JP5124039B2 - Copper foil and copper-clad laminate using the same - Google Patents

Description

  The present invention relates to a copper foil used for, for example, a flexible printed circuit (FPC) and a copper clad laminate in which the copper foil is laminated on at least one surface of a resin layer.

As a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed circuit (FPC) or a chip of flexible circuit (COF) is used. The FPC and COF are formed by using a copper clad laminate (CCL) in which a copper foil is laminated on one side or both sides of a resin layer and forming a circuit pattern on the copper foil.
In order to reduce the size and increase the functionality of such an electronic device, a method is adopted in which the FPC is folded and accommodated in a narrow space inside the case. For example, in the case of a COF used around a liquid crystal display, the copper wiring of the COF is folded back to the back side of the liquid crystal substrate in order to make the bezel (so-called “frame”) thin.

However, when FPC or COF is folded, there is a problem that a large deformation load is applied to the copper foil portion and it is easy to break.
Thus, it has been reported that an FPC in which the wiring pattern is not easily broken can be obtained by forming the FPC from an electrolytic copper foil containing columnar copper crystal particles and having an elongation of 5% or more at 25 ° C. (Patent Document 1). ).

JP 2007-335541 A

Conventionally, it has been considered that the bendability of a copper foil of CCL has a correlation with the elongation of the copper foil. Therefore, as described in Patent Document 1, an electrolytic copper foil having a large elongation is used.
However, the present inventors have found that even when a rolled copper foil having a large elongation is used, the bendability of CCL may not be improved.
That is, the present invention has been made to solve the above-described problems, and an object thereof is to provide a copper foil excellent in bendability when used in a copper-clad laminate and a copper-clad laminate using the same. .

As a result of various studies, the present inventors have found that work hardening index (n value) is important as a factor for improving the bendability of CCL, not the elongation of copper foil.
In order to achieve the above object, the copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and annealed at 350 ° C. for 0.5 hour. The later work hardening index is 0.3 or more and 0.45 or less, and oxygen-free copper or tough pitch copper is selected from the group of In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V It contains 20 to 500 mass ppm in total of one or more elements .
The copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3. 2 or more elements selected from the group consisting of Ag , In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper. In a total of 20 to 500 ppm by mass.
The copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3. 2 or more elements selected from the group consisting of Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper In a total of 20 to 500 ppm by mass.
The copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3. It is 0.45 or less, and oxygen-free copper or tough pitch copper is selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. Of 20 to 500 mass ppm in total.

The semi-softening temperature of the copper foil of the present invention is preferably 150 ° C. or lower.
When the total thickness of the resin layers laminated on one side of the copper foil is 50 μm or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil It is preferable that the number of times of bending until rupture is 4 or more.
It is preferable that the total degree of work at the time of the final cold rolling is 85% or more and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions.

  It is preferable that the total degree of work at the time of the final cold rolling is 85% or more and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions. However, the oil film equivalent of the last two passes; 25000 or less, the oil film equivalent of the previous one of the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less. Here, after manufacturing the copper foil through cold rolling after hot rolling the ingot, cold rolling and annealing are alternately performed in the cold rolling. The last cold rolling performed after the last annealing is referred to as “final cold rolling”.

  The copper clad laminate of the present invention is formed by laminating the copper foil on at least one surface of the resin layer.

  According to the present invention, a copper foil excellent in bendability when used in a copper clad laminate can be obtained.

It is a figure which shows the method of the sliding bending by an IPC sliding bending apparatus.

Hereinafter, the copper foil which concerns on embodiment of this invention is demonstrated. In the present invention, “%” means “% by mass” unless otherwise specified.
The copper foil according to the embodiment of the present invention has a thickness of 5 to 30 μm, integrated intensity I (200) of (200) diffraction peak by X-ray diffraction after annealing at 350 ° C. for 0.5 hour, and integration of I (220) diffraction peak. The ratio I (220) / I (200), which is the ratio to the strength, is 0.11 or less, and the work hardening index after annealing at 350 ° C. for 0.5 hours is 0.3 or more and 0.45 or less.

