JPH0813096A - High-strength low-thermal-expansion alloy sheet for electronics with excellent etching property and surface treatment property and its manufacturing method - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain a high-strength low-thermal-expansion alloy thin plate for electronics, which is excellent in etching property and surface treatment property. [Composition] Ni: 30 to 50% by weight, C: 0.00
1 to 0.10%, balance Fe, crystal grain aspect ratio 1.3 to 50, Vickers hardness 200 to 280
A high-strength, low-thermal-expansion alloy thin plate for electronics that has excellent etching and surface treatment properties. In addition to the above components, Ti, Zr, N
0.00% by weight of at least one of b, Si, Y, W, Mo, Mn, Mg, Al, Cu and Ca.
A high-strength low-thermal-expansion alloy thin plate for electronics, containing 1 to 0.10% and excellent in etching property and surface treatment property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-strength low-thermal-expansion alloy sheet for electronic use which is used as a material for shadow masks, aperture grilles, lead frames and the like and which has excellent etching properties and surface treatment properties, and a method for producing the same.

[0002]

2. Description of the Related Art Fe-Ni alloys containing 30 to 50% by weight of Ni are used as materials for lead frames for IC packages and shadow masks for TV images.

At present, the lead frame is required to have a large number of pins and a thin wall as the IC is highly integrated, and accordingly, the material is also required to have a high strength. In addition, shadow masks and aperture grills for TV picture tubes also need to have high freshness and high image quality.
Similarly, the material is required to be thin and have high strength.

Further, these electronic materials are required to have a good surface treatment property, and it is required that the lead frame have a good Ag plating property and the shadow mask and the aperture grill have a good blackening property. As a material for such a demand, as a lead frame material, Fe-Ni-C disclosed in Japanese Patent Laid-Open No. 3-166340 is disclosed.
There are o-based alloys.

[0005]

However, the above-mentioned conventional Fe-Ni-Co alloys have the following problems. That is, since Co is added, the hardness is increased, but martensite is generated during processing, so that the etching property and the surface treatment property are deteriorated.

Further, since Co is added, it is expensive. Furthermore, it lacks high strength as a material for shadow masks and aperture grills.

The present invention has been made in order to solve the above-mentioned problems of the prior art, and is excellent in etching property and surface treatment property, and has high strength, and a Fe-Ni alloy thin plate for electronic use and Its purpose is to provide a manufacturing method thereof.

[0008]

The high-strength, low-thermal-expansion alloy thin plate for electronic devices excellent in etching property and surface treatment property according to the present invention is (1) Ni: 30 to 50% by weight, C: 0.001 ~
0.10%, Sb is 0.10% or less (including 0), the balance is substantially Fe, and the aspect ratio of the crystal grains is 1.3.
The Vickers hardness of 200 or more and 50 or less is 200 to 280.

(2) In addition to the above components, Ti, Z
r, Nb, Si, Y, W, Mo, Mn, Mg, Al, C
The content of at least one of u and Ca is 0.001 to 0.10% by weight.

(3) In addition to the above (1) and (2), the crystal grain size is 2 to 20 μm.

(4) Furthermore, according to the present invention, there is provided a method for producing a high-strength low-thermal-expansion alloy thin plate for electronic use which is excellent in etching property and surface treatment property.
When manufacturing through the step of cold rolling and annealing, the cold rolling rate is 25 to 95%, and the annealing temperature is 300 to 650.
It is performed under the conditions of a temperature rise rate of 10 ° C./sec or more.

(5) In addition, when the alloy thin plate having the above-mentioned composition is subjected to primary cold rolling, primary annealing, secondary cold rolling and secondary annealing, the primary cold rolling is performed. The cold rolling rate of 50% or more, and the primary annealing is performed at an annealing temperature of 650 to 10
00 ° C, annealing time 0.5 to 300 seconds, temperature rising rate 10 ° C /
The second cold rolling is performed at a temperature of 300 to 650 and the cold rolling rate of the secondary cold rolling is set to 25 to 95%.
It is performed under the conditions of a temperature rise rate of 10 ° C./sec or more.

