KR960008889B1 - Thin alloy sheet for electronic instrument having excellent etching workability - Google Patents

Abstract

None.

Description

Alloy plate with excellent etching processability

FIG. 1 is a graph showing the relationship between the surface roughness of the surface of an etching hole, Ra and the light transmittance of a flat mask, according to preferred embodiment-1 of the present invention.

2 is an integration ratio of each crystal plane of {331}, {210} and {211} on the surface of the alloy plate according to the preferred embodiment-1 of the present invention, {210} / ({331} + {211}). And a graph showing the relationship between the etching rate and the state of formation of the stained periphery of the etching hole of the flat mask.

3 shows the average crystal grain size in the alloy plate thickness direction and the integration ratio of {331}, {210} and {211} crystal planes on the surface of the alloy plate according to the preferred embodiment-1 of the present invention, {210} / ( A graph showing the effect of {331} + {211}) on the etching rate.

4 is a graph showing the relationship between the average grain size and the etching rate in the thickness direction of the alloy plate when the value of {210} / ({331} + {211}) is 0.25.

5 is an exemplary view showing the definition of the etching rate and the etching hole cross section.

6 is a graph showing the relationship between the surface roughness on the surface of the etching hole and the light transmittance of the flat mask according to the preferred embodiment-2 of the present invention.

7 shows the ratio of the degree of integration of the crystal plane, ({100} + {311} + {210}) / ({100} + {111} + {331} + {211}, according to the preferred embodiment-2 of the present invention. ) And a graph showing the relationship between the etching rate and the state of formation of the stained periphery of the etching hole.

8 shows the ratio of the degree of integration of the crystal plane, ({100} + {311} + {210}) / (using the crystal grain size in the thickness direction of the alloy plate as a parameter according to the preferred embodiment-2 of the present invention. {100} + {111} + {331} + {211}) and a graph showing a relationship between etching rates.

9 is a graph showing the relationship between the crystal grain size and the etching rate in the thickness direction of the alloy plate according to the preferred embodiment-2 of the present invention.

The present invention relates to an alloy plate for an electronic device having high etching processability, particularly an alloy plate suitable as a material for a shadow mask of a color cathode ray tube and an IC lead frame.

Fe-Ni-based alloys have been used as materials for shadow masks and IC lead frames of colored cathode ray tubes. Fe-Ni-based alloys have a significantly lower coefficient of thermal expansion compared to low carbon steels that have conventionally been used as materials for electronic devices. For this reason, for example, a shadow mask made of a Fe—Ni-based alloy plate hardly generates a problem of color phase shift due to thermal expansion even when heated by an electron beam.

Photo-etching is performed on the Fe-Ni type alloy plate used as a shadow mask and an IC lead frame material. However, the conventional Fe-Ni-based alloy plate has a disadvantage of lower etching workability than low carbon steel. Specifically, the Fe-Ni-based alloy exhibits significantly lower corrosiveness to the etching solution compared to the low carbon steel and has a large crystal grain size. Therefore, when the Fe-Ni-based alloy plate is punched by etching, the distribution of the hole diameter and the hole shape are dispersed. Because of these disadvantages, the Fe-Ni-based alloy plate used as the material for the shadow mask results in peripheral portions stained on the mask when light passes through the fine etching holes. In addition, the brightness of the light-transmitted mask is lower than that of the low carbon steel mask. In particular, high-precision masks with fine pitches and fine pores, which are in great demand in the electronics market, are susceptible to the above-mentioned problems that significantly degrade the quality of color cathode ray tubes. In addition, recently, the cathode ray tube is strongly required to have a high screen brightness, and when the brightness of the mask drops, the product competitiveness is inferior. As for the material for the IC lead frame, high density (high integration) requires a fine pitch of the pin arrangement of the lead frame. Since the conventional Fe-Ni-based alloy has the problems described above, it cannot cope with the fine pitch of the pin arrangement. In addition, the conventional Fe-Ni-based alloy has a disadvantage of poor plating after etching.

The following various techniques for solving the problem of etching workability of Fe—Ni alloys have been proposed.

(1) Japanese Patent Application Laid-Open No. 2-9665 discloses an alloy plate having an integration degree of {100} crystal surface on the plate surface as an Invar alloy capable of realizing high precision and uniform etching.

(2) Japanese Patent Application Laid-Open No. 62-243782 proposes a method for producing Fe-Ni-based inba alloy which improves the etching speed and reduces the staining around the etching hole, and this alloy has a range of 0.2-0.7 mu m. It has surface roughness, Sm of 100 µm or less, a grain size number of 8.0 or more, and a {100} crystal plane on its surface.

(3) Japanese Unexamined Patent Publication No. 2-270941 proposes a method for producing an Fe-Ni-based invar alloy which improves the etching rate, and this alloy integrates more than 50% {200} plane on the surface thereof, and 0.007 Impurities of up to wt.% C, up to 0.005 wt.% P and 0.005 wt.% S, up to 1.10 wt.% other impurities.

However, although the precision and uniformity of etching are improved by the above technique (1), the occurrence of the uneven portion of the manufactured shadow mask cannot be prevented, and the mask brightness is not good as compared with the conventional mask made of low carbon steel. In the technique of (2), although the etching rate is improved and the spots of the etching holes are improved, the brightness of the manufactured mask is lower than that of the mask made of low carbon steel.

The IC lead frame manufactured by the technique of (3) has a problem that the side etching is excessively performed and the processing precision is poor when processed as the lead frame.

Such a technique has a problem in that the plating property of the IC lead frame processed by etching is poor. For example, when the IC lead frame obtained by the technique of (3) is soldered, abnormal growth of a needle crystal called whisker occurs, resulting in a quality problem.

An object of the present invention is to provide an alloy thin plate having excellent etching processability and plating property.

In order to achieve the object of the present invention, the present invention provides an alloy plate having a good etching hole surface, the alloy plate having: {331}, {210} and {211} crystal planes on the surface; The degree of integration of the {311} crystal plane is 14% or less, the degree of integration of the {210} crystal plane is 14% or less, and the {211} crystal plane is 14% or less; The density ratio given by the formula {210} / ({331} + {211}) is 0.2-1.