<Work hardening index (n value)>
The work hardening index (n value) is represented by an index n when the relationship between stress and strain in the plastic deformation region above the yield point is approximated by the following formula 1 (Hollomon formula).
[True stress] = [material constant] × [true strain] ⁿ (1)
As the work hardening index is larger, local deformation is less likely to occur and is less likely to break when deformed. In addition, a material having a high work hardening index is excellent in drawing workability and suitable for press working. And when copper foil is laminated on at least one side of the resin layer to produce a copper clad laminate, and the bendability of this copper clad laminate is evaluated, the copper foil having a work hardening index of 0.3 or more is not locally deformed. It is unlikely that the copper foil will break, because the entire bent part is deformed. However, a material having a work hardening index exceeding 0.45 is not suitable for a copper clad laminate because the strength after annealing is low and the handleability deteriorates.

  Here, the reason why the work hardening index after annealing at 350 ° C. for 0.5 hour is defined is that the heating conditions for producing the copper clad laminate are about this level. In addition, when the resin layer of a copper clad laminated board is obtained by applying and curing a resin composition on a copper foil (in the case of a two-layer CCL in which no adhesive layer is interposed between the resin layer and the copper foil), the above heating conditions Thus, the resin is cured.

The reason why the work hardening index (n value) is important as a factor for improving the bendability of the copper foil, not the elongation of the copper foil, is considered as follows.
First, the work hardening index is one of the values indicating the work hardening behavior of a material. The larger this value, the easier the material is to work harden. Here, when the material is subjected to tensile deformation, the material is locally constricted and fractured. However, in a material having a large work hardening coefficient, the constricted portion is work hardened and the constricted portion is hardly deformed. Therefore, instead of the constricted portion that is difficult to deform, the other portions begin to deform. By repeating this, the entire material is uniformly deformed. On the other hand, since the elongation is an index captured macroscopically without considering such a situation, even if the elongation is large, the work hardening index is not always large.

  Conventionally, as an index of the ease of uniform deformation of the entire material, there is an example where work hardening index is used in drawing of a thick material, but thin material such as copper foil is drawn. In the past, no work hardening index was used as an index. In the present invention, it was considered that if the work hardening index of the copper foil is increased, even in the 180 degree close contact bending of the CCL, the entire bent portion is uniformly deformed and does not break.

  Furthermore, the work hardening index after annealing at 200 ° C. for 0.5 hour is also preferably 0.3 or more and 0.45 or less. This is because a laminating temperature at the time of producing a three-layer CCL in which a film is used as a resin layer and a film and a copper foil are laminated via an adhesive layer is about 200 ° C. Since the work hardening index increases when the copper foil is recrystallized by heating, if the work hardening index is 0.3 or more at 200 ° C. lower than 350 ° C., a work hardening index of 0.3 or more can be obtained even at 350 ° C. Further, in order to obtain a recrystallized structure sufficiently by the annealing, the semi-softening temperature of the copper foil is preferably 150 ° C. or less.

(Thickness)
Conventionally, there is an example in which a work hardening index, which is an index of the ease of uniform deformation of the entire material, is used in drawing a thick material such as a structural member, but it is as thin as a copper foil. Since the material is not subjected to processing such as drawing, the work hardening index was not used as an index.
For this reason, the thickness of the rolled copper foil of the present invention is specified to be 5 to 30 μm.

  Also, when the copper foil thickness is relatively thin, 5-30 μm, the ratio of crystal grains facing the material surface increases, so dislocations introduced by deformation do not accumulate at the crystal grain boundaries and are released from the material surface. The ratio becomes higher. For this reason, the work hardening index of copper foil becomes low compared with a comparatively thick material. On the other hand, the work hardening index is determined by the amount of dislocations introduced into the material by deformation and the ease of movement of dislocations. That is, the work hardening index increases if there are precipitates that can cause dislocation loops, solid solution elements that hinder the movement of dislocations, and grain boundaries. However, the addition of a solid solution element that greatly hinders the movement of dislocations or an alloy element that can generate precipitates causes a decrease in conductivity, and thus is not preferable as a copper foil for flexible wiring boards.