[0013]

In the present invention, the reasons for limiting the component composition and material of the alloy thin plate will be described below.

(1) Chemical composition Ni: 30 to 50% by weight as a range in which low thermal expansion characteristics required for shadow masks, aperture grills, lead frames and the like can be obtained. C: An essential element for enhancing work hardening of the present alloy.
However, if less than 0.001%, the effect is poor, and
If it exceeds 10%, the surface treatment properties such as etching property, blackening property and plating property deteriorate, so the content range of C was made 0.001 to 0.10% by weight. A more preferable range in terms of surface treatability is 0.01% or less. Sb: An impurity element in the present alloy, which is a harmful element for surface treatment. If it exceeds 0.10%, the Ag plating property as the lead frame material deteriorates, and the blackening processability as the shadow mask or the aperture grill material deteriorates, so 0.10% by weight was made the upper limit. A more preferable level from the surface treatability is 0.01% by weight or less. Ti, Zr, Nb, Si, Y, W, Mo, Mn, Mg,
Al, Cu and Ca: at least one kind and 0.00
By containing 1% or more, the work hardening of the present alloy can be enhanced and a high hardness thin plate can be obtained, but if it exceeds 0.10%, the surface treatment property deteriorates, so the content range is 0.00
It was set to 1 to 0.10% by weight.

(2) Aspect ratio Control of the aspect ratio, which indicates the ratio of the major axis to the minor axis of the crystal grain size, is necessary to obtain high hardness and excellent etching properties, and this value is 1 When it is 0.3 or more, the etching property intended in the present invention can be obtained. However, if it exceeds 50, the workability deteriorates, so the aspect ratio is set to 1.3 to 50. Incidentally, the aspect ratio, the cross section in the rolling direction is observed, the grain size in the rolling direction is the long axis,
It is a value showing the ratio of the particle diameter in the plate thickness direction as the minor axis.

(3) Hardness The required hardness of the electronic Fe-Ni alloy targeted by this alloy is HV 200 or more. Even within this range, the higher the hardness, the thinner the electronic component is achieved,
If the hardness exceeds HV 280, the workability such as punching and bending deteriorates, so the hardness range is HV 200-2.
It was set to 80.

(4) Crystal Grain Size In order to achieve high strength in the present alloy, it is preferable to control the crystal grain size. If the crystal grain size exceeds 20 μm, the high strength and surface treatability intended by the present invention cannot be stably obtained. On the other hand, the crystal grain size that can be produced in terms of production technology is 2 μm. Therefore, the crystal grain size is 2
˜20 μm is preferred. Within the above range, the high strength and surface treatability intended by the present invention can be obtained, but the smaller the crystal grain size, the better the characteristics. The crystal grain size here is 45 ° with the rolling direction axis in the rolling direction cross section.
It is a value obtained by intersecting the directions forming the angle.

Next, the high-strength Fe-Ni alloy thin plate for electronic devices excellent in etching property and surface treatment property according to the present invention is prepared.
The reason for limiting the manufacturing conditions when manufacturing in the cold rolling-annealing step will be described.

(1) When the cold rolling rate is less than 25%, the aspect ratio does not exceed 1.3,
High hardness and good etching property cannot be obtained. Also,
If it exceeds 95%, the crystal grains are excessively spread and the workability is deteriorated. Therefore, the cold rolling rate is set to 25 to 95%.

(2) Annealing temperature At an annealing temperature of less than 300 ° C., strain cannot be removed and residual stress cannot be eliminated, so that good etching property (high etching factor) cannot be obtained and workability is poor. If the annealing temperature exceeds 650 ° C., recrystallization occurs, and the hardness and etchability deteriorate. Therefore, the annealing temperature is 300 to 650 ° C.
And

(3) Rate of temperature increase: If the rate is less than 10 ° C./sec, recovery occurs and high hardness cannot be obtained. Therefore, the rate of temperature increase was set to 10 ° C./sec or more.

