JP2009185384A - High flexible copper foil with low roughness and, manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel method by which the flexibility of an electrolytic copper foil is improved. <P>SOLUTION: An untreated copper foil is surface-treated to have ≤310 Hv Vickers hardness, flexibility factor (F) of ≥0.01, 1.0-3.5 μm roughness Rz of coarse roughness, 0.5-2.5 μm roughness Rz of bright surface, ≤0.1% carbon content, ≤0.05% sulfur content, 10-100% crystal orientation, ≤2 g/m<SP>2</SP>weight deviation and 20-200 pieces/100 μm<SP>2</SP>nodule number. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrolytic copper foil, and more particularly, to an electrolytic copper foil excellent in bending resistance and a method for producing the same.

Printed circuit boards are often used for electronic circuits in electronic devices. Among them, the flexible printed circuit board (FPC) is particularly flexible, and the board itself is thin. Therefore, a TAB method (Tape method) in which a driver IC is mounted on a tape carrier. (Automated Bonding). In recent years, a COF method (Chip On Film) in which a bare IC chip is directly mounted on a film carrier tape has been developed as a mounting method for performing higher-density mounting in a narrower space. Possible flexible printed circuit boards have come to be sought.
In particular, such flexible printed circuit boards are widely used in electronic devices that require flexibility, flexibility, and high-density mounting, such as operating parts in hard disks and hinges of mobile phones. As a result, high flexibility is demanded from the copper foil constituting the flexible printed circuit board.
Under such circumstances, as a means for improving the flexibility of the copper foil, it is known to reduce the thickness of the copper foil. In this case, the deformation generated on the outer periphery of the bent portion during bending is reduced, and the flexibility is improved. However, there is a limit that design is restricted only by making the copper foil thinner.

In addition, a rolled copper foil is known as a copper foil having excellent flexibility. As a manufacturing method of rolled copper foil, copper is cast into an ingot, and rolling and annealing are repeated to form a foil. The copper foil produced by this method has a high elongation rate and a smooth surface, so that cracks are hardly generated and resistance to bending is excellent. However, the rolled copper foil is expensive, and it is difficult to produce a copper foil having a width of 1 m or more due to mechanical restrictions during production. In addition, it is difficult to stably produce a thin rolled copper foil, and it has been necessary to perform a process such as half-etching in order to reduce the thickness and improve the flexibility.
On the other hand, there is an electrolytic copper foil as a copper foil that is inexpensive and can be adjusted in thickness relatively easily. The electrolytic copper foil is produced by first submerging a cylindrical cathode having a diameter of 2 m to 3 m, called a drum, in an electrolytic solution mainly composed of copper sulfate, and wrapping it around the anode. Is provided. Then, this is rotated while electrodepositing copper on the drum, and the deposited copper is sequentially peeled off and wound up.

However, there is a problem that such an electrolytic copper foil is significantly less flexible than a rolled copper foil. Therefore, various efforts have been made to improve the flexibility of the electrolytic copper foil.
Patent Document 1 discloses a method in which an untreated copper foil produced through a foil-making process is heat-treated to grow the average crystal grain size to 2 to 8 times that before the heat-treating process.
Patent Document 2 discloses a method in which the crystal grain size is adjusted to 2 μm or more by heat treatment, and the surface roughness (Rz) of the copper foil is adjusted to 2.5 μm or less.
Patent Document 3 discloses an electrolytic copper foil that can be finely patterned by adjusting the carbon content to 18 ppm or less.

Korean Patent Publication No. 2007-14067 Korean Patent Publication No. 2006-129965 Japanese Patent Laid-Open No. 9-272994

An object of this invention is to show the new method for improving the bending resistance of electrolytic copper foil. That is, the surface roughness of the S surface (glossy surface) and the M surface (rough surface), carbon and sulfur content, weight deviation, crystal orientation, bending factor, Vickers hardness, which affect the bending resistance of the electrolytic copper foil, By adjusting factors such as the number of nodules per unit area, the optimum bending resistance will be realized.
Other objects and advantages of the present invention can be understood by the following description, and become more apparent from the embodiments of the present invention. It will also be readily apparent that the objects and advantages of the invention may be realized by the instrumentalities and combinations set forth in the appended claims.