(composition)
The copper foil of the present invention preferably has a composition of tough pitch copper standardized to JIS-H3100 alloy number C1100 or oxygen-free copper standardized to alloy number C1020 of JIS-H3100. When the composition is close to that of the pure copper described above, the conductivity of the copper foil does not decrease and is suitable for FPC and COF. The oxygen concentration contained in the rolled copper foil is 0.01 to 0.05% by mass in the case of tough pitch copper, and 0.001% by mass or less in the case of oxygen-free copper.
Moreover, the oxygen-free copper which standardizes to the alloy number C1011 of JIS-H3510 can also be used as oxygen-free copper.
Furthermore, you may contain 1 or more types chosen from the group of Ag and Sn in total 500 mass ppm or less. When Ag or Sn is added to the rolled copper foil, the movement of dislocation is hindered, so that the work hardening coefficient is increased. When the total amount of Ag or Sn added to the rolled copper foil exceeds 500 ppm by mass, the electrical conductivity decreases and the recrystallization temperature increases, and recrystallization annealing may be performed while suppressing surface oxidation of the copper foil in the final annealing. It can be difficult. In addition, although the minimum in particular of the total addition amount of Ag and Sn is not prescribed | regulated, Usually, it is 20 mass ppm or more in total.
In addition, one or more elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V are added to the tough pitch copper or the oxygen-free copper. You may contain 20-500 mass ppm in total.

As a method of managing the work hardening index of copper foil after annealing at 350 ° C for 0.5 hour to 0.3 or more, the total work degree during final cold rolling should be 85% or more, and the oil film in the final three passes in final cold rolling Adjusting the equivalent weight can be mentioned. Specifically, the oil film equivalent of the last two passes in the final cold rolling: 25000 or less, the oil film equivalent of the one before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less.
Since the oil film equivalent tends to increase as the material thickness decreases, the oil film equivalent value in the final three passes gradually increases. Therefore, it is necessary to set an appropriate oil film equivalent for the final three passes having different thicknesses.
If the rolling oil viscosity and the material yield stress are equal in all passes in the final cold rolling, the oil film equivalent is proportional to (rolling speed) / (engagement angle). If the degree of processing is the same, the biting angle decreases as the material thickness decreases, and therefore the oil film equivalent tends to increase as it approaches the final pass. In order to maintain productivity, it is necessary to increase the rolling speed as the material passes closer to the final pass, and the oil film equivalent tends to increase as the material approaches the final pass.

If the oil film equivalent in the intermediate pass in the final cold rolling is large, the work hardening index cannot be increased to 0.3 or more even if the oil film equivalent is kept low in the final pass. For this reason, the oil film equivalent in the final three passes in the final cold rolling is managed.
In order to reduce the oil film equivalent, the rolling degree of the final pass should be 25% or more.

The oil film equivalent is represented by the following formula. (Oil film equivalent) = {(rolling oil viscosity, kinematic viscosity at 40 ° C .; cSt) × (rolling speed; m / min)} / {(yield stress of material; kg / mm ² ) × (roll biting angle; rad )}
Rolling oil viscosity about 4.0～8.0CSt, rolling speed 200～600M / min, bite angle of roll can be a 0.001~0.04rad For example.