Next, the high-strength Fe-Ni alloy thin plate for electronic devices excellent in etching property and surface treatment property according to the present invention is prepared.
The reason for limiting the manufacturing conditions in the case of manufacturing in the steps of primary cold rolling-primary annealing-secondary cold rolling-secondary annealing will be described.

(1) When the primary cold rolling rate is 50% or more, the mixed grain structure of the hot-rolled sheet is eliminated, the structure becomes granular and the etching property is improved. Therefore, the primary cold rolling rate is 50% or more. And

(2) When the primary annealing temperature is lower than 650 ° C., recrystallization is not sufficiently performed and good workability cannot be obtained. Further, when the temperature exceeds 1000 ° C., recrystallized grains are coarsened and the grain size exceeds 20 μm. Therefore, high hardness cannot be obtained even after secondary cold rolling, and good etching property cannot be obtained. The annealing temperature was 650 to 1000 ° C.

(3) Primary annealing time If the annealing time is less than 0.5 seconds, recrystallization will not occur, and if it exceeds 300 seconds, coarse grains will be formed. Therefore, the primary annealing time was set to 0.5 to 300 seconds.

(4) Primary annealing temperature rising rate If the temperature is less than 10 ° C./second, recovery occurs and high hardness cannot be obtained. Therefore, the temperature rising rate is set to 10 ° C./second or more.

(5) Secondary Cold Rolling Rate Below 25%, the aspect ratio does not exceed 1.3,
High hardness and good etching property cannot be obtained. Also,
If it exceeds 95%, the crystal grains are excessively spread and the workability is deteriorated. Therefore, the primary cold rolling rate is set to 25 to 95%.

(6) Secondary annealing temperature At an annealing temperature of less than 300 ° C., strain cannot be removed and residual stress cannot be eliminated, so that good etching property (high etching factor) cannot be obtained and workability is poor. If the annealing temperature exceeds 650 ° C., recrystallization occurs, and the hardness and etchability deteriorate. Therefore, the primary annealing temperature is 300 to 65.
It was set to 0 ° C.

(7) Secondary annealing temperature rising rate If the temperature is less than 10 ° C./second, recovery occurs and high hardness cannot be obtained. Therefore, the temperature rising rate is set to 10 ° C./second or more.

[0030]

【Example】

Example 1 Material No. shown in Table 1. 1 to 13 of the present invention alloy sheets and material Nos. In order to obtain the comparative alloy thin plates of Nos. 14 to 19, the respective material Nos. After melting and refining an alloy having an alloy component corresponding to No. 1 in an electric furnace, the material No. 1-4, 6, 7, 1
Nos. 4 to 19 were made into steel ingots and then slabbing, and the material N
o. 5 and 8 to 13 are slabs made by the continuous casting method,
It was hot-rolled into a hot-rolled sheet having a plate thickness of 2.5 mm.

[0031]

[Table 1]

After removing the scale of the obtained hot-rolled sheet, primary cold-rolling was performed at a cold rolling rate of 75%, followed by an annealing temperature of 860 ° C., a holding time of 12 seconds, and a heating rate of 20 ° C./second. Primary annealing was performed. Further, the secondary cold rolling is performed at a cold rolling rate of 85%, and then the annealing temperature is 450 ° C. and the heating rate is 30 ° C./sec.
Subsequent annealing was performed and the characteristic value of each material was investigated. The results are shown in Table 2.

[0033]

[Table 2]

The particle size and aspect ratio in Table 2 were determined by the linear intersect method. Further, the hardness indicates the hardness of the plate surface of the material by Vickers hardness (HV),
As shown in FIG. 2, the etching factor, which is an index of the etching property, is generated in the material to be etched 21 when the material to be etched 21 is resist-etched with a resist film 22 having an opening 22a having a diameter of d _1. The maximum diameter of the etched portion 23 is d ₂ , and the etching depth is
When H, it is the numerical value shown by the formula (1).

