KR20030043635A - Fe-Ni BASED ALLOY STOCK AND Fe-Ni-Co BASED ALLOY STOCK FOR SHADOW MASK - Google Patents

Abstract

PURPOSE: A high-strength Fe-Ni based and Fe-Ni-Co based alloy bar with high strength for a shadow mask capable of effectively preventing the occurrence of mask unevenness is provided. CONSTITUTION: In the Fe-Ni based and Fe-Ni-Co based alloys which contain Ni of 34 to 38 mass%, Mn of 0.1 to 1.0 mass%, C of 0.10 mass% or less and Al of 0.05 mass% or less, the average value of αAVE of the {100} integration degree distribution in the plate thickness direction on a plate surface is 60% or less and the {100} integration degree αc on the plate surface after removing up to 50% of the plate thickness by etching is larger than the {100} integration degree αs on the plate surface.

Description

Iron-nickel and iron-nickel-cobalt alloy baths for shadow masks {Fe-Ni BASED ALLOY STOCK AND Fe-Ni-Co BASED ALLOY STOCK FOR SHADOW MASK}

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a shadow mask bath used for color-selective electrodes installed in a CRT of a high-definition, high-definition display for color television or personal computers.

The bath used for the shadow mask is produced by performing hot forging and hot rolling on an ingot made by melting and casting, repeating cold rolling and annealing, and then performing final cold rolling. The shadow mask bath is perforated by applying a photoresist to both sides after degreasing and frontal treatment in an etching maker, baking and developing the shadow mask pattern, and then spraying the ferric chloride solution on both sides. The shadow mask is produced.

Background Art In recent years, with the fine pitch of holes due to high precision and high resolution of personal computer displays, shadow mask baths are highly demanded for high etching perforation, high strength, low thermal expansion characteristics, and the like, which suppress the occurrence of mask deviation. In order to puncture with fine pitch while suppressing the occurrence of mask deviation, it is necessary to make the material thickness thin, but when the thickness is made thin, the rigidity becomes weak, and there are problems such as deformation during handling and impact resistance after mounting of the CRT. For this reason, it is desired for the material for shadow masks to be excellent in nicking perforation and strength.

One of the indexes for evaluating etching permeability is an etching factor (hereinafter referred to as EF). EF is the ratio of the etching depth to the side etching amount (dimension of the opening of the resist minus the radius of the hole after etching), and the larger this value, the better the etching permeability. In order to increase this EF, it is necessary to increase the degree of integration in the {100} direction (hereinafter referred to as "{100} density") on the plate surface, and particularly excellent etching permeability when the {100} density is 60% or more. It is known that this is obtained. However, in order to obtain a {100} density of 60% or more on the plate surface, it is necessary to suppress the workability in the final cold rolling to a low level. Therefore, since the degree of work hardening is limited, it is in a situation where a response to high strength cannot be achieved.

1 is a view showing a cross-sectional shape of a hole drilled by etching.

2 is a view showing a planar shape of a hole drilled by etching.

3 is a diagram illustrating a distribution of {100} density in the present invention.

Fig. 4 is a diagram showing a method for approximating the average value α _AVE in the plate thickness direction distribution of the degree of integration on the plate surface.

The present inventors have intensively studied the relationship between the distribution in the plate thickness direction in the {100} direction with respect to the plate surface and the etching perforation, and as a result, in order to suppress the mask variation, the plate thickness is higher than the etching factor is increased. By optimizing the density distribution in the {100} direction in the direction, it has been found to be effective to improve the cross-sectional shape of the hole.

The Fe-Ni-based alloy bath for shadow mask of the present invention is made based on the above findings, and contains Ni: 34-38 mass%, Mn: 0.1-1.0 mass%, C: 0.10 mass% or less, Si: 0.1 It has a composition which consists of mass% or less, Al: 0.05 mass% or less, inevitable impurities, and substantial Fe remainder, the average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less, and the plate thickness The {100} density α _C at the surface after removing up to 50% of the surface by etching is larger than the {100} density α _{S on the} surface of the plate surface.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for explaining the operation of the present invention, showing a cross section of a hole drilled by etching. Fig. 1 (A) shows the plate thickness direction of {100} density on the plate surface of the bath when the mean value α in the plate thickness direction distribution of the {100} density on the plate surface of the bath is 60% or less. The cross-sectional shape of the hole in the case where average value (alpha) in distribution exceeds 60% or more is shown. From these drawings, it can be seen that EF is higher in the case of FIG. 1B than in the case of FIG. In addition, in the case of FIG. 1A where EF is low, the boundary between the inner circumferential surface and the surface of the hole becomes a sharp cross-sectional shape. As shown in FIG. As a result, mask deviation tends to occur.