  As a result of intensive studies to improve the bending resistance of the electrolytic copper foil, the present inventors used an untreated copper foil having specific characteristics, and electrochemically or chemically treated the surface of the untreated copper foil. It has been found that the above-described problems can be solved by processing, and the present invention has been completed.

The electrolytic copper foil according to one embodiment of the present invention can be obtained by surface-treating an untreated copper foil generated through electrolysis. The electrolytic copper foil thus obtained has a Vickers Hardness of 310 Hv or less, preferably 100 to 310 Hv.
Further, the electrolytic copper foil according to the present invention is characterized in that the bending factor (F) is 0.01 or more (where F = K × E × T and K (bending correlation coefficient) = 0. 001 mm ² / kgf, E: Elongation rate, T: Represents tensile strength).
Furthermore, the electrolytic copper foil according to the present invention has a rough surface (M surface) having a surface roughness (Rz) of 1.0 to 3.5 μm and a glossy surface (S surface) having a surface roughness (Rz) of 0.5 to 3.5. 2.5 μm, carbon content is 0.1% or less, sulfur content is 0.05% or less, crystal orientation (crystal orientation = [I (200) / I _all ] × 100, where I (200 ): Relative peak intensity of diffraction lines on the (200) plane among diffraction lines obtained by X-ray diffraction analysis on the surface of the copper foil, I _all : (110), (111), (200), ( 311) The sum of the relative peak intensities of diffraction lines on each surface is preferably 10% to 100%.

Furthermore, the electrolytic copper foil according to the present invention desirably has a weight deviation of 2 g / m ² or less and a number of nodules per unit area of 20/100 μm ² to 200/100 μm ² .

The method for producing an electrolytic copper foil according to another aspect of the present invention has crystal orientation (crystal orientation = [I (200) / I _all ] × 100, where I (200): relative to the surface of the copper foil. Relative peak intensity of diffraction lines on (200) plane among diffraction lines obtained by X-ray diffraction analysis, I _all : (110), (111), (200), (311) Relative diffraction lines on each plane The foil-making process for producing an untreated electrolytic copper foil having a sum of peak intensities of 10% to 100%, and the surface of the untreated electrolytic copper foil is electrochemically or chemically treated to produce an electrolytic copper foil. A surface treatment step of producing a surface-treated electrolytic copper foil having a value of Vickers hardness of 310 Hv or less, preferably 100 to 310 Hv.
Moreover, the electrolytic copper foil that has undergone the surface treatment step is characterized in that the bending factor (F) has a value of 0.01 or more (where F = K × E × T, and K (bending phase)). Number of relationships) = 0.001 mm ² / Kgf, E: Elongation rate, T: Represents tensile strength).
Furthermore, the electrolytic copper foil subjected to the surface treatment step has a nodule number per unit area of 20/100 μm ² to 200/100 μm ² , and a rough surface (M surface) has a surface roughness (Rz) of 1.0 to 1.0. The surface roughness (Rz) of the glossy surface (S surface) is 0.5 to 2.5 μm, the carbon content is 0.1% or less, the sulfur content is 0.05% or less, and the weight deviation is 2 g. / M ² or less.

  Still another embodiment of the present invention relates to a flexible copper-clad laminate in which a polyimide resin layer is applied to at least one surface of an electrolytic copper foil produced by the above-described production method, and a flexible printed board to which the copper-clad laminate is applied.

  The electrolytic copper foil according to the present invention is capable of fine circuit processing and is excellent in bending resistance. Therefore, it is possible to implement an electrolytic copper foil for a flexible circuit board at a low cost and at the same level as a rolled copper foil.