Ef = 2H / (d ₂ −d ₁ ) (1) That is, as the etching factor increases, the etching hole does not become larger than necessary and deep etching is possible.

Regarding the Ag plating property, after solvent degreasing, electrolytic degreasing and acid treatment, Cu with a thickness of 0.5 μm is used.
Strike-plated, 2 μm-thick Ag-plated alloy thin plate on the surface of the alloy sheet at a temperature of 450 ° C. for 5
It was heated for a minute, and the presence or absence of blistering on the plating layer was examined 50 times more.

Among the surface treatability, the blackening treatability is
It was judged by the blackness of the surface oxide film after heating the test material at 590 ° C. for 5 minutes.

From Table 2, the material No. which satisfies the component definition, aspect ratio and hardness of the present invention. Each of the test materials 1 to 13 has etching property and surface treatment property (Ag plating property).
It turns out that it is excellent. In particular, the material No. with a low content of C and Sb. It can be seen that the materials of Nos. 1 and 2 are much more excellent in surface treatability.

Material No. 5 to 13 are C and S
In addition to b, Ti, Zr, Nb, Si, Y, W, Mo,
It is understood that at least one kind of Mn, Mg, Al, Cu and Ca is added within the compositional rule, but higher hardness is obtained as compared with other invention alloys. For these invention alloys, the material No. 1
In the material of No. 4, the content of C is less than the lower limit value of the component regulation of the present invention, and the required hardness is not obtained.

Material No. of the comparative material The material of No. 15 has a C content exceeding the upper limit of the component regulation of the present invention,
The hardness exceeds the upper limit specified in the present invention, and the etching property, surface treatment property and workability are poor.

Material No. of the comparative material The material of No. 16 has an Sb content exceeding the upper limit of the component regulation of the present invention, and is inferior in surface treatability.

Material No. of the comparative material The material of No. 17 has a particle size exceeding the upper limit of the component regulation of the present invention, has low hardness, and is inferior in etching property and surface treatment property.

Material No. of the comparative material The materials of No. 18 have an aspect ratio of less than the lower limit specified by the present invention, failing to obtain the required hardness, and are inferior in etching property and surface treatment property.

Material No. of the comparative material The material of No. 19 has an aspect ratio exceeding the upper limit defined by the present invention, a hardness exceeding the regulation defined by the present invention, and excellent workability is not obtained. As described above, the particle size, aspect ratio, and
It can be seen that the hardness, etching property and surface treatment property are achieved only when the component specifications of the present invention are satisfied.

Example 2 Alloy No. 1 whose composition is shown in Table 1. Table 3 and Table 4 show cold rolling and annealing using hot rolled sheets corresponding to Nos. 1, 3 and 5 as raw materials.
Material No. 20-42 cold rolled materials were produced. Material No. Alloy Nos. 20 to 25, 38 and 39 are alloy Nos. 1
Material No. 26 to 31, 40 are alloy N
o. Material No. 3 corresponding to 32-37, 41,
42 is alloy No. It corresponds to 5.

[0046]

[Table 3]

[0047]

[Table 4]

Table 3 shows the manufacturing conditions specified in the present invention, and Table 4 shows the manufacturing conditions deviating from the manufacturing conditions specified in the present invention.

Regarding the test material manufactured in this way,
The characteristic values were investigated in the same way as described in Table 2. The results are shown in Tables 5 and 6.

[0050]

[Table 5]

[0051]

[Table 6]

The materials in Table 5 were manufactured under the manufacturing conditions specified in the present invention, and the materials in Table 6 were manufactured under manufacturing conditions deviating from the manufacturing conditions specified in the present invention. Table 5
As is clear from the above, the material manufactured under the manufacturing conditions specified in the present invention satisfies the required particle size, aspect ratio, hardness, etching property and surface treatment property (Ag plating property) intended in the present invention. .

On the other hand, the material No. shown in Table 6 was used. 38
The material of, the cold rolling rate is less than the lower limit of the specified value of the present invention,
The aspect ratio is low, and as a result, the hardness and etchability do not reach the required level.