<I (220) / I (200)>
In the copper foil of the present invention, I (220) / I (200) is 0.11 or less. The pure copper-type recrystallized texture is characterized in that the (200) plane faces in the direction of the copper foil surface. At this time, the (200) plane also faces in the rolling parallel direction and the direction perpendicular to the rolling. In general, when bending a copper foil, the bending axis is taken in the direction parallel to the rolling or the direction perpendicular to the rolling. A high work hardening index can be obtained. On the other hand, when the crystal orientation other than the (200) plane is dominant, sufficient multiple slip does not occur and a high work hardening index cannot be obtained. For the above reasons, the more crystals having the {001} orientation with respect to the bending axis, the better the copper foil becomes.
Here, since the recrystallized texture of the pure copper type has the {001} direction in each of the ND direction (rolling surface normal direction), RD direction, and TD direction, the RD direction and TD direction which are bending directions are Alternatively, the (200) plane diffraction intensity in the ND direction, which can be easily measured, can be used as an index.
In addition, the copper foil of this invention makes I (220) / I (200) after the process (annealing at 350 degreeC for 0.5 hour) equivalent to the heat processing equivalent at the time of CCL formation 0.11 or less. The annealing atmosphere is preferably a non-oxidizing atmosphere in order to prevent surface oxidation.

Moreover, since it is necessary to obtain a recrystallized structure sufficiently by annealing for the following reasons, the semi-softening temperature of the copper foil is preferably set to 150 ° C. or lower. In order to sufficiently obtain a recrystallized structure, it is necessary to adjust the composition and processing degree of the copper foil and appropriately control the recrystallization temperature, but if the copper foil composition and the processing degree are defined in the above range, The recrystallization temperature is about 120 to 150 ° C., and the semi-softening temperature can be 150 ° C. or less.
Here, the non-recrystallized structure has a work strain remaining, and since it has already been work hardened, it is difficult to work harden by bending deformation, the work hardening index becomes small, and the bendability deteriorates. In order to increase the work hardening index, it is necessary that the state in which the copper foil is laminated on the CCL is a state in which the work hardening is not performed, that is, a state in which the work strain is removed. In other words, the copper foil undergoes a heat treatment in the CCL manufacturing process, but the strain is removed by the heat treatment, and it is necessary to recrystallize. And if the semi-softening temperature of copper foil is 150 degrees C or less, recrystallization of copper foil can be anticipated also by the heat processing received to a CCL manufacturing process, and a work hardening index | exponent can be enlarged.

Furthermore, the total thickness of the resin layers laminated on one side of the copper foil according to the embodiment of the present invention is 50 μm or less, and a sample having a width of 3 mm or more and 5 mm or less is used, and 180 ° adhesion bending is performed with the exposed surface of the copper foil as the outside In this case, the number of times of bending until the copper foil breaks is preferably 4 times or more.
A sample having a total thickness of 50 μm or less, in which a resin layer is laminated on one side of a copper foil, imitates a copper-clad laminate, and the number of bends of 180-degree contact bending evaluated the bendability of the copper-clad laminate. It will be.
As the resin layer, polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; thermoplastic resin such as saturated polyester resin can be used, but is not limited thereto. In addition, varnish (for example, polyamic acid solution of polyimide precursor) in which the components of these resin layers are dissolved in a solvent is applied to one side of a copper foil, and the solvent is removed by heating to react (for example, imidization reaction). May be allowed to proceed and cured.

  180 degree contact bending is performed by folding the sample so that the crease is parallel to its own width direction, and crushing and stacking with a hand press. And the presence or absence of a fracture | rupture of the copper foil part of the cross section of a bending part is observed with an optical microscope. If there is no break, the sample after close contact bending is opened, stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of times of bending until the copper foil breaks is determined.

  The copper clad laminate of the present invention is formed by laminating the above copper foil on at least one surface of the resin layer. Since the copper foil which concerns on embodiment of this invention is excellent in bendability, the copper clad laminated board using this is also excellent in bendability. For example, the copper-clad laminate of the present invention can be suitably used for applications that bend 90 to 180 degrees with a radius of 5 mm or less.

