WO2013027437A1

WO2013027437A1 - Rolled copper foil

Info

Publication number: WO2013027437A1
Application number: PCT/JP2012/058848
Authority: WO
Inventors: 嘉一郎中室
Original assignee: Jx日鉱日石金属株式会社
Priority date: 2011-08-23
Filing date: 2012-04-02
Publication date: 2013-02-28
Also published as: KR101632515B1; JP5752536B2; JP2013060651A; CN103748251A; TW201309818A; TWI453290B; CN103748251B; KR20140037962A

Abstract

This rolled copper foil exhibits an I(311)/I(200) ratio of 0.001 to 0.01 after annealing at 200°C for 0.5 hour, wherein I(311) is the integrated intensity of an X-ray diffraction peak attributed to the (311) plane, and I(200) is the integrated intensity of an X-ray diffraction peak attributed to the (200) plane. The rolled copper foil ensures stable flexibility.

Description

Rolled copper foil

The present invention relates to a rolled copper foil used for, for example, a flexible printed circuit (FPC) and suitable for a copper-clad laminate.

A flexible wiring board (FPC) is formed by laminating a resin layer and a copper foil, and is suitably used for repeated bent portions. As a copper foil used for such FPC, a rolled copper foil excellent in flexibility is widely used. As a method for improving the flexibility of the rolled copper foil, a technique for developing a cubic texture after recrystallization annealing has been reported (Patent Document 1). In addition, as a method of developing a cube texture after recrystallization annealing, there are specified final rolling work degree and rolling conditions (Patent Document 2), and leaving a cube orientation after rolling (Patent Document 3). Yes.

Japanese Patent No. 3009383 JP 2009-185376 A JP 2010-150597 Gazette

However, the conventional method of developing a cube texture is to adjust the final rolling work degree, so that the thickness of the copper foil material during annealing before final rolling where the cube texture grows is changed according to the thickness of the final product. Further, it is necessary to perform rolling under special conditions, and there is a problem that productivity is lowered.
Even if the degree of development of the cube texture (X-ray diffraction intensity in the (200) direction on the copper foil surface) is about the same, the flexibility may be different. It is difficult to stably obtain an excellent rolled copper foil.

That is, the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a rolled copper foil that can stably obtain flexibility.

As a result of various studies, the present inventors have found that not only the (200) orientation of the copper foil but also crystal grains having the (420) orientation and the (311) orientation affect the flexibility. The crystal grains having the (420) orientation and the (311) orientation are less likely to cause slip deformation because the stress application direction and the slip direction are close to each other at the time of bending, so that the flexibility tends to be lowered.

That is, the rolled copper foil of the present invention has an integrated intensity I (200) of the X-ray diffraction peak of the (200) plane after annealing at 200 ° C for 0.5 hour, and an integrated intensity I (311) of the X-ray diffraction peak of the (311) plane. Ratio I (311) / I (200) is 0.001 or more and 0.01 or less.

Further, the rolled copper foil of the present invention has an integrated intensity I (200) of the X-ray diffraction peak of the wrinkle (200) plane after annealing at 200 ° C. for 0.5 hour and an integrated intensity I (420) of the X-ray diffraction peak of the wrinkle (420) plane. ) Ratio I (420) / I (200) is 0.005 or more and 0.02 or less.

Further, the rolled copper foil of the present invention has an integrated intensity I (200) of the (200) plane X-ray diffraction peak after annealing at 200 ° C. for 0.5 hour and an integrated intensity I (311 of the X-ray diffraction peak of the ridge (311) plane. ) And I (311) / I (200) is 0.001 or more and 0.01 or less, and the integrated intensity I (200) of the X-ray diffraction peak of the (200) plane after annealing at 200 ° C. for 0.5 hour and (420) The ratio I (420) / I (200) of the X-ray diffraction peak of the surface with the integrated intensity I (420) is 0.005 or more and 0.02 or less.

The rolled copper foil according to claim 1 or 3 is a ratio I (311) b between I (200) b and I (311) b which is an integrated intensity of an X-ray diffraction peak before final rolling and after recrystallization annealing. It is preferable that the copper foil material having b / I (200) b of 0.01 or more and 0.02 or less is finally rolled.