On the other hand, in order to raise the {100} integration degree, as mentioned above, it is necessary to suppress the workability in final cold rolling low, and cannot cope with high strength. This invention obtains the hole as shown to FIG. 1 (B) and FIG. 2 (B), making the average value (alpha) in the plate thickness direction distribution of {100} integration degree into 60% or less. That is, in the Fe-Ni-based alloy bath for shadow mask of the present invention, since the {100} density of the plate thickness surface layer portion is lower than the inside (EF is small), in the vicinity of the surface layer, etching in the horizontal direction with respect to the spray injection direction is performed. As the speed increases, as shown in Fig. 1B, a smooth cross-sectional shape of the edge of the hole can be obtained, and as shown in Fig. 2B, a hole close to a round circle can be obtained. In this way, when the hole is drilled by spray injection, the distribution of the degree of integration in the plate thickness direction is small in the vicinity of the surface layer, and a cross-sectional shape of a hole having a good inside can be obtained. Moreover, since the {100} integration degree is high in the inside of the plate thickness direction, EF is high and a favorable etching perforation can be obtained.

Moreover, in this invention, since the average value (alpha) _AVE in the plate thickness direction distribution of the {100} integration degree in a plate surface is 60% or less, the grade of work hardening in final rolling is high, and therefore intensity | strength can be raised. Here, the {100} density is calculated by the following equation (1). The integral intensity I (hkl) of each crystal plane is the intensity obtained by subtracting the background from the integral intensity in the range of ± 3 ° of the azimuth peak position 2θ by X-ray diffraction (hereinafter referred to as XRD).

{100} Density (%) α =

I (200) / {I (111) + I (200) + I (220) + I (311)} × 100

The average value α _AVE in the plate thickness direction distribution of the degree of integration on the plate surface is defined by the following expression (2). 3 is a diagram showing a distribution of {100} integration degrees in the present invention.

In practice, the average value α _AVE can be approximately obtained as shown in FIG. 4. XRD was used to remove 12 μm (equivalent to 10% of the plate thickness), 36 μm (equivalent to 30% of the plate thickness) and 60 μm (equivalent to 50% of the plate thickness) from one side by surface and spray etching of each alloy. Measured.

In order to reliably obtain the operation and effect of the present invention as described above, the {100} integration degree (α _S ) of the surface of the plate surface of the {100} integration degree (α _C ) in the plane after removing up to 50% of the plate thickness by etching. It is preferable that ratio with respect to is 1.2 or more.

The above Fe-Ni alloy baths for shadow masks fall into the category of Invar alloys, but the Fe-Ni-Co alloy baths have lower thermal expansion and higher strength than Fe-Ni alloy baths, which is superior for shadow masks. Therefore, it is one of the characteristics of this invention. That is, the Fe-Ni-Co alloy bath for shadow masks of this invention contains 28-34 mass% of Ni, 2-7 mass% of Co, Mn: 0.1-1.0 mass%, and C: 0.10 mass% or less , Si: 0.1% by mass or less, Al: 0.05% by mass or less, an unavoidable impurity and a substantial Fe balance, and the average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less. In addition, the {100} density α _C after removing up to 50% of the plate thickness by etching is larger than the {100} density α _S of the plate surface. Moreover, in the said alloy bath, content of Ni is reduced to 28-34 mass% by adding Co which has a function similar to Ni.

The shadow bath alloy bath can also obtain the same effect and effect as above. In addition, in order to reliably obtain such an operation and effect of the present invention, the {100} integration degree (α _S ) of the surface of the plate surface of the {100} integration degree (α _C ) in the plane after removing up to 50% of the plate thickness by etching. The ratio of to is preferably 1.2 or more.

In addition, in the said Fe-Ni-type and Fe-Ni-Co-type alloy baths for shadow masks, "the actual Fe remainder" means that it can contain as long as it is an element which does not change the characteristic of the alloy bath of this invention other than Fe.