Material No. In the material No. 39, the cold rolling rate exceeds the upper limit of the specified value of the present invention, the aspect ratio is high, and as a result, the hardness is too high, and good workability is not obtained.

Material No. In the material of No. 40, the temperature rising rate was less than the lower limit specified in the present invention, so that a recovery phenomenon occurred and the hardness did not reach the required value.

Material No. The material No. 41 has an annealing temperature lower than the lower limit specified by the present invention, and therefore has a hardness exceeding the upper limit specified by the present invention, and the required etching property and workability are not obtained.

Material No. The material of No. 42 has an annealing temperature higher than the upper limit specified by the present invention, so that the hardness is less than the lower limit specified by the present invention, and good surface treatability is not obtained.

As described above, in order to obtain the desired aspect ratio, hardness, etching property and surface treatment property (Ag plating property) in the present invention, the definition of the manufacturing conditions in the present invention is also an important requirement.

Example 3 Alloy No. whose composition is shown in Table 1 is as follows. Using the hot-rolled sheets corresponding to Nos. 1, 3 and 5 as raw materials, primary cold rolling, primary annealing and secondary cold rolling, and secondary annealing were performed under the conditions of Tables 7 and 8, and the material N
o. Cold rolled materials of 43 to 68 were manufactured. Material No. 43 ~
47 and No. 47. Nos. 58 to 62 are alloy Nos. Material No. 1 48-52 and No. 63 to 65 are alloy Nos. Material No. 3 corresponding to 53-57 and No. Alloy Nos. 66 to 68 are alloy Nos. It corresponds to 5.

[0060]

[Table 7]

[0061]

[Table 8]

Table 7 shows manufacturing conditions specified in the present invention, and Table 8 shows manufacturing conditions deviating from the manufacturing conditions specified in the present invention.

Regarding the test materials manufactured in this way,
The characteristic values were investigated in the same way as described in Table 2. The results are shown in Tables 9 and 10.

[0064]

[Table 9]

[0065]

[Table 10]

The materials in Table 9 were manufactured under the manufacturing conditions specified in the present invention, and the materials in Table 10 were manufactured under manufacturing conditions deviating from the manufacturing conditions specified in the present invention. As is apparent from Table 9, No. manufactured under the manufacturing conditions specified in the present invention. The materials of Nos. 43 to 57 satisfy the required grain size, aspect ratio, hardness, etching property and surface treatment property (Ag plating property) intended in the present invention.

On the other hand, the material No. shown in Table 10 was used. 5
In the material of No. 8, the primary cold rolling rate is less than the lower limit of the specified value of the present invention, the coarse grain / mixed grain structure in hot rolling is not sufficiently eliminated, and the crystal grain size is the upper limit specified by the present invention. Is exceeded,
The required etching property is not obtained.

Material No. The material No. 59 had a primary annealing temperature below the lower limit specified in the present invention, and therefore the material was not sufficiently recrystallized and good workability was not obtained.

Workability is not obtained. Also, the material N
o. The material of No. 60 had a primary annealing temperature exceeding the upper limit specified in the present invention, so that the structure became coarse, and the crystal grain size exceeded the specified value in the present invention. Processability is not obtained.

Material No. The material of No. 61 has a primary annealing time of less than the lower limit specified in the present invention, and therefore has low hardness and poor etching property and workability.

Material No. The material of No. 62 has a primary annealing time exceeding the upper limit specified by the present invention, and therefore has too high hardness and poor etching property and surface treatment property.

Material No. The material of No. 63 has a rate of temperature rise in the primary annealing less than the lower limit specified by the present invention, so that recovery occurs, the hardness is low, and the etching property is poor.

Material No. The material of No. 64 has a secondary cold rolling rate of less than the lower limit of the specified value of the present invention, has low hardness, and has poor etching properties.

Material No. The material of No. 65 has a secondary cold rolling rate exceeding the upper limit of the specified value of the present invention, has too high hardness and is poor in workability.

