 to 403 eV. In addition to the above-mentioned BN which is present especially on the outermost surface and inhibits the blackening property, Compounds bonded to Si, or their composite compounds, and nitrogen as metal can be analyzed.
To measure N with an Auger electron spectrometer, use the KLL peak at 350 to 410 eV in the differential spectrum, and perform element mapping using this peak. N distribution information can be obtained.

Next, Si and Mn present on the outermost surface are mainly in a state of bonding with oxygen. The blackened film is mainly an oxide film of iron, but if Si and Mn in the bonded state are mainly distributed at the grain boundaries, the adhesion of the blackened film is deteriorated, and the blackened film causes uneven oxidation spots. It is possible to suppress the generation of B, N, or their compounds, which are the main causes, by diffusion at the grain boundary to the surface, and it is particularly effective in suppressing the diffusion of the grain boundary to the surface of BN. % And 1.0% or more of Mn must be present on the surface. In this connection, Si,
Mn forms not only simple oxides of Si and Mn at the grain boundaries, but also forms a complex compound composed of these elements and oxygen, and forms oxides or the above-described complex compounds not only at the grain boundaries but also at the entire outermost surface. Then, it is considered that the formation of B alone or complexed compound, N alone or complexed compound, and further the formation of these complex compounds are suppressed, but the mechanism is not elucidated at present.

In the present invention, the upper limit of Si is preferably 8% by atom%, more preferably 5% by atom, and the upper limit of Mn is 6% by atom%, more preferably 4% by atom. If so, it is possible to suppress the occurrence of deterioration in blackness due to the presence of a large amount of Si and Mn in a bonded state. In the present invention, the measurement of Si, the binding energy is performed in the range of 97 to 105 eV, it is good to be performed in the Mn binding energy of 45 to 50 eV, Si, Mn measured in this range is only a simple oxide Instead, form a compound compound consisting of these elements and oxygen,
It is possible to know the bonding state of Si and Mn which have an effect of suppressing the formation of B, N, or their compounds, which precipitate at the grain boundaries.

Further, in the present invention, B,
When the outermost surface of the material in which N, Si, and Mn are controlled is observed and analyzed with a scanning electron microscope, a hemispherical oxide is observed. Quantitative analysis of this hemispherical oxide with an X-ray analyzer shows that either Si or Mn is the main component (50% or more) or both Si and Mn are the main components (50% or more). ing.
Of course, the influence of the matrix (base) of Fe-Ni is detected as an analysis value, but the main elements of the matrix, Fe, Ni (Co
Is considered to have no effect).
Look at the analysis values.

As described above, Si and Mn in a bonded state form an oxide or the above-mentioned composite compound not only at the grain boundaries but also on the entire outermost surface, thereby suppressing the surface diffusion of B, N and their composite compounds. However, in this case, if the hemispherical oxide can see a specific ratio or more in the viewing area ratio, the uniformity of the blackened film tends to be further improved, and according to the detailed research of the present inventors, The hemispherical oxide is 0.5 times at an observation magnification of about 1500 times.
It has been found that when measuring a grain having a size of not less than μm, the viewing area ratio should be 12% or more. Therefore, in the present invention, when the outermost surface of the shadow mask material is observed with a scanning electron microscope, the hemispherical oxide is defined to have a viewing area ratio of 12% or more. Note that if the oxide is formed in excess of 25%, the distribution of the oxide becomes local, so the upper limit is preferably 25% or less.

In order to limit the above-mentioned specific element to the specific amount specified in the present invention on the outermost surface, it is preferable to select an element having the following alloy composition. Ni is a major component of alloys for shadow masks, and provides low thermal expansion characteristics required for shadow masks. 3.0 × 10 ⁻⁶ / 30 ° C./30° C./30×10 ^-6 /
A coefficient of thermal expansion of not more than ℃ is required. Assuming that Co is added in order to satisfy this coefficient of thermal expansion, the content of Ni may be in the range of 32 to 38% by mass%, and when Co is not added, the Ni content is 29% by mass. The range may be up to 45%.

