Harmonized copper foil, copper-clad laminates, and printed circuit boards

Abstract

A copper foil with a harmonizing treatment is provided, which is capable of achieving both excellent transmission characteristics and high peel strength when used in a copper laminate or printed circuit board. This copper foil with a harmonizing treatment surface has a harmonizing treatment surface on at least one side. The harmonizing treatment surface has a micro-tip particle volume of 1.300 μm³ / particle or less, calculated by the formula (Vmp+Vmc) / Spd based on the actual volume Vmp of the protruding peak, the actual volume Vmc of the core, and the peak apex density Spd of the peak, and also has a cutting level difference Rdc of 0.95 μm or more. Vmp, Vmc, and Spd are values ​​measured in accordance with ISO 25178, and Rdc is a value obtained as the difference in cutting level c in the height direction at load length rates of 20% and 80% in accordance with JIS B0601-2013.

Description

Technology Field

[0001] The present invention relates to a copper foil with a harmonizing treatment, a copper-clad laminate, and a printed circuit board. Background Technology

[0002] In the manufacturing process of printed circuit boards (PCBs), copper foil is widely used in the form of copper-clad laminates bonded to an insulating resin substrate. In this regard, to prevent delamination of wiring during PCB manufacturing, it is desired that the copper foil and the insulating resin substrate possess high adhesion. Therefore, in conventional copper foils for PCB manufacturing, adhesion is improved by applying a texture treatment to the bonding surface of the copper foil to form irregularities consisting of fine copper particles, and then causing these irregularities to penetrate into the insulating resin substrate through press processing to exert an anchoring effect.

[0003] As a copper foil subjected to such a roughening treatment, for example, Patent Document 1 (Japanese Patent Publication No. 2018-172785) discloses a surface-treated copper foil having a copper foil and a roughening treatment layer on at least one surface of the copper foil, wherein the arithmetic mean roughness Ra of the surface on the roughening treatment layer side is 0.08 μm or more and 0.20 μm or less, and the glossiness of the TD (width direction) of the surface on the roughening treatment layer side is 70% or less. According to this surface-treated copper foil, the detachment of roughening particles provided on the surface of the copper foil is well suppressed, and the occurrence of wrinkles and streaks during bonding with an insulating substrate is also well suppressed.

[0004] However, with the recent increase in functionality of portable electronic devices, signals—regardless of whether they are digital or analog—are becoming higher frequency to enable high-speed processing of large amounts of data, thereby requiring printed circuit boards suitable for high-frequency applications. For such high-frequency printed circuit boards, a reduction in transmission loss is desired to enable transmission without degradation of high-frequency signals. While a printed circuit board is equipped with copper foil processed into a wiring pattern and an insulating substrate, the main sources of transmission loss are conductor loss caused by the copper foil and dielectric loss caused by the insulating substrate.

[0005] In this regard, a copper foil with a harmonization treatment that aims to reduce transmission loss has been proposed. For example, Patent Document 2 (Japanese Patent Publication No. 2015-148011) discloses, for the purpose of providing a surface-treated copper foil with low signal transmission loss and a laminate using the same, controlling the skewness Rsk of the copper foil surface based on JIS B0601-2001 to a predetermined range of -0.35 or higher and 0.53 or lower by surface treatment. Prior art literature

[0006] Japanese Patent Publication No. 2018-172785 and Japanese Patent Publication No. 2015-148011

[0007] As mentioned above, in recent years, there has been a demand to improve the transmission characteristics (high-frequency characteristics) of printed circuit boards. To meet this demand, finer shaping treatments have been attempted on the bonding surface of copper foil with the insulating resin substrate. Specifically, to reduce surface irregularities of the copper foil that increase transmission loss, it is considered to perform fine shaping treatments on copper foil surfaces with low waviness (e.g., the surface of double-sided smooth foil or the electrode surface of electrolytic copper foil). However, when copper foil treated with such shaping is used to process copper-clad laminates or manufacture printed circuit boards, a problem may arise in which the peel strength between the copper foil and the substrate is generally low, resulting in reduced adhesion reliability.

