JPH06322485A - Fe-ni base thin sheet for high temperature and low baume degree etching treatment and its production - Google Patents

Abstract

PURPOSE:To produce an Fe-Ni base thin sheet capable of etching treatment at a high temp. and low Baume degree having an effect of improving etching efficiency and suppressing side-etching. CONSTITUTION:In an Fe-Ni base alloy contg., by weight, 30 to 60% Ni, the accumulating degree in the {100} orientation in the plane parallel to the rolling surface is regulated to >=85%, and the microstructure in the section vertical to the sheet width direction of the rolled stock is formed into a fibrous rolled structure. Furthermore, the Fe-31 to 60% Ni base alloy is subjected to hot working and is thereafter subjected to cold rolling and annealing to sufficiently increase the accmulating degree in the {100} orientation in the plane parallel to the rolling surface and to stabilize the crystalline otientation, and after that, cold rolling at a draft not exceeding the draft in the same cold rolling and annealing in the temp. range in which recrystallzation does not occur are executed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to improving etching efficiency,
The present invention relates to a Fe—Ni-based thin plate capable of fine etching even at high temperature and / or low bowing degree etching, which has an effect of reducing side etching, and more specifically, a high-definition shadow mask and a fine pitch IC lead frame.
The present invention relates to a Fe—Ni-based thin plate for fine etching such as a spacer and a frame for a display tube.

[0002]

2. Description of the Related Art Conventionally, for example, aluminum killed steel has been used as a shadow mask material for a color cathode ray tube, but recently, an amber material (Fe-36) having a low coefficient of thermal expansion has been used.
Ni alloys) have come to be used and are manufactured by fine etching. As the IC lead frame material, 42 alloy (Fe-42Ni alloy) is used due to its low thermal expansion property, and multi-pin products having more than 100 pins are manufactured by fine etching. In addition, Fe-50Ni alloys, Fe-52Ni alloys, Fe-42Ni-6Cr alloys and other Fe-Ni alloys are used as materials for various electronic components such as display tubes and electron guns.

Compared with pure iron, these Fe--Ni alloys are
The etching rate is slow and not only hinders the improvement of work efficiency, but also side etching is large, which is a big problem in the production of shadow masks and IC lead frames that require fine processing, and is excellent in etching processability. Fe-
There was a demand for Ni-based materials. Up to now, regarding improvement of etching property, as disclosed in JP-B-4-43980 and JP-B-2-51973, the impurity elements such as C, O and N are reduced to improve the etching rate. 61
By defining the crystal grain size as in No. 39343 and the crystal orientation as in Japanese Patent Publication No. 2-9655,
Proposals for improving the etching property have been made.

[0004]

In recent years, shadow masks have been made ultra fine with a pitch of 200 μm, and the quality requirements have become more stringent in terms of the roughness of the etching surface and the size and shape of the etching holes. In addition, the IC lead frame has increased from 160-pin class to 240-pin and further to 350-pin class or more, and the narrowing of the lead due to side etching has become a problem. It was difficult to solve the problem. Generally, the higher the etching rate is, the less side etching is, the better the processing accuracy is, and it is also preferable from the viewpoint of working efficiency. In order to increase the etching rate, it is known to perform the etching at a high temperature or to reduce the concentration of the etching solution (low degree of body). However, the etching surface becomes rough in the conventional material, and the shadow mask becomes It is not suitable for fine etching because it causes scattering of electron beams and the lead frame has a jagged edge in the lead frame. It is an object of the present invention to provide an Fe-Ni alloy thin plate that produces a smooth etched surface even under high temperature or low-bome etching conditions from the viewpoints of work efficiency, side etching prevention and the like.

[0005]

According to the present invention, as a result of repeated studies on the relationship between the etching surface roughness with respect to the structure of the Fe-Ni alloy and the etching conditions (temperature / boehm degree), the microstructure was identified. This is based on the finding of a Fe—Ni-based thin plate and a method for producing the same that can obtain a finely etched surface even if the etching rate is increased by increasing the etching temperature by lowering the temperature and body temperature. Conventionally, an Fe-Ni-based thin plate for etching processing generally has a recrystallized structure. On the other hand, since the etching rate is determined in crystal grain units, unevenness occurs on the etched surface. Therefore, in order to obtain a finely etched surface, there has been a proposal to define the crystal grain size in the fine range as described above.