In addition, the present invention provides an alloy plate having an etching hole surface excellent in etching processability, the alloy plate is: {111}, {100}, {110}, {311}, {331}, {210} and {210} 211} crystal plane; The degree of integration (S ₁ ) of the {111} crystal plane is 1-10%, the degree of integration (S ₂ ) of the {100} crystal plane is 50-94%, and the degree of integration (S ₃ ) of the {110} crystal plane is 1-24%. , The density of the {311} plane (S ₄ ) is 1-14%, the density of the {331} plane (S ₅ ) is 1-14%, and the density of the {210} plane (S ₆ ) is 1-14% The density of the {211} crystal plane (S ₇ ) is 1-14%, and the density ratio given by the formula (S ₂ + S ₄ + S ₆ ) / (S ₁ + S ₃ + S ₅ + S ₇ ) is 0.8-20.

Preferred Example-1

In order to form an etching hole having a uniform size and shape with respect to the entire surface area of the Fe-Ni-based alloy sheet, the inventors have to keep the etching rate constant and high enough for the entire material area. (Defined in FIG. 5), and the etching rate is effectively increased by a large ratio by controlling the density ratio of a specific crystal surface of the etching surface (alloy surface) and controlling the grain size in the thickness direction of the alloy plate. I figured it out. In addition, the inventors of the present invention are important to control the surface roughness Ra on the surface of the etching hole to a specific level to maintain the plating workability after etching and the brightness of the shadow mask below an excellent level. Was obtained by controlling the degree of integration of a particular crystal plane,

The alloy sheet of the present invention is composed of a component composition containing Fe and Ni as a main component and a component composition containing Fe, Ni, Co and / or Cr as a main component. Preferred contents and reason for limitation of these main component elements are described below.

The alloy plate used as the material for the shadow mask will now be described.

In order to prevent color abnormality, the Fe-Ni alloy plate for shadow masks requires 2.0 x (1/10 ⁶ ) / 占 폚 as an upper limit of the average coefficient of thermal expansion in a temperature range of 30-100 占 폚. The coefficient of thermal expansion depends on the Ni content of the alloy, and the range of Ni content giving the above-described coefficient of thermal expansion is 34-38 wt.%. Therefore, it is preferable that Ni content is limited to 34-38 wt.%. In order to obtain an average coefficient of thermal expansion lower than the specific value, the Ni content is preferably limited to the range of 35-37 wt.%, More preferably 35.5-36.5 wt.%. Generally, Co is present in Fe—Ni based alloys as an unavoidable impurity. Cobalt content of less than 1 wt.% Has little effect on the alloy properties. Although Ni content is also preferable in the above-mentioned range, when the alloy contains 1-7 wt.% Of Co, the Ni content which satisfies the above-mentioned average thermal expansion coefficient range is 28-38 wt.%. Therefore, when the alloy contains 1-7 wt.% Co, the Ni content is preferably in the range of 28-38 wt.%. 3-6 wt.% Co and 30-33 wt.% Ni also give a low average coefficient of thermal expansion. When the Co content exceeds 7 wt.%, The coefficient of thermal expansion increases. Therefore, the upper limit of the Co content is preferably 7 wt.%.

As for the alloy plate for the IC lead frame, the Ni content satisfying the condition of the average thermal expansion coefficient required for the Fe-Ni-based alloy plate for the IC lead frame is in the range of 38-52 wt.%. If the Ni content is less than 38 wt.% Or more than 52 wt.%, The average thermal expansion coefficient of the alloy becomes too large, resulting in poor compatibility with the semiconductor element glass and the ceramic. Therefore, the Ni content is preferably limited to 38-52 wt.%. As described above, Co is present in the Fe-Ni-based alloy as an unavoidable impurity, and if the Co content is less than 1 wt.%, It hardly affects the alloy properties, so the Ni content is preferably within the above range.

On the other hand, the alloy plate for IC lead frame can increase the compatibility with semiconductor elements, glass, and ceramics by adding 1-20 wt.% Of Co. The effect is not obtained when the Co content is less than 1 wt.% Or exceeds 20 wt.%. When the alloy contains 1-20 wt.% Co, the range of Ni content satisfying the condition of the average thermal expansion coefficient as the material for the IC lead frame is 27-32 wt.%. If the Ni content is less than 27 wt% or more than 32 wt%, the coefficient of thermal expansion increases. Thus, when the alloy contains 1-20 wt.% Co, the preferred Ni content range is 27-32 wt.%.

Chromium is an element that improves mechanical properties but is an element that lowers thermal expansion characteristics. Since the upper limit of Cr for obtaining the thermal expansion characteristic intended by this invention is 3.0 wt.%, Cr can contain 3.0 wt.% As an upper limit.

The elements other than the above main component elements are 0.0050 wt.% Or less C, 0.05 wt.% Or less Mn, 0.20 wt.% Or less Si, 0.0050 wt. It is preferable to set it as N of% or less, O of 0.0050 wt.% Or less, and B of 0.0050 wt.% Or less.

Next, the most notable features of the present invention will be described with respect to the degree of integration of the crystal plane on the surface of the alloy plate, the ratio of the degree of integration, and the average grain size in the alloy plate thickness direction.

By controlling the degree of integration of {331}, {210}, and {211} crystal planes on the surface of the alloy plate having the above-described composition, and the ratio of the degree of integration of these crystal planes within a specific range, the present invention effectively improves the etching rate, The surface roughness Ra of the surface of the etching hole indicated by the symbol (a) can be reduced, the brightness of the shadow mask can be increased, and the plating property after etching can be improved to an excellent level.

1 shows the relationship between the light transmittances of the flat masks. Flat masks, which are alloy plates for shadow masks punched out by etching, are Fe-Ni-based alloy plates and Fe-Ni-Co-based alloys in which the degree of integration of {331}, {210}, and {211} crystal planes on the surface of the alloy plate is changed. The alloy plate, the Fe-Ni-Cr type alloy plate, and the Fe-Ni-Co-Cr type alloy plate were photo-etched and obtained. The light transmittance of the flat mask was determined by measuring the light transmittance of the flat mask, and dividing the light transmittance by the light transmittance of the flat mask of a small low carbon steel. The surface roughness of the etching hole surface was measured by the method of the example mentioned later.