Usually, Si and Mn are contained in a small amount in alloy thin plates for shadow masks for the purpose of deoxidation. However, if they are added excessively, not only the concentration near the surface layer portion is promoted, but also segregation occurs. It is desirable that Si is 0.03% or less and Mn is 0.3% or less, since it becomes easy. When Si is added in excess of 0.03% and Mn in excess of 0.3%, the active alloy diffuses and concentrates near the surface in the softening annealing heat treatment of alloy sheets for shadow masks.
Si and Mn form excessive oxides and form S at the grain boundaries.
The i and Mn oxides are locally formed not only at the grain boundaries but also within the grains from the outermost surface to a depth of 1 nm.
Since these are formed on the outermost surface, they degrade surface treatment properties and suppress the initial etching speed at the time of forming the mask holes, so that the etching characteristics are deteriorated. Where S
For i and Mn, the lower limit of Si is 0.001% or more, and Mn is 0.01% or more, because the compound of B or N alone or in combination forms a minimum oxide capable of suppressing concentration near the surface layer. It is preferred that

B easily diffuses into the grain boundaries simultaneously with the improvement of hot workability. If the content exceeds 0.003%, the diffusion of B changes from grain boundary diffusion to surface diffusion in the softening annealing heat treatment of the alloy sheet for shadow mask, and B enrichment occurs over a wide range of the outermost surface. As described above, B, which is concentrated on the outermost surface to form a compound, not only impairs the blackening property, but also deteriorates the surface conditioning property and the etching property. Further, since excessive B deteriorates hot workability, 0.003% or less is preferable,
No additive (0%) may be used.

N is an element existing as an unavoidable impurity in the alloy. N forms AlN in steel and becomes an inclusion, thereby impairing the etching property and the soft annealing property. If the content exceeds 0.005%, the inclusions become too large, so that not only the etching property and the soft annealing property are deteriorated, but also N becomes concentrated on the outermost surface in the soft annealing heat treatment of the alloy sheet for the shadow mask. Further, N combines with B that has been surface-diffused to form BN, and thus promotes the B surface concentration. In addition, since the N compound is relatively stable, it impairs the surface treatment property and the etching property. For the above reasons, N is set to 0.005% or less.

In the present invention, a part of the above-mentioned Ni is reduced by 7%.
The following Co may be substituted. Co is an element that lowers the coefficient of thermal expansion similarly to Ni. When Co is replaced with Ni, the Curie point rises and the coefficient of thermal expansion can be kept low up to higher temperatures. In addition, Co forms a solid solution in the Fe-Ni alloy and has an effect of increasing the hardness during annealing, thereby increasing the hardness after final cold rolling. However, no further effect is seen with the addition of 7% or more. Therefore, the amount of Ni substitution by Co is limited to 7% or less.

In order to obtain a shadow mask alloy thin plate in which the specific element of the present invention is limited to the specific amount specified in the present invention on the outermost surface, the blackening containing at least 29 to 45% by mass of Ni is required. The material before the treatment may be appropriately adjusted for the annealing temperature and atmosphere, for example, at a dew point of + 10 ° C to -10 ° C and a temperature of 4 to 70 ° C.
It is preferable to perform heating at 800 ° C. for 30 minutes in a hydrogen atmosphere of l / min. It is natural that the flow rate differs depending on the size of the heating furnace, and an optimum flow rate may be selected according to the capacity of the heating furnace. At this time, it is needless to say that the chemical composition of the material before the blackening treatment is preferably adjusted within the range of the alloy thin plate for a shadow mask of the present invention.

Further, the alloy thin plate for a shadow mask having the outermost surface adjusted to the range specified in the present invention described above,
Analysis by a photoelectron spectrometer of the outermost surface after the blackening treatment performed thereafter has also confirmed that it has a characteristic composition. Specifically, in the alloy thin plate for a shadow mask having the outermost surface having a composition out of the composition range of the outermost surface defined in the present invention, the blackened film is unevenly unevenly formed. When the surface is analyzed with a photoelectron spectrometer, the amount of C and O is smaller than that of the thin plate after blackening of the material of the present invention,
It was found to be high.

That is, using the alloy thin plate of the present invention, for example,
If subjected to blackening treatment to heat brown gas mixed with nitrogen and hydrogen at a flow rate of 20 to 50 l / min at 500 ° C for 15 minutes,
When the outermost surface of the shadow mask material is measured with a photoelectron spectrometer, C is 25% or less and O is 50% or less in atomic%. In addition, on the outermost surface after the blackening treatment, C was 30% in atomic%, and O
In the blackened film having the outermost surface of which exceeds 50%, oxidation spots are visually confirmed.

When the alloy thin plate for a shadow mask of the present invention described above is used as a material for the shadow mask, a shadow mask free from oxidation spots can be obtained.