  Oxygen-free copper (JIS H0500) or tough pitch copper (JIS H0500) was dissolved, and the elements shown in Tables 1 and 2 were added and cast as necessary to produce ingots having a thickness of 20 mm and a width of 60 mm. After hot rolling the ingot to a thickness of 10 mm, cold rolling and annealing were repeated as appropriate to produce a copper foil. In order to adjust the softening temperature, use a roll with a smooth surface (Ra ≦ 0.1μm in the roll axis direction) in order to reduce the surface roughness to a total workability of 85% or more during final cold rolling. Final cold rolling was performed to produce a copper foil. The rolling oil viscosity is set to about 4.0 to 8.0 cSt, the rolling speed is adjusted to 200 to 600 m / min, and the roll biting angle is 0.003 to 0.03 rad, and the oil film equivalent in the final three passes in the final cold rolling is 35,000 for all. The oil film equivalent before the final pass; 25000 or less, the oil film equivalent before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less.

<Work hardening index>
The obtained copper foils were annealed at 200 ° C. for 0.5 hours and 350 ° C. for 0.5 hours, respectively, and then subjected to a tensile test (based on JIS-Z2241) to obtain a work hardening index. Note that the work hardening index needs to be obtained using the uniform elongation and stress after the material yields, so the value from the elongation of 2% to the maximum stress point was used. Then, a logarithmic graph of true strain and true stress obtained from the measured elongation and stress was approximated by the method of least squares, and a work hardening index was obtained from the slope of the graph. True strain and true stress were determined by the following formulas.
[True strain] ＝ ln (1+ [Strain])
[True stress] = (1+ [true strain]) x [stress]
The elongation at break was also determined by this tensile test. Accordingly, the elongation at break in Tables 1 and 2 is a value after annealing at 350 ° C. × 0.5 hours.

<Semi-softening temperature>
The obtained copper foil was annealed in a non-oxidizing atmosphere at 100 to 400 ° C. for 0.5 hour, respectively, and then a tensile test was performed to determine the strength (tensile strength) against the heat treatment conditions. The annealing temperature at which the strength after annealing was an intermediate value between the strength after rolling (before annealing) and the strength after being completely softened (annealed at 300 ° C. for 30 minutes) was defined as the semi-softening temperature.

<Number of bending of copper clad laminate>
Next, a polyimide layer having a thickness of about 20 μm was formed on one side of the obtained copper foil by a casting method to produce a single-sided CCL. Specifically, one side of the obtained copper foil was chemically treated (plated), and a polyimide resin precursor varnish (U-Vanice A-U Varnish A) was applied to this side so as to have a thickness of 20 μm. After that, it is dried for 30 minutes in a hot air circulation high temperature bath set at 130 ° C., and heated up to 350 ° C. over 2000 seconds and cured (imidized) to form a resin layer (polyimide layer). Single-sided CCL was prepared.
180 degree contact bending was performed according to the following procedure. First, this single-sided CCL is 3.2 mm wide, 30 mm long, cut out so that the length direction of the test piece is parallel to the rolling direction, and made into a test piece, looped with the resin layer side inside, and crushed with a hand press 180 degree close contact bending was performed. And the presence or absence of the fracture | rupture of the copper foil part of the cross section of a bending part was observed with the optical microscope. If there was no break, the sample after close contact bending was opened and stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of bendings until the copper foil broke was determined.

<Number of sliding and bending of copper foil>
Next, the obtained copper foil was cut out to have a width of 12.7 mm and a length of 200 mm so that the length direction of the test piece was parallel to the rolling direction, and it was recrystallized by heating at 200 ° C. for 30 minutes. I let you. This was measured for the number of IPC sliding bends using an IPC (American Printed Circuit Industry Association) slide bending apparatus shown in FIG. This apparatus has a structure in which a vibration transmission member 3 is coupled to an oscillation driver 4, and the test piece 1 is fixed to the apparatus at a total of four points including a screw 2 portion and an end portion 3 indicated by arrows. . When the vibration part 3 is driven up and down, the intermediate part of the test piece 1 is bent into a hairpin shape with a predetermined radius of curvature r. In this test, the number of times to break when bending was repeated under the following conditions was obtained.
The test was performed under the conditions of a radius of curvature r: 2.5 mm, a vibration stroke: 25 mm, and a vibration speed: 1500 times / minute. However, in Example 17, the radius of curvature r was 0.9 mm. This is because the amount of strain applied to the copper foil at the time of bending is made equal to that of another example thicker than Example 17.