The following drawings attached to the specification illustrate preferred embodiments of the present invention, and together with the detailed description, serve to further understand the technical idea of the present invention. It should not be construed as being limited to the matters described in the drawings.
It is explanatory drawing which shows the structure of an electrolytic metal foil manufacturing apparatus.

The present invention will be described in detail below.
The electrolytic copper foil of the present invention uses the following terms depending on the stage of the process. First, the copper foil manufactured through the ordinary electrolytic foil making apparatus shown in FIG. 1 is referred to as “untreated copper foil”, and the surface of the untreated copper foil is subjected to electrochemical or chemical surface treatment. Is referred to as “surface-treated copper foil”.
First, the untreated copper foil according to the present invention is manufactured through the electrolytic foil making apparatus of FIG. Referring to the drawing, a drum 20 functioning as a cathode and an anode 30 are provided in a container C to which the electrolytic solution 10 is continuously supplied. The drum 20 rotates in the direction of the arrow, and the drum 20 and the anode 30 are separated so that the electrolytic solution 10 can be interposed therebetween.

In manufacturing the electrolytic copper foil, a current is applied between the drum 20 and the anode 30. At this time, the drum 20 is rotating in the direction of the arrow. Thereby, after the electrolytic copper foil 40 is electrodeposited on the surface of the drum 20, it is wound up via the guide roll 50.
The electrolytic solution 10 is mainly composed of copper sulfate, and various additives such as gelatin, HEC, SPS, and nitride are added thereto, and the current density is preferably 10 ASD to 80 ASD. The detailed contents of the production of such untreated electrolytic copper foil can be referred to Korean Patent Registration Nos. 0694382 and 0571561 filed earlier by the present applicant, and are omitted here.

The untreated electrolytic copper foil has a weight deviation, a (200) texture ratio, a carbon content, a sulfur content, and a surface roughness by adjusting the composition, current density, or type and content of the additive. And other factors can be adjusted.
The untreated copper foil 40 thus manufactured must have a crystal orientation of 10% to 100%. Here, the crystal orientation refers to the relative peak intensity of diffraction lines on the (200) plane among the diffraction lines obtained by X-ray diffraction analysis on the S plane of the electrolytic copper foil, 110), (111), (200), (311) when the sum of the relative peak intensities of the diffraction lines of each face and _{I all,} refers to the percentage of _{[I (200) / I all} ].

Thus, when the (200) texture is dominant among the texture of the untreated copper foil, the orientation of the stress concentration portion and the crystal structure is reversed, and the bending resistance is improved.
The untreated copper foil is completed as a surface-treated copper foil through surface treatment steps such as nodule treatment (or surface roughening treatment), chemical resistance treatment, heat resistance treatment, rust prevention treatment, and silane treatment. Since such a surface treatment process is specifically disclosed in Korean Patent Registration No. 0610751 filed earlier by the present applicant, it is omitted here.

The Vickers hardness, weight deviation, carbon content, sulfur content, and the like of the copper foil may vary depending on the types and contents of various organic substances used in the surface treatment process.
The surface-treated electrolytic copper foil according to the present invention finally completed in this way has a rough surface (M surface) with a surface roughness (Rz) of 1.0 to 3.5 μm and a glossy surface (S surface) with a surface roughness ( Rz) is preferably 0.5 to 2.5 μm. If the surface roughness of the M surface and S surface is 3.5 μm or more, stress concentrates and breaks easily, and if the surface roughness of the M surface is 1.0 μm or less, polyimide adhered to the copper foil Adhesion with is reduced.

The surface-treated electrolytic copper foil is characterized in that the carbon content is 0.1% or less and the sulfur content is 0.05% or less. If the carbon content of the electrolytic copper foil is 0.1% or more, when the flexible circuit board (FCCL) is manufactured, heat is received and the carbon inside the copper foil becomes carbon dioxide, resulting in fine fracture. Similarly, if the sulfur content of the electrolytic copper foil is 0.05% or more, when the flexible circuit board (FCCL) is manufactured, the copper foil undergoes heat and the microfracture occurs while the copper foil becomes sulfur dioxide. Arise.
Furthermore, as a characteristic value representing the bending resistance of the surface-treated electrolytic copper foil, a bending factor F represented by the following mathematical formula can be considered.