[0008] The inventors have found that, in the surface of a copper foil treated with a harmonization process, by controlling the volume of micro-tip particles calculated based on the actual volume Vmp of the protruding peak, the actual volume Vmc of the core, and the peak density Spd, and the cutting level difference Rdc within a predetermined range, excellent transmission characteristics and high peel strength can be achieved in a copper-clad laminate or printed circuit board manufactured using the same.

[0009] Accordingly, the objective of the present invention is to provide a copper foil with a harmonizing treatment that can achieve both excellent transmission characteristics and high peel strength when used in copper laminates or printed circuit boards.

[0010] According to the present invention, the following embodiments are provided.

[0011] [Mode 1]

[0012] As a copper foil with a harmonized surface on at least one side,

[0013] The above-mentioned harmonized surface has a substantial volume Vmp (㎛) of protruding peaks per unit area. 3 / ㎛ 2 ), actual volume of the core per unit area Vmc (㎛ 3 / ㎛ 2), and peak density of mountains per unit area Spd (pieces / ㎛) 2 Based on ), the micro-tip particle volume calculated by the formula (Vmp+Vmc) / Spd is 1.300㎛ 3 / piece or less, and also, the cutting level difference Rdc is 0.95㎛ or more, and

[0014] The above Vmp, Vmc, and Spd are values ​​measured in accordance with ISO25178 under conditions of a magnification of 200x, a cutoff wavelength of 0.3㎛ for the S filter, and a cutoff wavelength of 5㎛ for the L filter.

[0015] The above Rdc is a value obtained as the difference in height direction cutting level c (c(Rmr1)-c(Rmr2)) at load length ratio (Rmr1) 20% and load length ratio (Rmr2) 80% in a roughness curve measured under conditions of a cutoff wavelength of 320 μm with a cutoff value λc and no cutoff with a cutoff value λs, in accordance with JIS B0601-2013.

[0016] [Mode 2]

[0017] The above-mentioned harmonized surface is a harmonized copper foil described in Embodiment 1, wherein the cutting level difference Rdc is 1.10㎛ or more and 20.00㎛ or less.

[0018] [Mode 3]

[0019] The above-mentioned harmonized surface has an actual volume Vmc of the core part per unit area of ​​0.360㎛ 3 / ㎛ 2 Copper foil treated with harmony as described in embodiment 1 or 2, which is below.

[0020] [Mode 4]

[0021] The above-mentioned harmonic treatment surface has a sum Vmp+Vmc, which is the sum of the actual volume Vmp of the protruding peak and the actual volume Vmc of the core part, of 0.380㎛ 3 / ㎛ 2 Copper foil treated with harmonization as described in any one of embodiments 1 to 3, as described below.

[0022] [Mode 5]

[0023] A copper foil treated with a harmonization process as described in any one of embodiments 1 to 4, wherein the above-mentioned harmonization process surface has an interface development area ratio Sdr of 70% or less, and the Sdr is a value measured under conditions of a magnification of 200x, a cutoff wavelength of 0.3 μm by an S filter, and a cutoff wavelength of 5 μm by an L filter in accordance with ISO 25178.

[0024] [Mode 6]

[0025] A copper foil treated with a harmonization process as described in any one of embodiments 1 to 5, wherein the above-mentioned harmonization process surface has a level difference Sk of 1.50 μm or more in the core portion, and the Sk is a value measured under conditions of 20x magnification, without cutting off by an S filter, and a cut-off wavelength of 320 μm by an L filter in accordance with ISO 25178.

[0026] [Mode 7]

[0027] A harmonized copper foil described in any one of embodiments 1 to 6, wherein the above-mentioned harmonized surface has a pole height Sxp of 1.10 μm or more, and the above-mentioned Sxp is a value measured under conditions of 20x magnification, without cutting off by an S filter, and a cut-off wavelength of 320 μm by an L filter in accordance with ISO 25178.