Material No. The material of No. 66 has a secondary annealing temperature lower than the lower limit of the specified value of the present invention, and therefore has high hardness, and the required etching property and workability are not obtained.

Material No. The material of No. 67 has a secondary annealing temperature exceeding the upper limit of the specified value of the present invention, has low hardness, and has poor etching properties.

Material No. The material of No. 67 has a rate of temperature rise in the secondary annealing less than the lower limit specified by the present invention, so that recovery occurs and the hardness is low.

As described above, in order to obtain the desired aspect ratio, hardness, etching property and surface treatment property (Ag plating property) in the present invention, the definition of the above manufacturing conditions in the present invention is also important. It is a requirement. FIG.
The graph of (a) shows the relationship between the aspect ratio and hardness, the C content and the crystal grain size as parameters, and FIG.
In the graph of (b), the relationship between the aspect ratio and the etching factor is shown with the C content and the crystal grain size as parameters. From this graph, it can be seen that there is a range of good workability in the combination of the aspect ratio and hardness, and a range of good etching properties in the combination of the relationship between the aspect ratio and the etching factor.

[0079]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a high-strength Fe-Ni alloy thin plate for electronic use which is excellent in etching property and surface treatment property and has high strength.

[Brief description of drawings]

FIG. 1A is a graph showing a relationship between an aspect ratio and hardness, and FIG. 1B is a graph showing a relationship between an aspect ratio and an etching factor.

FIG. 2 is an explanatory diagram showing the concept of an etching factor.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isamu Kamo 1-2-2 Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Makoto Yamada 1-2-1 Marunouchi, Chiyoda-ku, Tokyo Inside the Steel Pipe Co., Ltd. (72) Inventor Hiroshi Wakasa 1-2 1-2 Marunouchi, Chiyoda-ku, Tokyo Inside Nihon Steel Pipe Co., Ltd.

Claims (5)

[Claims] 1. Ni: 30 to 50% by weight, C: 0.
001 to 0.10%, Sb 0.10% or less (including 0), the balance substantially consisting of Fe, the aspect ratio of crystal grains is 1.3 or more and 50 or less, Vickers hardness is 200 to 2
A high-strength low-thermal-expansion alloy thin plate for electronic use excellent in etching property and surface treatment property, which is 80. 2. Ti, Zr, Nb, Si, Y, W, M
O, Mn, Mg, Al, Cu, and Ca are contained in 0.001 to 0.10% by weight%, and the etching property and the surface treatment property according to claim 1. Excellent high strength and low thermal expansion alloy sheet for electronics. 3. The crystal grain size is 2 to 20 μm.
3. A high-strength, low-thermal expansion alloy thin plate for electronics, which is excellent in etching property and surface treatment property according to claim 2. 4. Claim 1 or claim 2 or claim 3.
When manufacturing an alloy thin plate having the component composition described in 1) through a step of cold rolling and annealing, the cold rolling rate is 25 to 95%.
And annealing is performed at an annealing temperature of 300 to 650 ° C. and a heating rate of 10
A method for producing a high-strength, low-thermal-expansion alloy sheet for electronic use, which is excellent in etching property and surface treatment property, characterized in that it is applied under the condition of ° C / sec or more. 5. Claim 1 or claim 2 or claim 3.
1. Cold-rolling the alloy thin plate having the composition described in 1.
After the secondary annealing, the secondary cold rolling and the secondary annealing are carried out. In the manufacturing, the cold rolling rate of the primary cold rolling is set to 50% or more,
The primary annealing was performed at an annealing temperature of 650 to 1000 ° C. and an annealing time of 0.
5 to 300 seconds, the rate of temperature rise is 10 ° C./second or more, and the cold rolling rate of the secondary cold rolling is set to 25 to 95%, and the secondary annealing is performed at an annealing temperature of 300 to 650 ° C. and a temperature rise rate of 10 ° C. A method for producing a high-strength low-thermal-expansion alloy sheet for electronic use, which is excellent in etching property and surface treatment property, characterized by being applied under the condition of not less than 1 sec / sec.