The inventors of the present invention have conducted repeated research on the idea that the influence of crystal grains can be prevented by forming a fibrous structure having no clear crystal grain boundaries, and as a result, by adopting a specific manufacturing process, Is stabilized, and the conditions for cold rolling and annealing thereafter are slightly restricted, so that the fibrous shape can be maintained without recrystallization while maintaining the high degree of {100} orientation integration of the plane parallel to the rolling surface. It is possible to obtain an Fe-Ni-based thin plate having a rolling structure, and to obtain a very smooth etched surface in this Fe-Ni-based thin plate, and thus to enable etching at a high temperature and a low degree of deformation. Found and made the present invention.

That is, first, the second aspect of the present invention is to use Ni by weight.
After hot working an Fe-Ni-based alloy containing 30 to 60%, cold rolling and annealing are performed, and {10
0} orientation After sufficiently increasing the degree of integration to stabilize the crystal orientation (this state is referred to as a precursor material in the present application), the precursor material is further cold-rolled at a rolling rate not exceeding the rolling rate of the cold rolling. By rolling and annealing in a temperature range that does not cause recrystallization, the degree of {100} orientation integration of the plane parallel to the rolled surface is 85%.
Above, and is a method for producing a Fe-Ni-based thin plate for high-temperature low-Baume degree etching treatment, characterized in that the microstructure in a cross section perpendicular to the plate width direction of the rolled material is a fibrous rolled structure. According to the first invention of the present application, Ni30-6 by weight% is used.
In a Fe-Ni alloy containing 0%, the {100} orientation integration degree of the plane parallel to the rolled surface is 85% or more, and
A Fe-Ni-based thin plate for high temperature / low Baume degree etching treatment, characterized in that a microstructure of a cross section perpendicular to the plate width direction of a rolled material has a fibrous rolled structure.

[0008]

First, the material of the present invention and its effect will be outlined.
1 and 2 are scanning electron micrographs of a microstructure and an etched surface of a material of the present invention (a) and a conventional Fe-Ni-based material (b) having a recrystallized structure in a cross section perpendicular to the width direction of a rolled plate, respectively. Indicates. After the microstructure was corroded with aqua regia saturated with cupric chloride (about 10 seconds), 400
It was observed with a double microscope. The material (a) of the present invention has a fibrous rolling structure, and is characterized in that it is difficult to recognize clear crystal grain boundaries as in the comparative material (b). by this,
As shown in FIG. 2, the material (a) of the present invention is the comparative material (b).
As shown in FIG. 2, the unevenness of the etching surface due to the influence of crystal grains, which is a problem with
It is clear from the comparison of.

In general, an Fe-Ni alloy has a cubic structure (each {100} face of the crystal is the length of the rolled material in the recrystallization process,
It is easy to form a width and a thickness, which are arranged at right angles to the respective directions. To obtain a stable cubic tissue, for example, 8
A combination of a cold rolling rate of 5% or more and annealing at 700 ° C or more is suitable. By this process, {10
The degree of orientation integration of the 0} plane is sufficiently increased. That is, in the method for producing the material of the present invention, it is very important to recrystallize the precursor material at least once in the process before finish rolling to obtain a sufficient cubic structure in order to obtain an optimal fibrous rolling structure. Is important to.

FIG. 3 and FIG. 4 respectively show the Fe-36Ni precursor material of the present invention (circle mark) of the present invention having a sufficiently cubic structure developed by rolling and annealing under the conditions shown in the figures, and a cold rolling rate of 85. % Of Fe or an annealing temperature of less than 700 ° C. and a comparative material Fe− having an insufficient cubic structure
With respect to the 36Ni precursor material (marked with Δ and diamond), the relationship between the hardness as it was when annealed as described above (only in FIG. 4), then cold rolled at a reduction rate of 80%, and then annealed at each temperature, and rolling. It shows the relationship of the {100} orientation integration degree (%) of the plane. From FIG. 3, the precursor material of the present invention is
The recrystallization temperature is shifted to the high temperature side, and the Vickers hardness is about 130 or more even at an annealing temperature of 875 ° C. or less, and the crystal structure is very stable as compared with the comparative material. From FIG. 4, there is almost no change in the {100} orientation integration degree up to 80% cold rolling and the subsequent annealing temperature of 850 ° C. Therefore, there is no effect on the change in crystal orientation by cold rolling or annealing. It turns out that receiving is very small. Therefore, the material of the present invention has a high {100}
It is possible to have a fibrous rolling structure while maintaining the orientation integration degree.