The degree of integration of each crystal plane is determined by the X-ray diffraction of the (111), (200), (220), (311), (331), (420) and (422) measured by the X-ray diffraction method of the plate surface. It is determined from the diffraction intensity. For example, the degree of integration of the {311} crystal plane is determined by the relative X-ray diffraction intensity ratios of the (331) diffraction plane being (111), (200), (220), (311), (331), (420) and (422). It is determined by dividing by the sum of the relative X-ray diffraction intensity ratios of each diffraction plane. The degree of integration of the {210} and {211} crystal faces is determined in a similar manner. The relative X-ray diffraction intensity ratio is defined as the X-ray diffraction intensity measured on each diffraction surface divided by the theoretical X-ray diffraction intensity of the diffraction surface. For example, the relative X-ray diffraction intensity ratio of the (111) diffraction surface is determined by dividing the relative X-ray diffraction intensity of the (111) diffraction surface by the theoretical X-ray diffraction intensity of the (111) diffraction surface.

The integration degree of the {210} crystal plane is divided by the sum of the relative X-ray diffraction intensity ratios of the seven diffraction planes of (111) (422) described above by the relative X-ray diffraction intensity ratio of the (420) diffraction plane that is isotropic to this crystal plane. Is determined by. The integration degree of the {211} crystal plane is determined by dividing by the relative X-ray diffraction intensity ratio of the (422) diffraction plane.

In FIG. 1, a white circle (○) indicates that the degree of integration of the {331} crystal plane is 14% or less, the degree of integration of the {210} crystal plane is 14% or less, and the {211} crystal plane is 14% or less, and the black circle (●) ) Corresponds to one of 14% or more of the {331} crystal plane, 14% or more of the {210} crystal plane, and 14% or more of the {211} crystal plane.

According to FIG. 1, when the degree of integration of each of the {331}, {210}, and {211} crystal surfaces is 14% or less, the surface roughness of the surface of the etching hole, Ra is 0.9 µm or less, and the light transmittance of the flat mask is 1.0. By raising the above, brightness higher than the conventional flat mask of the low carbon steel is provided. As to the plating property of the alloy plate for IC lead frame after etching, according to an experiment conducted by the inventor, the surface roughness, Ra, controls the integration degree of each crystal plane of {331}, {210} and {211} to 14% or less. As a result, it became 0.90 or less, and it confirmed that this provided the outstanding solder plating property.

When the degree of integration of the {331}, {210} or {211} crystal plane is out of the above-mentioned range, the surface roughness Ra of the surface of the etching hole, Ra exceeds 0.9 µm, so that the above-described characteristics cannot be obtained. By microscopic observation of the surface of the etching hole of such an alloy plate, it was found that minute pits (irregularity) were formed on the entire surface. Therefore, such a pit is probably considered to be because the surface roughness of the surface of the etching hole, Ra, is increased to 0.9 µm or more. The effect of other parameters on the relationship between the brightness of the shadow mask and the surface roughness of the etch hole surface has been studied. Among these various factors, the centerline mean roughness (Ra) was the most closely related.

Therefore, the present invention stipulates the degree of integration of {331}, {210} and {211} crystal planes of 14% or less as a condition for obtaining excellent plating property after etching and brightness of a flat mask having an excellent level.

In order to effectively increase the etching rate, it is necessary to control the ratio of the degree of integration of each of the {331}, {210} and {211} crystal surfaces on the alloy plate surface. 2 shows the relationship between the ratio of the degree of integration of the {331}, {210} and {211} crystal surfaces on the surface of the alloy plate and the etching rate, and the degree of formation and the degree of integration between the spots of the periphery of the surface of the etching hole of the flat mask. Shows the relationship. The alloy plate is a photo-etched Fe-Ni-based alloy plate, a Fe-Ni-Co-based alloy plate, a Fe-Ni-Cr-based alloy plate, and a Fe-Ni-Co-Cr-based alloy plate. The alloy plate has an degree of integration within the scope of the present invention, and has a ratio of various degrees of integration given by the formula {211} / {210} + {211}.

This invention limits the etching rate to 1.8 or more which does not become a problem practically. The degree of integration of each of the {311}, {210} and {211} crystal planes was determined by the X-ray diffraction method described above, and the etching rate was obtained by the same method as the example described later. The formation of the stained periphery of the etching holes was visually observed and determined according to the following criteria.

A: The stained periphery of the etching hole was not observed at all.

B: The stained periphery of the etching hole is slightly formed, but it is not a problem in practical use.

C: Although the formation of the stained periphery of the etching hole was found to some extent, it is not a problem in practical use.

D: The stained peripheral part of the etching hole which becomes a problem practically is formed.

E: The stained periphery of the etching hole is remarkably formed, causing problems in practical use.

A-C grades are not a practical problem.

According to FIG. 2, when the value of {210} / ({331 + 211}) increases, the value of the etching rate also increases, and this value becomes 0.2 or more and the etching rate becomes 1.8 or more. On the other hand, when the value of {201} / ({331} + {211}) exceeds 1.0, the degree of formation of the stained periphery of the etching hole deteriorates, causing a practical problem. Accordingly, the present invention provides the value of {210} / ({331} + {211}) in the range of 0.2-1.0 so as to obtain a low degree of formation and a high etching rate of the stained periphery of the etching holes intended for the present invention. It is prescribed. It is even more preferable that this value is in the range of 0.25-0.6 in which the stained periphery of the etching hole is formed.

Thus, by controlling the ratio of the degree of integration of the specific crystal plane on the surface of the alloy plate, the etching rate can be effectively increased. However, in order to further improve the etching rate, it is also effective to limit the average crystal grain size in the thickness direction of the alloy plate. Japanese Patent Laid-Open No. 2-243782 (Prior Art (2)) specifies the particle size to particle number 8.0 or more. However, the particle number disclosed in this specification is No. 10, which is made as small as possible, and is 11 μm ([crystal grain size number] = 16.6439-6.6439 log (calculated as [average crystal grain size] /1.125)). In contrast, the alloy plate of the present invention, which controls the density and the ratio of a specific crystal plane, reduces the average crystal grain in the plate thickness direction to 10 μm or less (10.3 or more crystal grain size number) smaller than the level of the prior art. Etch rate can be improved.