Here, K (flexural correlation coefficient) = 0.001 mm ² / kgf, E: elongation rate, and T: tensile strength.

  The bending factor F must have a value of at least 0.01 in order to realize good bending resistance. If the bending factor F falls below 0.01, the surface-treated electrolytic copper foil There is a problem that the fatigue life of the steel sheet becomes short and is easily broken when applied to a bending part. Further, the higher the bending factor F, the better the bending resistance can be realized, but it is desirable that the bending factor F is 0.7 or less.

Further, the surface-treated electrolytic copper foil is formed with a trace by applying an appropriate load with a diamond pyramid-shaped indenter with a facing angle of 136 degrees, and the Vickers hardness expressed as pressure per unit area of the contact surface is 310 Hv or less, Desirably, it has a value of 100 to 310 Hv. When the Vickers hardness of the electrolytic copper foil is less than 100 Hv, surface defects occur in the copper foil manufacturing and FCCL (Flexible Copper Clad Laminate) manufacturing process, resulting in a decrease in flexural resistance. When the electrolytic copper foil exceeds 310 Hv, the FCCL At the time of manufacture, crystal growth does not occur and flexibility is lowered.
The surface-treated electrolytic copper foil has a weight deviation of 2 g / m ² or less, and the number of nodules per unit area is preferably 20/100 μm ² to 200/100 μm ² . When the weight deviation is 2 g / m ² or more, stress concentrates on a portion having a high weight and is easily broken. Moreover, if the number of nodules per unit area is 20 or less, stress concentrates on the lower part of the nodules and is easily broken, and if it is 200 or more, the adhesion strength between the copper foil and the polyimide is weakened.

In general, the surface roughness (Rz) (S-plane and M-plane), bending factor, and Vickers hardness of the electrolytic copper foil change depending on the surface treatment process, but the (200) texture ratio (ie, crystal orientation) is It does not change.
Also, a copper-clad laminate (single-sided copper-clad laminate or double-sided copper-clad laminate) by laminating an insulating layer such as a polyimide resin layer on the M surface alone or both the M surface and S surface of the surface-treated electrolytic copper foil ) Can be manufactured. The polyimide resin layer can be produced by polymerizing a known diamine and acid anhydride in the presence of a solvent. Moreover, a flexible circuit board (FCCL) can also be manufactured by applying the copper-clad laminate.

  Specific examples of the implementation of the above-described foil making process and surface treatment process and implementation of the copper clad laminate are Korean Patent Publication No. 2007-0014067, Korean Patent Publication No. 2006-0129965, Korean Patent Publication No. 2006-0093280. JP-A-9-272994, JP-A-7-268678, JP-A-2006-524441, Korean Patent Publication No. 2005-0114701, JP-A-8-283886, and JP-A-2000-182623. ing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by this. In the following examples, unless otherwise specified, various evaluations are as follows.

1) Surface roughness (Rz)
The surface roughness of the M plane and the S plane is a 10-point average surface roughness, and represents the roughness according to the JISB 0601-1994 standard. It measured in the length direction of the copper foil surface by 2000 times using the ultra-deep shape measuring microscope.
2) Crystal orientation Of the diffraction lines obtained by X-ray diffraction analysis on the S plane of the copper foil, the relative peak intensity of the (200) plane diffraction lines is I (200), and (110), (111 ), (200), (311) when the sum of the relative peak intensities of the diffraction lines of each face and _{I all,} refers to the percentage of _{[I (200) / I all} ]. That is, crystal orientation (%) = [I (200) / I _all ] × 100
3) Bending factor When the bending correlation coefficient having a value of 0.001 mm ² / kgf is K, the elongation is E, and the tensile strength is T, it means the bending factor (F) = [K × E × T]. .
Here, the elongation (E) and tensile strength (T) were measured according to the IPC-TM-650 Test Methods Manual standard.
4) MIT flex test An MIT flex test was performed using an MIT flex test apparatus. The bending was repeated under the following conditions, and the number of times until the test piece was disconnected was determined as the number of bendings.
JIS C 6471 bending radius: 0.38 mm, load: 500 g, bending speed: 90 times / minute, bending angle: 135 ° 5) Vickers hardness (Vickers Hardness)
After polishing the S surface, a pyramid diamond indenter is applied to the S surface and pressed under the following conditions to create pits (pits), remove the load, and then measure with a hardness meter did.
Load (Indenting Load): 150 mN, Time (Dwell Time): 15 seconds