[0028] [Mode 8]

[0029] The above-mentioned harmonic treated surface has a peak density Spd of the above-mentioned mountains per unit area of ​​0.12 / ㎛ 2 0.46 or more / ㎛ 2 Copper foil treated with harmonization as described in any one of embodiments 1 to 7, below.

[0030] [Mode 9]

[0031] A copper foil treated with rust prevention treatment layer and / or a silane coupling agent treatment layer as described in any one of embodiments 1 to 8, having the above-mentioned treated surface further provided with the above-mentioned treated surface.

[0032] [Mode 10]

[0033] A copper foil treated with a harmonizing agent as described in any one of embodiments 1 to 9, wherein the copper foil treated with a harmonizing agent is an electrolytic copper foil, and the surface treated with a harmonizing agent is located on the precipitation surface side of the electrolytic copper foil.

[0034] [Mode 11]

[0035] A copper-clad laminate having a copper foil treated with harmonization as described in any one of embodiments 1 to 10.

[0036] [Mode 12]

[0037] A printed circuit board having a copper foil treated with a harmonization process as described in any one of embodiments 1 to 10. Brief explanation of the drawing

[0038] Figure 1 is a drawing for explaining the load curve of the roughness curve determined in accordance with JIS B0601-2013. Figure 2 is a drawing for explaining the load length ratio Rmr(c) determined in accordance with JIS B0601-2013. Figure 3 is a drawing for explaining the cutting level difference Rdc determined in accordance with JIS B0601-2013. Figure 4 is a diagram illustrating the load curve and load area ratio Smr(c) of a surface determined in accordance with ISO25178. Figure 5 is a diagram illustrating the load area ratio Smr1 separating the protruding peak and the core portion, the load area ratio Smr2 separating the protruding bone and the core portion, and the level difference Sk of the core portion, which are determined in accordance with ISO25178. Figure 6 is a drawing for explaining the actual volume Vmp of the protruding part and the actual volume Vmc of the core part determined in accordance with ISO25178. Figure 7 is a diagram illustrating the pole height Sxp determined in accordance with ISO25178. Figure 8 is a diagram illustrating that the surface roughness of a copper foil with a harmonic treatment consists of harmonic particle components and wavy components. Figure 9 is a schematic cross-sectional view of a harmonic particle and is a diagram to explain the volume of a micro-tip particle. FIG. 10 is a schematic diagram illustrating an example of a copper foil treated with the harmonization process of the present invention. Specific details for implementing the invention

[0039] definition

[0040] Definitions of terms and parameters used to specify the present invention are provided below.

[0041] In this specification, "load curve of a roughness curve" refers to a curve that represents the ratio of the actual part appearing when the roughness curve is cut at a cutting level c, as shown in FIG. 1 and determined in accordance with JIS B0601-2013, as a function of c. That is, the load curve of a roughness curve can also be described as a curve representing the height at which the load length ratio Rmr(c) becomes 100% from 0%. The load length ratio Rmr(c) is a parameter that represents the ratio of the load length of the roughness curve element at the cutting level c to the evaluation length, as shown in FIG. 2 and determined in accordance with JIS B0601-2013.

[0042] In this specification, "cutting level difference Rdc" or "Rdc" refers to two load length ratios Rmr1 and Rmr2 (wherein Rmr1) in the load curve of the roughness curve measured in accordance with JIS B0601-2013 as shown in FIG. 3. <Rmr2)에 있어서의 높이 방향의 절단 레벨 c의 차(c(Rmr1)-c(Rmr2))를 나타내는 파라미터이다. 본 명세서에서는, Rmr1을 20% 및 Rmr2를 80%로 지정하여 Rdc를 산출하는 것으로 한다.