In the rolled copper foil according to claim 4, when the final rolling work degree is η and η = Ln {(thickness before final rolling) / (thickness after final rolling)}, η ≧ 2.3. preferable.
In the rolled copper foil according to claim 4 or 5, I (311) b / I (200) b / η is preferably 0.1 or more and 0.7 or less.
The rolled copper foil according to

claim

2 or 3, wherein the ratio I (200) b and I (420) b, which is the integrated intensity of the X-ray diffraction peak before final rolling and after recrystallization annealing, is calculated as I (420 ) Preferably, the copper foil material having b / I (200) b of 0.02 or more and 0.04 or less is finally rolled.
In the rolled copper foil according to claim 7, when the degree of final rolling work is η and η = Ln {(thickness before final rolling) / (thickness after final rolling)}, η ≧ 2.3. preferable.

In the rolled copper foil according to claim 7 or 8, when the final rolling degree is η and represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)}, I (420) b / I (200) b / η is preferably 0.5 or more and 1.2 or less.
The rolled copper foil according to claim 3 has a ratio I (311) b / I (200) b / I (311) b which is an integrated intensity of an X-ray diffraction peak before final rolling and after recrystallization annealing. I (200) b is 0.01 or more and 0.02 or less, and the ratio I of I (200) b and I (420) b is the integrated intensity of the X-ray diffraction peak before final rolling and after recrystallization annealing I It is preferable that the (420) b / I (200) b is finally rolled from a copper foil material having 0.02 or more and 0.04 or less.

The rolled copper foil according to claim 10, wherein the final rolling degree is η, and η ≧ Ln {(thickness before final rolling) / (thickness after final rolling)}}. Is preferred.
In the rolled copper foil according to claim 10 or 11, when the final rolling work degree is η, and expressed by η = Ln {(thickness before final rolling) / (thickness after final rolling)}, I (311) It is preferable that b / I (200) b / η is 0.1 or more and 0.7 or less and I (420) b / I (200) b / η is 0.5 or more and 1.2 or less.

According to the present invention, a rolled copper foil having excellent flexibility can be obtained stably.

It is a figure which shows the method of measuring a bending fatigue life with a bending test apparatus.

Hereinafter, the rolled copper foil according to the embodiment of the present invention will be described.

<Ingredient composition>
As the component composition of the copper foil, tough pitch copper (TPC) standardized to JIS-H3100 (C1100) or JIS-H3100 (C1020) oxygen-free copper (OFC) can be suitably used. The additive element may contain 10 to 500 ppm by mass of Sn and / or 10 to 500 ppm by mass of Ag, and the remainder may be tough pitch copper or oxygen-free copper.
Further, it contains 20 to 500 mass ppm in total of one or more elements consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V as additive elements, and the balance May be tough pitch copper or oxygen-free copper.
In addition, since the rolled copper foil used for FPC is required to be flexible, the thickness of the rolled copper foil is preferably 20 μm or less.

<Rolled copper foil according to the first aspect>
The rolled copper foil according to the first aspect of the present invention has an integrated intensity I (200) of the (200) plane X-ray diffraction peak and an integration of the (311) plane X-ray diffraction peak after annealing at 200 ° C. for 0.5 hour. The ratio I (311) / I (200) with the intensity I (311) is 0.001 or more and 0.01 or less. When the rolled copper foil is annealed at 200 ° C. for 0.5 hour, a recrystallized structure is generated, and a cubic texture is developed to improve the flexibility of the rolled copper foil. On the other hand, crystal grains having the (420) orientation and the (311) orientation after recrystallization are unlikely to cause slip deformation because the stress application direction and the slip direction are close at the time of bending, so that the flexibility tends to be lowered.

For this reason, if the ratio of the (311) orientation is small compared to the (200) orientation, the flexibility is improved, so the ratio I (311) / I (200) is set to 0.01 or less. When the ratio I (311) / I (200) exceeds 0.01, the ratio of the (311) orientation increases and the flexibility is lowered. The lower the ratio I (311) / I (200), the higher the flexibility and the better.