[Example 1]
The electrolytic cell of the apparatus shown in FIG. 1 is filled with an electrolytic solution (copper sulfate as a main component and gelatin, HEC, SPS, and nitride are added), and then an untreated electrolytic copper is passed between the electrodes. A foil was produced. The untreated electrolytic copper foil thus manufactured is subjected to a nodule treatment, a rust prevention treatment, a heat treatment, a chemical treatment, and a silane treatment using a surface treatment apparatus, and has a thickness of 12 μm and an S-surface roughness of 2. 5 μm, M-plane surface roughness of 3.5 μm, carbon content of 0.1%, sulfur content of 0.04%, weight deviation of 2.0 g / m ² , crystal orientation of 35%, bending factor An electrolytic copper foil having 0.18, the number of nodules per unit area of 25/100 μm ² , and a Vickers hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 2]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.0 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 3]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1. The thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 2.0 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 4]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 02%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 5]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.01%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 6]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 0.5 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 7]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 100%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 8]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.3, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 9]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.5, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 10]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, nodule number per unit area 170/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Example 11]
The foil-making process and the surface treatment process were performed in the same manner as in Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 203 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 1]
The electrolytic cell of the apparatus shown in FIG. 1 is filled with an electrolytic solution (copper sulfate as a main component and gelatin, HEC, SPS, and nitride are added), and then an untreated electrolytic copper is passed between the electrodes. A foil was produced. The untreated electrolytic copper foil thus manufactured is subjected to at least one of nodule treatment, rust prevention treatment, heat treatment, chemical treatment treatment, and silane treatment using a surface treatment apparatus, and the thickness is 12 μm, S Surface surface roughness is 3.0 μm, M surface roughness is 3.5 μm, carbon content is 0.1%, sulfur content is 0.04%, weight deviation is 2.0 g / m ² , crystal orientation An electrolytic copper foil having a thickness of 35%, a bending factor of 0.18, a number of nodules per unit area of 25/100 μm ² , and a Vickers hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 2]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 0.8 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 3]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 5.7 μm, and the carbon content was 0.00. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 4]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 5%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, nodule number per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 5]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.2%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 6]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 4.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 7]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 5%, bending factor 0.18, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 8]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.005, number of nodules per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 9]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.002, nodule number per unit area 25/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 10]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 15/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 11]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 314/100 μm ² , Vickers An electrolytic copper foil having a hardness of 145 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 12]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 25 / 100μm ² , Vickers An electrolytic copper foil having a hardness of 78 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

[Comparative Example 13]
The foil-making process and the surface treatment process were performed in the same manner as in Comparative Example 1, and the thickness was 12 μm, the S-surface roughness was 2.5 μm, the M-surface roughness was 3.5 μm, and the carbon content was 0.1. 1%, sulfur content 0.04%, weight deviation 2.0 g / m ² , crystal orientation 35%, bending factor 0.18, number of nodules per unit area 28/100 μm ² , Vickers An electrolytic copper foil having a hardness of 352 Hv was obtained.
The surface-treated electrolytic copper foil was subjected to an MIT bending test, and the results are shown in Table 1.