FIG. 3 is a Fe-Ni-based alloy plate which is photoetched in advance, and has a degree of integration of each crystal plane of {331}, {210} and {211} of 14% or less, and has an average grain size different in the thickness direction of the alloy plate, Fe Average Crystal Grain Size and {210} / ({331} + {211}) Values on Etch Rate of -Ni-based Alloy Sheet, Fe-Ni-Cr-based Alloy Plate, and Fe-Ni-Co-Cr-based Alloy Plate Shows the impact. According to FIG. 3, even if the value of {210} / ({331} + {211}) is the same, a finer average grain size gives a higher etching rate. When the average particle size exceeds 10 mu m, the etching rate decreases to 1.8 or less in that the value of {210} / ({331} + {211}) is 0.2. However, when the average particle size is kept below 10 mu m, the etching rate exceeds 1.8 even if the value of {210} / ({331} + {211}) is 0.2. Therefore, in order to further improve the etching rate, it is preferable to limit the average crystal grain in the thickness direction of the alloy plate to 10 µm or less. If the average grain size is 6 mu m or less, the etching rate is further increased in that range.

4 shows the relationship between the etching rate of 0.25 days and the average crystal grain size in the thickness direction of the alloy plate in which the value of {210} / ({331} + {211}) is 0.25.

In order to obtain the degree of integration of each of the {331}, {210} and {211} crystal faces defined by the present invention, it is necessary to be controlled so that these crystal faces are not formed as the manufacturing process conditions of the alloy plate. For example, when the alloy sheet of the present invention is manufactured from a hot rolled sheet obtained from a rolling slab or a continuous casting slab, or from a hot rolled sheet obtained by hot rolling a cast plate or a cast plate obtained by directly casting an alloy, Annealing and controlling annealing temperature suitably within the range of 910-990 degreeC are effective in suppressing formation of each crystal surface mentioned above.

In order to obtain the ratio of the degree of integration of each of the crystallographic planes {331}, {210} and {211} within the prescribed range of the present invention, after annealing the hot rolled plate described above, the {331), {210} and {211} crystal planes Depending on the degree of integration, it is effective to optimize the cold rolling rate, the recrystallization annealing conditions (annealing temperature, time and heating rate) and the finishing cold rolling conditions in the serial process of cold rolling-recrystallization annealing to smoothing cold rolling.

In order to obtain the degree of integration of the crystal plane defined by the present invention, it is not preferable to uniformly heat-treat the slab obtained during slabing or continuous casting during the alloy plate manufacturing process. For example, when the uniform heat treatment is performed at a temperature of 1200 ° C. or more for 10 hours or more, at least one of the degree of integration of each of the {331}, {210}, and {211} crystal planes is outside the scope of the present invention. Should be avoided.

In addition to the above-described method, the degree of integration of each crystal plane defined by the present invention can be obtained by employing a quench solidification method or by controlling the structure by controlling recrystallization during hot working.

Yes

Alloy ingots having the compositions of A-C, J and L shown in Tables 1 and 3 were obtained by ladle refining. Ingots were prepared to prepare hot rolled plates, followed by slabing, surface scarfing and hot rolling (3 hours at 110 ° C.). Alloys having the compositions of D-I and K shown in Tables 1- 3 were dissolved, refined outside the furnace and cast directly to form cast plates. Subsequently, hot rolling was performed at 1350-1000 ° C. at a 30% reduction rate and then coiled at 75 ° C. to prepare a hot rolled plate.

After the obtained hot rolled sheet is annealed at 910-990 ° C., cold rolling, recrystallization annealing and finishing cold rolling are performed, and the alloys having the crystal grain density and the average grain size in the thickness direction as shown in Tables 4 and 5 Plate No.1-No.31 was obtained. The degree of integration of each of the {331}, {210} and {211} crystal planes was measured by the X-ray diffraction method described above.

A resist pattern was formed on each of the prepared alloy plates, and the etching rate was measured at 135 mu m of d1 shown in FIG. Etch rate measurement is illustrated in FIG. Etch rates were measured by etching the alloy plate in a 45 bomedo ferric chloride solution bath at 40 ° C. under a spray pressure of 2.5 kg / cm ² for 50 seconds. Etch rate is represented by the equation of Ef = 2H / (d2-d1).

The alloy plates of materials No.1-No.24 and No.29-No.31 were photoetched to secrete a flat mask, and the amount of light transmission through them was measured. The measured light transmittance was divided by the light transmittance of the low carbon steel flat mask having the same size as the processed flat mask. The calculated value is treated as the light transmittance of the flat mask. The surface roughness of the etched hole surface of each processed flat mask was measured with a non-contact laser illuminometer. The cutoff value was 0.02 mm, the tapered region of the etching hole surface was removed as a wave component to show the roughness curve, and the centerline average roughness Ra was obtained from the roughness curve. The stained periphery of the etching hole of each flat mask was determined by visual observation thereof according to the same criteria used in FIG.

As for the alloy plate of material No. 25-No. 28, the surface roughness of the surface of the etching hole after photoetching was measured by the method as described above. These materials were soldered to evaluate their solder plating properties.

As shown in Table 3 and Table 4, the material No. having a degree of integration and a value of {210} / ({331} + {211}) of each crystal plane of {331}, {210} and {211} within the scope of the present invention. .6-No.27 and No.29-No.31 showed surface roughness on the surface of an etching hole, Ra was 0.90 micrometer or less, and the light transmittance of the flat mask as a shadow mask showed 1.0 or more. Thus, it appears that the brightness is higher than the conventional flat mask of low carbon steel. In addition, these materials exhibited excellent solder plating properties as materials for IC lead frames. The etching rate of these materials was 1.8 or more, and the flat mask formed of material No. 6-No. 24 had no problem in practical use in the state of formation of the stained periphery of the etching hole.