[0043] In this specification, "surface load curve" refers to a curve representing the height at which the load area ratio is 0% to 100%, determined in accordance with ISO 25178. The load area ratio is a parameter representing the area of ​​a region above a certain height c, as shown in FIG. 4. The load area ratio at height c corresponds to Smr(c) in FIG. 4. As shown in FIG. 5, the secant line of the load curve, drawn from the load area ratio of 0% along the load curve with a difference of 40%, is moved from the load area ratio of 0% to the point where the slope of the secant line becomes gentlest, and this point is called the central part of the surface load curve. The straight line at which the sum of squares of deviations in the longitudinal direction is minimized with respect to this central part is called the equivalent straight line. The part included in the height range of the load area ratio of 0% to 100% of the equivalent straight line is called the core part. The part higher than the core part is called the protruding peak part, and the part lower than the core part is called the protruding valley part.

[0044] In this specification, “load area ratio Smr1 separating the protruding peak and the core part” is a parameter representing the load area ratio at the intersection of the upper height of the core part and the load curve of the surface, determined in accordance with ISO25178 as shown in FIG. 5 (i.e., the load area ratio separating the core part and the protruding peak). In this specification, “load area ratio Smr2 separating the protruding valley and the core part” is a parameter representing the load area ratio at the intersection of the lower height of the core part and the load curve, determined in accordance with ISO25178 as shown in FIG. 5 (i.e., the load area ratio separating the core part and the protruding valley).

[0045] In this specification, “level difference Sk of the core part” or “Sk” is a value obtained by subtracting the minimum height from the maximum height of the core part, measured in accordance with ISO 25178, and is a parameter calculated by the difference in height between the equivalent straight line load area ratios of 0% and 100% as shown in FIG. 5.

[0046] In this specification, "actual volume of the protruding peak Vmp" or "Vmp" is a parameter representing the volume of the protruding peak measured in accordance with ISO25178, as illustrated in FIG. 6. In addition, in this specification, "actual volume of the core Vmc" or "Vmc" is a parameter representing the volume of the core measured in accordance with ISO25178, as illustrated in FIG. 6. In this specification, Vmp and Vmc are calculated by specifying the load area ratio Smr1 separating the core and the protruding peak as 10%, and the load area ratio Smr2 separating the core and the protruding bone as 80%.

[0047] In this specification, "peak density Spd" or "Spd" is a parameter representing the number of peaks per unit area, measured in accordance with ISO 25178. Spd can be calculated by dividing the number of peaks included in the contour surface by the projected area of ​​the contour surface. In this specification, Spd is calculated by counting only peaks greater than 5% of the maximum amplitude in the contour surface.

[0048] In this specification, "micro-tip particle volume" refers to the actual volume Vmp (㎛) of the protruding peak per unit area. 3 / ㎛ 2 ), actual volume of the core per unit area Vmc (㎛ 3 / ㎛ 2 ), and peak density of mountains per unit area Spd (pieces / ㎛) 2 It refers to a parameter calculated by the formula (Vmp+Vmc) / Spd based on ). Furthermore, in this specification, “Vmp+Vmc” refers to the actual volume Vmp (㎛) of the protruding peak per unit area. 3 / ㎛ 2 ) and the actual volume of the core per unit area Vmc (㎛ 3 / ㎛ 2 It refers to the parameter calculated by the sum of ).

[0049] In this specification, “pole height Sxp” or “Sxp” is a parameter representing the difference in height between a load area ratio p% and a load area ratio q%, measured in accordance with ISO 25178 as illustrated in FIG. 7. Sxp represents the difference between the average surface and the height of the surface after removing particularly high mountains from the surface. In this specification, Sxp is calculated by specifying the load area ratio p as 2.5% and the load area ratio q as 50%.

[0050] In this specification, "interface development area ratio Sdr" or "Sdr" is a parameter that indicates, as a percentage, how much the development area (surface area) of a defined region has increased relative to the area of ​​a defined region, measured in accordance with ISO 25178. The smaller this value, the more flat the surface shape is, and the Sdr of a completely flat surface is 0%. On the other hand, the larger this value, the more uneven the surface shape is.