<I (220) / I (200)>
The obtained copper foil was annealed in a non-oxidizing atmosphere at 350 ° C. for 0.5 hour, and then X-ray diffraction was performed on the rolled surface, and the integrated values of diffraction peak intensities on the (220) plane and (200) plane, respectively ( I).

The obtained results are shown in Tables 1 and 2. In the compositions of Tables 1 and 2, OFC and TPC indicate oxygen-free copper and tough pitch copper (JIS H3100), respectively, and Ag100 ppm TPC indicates that 100 mass ppm of Ag is added to tough pitch copper.
The oxygen-free copper specified in JIS H3100 and the oxygen-free copper specified in JIS H0500 are both the same in alloy number C1020. Moreover, the tough pitch copper specified in JIS H3100 and the tough pitch copper specified in JIS H0500 are both the same in alloy number C1100.

As is clear from Tables 1 and 2, in the case of Examples 1 to 20 where I (220) / I (200) is 0.11 or less and the work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more, 180 The number of times of bending when performing close contact bending was 4 times or more, and the bending property was excellent.
On the other hand, in Comparative Examples 3, 5, 6, and 7 in which the total degree of work during the final cold rolling was less than 85%, the work hardening index after annealing at 350 ° C. for 0.5 hours was less than 0.3, and the 180 degree adhesive bending was performed. The number of bendings performed was less than 4 and the bendability deteriorated. In addition, in the case of the comparative example 1, since the addition amount of Sn in copper foil exceeded 500 mass ppm, it is thought that the semisoftening temperature exceeded 150 degreeC and the work hardening index became less than 0.3.
In Comparative Examples 1, 6, and 7 where the semi-softening temperature exceeded 150 ° C, the work hardening index after annealing at 350 ° C for 0.5 hour was less than 0.3, and the number of bendings when the 180 ° contact bending was performed was 4 times. As a result, the bendability deteriorated.

As the oil film equivalent in the final three passes in the final cold rolling, the oil film equivalent in the last two passes; over 25000, the oil film equivalent in the previous one in the final pass; over 30000, the oil film equivalent in the final pass; 35000 In the case of the comparative example 2 that exceeded, the number of bendings when the 180-degree contact bending was performed was less than 4, and the bendability deteriorated.
In the case of Comparative Example 4 in which the oil film equivalent of the last three passes in the final cold rolling exceeds 25000, the number of times of bending when 180 degree contact bending is performed is less than four times. The bendability deteriorated.

  In the case of Comparative Examples 1 to 7, the number of IPC sliding bends, which is a conventional evaluation of bendability, is equivalent to each example, and the bendability of the copper-clad laminate cannot be evaluated by the slide bend test. Recognize.

Claims (8)

A copper foil having a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 to 0.45. ,
Copper containing 20 to 500 mass ppm in total of one or more elements selected from the group of In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper Foil. A copper foil having a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 to 0.45. ,
20 to 500 mass in total of two or more elements selected from the group of Ag , In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper Copper foil containing ppm. A copper foil having a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 to 0.45. ,
  20 to 500 mass in total of two or more elements selected from the group of Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper Copper foil containing ppm. A copper foil having a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 to 0.45. ,
  Oxygen-free copper or tough pitch copper with a total of 20 to 3 elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V Copper foil containing 500 mass ppm. Semi-softening temperature is 150 degrees C or less, Copper foil in any one of Claims 1-4. When the total thickness of the resin layers laminated on one side of the copper foil is 50 μm or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil The copper foil according to any one of claims 1 to 5, wherein the number of times of bending until breakage is 4 or more. The total work degree at the time of final cold rolling is 85% or more, and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions. Copper foil.
  However, the oil film equivalent before the final pass; 25000 or less, the oil film equivalent before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less The copper clad laminated board formed by laminating | stacking the copper foil in any one of Claims 1-7 on the at least single side | surface of a resin layer.

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