Further, the rolled copper foil according to the first aspect is a copper foil material having a ratio I (311) b / I (200) b of 0.01 or more and 0.02 or less before final rolling and after recrystallization annealing, η = It can be manufactured by final rolling at a working degree of 2.3 or more.
Here, the (420) orientation and (311) orientation after recrystallization annealing of the copper foil originate from the crystal grains having the (420) orientation and (311) orientation present in the rolled structure before recrystallization annealing. It is thought that it will develop as. Further, the (420) orientation and (311) orientation in the rolled structure are considered to be derived from the structure before rolling. That is, before the final rolling and after recrystallization annealing, by controlling the degree of development of the (420) orientation and (311) orientation, the (420) orientation and (311) after recrystallization annealing of the foil after final rolling. ) Direction can be controlled.
For this reason, if the ratio I (311) b / I (200) b after recrystallization annealing exceeds 0.02 before final rolling, many grains with (311) orientation remain after final rolling. However, since the proportion of crystal grains having the (311) orientation increases, sufficient flexibility may not be obtained. On the other hand, if the ratio I (311) b / I (200) b is less than 0.01, the crystal grains are coarsened by annealing, so that sufficient strain cannot be applied in the final rolling, and the foil after the final rolling In some cases, sufficient flexibility cannot be obtained after recrystallization annealing.
When the final rolling degree is less than η = 2.3, sufficient strain cannot be applied in final rolling, and sufficient flexibility may not be obtained after recrystallization annealing of the foil after final rolling. .

In the rolled copper foil according to the first aspect, I (311) b / I (200) b / η is preferably 0.1 or more and 0.7 or less. Further, I (311) b / I (200) b / η is more preferably 0.1 or more and 0.5 or less.
In general, in the copper foil manufacturing process, since the degree of work of the final rolling process is high, even if the structure before the final rolling is controlled, the effect tends not to remain sufficiently until after the rolling. Thus, by managing both the structure before final rolling and the degree of processing of final rolling, further sufficient flexibility can be obtained.
When I (311) b / I (200) b / η exceeds 0.5, many grains with (311) orientation remain after the final rolling, and the proportion of crystal grains with (311) orientation increases. In some cases, sufficient flexibility cannot be obtained. The lower the ratio I (311) b / I (200) b / η, the higher the flexibility and the better, but practically a value of 0.05 or more.

<Rolled copper foil according to the second aspect>
The rolled copper foil according to the second aspect of the present invention has an integrated intensity I (200) of the (200) plane X-ray diffraction peak and an integration of the (420) plane X-ray diffraction peak after annealing at 200 ° C. for 0.5 hour. The ratio I (420) / I (200) with the strength I (420) is 0.005 or more and 0.02 or less.
As described above, crystal grains having the (420) orientation and the (311) orientation after recrystallization are less likely to cause slip deformation because the stress application direction and the slip direction are close to each other during bending, and thus tend to lower the flexibility. That is, if the ratio of the (420) azimuth is smaller than the (200) azimuth, the flexibility is improved, so the ratio I (420) / I (200) is set to 0.02 or less. When the ratio I (420) / I (200) exceeds 0.02, the ratio of the (420) orientation increases and the flexibility is lowered. However, if the ratio I (420) / I (200) is less than 0.005, the ratio of the (200) orientation will be too large and sufficient flexibility will be obtained, but the copper foil will be too soft and handling will be reduced. To do.

The rolled copper foil according to the second aspect is preferably a copper foil material having a ratio I (420) b / I (200) b of 0.02 or more and 0.04 or less before final rolling and after recrystallization annealing. It can be manufactured by final rolling at a workability of η = 2.3 or more.
If the ratio I (420) b / I (200) b after final rolling and after recrystallization annealing exceeds 0.04, many grains with (420) orientation remain even after final rolling, and (420) orientation Since the ratio of crystal grains having a large number is increased, sufficient flexibility may not be obtained. On the other hand, if the ratio I (420) b / I (200) b is less than 0.02, the crystal grains become coarse due to annealing, so that sufficient strain cannot be applied in the final rolling, and the foil after the final rolling In some cases, sufficient flexibility cannot be obtained after recrystallization annealing.

In the rolled copper foil according to the second aspect, I (420) b / I (200) b / η is preferably 0.5 or more and 1.2 or less. Further, I (420) b / I (200) b / η is more preferably 0.5 or more and 1.0 or less.
Here, the crystal grains having the (420) orientation, which is a recrystallized structure, are rotated by rolling to become crystal grains having a different orientation. Therefore, when the rolling degree is high, the ratio of the (420) plane decreases and I (420) decreases. On the other hand, when the degree of processing is low, crystal grains having the (420) orientation tend to remain, and I (420) tends to increase.
For this reason, when I (420) b / I (200) b / η exceeds 1.0, many grains with (420) orientation remain after the final rolling, and grains with (420) orientation remain. In some cases, sufficient flexibility cannot be obtained. Further, if I (420) b / I (200) b / η is less than 0.5, sufficient flexibility can be obtained, but the handling property may be deteriorated because the copper foil is too soft.

