JP3211569B2 - High strength and low thermal expansion alloy sheet for electronics with excellent etching and surface treatment properties and its manufacturing method - Google Patents

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 thin plate for electronic devices which is excellent in etching properties and surface treatment properties and is used as a material for a shadow mask, an aperture grill and a lead frame.

[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.

[0003] At present, lead frames have been increased in the number of pins and thinned as the integration of ICs has increased, and accordingly, the materials have also been required to have higher strength. In addition, shadow masks and aperture grills for TV picture tubes also have a need for higher freshness and higher image quality.
Similarly, the material is also required to be thinner and stronger.

[0004] Further, these electronic materials are required to have good surface treatment properties, and are required to have good Ag plating properties for lead frames and good blackening properties for shadow masks and aperture grilles. As a material for such a demand, as a lead frame material, Fe-Ni-C disclosed in JP-A-3-166340 is used.
There are o-based alloys.

[0005]

However, the above-mentioned conventional Fe-Ni-Co alloy has the following problems. That is, although the hardness is increased by the addition of Co, martensite is generated during the processing, so that the etching property and the surface treatment property are poor.

Further, since Co is added, it is expensive. Furthermore, it lacks high strength as a material for a shadow mask or an aperture grill.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has excellent etching properties and surface treatment properties, as well as high strength Fe-Ni alloy thin plates for electronic devices. It is intended to provide a method for producing the same.

[0008]

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

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

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

(4) Further, the method for producing a high-strength, low-thermal-expansion alloy sheet for electronic devices according to the present invention, which is excellent in etching properties and surface treatment properties, comprises the steps of:
When manufacturing through the process of cold rolling and annealing, the cold rolling rate is 25 to 95%, and the annealing is performed at an annealing temperature of 300 to 650.
C. and a temperature rise rate of 10 ° C./sec or more.

(5) When the alloy thin plate having the above-mentioned composition is manufactured through the steps of primary cold rolling and primary annealing and then secondary cold rolling and secondary annealing, primary cold rolling is performed. And the primary annealing is performed at an annealing temperature of 650 to 10%.
00 ° C., annealing time 0.5 to 300 seconds, heating rate 10 ° C. /
In addition to the application under the condition of second or longer, the cold rolling reduction 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./sec or more.

[0013]

The reasons for limiting the composition and material of the alloy sheet in the present invention will be described below.

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

(2) Aspect ratio Control of the aspect ratio, which indicates the ratio between the major axis and the minor axis of the crystal grain size, is necessary to obtain high hardness and excellent etching properties. When it is at least 3, the etching property intended in the present invention can be obtained. However, when the ratio exceeds 50, the workability deteriorates, and the aspect ratio is set to 1.3 to 50. In addition, the aspect ratio refers to the observation of the cross section in the rolling direction, the particle diameter in the rolling direction is the major axis,
It is a value indicating the ratio of the particle diameter in the thickness direction as the minor axis.

(3) Hardness The required hardness required for the Fe—Ni alloy for electronic purposes, which is a target of the present alloy, is HV 200 or more. Even within this range, the higher the hardness, the thinner the electronic component is achieved,
If the HV exceeds 280, the workability such as punching and bending deteriorates.
80.

(4) Grain Size In the present alloy, in order to achieve high strength, it is preferable to control the crystal grain size. If the crystal grain size exceeds 20 μm, the high strength and surface treatment properties intended in the present invention cannot be stably obtained. On the other hand, the crystal grain size that can be manufactured from the viewpoint of manufacturing technology is 2 μm. Therefore, the crystal grain size is 2
~ 20 µm is preferred. Further, within the above range, the high strength and surface treatment properties intended in 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 respect to the axis in the rolling direction in the cross section in the rolling direction.
Is a value obtained by intersecting the direction forming the angle of.

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

(1) If the cold rolling rate is less than 25%, the aspect ratio does not become 1.3 or more,
High hardness and good etching properties cannot be obtained. Also,
If it exceeds 95%, the crystal grains are excessively expanded, and the workability is deteriorated. Therefore, the cold rolling reduction was set to 25 to 95%.

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

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

Next, a high-strength Fe-Ni alloy thin plate for electronic use according to the present invention, which is excellent in etching property and surface treatment property,
The reason for limiting the manufacturing conditions in the case of manufacturing in the steps of primary cold rolling, primary annealing, secondary cold rolling, and 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 texture becomes sized, and the etching property is improved. Therefore, the primary cold rolling rate is 50% or more. And

(2) If the primary annealing temperature is lower than 650 ° C., recrystallization is not sufficiently performed, and good workability cannot be obtained. On the other hand, when the temperature exceeds 1000 ° C., recrystallization coarsens and the particle size exceeds 20 μm, so that high hardness cannot be obtained even after secondary cold rolling and good etching properties cannot be obtained. The annealing temperature was 650-1000 ° C.

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

(4) Primary annealing temperature rise rate If the rate is lower than 10 ° C./sec, recovery occurs, and high hardness cannot be obtained.