The alloy plates of materials No. 6 and No. 9-No. 14 showed that the value of {210} / ({331} + {211}) was 0.25-0.26, but the alloy plates of No. 9-No. 14 The average crystal grain size in the silver thickness direction was 10 µm or less, thus exhibiting an etching rate higher than No. 6 having an average crystal grain size of 11.1 µm. Therefore, these materials are excellent in etching processability. Among the alloy plates of materials No. 9 to No. 14, the smaller the average grain size in the thickness direction was, the higher the etching rate was. Therefore, it can be seen that the smaller average crystal grain size in the thickness direction is effective for increasing the etching rate.

With respect to the present example, material No. 1 is a comparative example in which the degree of integration of the {331} crystal plane exceeds the upper limit of the present invention. Material No. 2 is a comparative example in which the degree of integration of the {210} crystal plane exceeds the upper limit of the present invention. Material No. 3 is a comparative example in which the degree of integration of the {211} crystal plane exceeds the upper limit of the present invention. In these three comparative examples, the surface roughness of the surface of the etching hole, Ra was 0.9 µm or more, the light transmittance of the flat mask was 1.0 or less, and the brightness of the flat mask was lower than that of the example of the present invention. Material No. 4 has a degree of integration of {210} / ({331} + {211}) of each crystal plane exceeding the upper limit of the present invention, and is inferior to the example of the present invention in view of the stained periphery of the etching hole. It was determined. In material No. 5, the value of {210} / ({331} + {211}) was less than the lower limit of the present invention and had an etching rate of 1.80 or less, and the etching processability of the present invention was not obtained. Material No. 28 is a comparative example in which the degree of integration of the {210} and {211} crystal planes exceeds the upper limit of the present invention. The surface roughness of the surface of the etching hole, Ra, is higher than 0.90 µm, thereby deteriorating the solder plating property after etching. .

As apparent from the above description, the surface roughness of the surface of the etching hole and Ra are optimized by limiting the degree of integration of the {331}, {210} and {211} crystal surfaces with respect to the surface of the alloy plate to the range defined by the present invention. Thus, the light transmittance and solder plating property of the flat mask can be improved to an excellent level. In addition, by limiting the density ratio of each crystal plane, {210} / ({331} + {211}), within the range specified by the present invention, the etching rate can be effectively increased, and the formation of the faint peripheral portions of the etching holes can be reduced. Can be. In addition, the etching rate can be further improved by reducing the average grain size in the thickness direction of the alloy plate.

Preferred Example-2

The present invention provides a Fe-Ni-based, Fe-Ni-Co-based, Fe-Ni-Cr-based or Fe-Ni-Co-Cr-based alloy plate having a uniform and sophisticated form by performing photoetching on the front surface. In order to do this, it is important to maintain the etching rate at high speed over the entire surface and to increase the etching rate. Specifically, it is necessary to control the crystal grain size in the thickness direction of the alloy plate and to control the integration ratio of the specific surface of the etching surface (alloy surface).

In addition, in order to further increase the brightness of the light beam passing through the etched flat mask, it is important to reduce the surface roughness, Ra (centerline average roughness), of the etched alloy plate below a certain value. The present invention focuses on this method described above. The various limitations given for this method will now be explained.

The reason for limiting the ingredient content in percentage is as follows. When the Fe-Ni-based alloy plate of the present invention for electronic devices is used as the material for the shadow mask, the image transition caused by the material expansion will be prevented. Therefore, the average coefficient of thermal expansion of the alloy within the temperature range of 30-100 ° C. is 2.0 × 10. It is necessary to limit it to / degrees C or less. The Ni content satisfying the average thermal expansion coefficient condition is 34-38 wt.% For the Fe-Ni alloy plate. When the Fe-Ni-based alloy sheet for electronic devices is used as the ic lead frame material, the Ni content required to balance thermal expansion of the semiconductor, glass, and ceramic is 38 wt%-52 wt%. Therefore, Ni content is defined as 34-52wt.% In consideration of the two points mentioned above.

In the Fe-Ni-Co alloy, when the Co content is 20 wt.% Or less, the Ni content satisfying the average thermal expansion coefficient condition is 28-38 wt.%. When the Co content exceeds 20 wt.%, There is no Ni content that satisfies the coefficient of thermal expansion. Therefore, the Ni content of the Fe-Ni-Co-based alloy plate is limited to 28-38wt.%, And the Co content is limited to 20wt.% Or less.

Chromium is an element that improves the mechanical properties of alloys. However, the addition of Cr increases the average coefficient of thermal expansion. Therefore, in order to obtain the above-described average coefficient of thermal expansion, the Cr content should be 3wt.% Or less. As for the Fe-Ni-Cr alloy plate, the Ni content is limited to 34-52 wt.% And the Cr content is 3 wt.% Or less. For the Fe-Ni-Co alloy plate, the Ni content is 28 to 38 wt. %, Co content is limited to 20wt.% Or less, Cr content is limited to 3wt.% Or less.

The following explains the reason for limiting the degree of integration of each crystal plane. X-ray diffraction intensity of each diffraction surface of (111), (200), (220), (311), (331), (420) and (422) by X-ray diffraction analysis on the surface of the alloy plate Is given. The degree of integration of each crystal plane orientation is measured from the X-ray diffraction intensity. For example, the degree of integration of the {111} crystal plane indicates the relative X-ray diffraction intensity ratios of the (111) diffraction plane, (111), (200), (220), (311), (331), (420) and (420). 422) It is measured from the value divided by the sum of the relative X-ray diffraction intensity ratios of the respective diffraction surfaces.

The degree of integration of each of the crystal planes {100}, {110}, {311}, {311}, {210}, and {211} is measured in the same manner. Relative X-ray diffraction intensity ratio is defined as the X-ray diffraction intensity measured for each diffraction surface divided by the theoretical X-ray diffraction intensity of these diffraction surfaces. For example, the relative X-ray diffraction intensity ratio of the (111) diffraction surface is obtained from the X-ray diffraction intensity of the (111) diffraction surface divided by the theoretical X-ray diffraction intensity of the (111) diffraction surface.