<Manufacture of rolled copper foil>
The rolled copper foil according to the first and second embodiments can be manufactured by hot rolling an ingot, pre-annealing rolling, recrystallization annealing, and final rolling. Here, the stability of the recrystallization orientation is in the order of (200)>(311)> (420), and the higher the rate of temperature rise during recrystallization annealing, the more unstable (420) orientation and (311 ) The direction tends to increase. Accordingly, it is preferable to set the rate of temperature increase during recrystallization annealing to 5 to 50 ° C./s and to make the rate slower than before.
Further, it is preferable that the degree of processing is η = 1.6 or more of rolling before annealing, and the crystal grain size after recrystallization annealing and before final rolling is 10 μm or more and 30 μm or less. In the case of an annealing condition in which the crystal grain size before final rolling is 10 μm or less, there is a high possibility that an unrecrystallized structure remains. Also, if the crystal grain size before final rolling exceeds 30 μm, sufficient strain cannot be applied in final rolling, and sufficient flexibility cannot be obtained after recrystallization annealing of the foil after final rolling. is there.
Further, as described above, the final rolling may be performed with a workability of η = 2.3 or more.
The crystal grain size is measured by the cutting method of JIS H0501.

First, a copper ingot having the composition shown in Table 1 was manufactured and hot-rolled to a thickness of 10 mm. Then, annealing and rolling were repeated, and after rolling to a predetermined thickness, it was passed through a continuous annealing furnace at 750 ° C. and recrystallized and annealed. Furthermore, the final cold rolling was carried out at the workability shown in Table 1 to obtain a copper foil having the thickness shown in Table 1. Table 1 shows the rate of temperature increase during recrystallization annealing.

<Orientation degree>
After the copper foil obtained by final rolling was recrystallized by annealing at 200 ° C. for 0.5 hour, the strengths of the (200) plane, (311) plane, and (420) plane were determined by X-ray diffraction of the rolled plane. Each integral value (I) was determined.
Further, the integrated intensities of the X-ray diffraction peaks of the (200) plane, (311) plane, and (420) plane before final rolling and after recrystallization annealing were determined, respectively. This value is represented by the subscript “b” as in I (200) b.

<Flexibility>
After the copper foil sample obtained by final rolling was recrystallized by heating at 200 ° C. for 30 minutes, the bending fatigue life was measured with the bending test apparatus shown in FIG. This apparatus has a structure in which a vibration transmitting member 3 is coupled to an oscillation driver 4, and a copper foil 1 to be tested is fixed to the apparatus at a total of four points including a screw 2 part indicated by an arrow and a tip part of 3. Is done. When the vibration part 3 is driven up and down, the intermediate part of the copper foil 1 is bent into a hairpin shape with a predetermined radius of curvature r. In this test, the number of times until breakage when bending was repeated under the following conditions was determined.
The test conditions are as follows: Specimen width: 12.7 mm, Specimen length: 200 mm, Specimen sampling direction: Collected so that the length direction of the specimen is parallel to the rolling direction, curvature radius r : 1.5 mm, vibration stroke: 20 mm, vibration speed: 1000 times / min.
Further, the flexibility was evaluated according to the following criteria. If evaluation is (double-circle), (circle), or (triangle | delta), flexibility is favorable.
◎: The number of bendings is 200,000 times or more and the flexibility is the best. ○: The number of bendings is 100,000 or more and less than 200,000 times, and the flexibility is good. △: The number of bendings is 50,000 or more and less than 100,000. , Excellent flexibility ×: less than 50,000 times of bending, poor flexibility

The obtained results are shown in Tables 1 and 2.
Here, “TPC” in the composition column of Table 1 represents tough pitch copper (TPC) standardized to JIS-H3100 (C1100), and “OFC” represents oxygen-free copper (OFC) standardized to JIS-H3100 (C1020). Represents. Therefore, for example, “190 ppm Ag-TPC” in the composition column of Table 1 means a composition in which 190 mass ppm of Ag is added to tough pitch copper (TPC) specified in JIS-H3100 (C1100). In addition, “100 ppm Sn—OFC” in the composition column of Table 1 means a composition in which 100 mass ppm of Sn is added to oxygen-free copper (OFC) specified in JIS-H3100 (C1020).