In the bath used for the shadow mask, a concave-convex shape called a dull shape is applied to the rolled surface for the purpose of preventing adhesion (sticking) of the shadow masks in the heat treatment step after etching. This lesser shape is obtained by rolling with a rolling roll (hereinafter, referred to as a dull roll) which is appropriately roughened on the surface by, for example, shot processing. In the rolling process, the difference in the amount of deformation occurs between the surface layer portion and the interior as the workability is increased, and in particular, the tendency is remarkable because the frictional force with the material surface is higher than that of the vitriol in the dulrol. In the shadow bath alloy bath of the present invention, by using such a roll roll, the final rolling process and the diameter of the roll roll can be controlled to obtain an optimum distribution of {100} density with a low control of the {100} density of the surface layer portion. have.

In the present invention, the components are defined as described above, but the elements to be added are not limited to such components, and may contain any components as long as the functions of Ni, Mn, and the like are not impaired. Moreover, although Claim 1 is a Fe-Ni type alloy, trace amount (0.02% or less) Co is contained with addition of Ni. Therefore, when Co is contained at 0.02% or less, it is included in the category of Fe-Ni-based alloy.

Example

Next, an Example demonstrates this invention further in detail.

Alloys A and B having the compositions shown in Table 1 were dissolved by vacuum melting, and then the ingot was hot forged and hot rolled. In this case, alloy A is a composition stipulated in claims 1 and 2, and alloy B is a composition stipulated in claims 3 and 4. Subsequently, after the oxidation scale of the surface was removed, cold rolling and annealing were repeated, and final cold rolling was performed to prepare an alloy bath having a thickness of 0.12 mm. Table 2 shows the workability of the final cold rolling and the diameter of the dulol used in the cold rolling. Moreover, the 0.2% yield strength of each alloy bath was measured, and the result was written together in Table 2. In addition, XRD is used to remove 12 μm (equivalent to 10% of the plate thickness), 36 μm (equivalent to 30% of the plate thickness), 60 μm (equivalent to 50% of the plate thickness) from one side by surface and spray-etching of each alloy. It was measured by.

Ni Co Mn Al C S Si N Fe Alloy A 36.1 0.01 0.25 0.002 0.002 0.001 0.02 0.002 Bal. Alloy B 32.1 5.1 0.26 0.002 0.003 0.002 0.01 0.002 Bal.

The obtained integration degree was written together in Table 2. Also from these densities, the approximate to the ratio of the depth of up to 0-50% of the thickness as an average value in the thickness direction of the distribution shown in Figure 4 is obtained ever, the stage was in the Table 2, the average value _(AVE α). Moreover, the ratio of the {100} density ((alpha) _C ) in the center of the plate | board thickness with respect to the {100} density ((alpha) _S ) of the surface was calculated | required, and the result was written together in Table 2.

No. alloy Final Machinability (%) Roll diameter (mm) 0.2% YS (MPa) {100} Intensity (%) ^*) α _AVE (%) Mask strength Mask deviation Surface (0%) 12 μm (10%) 36 μm (30%) 60 μm (50%) Example One A 40 50 655 32 47 55 57 50.7 1.78 ○ ○ 2 A 40 50 659 30 45 55 56 49.7 1.87 ○ ○ 3 B 40 50 720 40 50 53 55 51.2 1.38 ○ ○ 4 B 40 50 722 41 49 50 51 49.0 1.24 ○ ○ 5 A 40 60 658 39 45 47 46 45.4 1.18 ○ △ 6 B 40 60 725 42 48 50 49 48.4 1.17 ○ △ Comparative example 7 A 30 100 618 69 70 70 71 70.1 1.03 × ○ 8 B 30 100 680 65 65 66 65 65.6 1.00 × ○ 9 A 30 50 630 65 68 70 79 70.7 1.22 × ○ 10 B 30 50 682 64 68 69 78 70.0 1.22 × ○ 11 A 40 100 643 50 50 49 49 49.4 0.98 ○ × 12 B 40 100 716 51 50 50 49 49.9 0.96 ○ × *) Surface (0%): Surface {100} density measurement result 12 µm (10%): 12 µm (10% of plate thickness) {100} Density measurement result after etching 36 µm (30%): 36 µm ( 30% of sheet thickness) {100} density measurement after etching 60µm (50%): 60µm (50% of sheet thickness) {100} density measurement after etching

Next, photoresist was applied to both sides of these alloy baths by a known photoetching method, and the pattern was baked and developed, followed by drilling by spraying ferric chloride solution on both sides to prepare a shadow mask. The obtained shadow mask was observed by transmitted light or reflected light in the dark room, and the presence or absence of mask deviation was confirmed. The case where mask deviation occurred was "x" and the case where it did not generate | occur | produced "(circle)" and the mask deviation generate | occur | produced but not having a problem in use was described in Table 2 together as "(triangle | delta)". Moreover, mask intensity | strength was evaluated from the measured 0.2% yield strength, and the case where the mask intensity | strength was inadequate was described in Table 2 by making "x" and sufficient case into "(circle)".