(5) If the secondary cold rolling reduction is less than 25%, the aspect ratio does not become 1.3 or more,
High hardness and good etching properties cannot be obtained. Also,
If it exceeds 95%, the crystal grains are excessively expanded, and the workability is deteriorated. Therefore, the primary cold rolling rate was 25 to 95%.

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

(7) Secondary annealing temperature rise rate If the rate is lower than 10 ° C./sec, recovery occurs and high hardness cannot be obtained.

[0030]

【Example】

Example 1 Material No. 1 shown in Table 1 was used. Nos. 1 to 13 and the alloy Nos. 1 to 13 of the present invention. In order to obtain comparative alloy thin plates of Nos. 14 to 19, each of the material Nos. After melting and refining an alloy having an alloy component corresponding to 1-4, 6, 7, 1
Nos. 4 to 19 are made from steel ingots and then subjected to slab rolling.
o. 5, 8 to 13 are made into slabs by the continuous casting method,
Hot rolling was performed to obtain a hot-rolled sheet having a 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%, and then an annealing temperature of 860 ° C., a holding time of 12 seconds, and a heating rate of 20 ° C./sec. Primary annealing was performed. Further, after the secondary cold rolling was performed at a cold rolling rate of 85%, an annealing temperature of 450 ° C. and a rate of temperature increase of 30 ° C./sec.
Next annealing was performed, and the characteristic value of each material was investigated. Table 2 shows the results.

[0033]

[Table 2]

The particle diameter and aspect ratio in Table 2 were determined by a linear intersect method. The hardness indicates the hardness of the plate surface of the material by Vickers hardness (HV),
Etching factor is an indication of the etch resistance, as shown in FIG. 2, the etched material 21, when etched with the resist in the resist film 22 having an opening 22a having a diameter of d _1, generated in the etching object material 21 The maximum diameter of the etched portion 23 to be etched is d ₂ , and the etching depth is
When H is set, it is a numerical value represented by equation (1).

Ef = 2H / (d ₂ −d ₁ ) (1) That is, as the etching factor increases, the etching hole does not become unnecessarily large and the etching can be deeply performed.

Regarding the Ag plating property, after solvent degreasing, electrolytic degreasing and acid treatment, the Cu plating of 0.5 μm thickness was performed.
A strike-plated alloy thin plate having a thickness of 2 μm on which an Ag plating was applied was placed in air at 450 ° C. for 5 minutes.
After heating for 1 minute, the presence or absence of blistering of the plating layer was examined by magnifying it 50 times.

Among the surface treatment properties, the blackening property is as follows.
After the test material was heated at 590 ° C. for 5 minutes, the blackness of the surface oxide film was determined.

From Table 2, it can be seen that Material No. satisfying both the component definition, aspect ratio and hardness of the present invention. Each of the test materials 1 to 13 has an etching property and a surface treatment property (Ag plating property).
It turns out that it is excellent. In particular, the materials No. It can be seen that materials 1 and 2 have much better surface treatment properties.

Material No. Materials 5-13 are C and S
b, Ti, Zr, Nb, Si, Y, W, Mo,
Although at least one of Mn, Mg, Al, Cu and Ca was added within the specified range of components, it can be seen that a higher hardness was obtained as compared with other invention alloys. For these invention alloys, the material No. of the comparative material was used. 1
In the material No. 4, the content of C was less than the lower limit of the component specification of the present invention, and the required hardness was not obtained.

Material No. of the comparative material The material No. 15 has a C content exceeding the upper limit of the component specification 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 inferior.

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

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

Material No. of the comparative material The material No. 18 has an aspect ratio less than the lower limit specified in the present invention, does not have a required hardness, and has poor etching properties and surface treatment properties.

Material No. of the comparative material In the material No. 19, the aspect ratio exceeds the upper limit specified in the present invention, the hardness exceeds the specified in the present invention, and excellent workability is not obtained. As described above, the particle size, aspect ratio,
It can be seen that the hardness, the etching property and the surface treatment property are achieved only when the component specifications of the present invention are satisfied.

Example 2 Alloy No. 1 having a composition of Table 1 Tables 3 and 4 show cold rolling and annealing using hot rolled sheets corresponding to 1, 3 and 5 as materials.
Of the material No. 20 to 42 cold-rolled materials were produced. Material No. 20 to 25, 38, and 39 are alloy Nos. 1
Corresponding to the material No. 26 to 31, 40 are alloy N
o. 3 corresponding to material No. 3 32-37, 41,
42 is alloy No. 5 corresponds to FIG.

[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.

With respect to the test material thus manufactured,
The characteristic values were examined in the same manner 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 deviated 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 Nos. 38
The material has a cold rolling reduction less than the lower limit of the specified value of the present invention,
The aspect ratio is low, so that the hardness and etchability do not reach the required levels.

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

Further, the material No. Material No. 40 has a heating rate lower than the lower limit specified in the present invention, so that a recovery phenomenon occurs and the hardness does not reach the required value.