As can be seen from Table 1 above, the electrolytic copper foil according to the example of the present invention records the number of MITs of at least 100 or more, while the electrolytic copper foil of the comparative example has the number of MITs of less than 100. That is, the electrolytic copper foil of the present invention has superior bending resistance characteristics as compared with the electrolytic copper foil of the comparative example.
The present invention has been described with reference to the embodiments and drawings. However, the present invention is not limited to the embodiments, and the technical idea and patent of the present invention can be obtained by those who have ordinary knowledge in the technical field to which the present invention belongs. It goes without saying that various modifications and variations are possible within the equivalent scope of the claims.

10 Electrolytic solution 20 Drum 30 Anode 40 Untreated electrolytic copper foil 50 Guide roll

Claims (12)

An electrolytic copper foil obtained by surface-treating an untreated copper foil produced through electrolysis,
The electrolytic copper foil, wherein the electrolytic copper foil has a Vickers Hardness of 310 Hv or less.   The electrolytic copper foil according to claim 1, wherein the Vickers hardness is 100 to 310 Hv. The electrolytic copper foil according to claim 1 or 2, wherein the bending factor (F) is 0.01 or more (where F = K x E x T and K (bending correlation coefficient). ) = 0.001 mm ² / kgf, E: Elongation, T: Tensile strength). (1) The surface roughness (Rz) of the rough surface (M surface) is 1.0 to 3.5 μm, and the surface roughness (Rz) of the glossy surface (S surface) is 0.5 to 2.5 μm.
(2) The carbon content is 0.1% or less, the sulfur content is 0.05% or less,
(3) Crystal orientation (crystal orientation = [I (200) / I _all ] × 100, where I (200): the diffraction line obtained by X-ray diffraction analysis on the surface of the copper foil Among them, the relative peak intensity of diffraction lines on the (200) plane, I _all : (110), (111), (200), (311) the sum of the relative peak intensities of diffraction lines on each plane is 10% to 100%. The electrolytic copper foil according to claim 3, wherein the electrolytic copper foil is present. 5. The electrolytic copper foil according to claim 4, wherein the weight deviation is 2 g / m ² or less. 6. The electrolytic copper foil according to claim 5, wherein the number of nodules per unit area is 20/100 μm ² to 200/100 μm ² . A method for producing an electrolytic copper foil,
(1) Crystal orientation (crystal orientation = [I (200) / I _all ] × 100, where I (200): the diffraction line obtained by X-ray diffraction analysis on the surface of the copper foil Among them, the relative peak intensity of diffraction lines on the (200) plane, I _all : (110), (111), (200), (311) the sum of the relative peak intensities of diffraction lines on each plane is 10% to 100%. A foil-making process for producing an untreated electrolytic copper foil;
(2) A surface treatment step of producing a surface-treated electrolytic copper foil having a Vickers hardness of 310 Hv or less by electrochemically or chemically treating the surface of the untreated electrolytic copper foil. A method for producing an electrolytic copper foil.   The method for producing an electrolytic copper foil according to claim 7, wherein the Vickers hardness satisfies 100 to 310 Hv. 9. The method for producing an electrolytic copper foil according to claim 8, wherein a bending factor (F) of the electrolytic copper foil that has passed through the surface treatment step has a value of 0.01 or more. E × T, K (flexural correlation coefficient) = 0.001 mm ² / kgf, E: elongation, T: represents tensile strength). The number of nodules per unit area of the electrolytic copper foil is 20/100 μm ² to 200/100 μm ² , the surface roughness (Rz) of the rough surface (M surface) is 1.0 μm to 3.5 μm, and the glossy surface (S Surface) has a surface roughness (Rz) of 0.5 μm to 2.5 μm, a carbon content of 0.1% or less, a sulfur content of 0.05% or less, and a weight deviation of 2 g / m ² or less. The manufacturing method of the electrolytic copper foil of Claim 9 characterized by the above-mentioned.   A flexible copper-clad laminate, wherein a polyimide resin layer is applied to at least one surface of an electrolytic copper foil produced by the production method according to any one of claims 7 to 10.   A flexible printed circuit board using the copper clad laminate of claim 11.

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