[0030]

EXAMPLE An alloy sheet material for a shadow mask having a chemical composition as shown in Table 1 was placed in a hydrogen atmosphere using a small experimental furnace at 800 ° C. for 30 minutes at a flow rate of 4 to 10 l / min to determine the dew point. The elements appearing on the outermost surface were controlled at -30 ° C, -20 ° C, -10 ° C, 0 ° C, and 10 ° C. The concentrated element on the outermost surface was investigated using a photoelectron spectroscopy analyzer (ESCA) in which the material obtained by heating was adjusted so that the analysis area could be measured in the range of 2 mm × 10 mm. This is because increasing the analysis area is advantageous for the purpose of obtaining average information on the surface and for detecting trace elements. No. 1 was a 36Ni-Fe alloy and No. 2 was a 32Ni-5Co-
Fe alloy, No. 3 is an alloy sheet material for shadow masks made of 36Ni-Fe (no B added) alloy.

[0031]

[Table 1]

A qualitative analysis of the outermost surface of the test material was performed to confirm the detected elements. When the amount of the detected element is extremely small, it may be difficult to perform quantitative evaluation depending on the background, so in performing the quantitative evaluation, each of the constituent elements of the thin plate, C, O, Fe, Ni, Co, Si, The Mn, B, N, S, and Al elements were set to be measured, and the elements recognized in the qualitative analysis and the state of the metal of each of the constituent elements described above, and each element within the binding energy range forming the compound Were collected multiple times and superimposed so that even small amounts of photoelectron peaks could be detected. For C, the binding energy is 275-285 eV for C, and for O
520-540 eV, Fe 700-740 eV, Ni 845-885 eV, Co 77
0 to 810 eV, B is 180 to 200 eV, N is 400 to 410 eV, S is 155 to 17
5 eV, Si measured 95 to 115 eV, Mn measured 43 to 63 eV, and Al measured a bond energy range of 65 to 85 eV.

Table 2 shows the measurement results of Samples 11 to 15 obtained by heat-treating the No. 1 sample in Table 1 under the above heat treatment conditions. In the table, the detection amount indicated as 0% (not detected) indicates the state of the metal of the element and the photoelectron peak of each element in the binding energy range forming the compound so that quantitative evaluation can be performed. Despite the fact that a peak is extremely small or cannot be recognized as a peak, it is indistinguishable from a background other than the peak because the peak is extremely small or cannot be recognized even though it is collected multiple times and superimposed so that it can be detected even in trace amounts. .

Table 3 shows the measurement results of Samples 21 to 25 obtained by heat-treating the No. 2 sample of Table 1 under the above heat treatment conditions.
Sample Nos. 31 to 35 heat-treated No. 3 sample under the above heat treatment conditions
Table 4 shows the measurement results. Note that the measurement results are quantified by integrating the peak areas of the respective elements using a relative sensitivity coefficient unique to the apparatus so that all of the detected elements become 100 atomic%. However, since the quantitative value of Al was not detected for all samples, it was omitted from these tables. However, depending on the element, even if the detection concentration of B in the entire material is less than 0.0001 mass% (no addition) as in the No. 3 sample, it may be detected on the surface through steps such as heat treatment. there were.

In each table, the surface of each sample is shown.
Using an Auger electron spectrometer, measure the visual field area ratio of the crystal grains of the surface segregation of B at 1500 times field of view and the hemispherical oxide field area ratio observed at 1500 times field of view with the scanning electron microscope. The results are shown in Tables 2 to 4. In addition, the analysis with the Auger spectrometer was performed with an integrated spectrum of 140 to 190 eV.
The KLL peak is adopted, this peak is scanned with an electron beam in a field of view of 1500 times, element mapping using the KLL peak of B is performed, and information on the spatial B distribution is obtained by observing the B concentration by Auger electron intensity. I got it.

FIG. 1 shows a material No. 11 having no oxidized spots.
2 shows the mapping of B by Auger spectroscopy after soft annealing, and FIG. 2 shows the mapping of B by Auger spectroscopy after soft annealing of material No. 13 in which oxidized spots were generated. B is locally distributed (the more the signal amount of B, the whiter it looks), and conversely, No.
It can be seen that B of 13 is distributed over the entire surface (the signal amount of B is large and the entire surface is white). FIG. 3 shows a scanning electron micrograph of a hemispherical oxide of No. 11 having no oxidation spots. It is prominent at the crystal grain boundaries and is also found in the crystal grains. This oxide is less frequently found in materials without oxidation spots.

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

Judging from the binding energy detected in the above energy range, the alloy composition, and the atmosphere of the heat treatment,
NIST (The US National Institute of Standards
and Technology) and a handbook of ULVAC-PHI CO., LTD. The result of the identification is described.