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

Further, the material No. In the material No. 42, the annealing temperature exceeded the upper limit specified in the present invention, and therefore, the hardness was less than the lower limit specified in the present invention, and good surface treatment properties were 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. having a component composition of Table 1 Using the hot rolled sheets corresponding to 1, 3, and 5 as materials, primary cold rolling, primary annealing, secondary cold rolling, and secondary annealing were performed under the conditions shown in Tables 7 and 8, and the material N
o. 43 to 68 cold-rolled materials were produced. Material No. 43 ~
47 and No. 47. Alloy Nos. 58 to 62 are alloy Nos. 1 corresponding to material No. 1 48-52 and No. 63 to 65 are alloy Nos. 3 corresponding to material No. 3 53-57 and No. Alloy Nos. 66 to 68 are alloy Nos. 5 corresponds to FIG.

[0060]

[Table 7]

[0061]

[Table 8]

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

With respect to the test material thus manufactured,
The characteristic values were examined in the same manner 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 deviated from the manufacturing conditions specified in the present invention. As is evident from Table 9, No. manufactured under the manufacturing conditions specified in the present invention. Materials 43 to 57 satisfy 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 Nos. 5
In the material of No. 8, the primary cold rolling ratio is less than the lower limit of the specified value of the present invention, the coarse-grained / mixed grain structure in hot rolling is not sufficiently eliminated, and the crystal grain size is the upper limit of the specified value of the present invention. Exceeds
The required etching properties have not been obtained.

The material No. Material 59 has a primary annealing temperature lower than the lower limit specified in the present invention, so that the material is not sufficiently recrystallized and good workability is not obtained.

No workability was obtained. The material N
o. In the material No. 60, the primary annealing temperature exceeded 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 has not been obtained.

The material No. The material of No. 61 has low hardness and poor etching and workability because the primary annealing time is less than the lower limit specified in the present invention.

The material No. Since the primary annealing time of the material No. 62 exceeds the upper limit specified in the present invention, the hardness is too high and the etching property and the surface treatment property are poor.

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

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

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

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

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

The material No. The material No. 67 has a rate of temperature rise in the secondary annealing below the lower limit specified in 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, it is also important to define the above manufacturing conditions in the present invention. Requirements. FIG.
FIG. 1A shows the relationship between the aspect ratio and the hardness, the C content and the crystal grain size as parameters, and FIG.
The graph of (b) shows the relationship between the aspect ratio and the etching factor, and the C content and the crystal grain size as parameters. From this graph, it can be seen that there is a good range of the workability in the combination of the aspect ratio and the hardness, and there is a good range of the etchability in the combination of the relationship between the aspect ratio and the etching factor.

[0079]

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

[Brief description of the 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 a concept of an etching factor.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Isamu Kamo 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (72) Inventor Makoto Yamada 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (72) Inventor Hiroshi Wakasa 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (56) References JP-A-6-158229 (JP, A) JP-A-3-197646 (JP) , A) JP-A-58-157949 (JP, A) WO 92/395 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C22C 38/00-38/60 C21D 8 / 02 C21D 9/46

Claims (5)

(57) [Claims] 1. Ni: 30 to 50% by weight, C: 0.
001 to 0.10%, Sb is 0.10% or less (including 0), the balance is substantially Fe, the aspect ratio of crystal grains is 1.3 to 50, and Vickers hardness is 200 to 2
80. A high-strength low-thermal-expansion alloy thin plate for electronic use, which is excellent in etching property and surface treatment property, characterized by being 80. 2. Ti, Zr, Nb, Si, Y, W, M
2. The etching property and the surface treatment property according to claim 1, wherein at least one of o, Mn, Mg, Al, Cu, and Ca is contained in an amount of 0.001 to 0.10% by weight. Excellent high strength 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 electronic use according to claim 2, which is excellent in etching properties and surface treatment properties. 4. The method according to claim 1, 2 or 3.
When the alloy thin plate having the component composition described in the above is manufactured through a process of cold rolling and annealing, the cold rolling rate is 25 to 95%.
And annealing 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 thin plate for electronic devices having excellent etching properties and surface treatment properties, wherein the method is performed at a temperature of at least C / sec. 5. The method according to claim 1, 2 or 3.
An alloy thin plate composed of the component composition described in 1 is firstly cold-rolled to 1
After the secondary annealing, the secondary cold-rolling and the secondary annealing are performed, and then, when manufacturing is performed, the primary cold-rolling rate is set to 50% or more,
The primary annealing is performed at an annealing temperature of 650 to 1000 ° C. and an annealing time of 0.
5 to 300 seconds, at a heating rate of 10 ° C./second or more, and at a secondary rolling reduction rate of 25 to 95%, secondary annealing at an annealing temperature of 300 to 650 ° C., and a heating rate of 10 ° C. A method for producing a high-strength low-thermal-expansion alloy thin plate for electronic use, which is excellent in etching properties and surface treatment properties, characterized by being applied at a rate of not less than / sec.