As can be seen from Table 2, in the example, 40% of the final processing was performed, so that the hardening of the alloy bath was sufficiently achieved, and sufficient mask strength was obtained. The average value (α _AVE ) in the directional distribution became 60% or less. In addition, in the Example, since the dil roll of 50-60 mm in diameter was used, the processing deformation of the surface layer part of an alloy bath became large, the {100} density ((alpha) _S ) of a surface became small, and (alpha) _C / (alpha) _S exceeded 1, and was used. In Examples 5 to 6 having a diameter of 60 mm, mask deviation occurred, but there was no problem in use, and Examples 1 to 4 having a diameter of 50 mm did not generate mask deviation. In addition, the mask intensity | strength was sufficient enough.

In contrast, in Comparative Examples 7 to 10, the final workability was low at 30%, and the distribution of the {100} integration degree α in the plate thickness direction exceeded 60%, so no mask deviation occurred regardless of the diameter of the roll. Did. However, since the final workability was low, the mask strength was insufficient. Moreover, although the mask strength of Comparative Examples 8 and 10 of B alloy is higher than Examples 1 and 2 of A alloy, it is inadequate as B alloy which may require high mask strength.

On the other hand, in Comparative Examples 11 and 12 in which the final workability was increased, the mask strength was sufficient, but a mask deviation occurred because the diameter of the roll was large. If the diameter of the dulol in the final processing is large, the processing strained layer becomes deep, and thus α _C / α _S becomes small, resulting in mask deviation.

As described above, according to the present invention, the average value (α _AVE ) in the plate thickness direction distribution of the {100} integration degree on the plate surface is 60% or less, and {in the plane after removing up to 50% of the plate thickness by etching. Since the 100} degree of integration α _C is larger than the {100} degree of integration α _{S on the} surface of the plate surface, an effect can be obtained that can effectively prevent occurrence of mask deviation while having a high strength.

Claims (4)

Ni: 34-38% by mass, Mn: 0.1-1.0% by mass, C: 0.10% by mass or less, Si: 0.1% by mass or less, Al: 0.05% by mass or less, unavoidable impurities, and a composition consisting of a substantial Fe balance , The average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less, and the {100} density (α _C ) on the surface after removing up to 50% of the plate thickness by etching An Fe-Ni-based alloy bath for shadow masks, which is larger than the {100} density (α _S ) of the plate surface. Ni: 34-38% by mass, Mn: 0.1-1.0% by mass, C: 0.10% by mass or less, Si: 0.1% by mass or less, Al: 0.05% by mass or less, unavoidable impurities, and a composition consisting of a substantial Fe balance , The average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less, and the {100} density (α _C ) on the surface after removing up to 50% of the plate thickness by etching. A Fe-Ni-based alloy bath for shadow masks, characterized in that the ratio of {100} density (α _S ) of the plate surface is 1.2 or more. Ni: 28-34 mass%, Co: 2-7 mass%, Mn: 0.1-1.0 mass%, C: 0.10 mass% or less, Si: 0.1 mass% or less, Al: 0.05 mass% or less, unavoidable impurity And {100} density after a composition consisting of a substantial Fe balance, the average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less, and up to 50% of the plate thickness is removed by etching. Fe-Ni-Co-based alloy bath for shadow mask, characterized in that (α _C ) is larger than {100} density (α _S ) of the plate surface. Ni: 28-34 mass%, Co: 2-7 mass%, Mn: 0.1-1.0 mass%, C: 0.10 mass% or less, Si: 0.1 mass% or less, Al: 0.05 mass% or less, unavoidable impurity And {100} density after a composition consisting of a substantial Fe balance, the average value (α _AVE ) in the plate thickness direction distribution of the {100} density on the plate surface is 60% or less, and up to 50% of the plate thickness is removed by etching. The ratio of {100} density ((alpha) _S ) of the plate surface of ((alpha) _C ) is 1.2 or more, The Fe-Ni-Co-type alloy bath for shadow masks characterized by the above-mentioned.