The degree of integration of the {100} crystal plane is (200) having the same orientation as the crystal plane of {100} and {200} divided by the sum of the relative X-ray diffraction intensity ratios of the seven diffractive planes of (111)-(422) described above. It is obtained from the relative X-ray diffraction intensity ratio of the diffraction surface. The integration degree of each crystal plane of {110}, {210}, and {211} is obtained from the relative X-ray diffraction intensity ratios of the diffraction planes of (220), (42), and (422).

From the study of the degree of integration of each crystal plane derived from the above-described method, the inventors have found that the surface of the Fe-Ni-based Fe-Ni-Co-based Fe-Ni-Cr-based or Fe-Ni-Co-Cr-based alloy plate surface is less than { By controlling the degree of integration of each of the crystal planes 111}, {100}, {110}, and {311}, it was found that bending of the alloy plate after etching can be suppressed, and formation of stained peripheral portions of the etching holes can be prevented.

When the degree of integration of the {100} crystal plane becomes higher than 50%, bending of the alloy plate after etching is suppressed. However, when the degree of integration of the {100} crystal plane exceeds 94%, a stained periphery of the etching holes is formed. Therefore, the degree of integration of the {100} crystal plane is defined as 50-94%.

On the other hand, due to the degree of integration of the {111}, {110} and {311} crystal surfaces, the amount of warpage of the alloy plate after etching increases. When the degree of integration of the {111} crystal plane is 10%, the degree of integration of the {110} crystal plane is 24%, and the degree of integration of the {311} crystal plane is more than 14%, the amount of warpage after etching becomes remarkable, thereby degrading the quality of the flat mask.

When the degree of integration of each of the {111}, {110} and {311} crystal planes is 1% or less, the etching rate is significantly reduced. Therefore, the degree of integration of the {111} crystal plane is defined as 1-10%, the degree of integration of the {110} crystal plane is 1-24%, and the degree of integration of the {311} crystal plane is 1-14%.

The inventors also found that {111}, {100}, {110} and {311 on the surfaces of Fe-Ni-based, Fe-Ni-Co-based, Fe-Ni-Cr-based and Fe-Ni-Co-Cr-based alloy plates. } Controlling the density ratio of each crystal plane and controlling the density of {331), {210} and {211} crystal planes reduces the surface roughness (Ra, centerline average roughness) of the etching hole cross section and increases the etching rate. We found that we can increase the brightness of the transmitted light through the flat mask.

6 shows the relationship between measured light transmittance: surface roughness Ra of the etching hole. In FIG. 6, the white circle (○) corresponds to the following condition:

Density of {111} crystal faces: 1-14%,

Density of {100} crystal plane: 50-94%,

Density of {110} crystal plane: 1-24%,

Density of {311} crystal plane: 1-14%,

{331} density of crystallites: 1-14%,

Density of {210} crystal faces: 1-14%,

Density of {211} crystal plane: 1-14%,

The black circle (●) is subject to the following conditions:

{331} density of crystallites: 1-14%,

Density of {210} crystal faces: 1-14%,

Density of {211} crystal plane: 1-14%,

Even when the degree of integration of the {111}, {100}, {110} and {311} crystal planes is controlled within the above-mentioned range, etching is performed when the degree of integration of the {331}, {210} and {211} crystal planes exceeds 14%. The surface roughness of the hole cross section is deteriorated. This is indicated by the black spot (●) in FIG. 6 showing the relationship between the light transmittance of the flat mask, the surface roughness of the end surface of the etching hole, and (Ra, µm). As shown in the figure, the surface roughness of the surface of the etching hole becomes poor, and the light transmittance of the flat mask becomes low or dark.

In contrast, when the degree of integration of the {331}, {210} and {211} crystal planes is controlled to 14% or less, the surface roughness of the etching hole surface is deteriorated, and the light transmittance of the flat mask is increased or brightened. It is shown by the white spot (○) in FIG. The light transmittance of the flat mask is defined as a value obtained by dividing the light transmittance of the flat mask made of the alloy plate material by the light transmittance of the flat mask formed of conventional low carbon steel and having the same etching hole as the alloy plate material. When the light transmittance is 1 or more, the flat mask of the present invention has higher brightness than a conventional mask.

Therefore, the degree of integration of the {331}, {210} and {211} crystal planes needs to be maintained at 14% or less. However, when these values are 1% or less, the etching rate is reduced. Therefore, the degree of integration of the {331} crystal plane is 1-14%, the degree of integration of the {210} crystal plane is 1-14%, and the density of the {211} crystal plane is 1-14%.

Controlling the degree of integration of the seven major crystal faces on the alloy plate surface is important for improving the etching rate. FIG. 7 is a graph showing the relationship between the etching rate, the stained periphery of the etching hole and the value of (S + S + S) / (S + S + S + S). The value of S) / (S + S + S + S) is the sum of the integration degree S of the {100} crystal plane, the integration degree S of the {311} crystal plane, and the integration degree {S} of the {210} crystal plane, {111}. } It is divided by the sum of the integration degree S of the crystal plane, the integration degree S of the {110} crystal plane, the integration degree S of the {331} crystal plane, and the integration degree S of the {211} crystal plane. The figure shows 1-10% for {111} crystal plane, 50-94% for {100} crystal plane, {110} for 1-24% for crystal plane, 1-14% for {311} crystal plane, {210 } 1-14% for the crystal plane and 1-14% for the {211} crystal plane. The state of formation of the stained periphery of the etching hole was determined by visually classifying as follows. A when no stained periphery of the etching hole is formed; When the stained periphery of the etching hole was formed to a serious extent, E and B-D were classified as belonging between A and E as not causing practical problems. The rating of A-C was defined as no problem at all in practical use.

As shown in FIG. 7, the etching rate increases as the value of (S + S + S) / (S + S + S + S) increases, and the state diagram of the formation of the stained periphery of the etching hole is (S + It tends to worsen when the value of S + S) / (S + S + S + S) is extremely reduced or increased. Therefore, the value of (S + S + S) / (S + S + S + S) is defined in the range of 0.8-20, which does not cause any problem in practical use. It is even more preferable since the stained periphery of the etching hole does not appear at all in the range of 1.5-11.5.