The C peak consists of a complex compound of C bonded to a surface hydrocarbon of 284.8 eV and oxygen of 288.3 eV.
The O peak is considered to correspond mainly to an oxide of 529.5 eV to 530.2 eV of Fe, but an oxide of Mn of 529.3 to 529.9 eV, 532.
The peak was considered to be composed of a composite oxide such as an oxide of Si of 4 to 534.3 eV and an oxide of B of 530.2 to 533.2 eV.

The Fe peak is 706.5 to 708.7 eV for metal and 709.
3~710.7eV of FeO, 710.3~711.6eV of Fe ₂ O _3, 711.0~71
It is considered to be a complex compound of 2.0 eV FeOOH, and from the shape of the peak, it is considered that the oxide is mainly contained. Ni peak is 853.5
~854.5eV of NiO, an oxide of Ni ₂ O ₃ of 856.0~857.0eV, 8
Metal of 52.5 to 853.8 eV was recognized, and the result was that mainly metal was mainly detected. Co peak between 780.0 and 781.0 eV
CoO, Co ₃ O ₄ of 778.2～780.3EV, and Co ₂ O ₃ or the like oxide 779.9EV, metal peak 778.1~778.5eV were detected.

The B peak is BN of 190.0-190.7ev and 192.0-19
It consists of a complex compound of 3.6 eV B ₂ O ₃ and the main component of the peak is BN
Met. FIG. 3 shows an example of a material No. 11 having no oxidation spots.
4 shows the ESCA profile of B after soft annealing, and FIG. 4 shows the ESCA profile of soft No. 13 of material No. 13 in which oxidation spots have occurred. B of the material No. 11 having no oxidation spots has a peak mainly due to the bonding state of B and oxidation, and the B peak of the material No. 13 having the oxidation spots is a peak mainly containing BN. As described above, these compounds are factors that alienate the adhesion of the blackened film or cause uneven oxidation spots. The detection amount of B tends to increase as the dew point is lower, and the samples 12 to 15, 22 to 25, and 34 to 35 having a higher B detection amount tend to cause uneven oxidation spots.

N peak is 397.4 to 398.0 eV SiN, 398.2 to 3
99.0 eV of BN, 398.9 eV of a complex compound such as S ₂ N ₄
The peak itself was mainly BN. S peak S ₂ N ₄ metal and 164.6eV of 164.0EV, peaked in complex compounds sulfides 160.0～163.5EV.

Si is SiO of 102.7 eV, SiO2 of 102.3 to 103.9 eV
And 101.5 to 102.0 eV of Si ₃ N ₄ . Mn
The MnO of 48.2EV, believed oxide of Mn ₃ O ₄ of Mn2O3,48.4eV of 49.7EV. In these results, the oxides of Si and Mn are detected more as the dew point is higher, and these oxides can suppress the complex compound of B and N, thereby suppressing the oxidation spots. However, since the binding energy peak is not necessarily ascertained from the existing database and the resolution of the apparatus, it is conceivable that other compounds may be present, or that each element may take a complex form of the compound.

Next, No. 11 to 15, No. 21 to 25, and No. 3
Samples from 1 to 35 were heat-treated in brown gas with a mixture ratio of nitrogen and hydrogen of 8:92 at 500 ° C for 15 minutes, and the surface was blackened by blackening. Photoelectron spectroscopy (ESCA) by
Table 5 shows the results of quantitative analysis of C, O, Fe, Co, and Ni.
Each of the constituent elements of the thin plate as in the measurements shown in Tables 2 to 4.
C, O, Fe, Ni, Co, Si, Mn, B, N, S, was set to measure the elements of Al, and the elements recognized in the qualitative analysis and the measurement of each of the constituent elements described above were performed. , C, O, Fe, Co, and Ni could only be detected, and the elements that could not be detected were omitted.

In this measurement, the qualitative analysis of the outermost surface of the sample was performed in the same manner as the above measurement, and the detected element was confirmed. In the quantitative evaluation, each of the main constituent elements of the thin plate and the elements detected by the qualitative analysis were measured, and the spot due to the blackening treatment was visually determined. Note that the measurement range of each element was the same as the above range, and all the detected elements were quantified to 100 atomic% using the relative sensitivity coefficient unique to the apparatus.

[0048]

[Table 5]

Judging from the binding energy detected in the above energy range, the alloy composition, and the heat treatment atmosphere, the NIST (The US National Institute of
dsand Technology) and a handbook of ULVAC-PHI, Inc. The result of the identification is described.