FIG. 5 shows Fe having the fibrous structure of the present invention.
-36Ni material (○, fibrous structure ≈ 100%, {10
Fe-36Ni material (0 mark, fibrous structure ≈ 0%, {10
0} azimuth degree of integration 90%), the relationship between the temperature of the etching solution and the etching surface roughness is shown when etching is performed with each of the 42-bore and 50-bore etching solutions. As can be seen from the comparison in the figure, the higher the temperature of the etching solution and the lower the degree of boke, the larger the etching surface roughness. The material of the present invention is 50 ° C,
The same level as the etched surface roughness at 50 bore (0.4
It can be seen that the one having a diameter of 70 μm is obtained at 70 ° C. and 42 boke. If the etching conditions are high temperature and low volume, the etching rate increases. Therefore, the material of the present invention promises effects such as a decrease in side etching due to an increase in etching rate, an increase in line speed, and a reduction in cleaning time after etching due to low brome.

Next, the reasons for limiting the numerical values of the present invention will be described. Ni
If the content is less than 30%, the austenite structure becomes unstable, while if it exceeds 60%, the coefficient of thermal expansion rises, and the original low coefficient of thermal expansion is not satisfied.
Limited to 60%. If the {100} orientation integration degree of the plane parallel to the rolled surface is less than 85%, the etching rate decreases, and the side etching amount increases accordingly. Therefore, the {100} orientation integration degree of the rolled surface is 85%. Limited to at least%. In the present invention, the Fe-Ni alloy means N
i30 to 60%, and the balance except for impurities, not only Fe-Ni alloy consisting essentially of Fe, but mainly in the range not to deteriorate the etching property, to increase the strength, improve the corrosion resistance,
Co added according to the purpose for the purpose of adjusting thermal expansion,
Includes Cr, Nb, Ti, Zr, Mo, V, W and Be added alone or in combination.

[0013]

EXAMPLES As shown in Table 1 by summarizing the outline components, processing conditions, characteristics, etc., various Fe-Ni alloys of A, B, C, D, E1 to 9 (F is the same as A) were used. Vacuum induction melting, casting, then forging at 1100 to 1150 ° C., hot rolling to obtain a hot rolled coil of a predetermined thickness, and pickling the surface,
After polishing, cold rolling shown in the column of precursor materials and subsequent annealing were performed to prepare precursor materials. Subsequently, cold rolling shown in the finishing material column is performed to make the thickness 0.15 mm,
Then, the annealing (final annealing) at the temperature shown in the same column was performed. The {100} orientation integration degree of the plane parallel to the rolled surface after annealing in each of the precursor material column and the finishing material column was measured, and the hardness of the material after the final annealing and the microscope in the cross section perpendicular to the width direction of the rolled plate The fibrous structure area ratio by the photograph and the etched surface roughness (Ra) by the etching test were measured.

The degree of {100} orientation integration is {111},
X of the main directions of {100}, {110}, and {311}
It was determined from the relative intensity I in line diffraction by the following formula. D {100}% = I {100} × 100 / (I {11
1} + I {100} + I {110} + I {311}) In the etching test, the 0.15 mm thick annealed material is degreased with hot alkali, and the photoresist of a predetermined pattern is masked, and then FeCl ₃ solution is used at 50 ° C. , 50 bom and 60
Spray etching was performed under the conditions of 42 ° C. and 42 ° C., respectively. The etching surface roughness was measured in the width direction of the etching surface. However, there was almost no difference from the rolling direction

[0015]

[Table 1]

The materials A1 to E9 of the present invention are subjected to cold rolling of 85% or more as shown in the precursor material column and annealing of 700 ° C. or more to the material after hot rolling, and Parallel plane {100} orientation integration is almost 1
A cubic structure with a stable cubic structure of 00% is obtained, and after that, after cold rolling that does not exceed the rolling rate of cold rolling in the preparation of the precursor material and subsequent annealing that does not exceed 850 ° C., FIG.
As described in 4, the recrystallization temperature shifts to the high temperature side and the {100} orientation concentration of the rolled surface is maintained high.