8 is a graph showing the relationship between the value of (S + S + S) / (S + S + S + S) and the etching rate using the particle size D in the thickness direction of the alloy plate as a parameter. to be. This figure shows 1-10% for {111} crystal plane, 50-94% for {100} crystal plane, 1-24% for {110} crystal plane, 1-14% for {311} crystal plane, {331} 1-14% for the crystal plane, 1-14% for the {210} crystal plane, and 1-14% for the {211} crystal plane. 9 is a graph showing the relationship between the particle size and the etching rate in the thickness direction of the alloy plate.

As shown in Figs. 8 and 9, the etching rate decreases as the crystal grain size in the thickness direction of the alloy plate increases. Therefore, when the crystal grain size in the thickness direction of the alloy plate is limited to 10 µm or less and the etching rate is 2 or more, practical problems do not occur. If the crystal grain size is 6 µm or less, the etching rate is further increased.

The present invention provides an alloy plate for an electronic device having an excellent etching invention rate, the main component of the Fe-Ni, Fe-Ni-Co-based, Fe-Ni-Cr-based alloys, the degree of integration and the density ratio of the crystal surface on the surface of the alloy plate And the grain size of the alloy plate surface in the thickness direction. As the component added to the main component, the alloy plate of the present invention is 0.05 wt.% Or less C, 0.60wt.% Or less Mn, 0.30wt.% Or less Si, 0.0030wt.% Or less N and 0.0060wt.% It is preferable to contain the following O.

Cobalt as an impurity does not affect the etching processability when the content is 1 wt.% Or less.

In order to make the degree of integration of the crystal plane of the surface of the alloy plate within the range defined by the present invention, it is preferable to select appropriate manufacturing conditions to prevent the crystal plane from forming during the step of processing the alloy plate in molten steel, and the step Solidification, hot rolling, cold rolling and annealing. For example, when the alloy sheet of the present invention is processed from a slab and a hot rolled steel sheet obtained by continuous casting and hot rolling the slab, it is preferable to anneal the hot rolled steel sheet after hot rolling. It is preferable to make annealing temperature into 910-990 degreeC according to the reduction ratio of hot rolling. It is preferable to make annealing temperature into 910-990 degreeC according to the reduction ratio of hot rolling.

The characteristics of the alloy plate of the present invention are realized by optimizing the conditions (temperature, time and heating rate) of the cold rolling and annealing rolling rate according to the degree of integration of each crystal surface on the surface of the alloy plate after annealing the hot rolled plate. Annealing is effective when the hot rolled alloy plate is sufficiently crystallized before annealing the hot rolled plate.

In order to obtain a satisfactory integration degree of the seven crystal planes which the present invention focuses on, it is not preferable to uniformly heat-treat the slab after slaving. For example, when uniform heat treatment is performed at a temperature of 1200 ° C. or more for 10 hours or more, at least one of the degree of integration of the seven crystal planes exceeds the range defined by the present invention. Therefore, such uniform heat treatment should be avoided.

[Yes]

The invention is explained in more detail in this example. Molten steel was refined into ladles and castings and processed into alloy ingots having the A-N composition shown in Table 6.

The ingots were subjected to surface scarping and then slabbed to obtain slabs. The slab was surface scarped, heated in a furnace at 1100 ° C. for 3 hours and then hot rolled to obtain a hot rolled plate. Alloy No. The alloy plate of N was refined outside the furnace and then directly cast into slabs, and hot rolled at 1350-1000 ° C. at a reduction ratio of 30% to process the steel sheet.

The hot rolled steel sheet obtained above was annealed at 910-990 ° C., and then cold rolled and annealed with varying rolling or annealing conditions. The obtained alloy plate is alloy No. A-N. Tables 7, 8 and 9 show the obtained material No. It shows the characteristic of 1-No.52, the density of seven crystal planes, the value of SS (%), (S + S + S) / (S + S + S + S + S), and the thickness direction of an alloy plate The crystal grain size in μm is described.

A resist pattern was formed on each of the obtained alloy plates, and the etching rate was measured at 135 µm of dl shown in FIG. The etching rate was measured by etching the alloy plate in a ferric chloride bath of 45 bomedo at 40 ° C. at a spray pressure of 2.5 kg / cm 2 for 50 seconds, and using the above equation (1).

The alloy plate processed under the same conditions was made into a flat mask by photoetching. The amount of warpage was measured by placing a flat mask on a horizontal block. The light transmittance of the flat mask was measured by irradiating light rays, and this amount was divided by the light transmittance of a flat mask of a conventional low carbon steel having etching holes having the same dimensions as the alloy plate to obtain a light transmittance.

In the flat mask of the alloy plate, the surface roughness of the surface of the etching hole was measured by a non-contact laser illuminometer. The cutoff value was 0.02 mm, and the surface of the etching hole removed the tapered portion with the wave component to obtain the roughness curve, and then the centerline average roughness Ra was obtained.

The stained peripheral shape of the etching hole was visually determined.

Tables 10, 11, and 12 describe the properties of materials No. 1 to No. 52, and the amount of warpage after etching (mm), the surface roughness of the etching hole surface (center line average roughness, Ra (µm)), and flat mask Includes a light transmittance (as defined above), a state of formation of a stained periphery of the etching hole (as defined above), and an etching rate.

In the alloy plate of material No.46-No.49, the surface roughness of the surface of the etching hole by photoetching was measured by the method mentioned above. These materials were soldered to evaluate solder plating properties.

The values of the degree of integration S, S, S, S, S, S of {111}, {100}, {110}, {311}, {210}, and {211} as defined by the present invention, and (S + S Material No. 15-No. 48 and Material No. 50-52 having a value of + S) / (S + S + S + S) had an amount of 2 mm or less after etching, and a small amount compared with the comparative example described later. to be. The surface roughness, Ra, of the surface of the etching holes of these materials was 0.90 µm or less, and the light transmittance of the flat mask was 1.0 or more. This indicates that the light rays transmitted through the flat masks obtained from these materials are brighter than the light rays transmitted through the conventional low carbon steel flat masks.

The etching rate of these materials was 2.0 or more, and the stained periphery state diagram of the etching hole was a level state which does not cause any problem practically.