As is clear from Table 1, in each example where I (311) / I (200) is 0.001 or more and 0.01 or less, or (420) / I (200) is 0.005 or more and 0.02 or less, the flexibility is excellent. It became a thing. In particular, in the case of Examples 1 to 12 and 15 to 21 in which I (311) / I (200) is 0.001 or more and 0.01 or less and I (420) / I (200) is 0.005 or more and 0.02 or less, Example 13 , 14, the flexibility was further improved.

On the other hand, in Comparative Examples 1 to 3 in which I (311) / I (200) exceeded 0.01 and I (420) / I (200) exceeded 0.02, the flexibility was inferior.

As is clear from Table 2, in each example, I (311) b / I (200) b is 0.01 or more and 0.02 or less, or I (311) b / I (200) b / η is 0.1. Above 0.7. In each example, I (420) b / I (200) b was 0.02 or more and 0.04 or less, or I (420) b / I (200) b / η was 0.5 or more and 1.2 or less. In particular, in Examples 1 to 12 and 15 to 21, I (311) / I (200) is 0.001 or more and 0.01 or less and I (420) / I (200) is 0.005 or more and 0.02 or less. outstanding.
On the other hand, in Comparative Examples 1 to 3, I (311) b / I (200) b exceeded 0.02 and I (311) b / I (200) b / η exceeded 0.7. Similarly, in Comparative Examples 1 to 3, I (420) b / I (200) b exceeded 0.04 and I (420) b / I (200) b / η exceeded 1.2.

Claims

Ratio I (311) / I of the integrated intensity I (200) of the (200) plane X-ray diffraction peak after annealing at 200 ° C for 0.5 hour and the integrated intensity I (311) of the X-ray diffraction peak of the (311) plane A rolled copper foil having (200) of 0.001 or more and 0.01 or less.
Ratio I (420) / I of the integrated intensity I (200) of the (200) plane X-ray diffraction peak after annealing at 200 ° C for 0.5 hour and the integrated intensity I (420) of the X-ray diffraction peak of the (420) plane A rolled copper foil having (200) of 0.005 or more and 0.02 or less.
Ratio I (311) / I of integrated intensity I (200) of X-ray diffraction peak of (200) plane after annealing at 200 ° C for 0.5 hour and integrated intensity I (311) of X-ray diffraction peak of ピーク (311) plane (200) is 0.001 or more and 0.01 or less, and the integrated intensity I (200) of the X-ray diffraction peak of the (200) plane after annealing at 200 ° C. for 0.5 hour, and the integrated intensity I of the X-ray diffraction peak of the (420) plane A rolled copper foil having a ratio I (420) / I (200) to (420) of 0.005 or more and 0.02 or less.
The ratio I (311) b / I (200) b of the integrated intensity of the X-ray diffraction peak before re-rolling and after recrystallization annealing is between 0.01 and 0.02 The rolled copper foil according to claim 1 or 3, wherein the rolled copper foil material is finally rolled.
The rolled copper foil according to claim 4, wherein η ≧ 2.3 when represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)} where η is the final rolling degree.
The rolled copper foil according to claim 4 or 5, wherein I (311) b / I (200) b / η is 0.1 or more and 0.7 or less.
The ratio of I (200) b and I (420) b, which is the integrated intensity of the X-ray diffraction peak before final rolling and after recrystallization annealing, is I2 (420) b / I (200) b 0.02 or more and 0.04 or less The rolled copper foil according to claim 2 or 3, wherein the rolled copper foil material is finally rolled.
The rolled copper foil according to claim 7, wherein η ≧ 2.3 when represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)} where η is a final rolling degree.
When the final rolling degree is η, and represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)},
The rolled copper foil according to claim 7 or 8, wherein I (420) b / I (200) b / η is 0.5 or more and 1.2 or less.
The ratio I (311) b / I (200) b of the integrated intensity of the X-ray diffraction peak before re-rolling and after recrystallization annealing is between 0.01 and 0.02 The ratio of I (200) b and I (420) b, which is the integrated intensity of the X-ray diffraction peak before final rolling and after recrystallization annealing, is I (420) b / I (200) b The rolled copper foil according to claim 3, obtained by final rolling a copper foil material having a thickness of 0.02 to 0.04.
11. The rolled copper foil according to claim 10, wherein η ≧ 2.3 when represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)} where η is a final rolling work degree.
When the final rolling degree is η, and represented by η = Ln {(thickness before final rolling) / (thickness after final rolling)},
The I (311) b / I (200) b / η is 0.1 or more and 0.7 or less, and the I (420) b / I (200) b / η is 0.5 or more and 1.2 or less. Rolled copper foil.