As a result, the cubic texture stabilizing effect and recrystallization retarding effect due to the high degree of {100} orientation integration results in
Due to the fact that the fibrous structure remains highly developed and the action of the fibrous rolled structure does not have clear grain boundaries as in the conventional case, the surface roughness Ra value of the etched surface of the material of the present invention is much higher than that of the conventional material. It is a low value. Therefore, the etching surface roughness of the material of the present invention at a high temperature and a low bow (60 ° C., 42 bow) is the same as that of the comparative material.
The value is low (Ra 0.32 to 0.37) that cannot be obtained even with high baume (50 ° C, 50 baume).

On the other hand, the comparative materials of F1 to F5 are not suitable for cold rolling conditions (F
1, F5) or inappropriate annealing conditions (F2, F5)
Due to insufficient cubic structure development, or inappropriate cold rolling conditions (F3 higher than the rolling ratio of the precursor material) as shown in the finishing material column, or inappropriate annealing conditions (excessive temperature exceeding 850 ° C). High temperature ... See Fig. 4 F4) destroys the cubic structure, and as a result, the microstructure of the finishing material becomes a recrystallized structure similar to the conventional one, resulting in high temperature and low body (60 ° C). , 42 bom) and of course low temperature / high bow, the surface roughness Ra value of the etched surface of the material of the present invention at high temperature / low bow is less than the Ra value of the corresponding material of the present invention. Further, the material of the present invention has an advantage that it has higher strength than the conventional material because of the high recrystallization temperature described in FIG.

[0019]

As described above, the Fe--Ni of the present invention is used.
The system thin plate has a fibrous rolling structure different from that of the conventional material having a recrystallization structure, and therefore, the etching property which has been obtained only under the etching conditions of low temperature and high brome at high temperature or And a Fe-Ni-based thin plate that can be obtained under low-bome etching conditions. Since it is possible to perform etching processing at high temperature and low volume, it is possible to increase the etching rate, reduce side etching, shorten etching time, and simplify cleaning with low volume. The above effect is extremely large.

[Brief description of drawings]

FIG. 1 is a photograph of a metal structure microstructure of a material of the present invention and a comparative material.

FIG. 2 is a scanning electron micrograph of the metal microstructures of the etched surfaces of the inventive material and the comparative material.

FIG. 3 is a correlation diagram between final annealing temperature and hardness.

FIG. 4 is a correlation diagram between final annealing temperature and {100} orientation integration degree.

FIG. 5 is a correlation diagram of etching surface roughness with respect to etching conditions.

Claims (2)

[Claims] 1. F containing 30-60% Ni by weight.
In an e-Ni-based alloy, the surface parallel to the rolling surface {10
F for high temperature and low bowing degree etching, characterized in that the degree of 0} orientation integration is 85% or more, and the microstructure of the cross section perpendicular to the sheet width direction of the rolled material has a fibrous rolled structure.
e-Ni type thin plate. 2. F containing 30-60% Ni by weight.
After hot working the e-Ni alloy, cold rolling and annealing are performed,
After increasing the {100} orientation integration degree of the plane parallel to the rolling plane to stabilize the crystal orientation, cold rolling at a rolling rate not exceeding the rolling rate of the cold rolling and the temperature at which recrystallization does not occur Annealed in the range, {100} on the surface parallel to the rolling surface
Fe-for high-temperature / low Baume degree etching treatment characterized in that the degree of orientation integration is 85% or more, and the microstructure in the cross section perpendicular to the sheet width direction of the rolled material is a fibrous rolled structure.
Manufacturing method of Ni-based thin plate.