It was confirmed that C was composed of 284.8 eV hydrocarbon. In addition, it was confirmed that the amount of C was large in the case where the heat treatment was performed in a state where the dew point was low in the heat treatment prior to the blackening treatment, and that the amount of C without B was large. O mainly corresponds to an oxide of 529.5 to 530.2 eV of Fe, and F
e is mainly composed of a composite oxide of 709.3 to 710.7 eV FeO and 710.3 to 711.6 eV Fe ₂ O ₃ , which is a main compound constituting the blackened film. Many of these were heat treatments performed at a low dew point in the heat treatment performed prior to the blackening treatment, and it was confirmed that the Fe-free material had a large amount of Fe oxide.

Ni is 853.5 to 854.5 eV NiO, 856.0 to 857.0 e
Peaks of Ni ₂ O _{3 of} V and a metal of 852.5 to 853.8 eV were detected, and the metal was mainly contained. For Co containing Nos. 31-35, the Co peak was 780.0-781.0 eV CoO, 778.2-780.3 eV
And Co ₃ O _4, etc. oxide Co ₂ O ₃ of 779.9eV of, 778.1～778.5EV
Was detected, and the metal was mainly contained.

From the results in Table 5, it is found that Nos. 11, 21, and 31 to 33 adjusted within the concentration range specified in the present invention are as follows:
%, O: 50% or less, and no spots are observed after the blackening treatment. On the other hand, No.12-15, No.22-25, No.34-35
The test material of C exceeds 30% in atomic% and O: 50%,
In any case, unevenness has occurred in the blackening process. From the above results, it was found that when the material controlled to be the outermost surface specified in the present invention was blackened, a blackened film without oxidation spots could be formed, and a shadow mask having a good blackened film was obtained. be able to.

[0053]

According to the present invention, the uniformity of blackness at the time of blackening can be remarkably improved, and the improvement of the blackening characteristics is indispensable for an alloy sheet for a shadow mask, which is required to be further improved. Technology.

[Brief description of the drawings]

FIG. 1 is a mapping of B by Auger spectroscopy on the surface of a soft alloy sheet for a shadow mask according to the present invention when it is softened and annealed.

FIG. 2 is a mapping of B by Auger spectroscopy of the surface when a comparative alloy thin plate for a shadow mask is soft-annealed.

FIG. 3 is an electron micrograph of an oxide observed on the surface of a material of a shadow mask alloy sheet of the present invention when the alloy sheet is softened and annealed.

FIG. 4 is a view showing an ESCA profile of B on the surface of the alloy thin plate for a shadow mask of the present invention.

FIG. 5 is a view showing an ESCA profile of B on the surface of an alloy thin plate for a shadow mask for comparison.

Claims (7)

[Claims] 1. A composition containing 29 to 45% of Ni by mass%,
The remainder is a shadow mask material substantially composed of Fe. When the outermost surface of the shadow mask material is measured by a photoelectron spectrometer, Si: 1.0% or more in atomic%, Mn:
0.5% or more, B: 25% or less (including 0%), N: 35
% Or less, which is excellent in blackening treatment properties. 2. Ni: 29 to 45% by mass%,
The remainder is a shadow mask material substantially composed of Fe. When the outermost surface of the shadow mask material is measured by an Auger electron spectrometer, crystal grains in which B segregates on the surface are 30% or less (0%) in view area ratio. And an alloy sheet for a shadow mask having excellent blackening properties. 3. When the outermost surface of the shadow mask material is observed with a scanning electron microscope, a hemispherical oxide has a viewing area ratio of 1%.
The alloy thin plate for a shadow mask having excellent blackening properties according to claim 1 or 2, wherein the content is 2% or more. 4. Ni: 29 to 45% by mass%, Si:
0.03% or less, Mn: 0.3% or less, B: 0.003
% Or less (including 0%), N: 0.005% or less, and the balance consists essentially of Fe and unavoidable impurities. Excellent alloy thin plate for shadow mask. 5. The alloy thin sheet for a shadow mask excellent in blackening treatment according to claim 4, wherein a part of Ni is replaced by Co of 7% or less by mass%. 6. Ni: 29 to 45% by mass%.
The remaining portion is subjected to blackening treatment on a shadow mask material substantially composed of Fe, and when the outermost surface of the shadow mask material after the blackening treatment is measured with a photoelectron spectrometer, C: 30% in atomic%
Hereafter, O: 50% or less, an alloy thin plate for a shadow mask, 7. A shadow mask using the alloy thin plate for a shadow mask according to any one of claims 1 to 6.