In contrast to the material of the present invention, material No. 1 represents the degree of integration of the {111} crystal plane, S, which is equal to or greater than the upper limit of the present invention, 2 represents the degree of integration, S, of the {100} crystal plane which is equal to or less than the lower limit of the present invention, 3 shows the degree of integration of the {100} crystal plane, S, which is equal to or greater than the upper limit of the present invention, 4 shows the degree of integration, S, of the {110} crystal plane that is equal to or greater than the upper limit of the present invention. 5 shows the degree of integration, S, of the {311} crystal plane that is greater than or equal to the upper limit of the present invention. Therefore, the amount of warpage after etching was 7 mm or more, and it was found to have a larger value than the example of the present invention.

Material No. 6 denotes the degree of integration, S, of the {331} crystal plane that is equal to or greater than the upper limit of the present invention. 7 indicates the degree of integration, S, of the {210} crystal plane that is equal to or greater than the upper limit of the present invention. 8 has shown the degree of integration, S, of the {211} crystal plane that is greater than or equal to the upper limit of the present invention. Therefore, the surface roughness Ra of the surface of the etching hole of these materials was 1.0 or less, which was not better than the example of the present invention.

Material No. 9 indicates the degree of integration of the {211} crystal plane that is less than or equal to the lower limit of the present invention, S. No. 12 indicates the degree of integration of the {110} crystal plane that is less than or equal to the lower limit of the present invention; 10 indicates the degree of integration, S, of the {210} crystal plane that is equal to or less than the lower limit of the present invention. 11 denotes the degree of integration S of the {311} crystal plane that is less than or equal to the lower limit of the present invention. 13 represents the value of (S + S + S) / (S + S + S + S) which is below the lower limit of this invention, respectively. Therefore, these materials exhibit an etching rate of 2.0 or less, which is not satisfied with the present invention.

Material No. 14 denotes a value of (S + S + S) / (S + S + S + S) which is greater than or equal to the upper limit of the present invention, so that these materials have increased stained periphery of the etching holes of the flat mask compared to the example of the present invention. It can be seen that.

Material No. Denoted at 49 is the degree of integration of the {210} crystal plane, S being the degree of integration of the {211} crystal plane, S, which is not less than the different value of the present invention. Therefore, these materials exhibit surface roughness, Ra, and 1.21 of the etching holes, which means that they are rougher than the examples of the present invention.

Material No. 3 indicates the degree of integration of the {210} crystal plane, the degree of integration of the {311} crystal plane, and S, which is equal to or less than the lower limit of the present invention, and the etching rate of this material is 2.0 or less, which is lower than that of the example of the present invention.

As mentioned above, the values of the degree of integration S, S, S, S, S, S and S of the crystal planes of {111}, {100}, {110}, {311}, {331}, {210} and {211} And controlling the value of (S + S + S) / (S + S + S + S) within the prescribed range of the ball invention reduces the amount of warpage after etching, reduces the roughness of the surface of the etching hole, Ra, The light transmittance of the mask is increased in quantity, the etch rate is increased, and the degree of staining peripheral formation is reduced.

In addition, when the crystal grain size is controlled within the range defined by the present invention as the thickness direction of the alloy plate, the etching rate can be increased.

The above detailed description of the present invention uses a flat mask as an example. However, in addition to the flat mask, the alloy plate of the present invention can also be used for an etched electronic device material.

Claims (6)

The alloy plate has crystal surfaces of {331}, {210} and {211} on its surface; The degree of integration of the {311} crystal plane is 14% or less, the degree of integration of the {210} crystal plane is 14% or less, and the density of the {211} crystal plane is 14% or less; The ratio of the degree of integration represented by the formula {210} / ({331} + {211}) is 0.2 to 1; The alloy plate may include a Fe—Ni-based alloy plate containing 34-38 wt% Ni suitable for a shadow mask or 38-52 wt% Ni suitable for an IC lead frame; Fe-Ni-Co-based containing 28-38wt% Ni and 1-7wt.% Co suitable for shadow mask or 27-32wt.% Ni and 1-20wt.% Co suitable for IC leadframe Alloy plate; Fe-Ni-Cr type alloy plate containing Cr 3wt% or less; And an alloy sheet having excellent etching workability, which is any alloy sheet selected from the group consisting of a Fe-Ni-Co-Cr-based alloy sheet. The alloy plate according to claim 1, wherein the alloy plate has an average crystal grain size of 10 µm or less in the thickness direction of the alloy plate. The alloy plate according to claim 2, wherein the alloy plate has an average crystal grain size of 6 µm or less in the thickness direction of the alloy plate. The alloy plate has crystal planes of {111}, {100}, {110}, {311}, {210} and {211}; Degree of integration of each crystal plane; Density of {111} crystal plane (S ₁ ): 1-10%, Density of {100} crystal plane (S ₅ ): 50-94%, Density of {110} crystal plane (S ₃ ): 1-24%, {311 } Integration degree of crystal plane (S ₄ ): 1-14%, {331} Integration degree of crystal plane (S ₅ ): 1-14% {210} Density of crystal plane (S ₆ ): 1-14% {211} (S ₇ ): 1-14%; The density ratio represented by the formula (S ₂ + S ₄ + S ₆ ) / (S ₁ + S ₃ + S ₅ + S ₇ ) is 0.8-20, and the alloy plate contains 34-52 wt.% Ni. Fe-Ni alloy plate made; Fe-Ni-Co alloy plate containing 28-38 wt.% Ni and 20 wt.% Or less of Co; Fe—Ni—Cr based alloy plate containing 34-52 wt /% Ni and 3 wt.% Or less of Cr; An alloy plate having excellent etching processability, which is any one alloy plate selected from the group consisting of Fe-Ni-Co-Cr based alloys containing 28-38 wt.% Ni, 20 wt% or less of Co, and 3 wt.% Of Cr. The alloy plate according to claim 4, wherein the alloy plate has an average crystal grain size of 10 µm or less in the thickness direction of the alloy plate. The alloy plate according to claim 5, wherein the alloy plate has an average crystal grain size of 6 µm or less in the thickness direction of the alloy palm.