[0051] Rdc can be calculated by measuring a surface profile of a predetermined measurement length on a surface treated with a commercially available laser microscope. Additionally, Vmp, Vmc, Spd, Sdr, Sk, and Sxp can each be calculated by measuring a surface profile of a predetermined measurement area on a surface treated with a commercially available laser microscope. In this specification, Vmp, Vmc, Spd, and Sdr are measured under conditions of a magnification of 200x, a cutoff wavelength of 0.3 μm using an S filter, and a cutoff wavelength of 5 μm using an L filter. Meanwhile, Rdc is measured under conditions of a magnification of 20x, without performing a cutoff using a cutoff value λs, and a cutoff wavelength of 320 μm using a cutoff value λc, and Sk and Sxp are measured under conditions of a magnification of 20x, without performing a cutoff using an S filter, and a cutoff wavelength of 320 μm using an L filter. In addition, when both the objective lens and the optical zoom are used in the measurement using a laser microscope, the magnification is equivalent to the value obtained by multiplying the magnification of the objective lens by the magnification of the optical zoom. For example, if the objective lens magnification is 100x and the optical zoom magnification is 2x, the magnification becomes 200x (=100×2). Furthermore, preferred measurement and analysis conditions for the surface profile using a laser microscope are to be shown in the examples described later.

[0052] In this specification, the “electrode surface” of the electrolytic copper foil refers to the side that is in contact with the negative electrode during the manufacture of the electrolytic copper foil.

[0053] In this specification, the term “precipitation surface” of the electrolytic copper foil refers to the side on which electrolytic copper is precipitated during the manufacture of the electrolytic copper foil, that is, the side not in contact with the cathode.

[0054] Harmony processing copper foil

[0055] The copper foil of the present invention is a harmonized copper foil. This harmonized copper foil has a harmonized surface on at least one side. This harmonized surface has a substantial volume Vmp (μm) of protruding peaks per unit area. 3 / ㎛ 2 ), actual volume of the core per unit area Vmc (㎛ 3 / ㎛ 2 ), and peak density of mountains per unit area Spd (pieces / ㎛) 2 Based on ), the micro-tip particle volume calculated by the formula (Vmp+Vmc) / Spd is 1.300㎛ 3 The number of particles is less than or equal to 1. In addition, the harmonized surface has a cutting level difference Rdc of 0.95 μm or more. By controlling the micro-tip particle volume and the cutting level difference Rdc on the surface of the harmonized copper foil to a predetermined range, excellent transmission characteristics (high frequency characteristics) and high peel strength (e.g., normal peel strength and moisture-resistant peel strength) can be achieved in the copper-clad laminate or printed circuit board manufactured using this.

[0056] Excellent transmission characteristics and high peel strength are inherently difficult to achieve in harmony. This is because, in order to obtain excellent transmission characteristics, it is required to reduce the surface irregularities of the copper foil, whereas in order to obtain high peel strength, it is required to increase the surface irregularities of the copper foil, and thus the two are in a trade-off relationship. Here, as shown in FIG. 8, the surface irregularities of the copper foil treated with fine harmonization consist of "fine particle components" and "wavyness components" that have a longer period than the fine particle components. Generally, to obtain excellent transmission characteristics, it is thought that fine harmonization treatment should be performed on copper foil surfaces with small waviness (e.g., the surface of a double-sided smooth foil or the electrode surface of an electrolytic copper foil) to form small fine particles; however, when a copper foil laminate or printed circuit board is manufactured using such a copper foil treated with fine harmonization, the peel strength between the copper foil and the substrate is generally lowered.

[0057] Regarding this issue, the inventors investigated the influence of harmonic particles and waviness of the irregularities on the surface of the copper foil on transmission characteristics and peel strength. As a result, it was found that, contrary to expectations, the waviness component of the copper foil has little effect on transmission characteristics, and that the size of the harmonic particles primarily affects transmission characteristics. Furthermore, the inventors discovered that by miniaturizing the protrusions (harmonic particles) to improve transmission characteristics, and by compensating for the lack of adhesion caused by this with the waviness of the copper foil, which has minimal influence on transmission characteristics, it is possible to achieve both excellent transmission characteristics and adhesion reliability through high peel strength. Specifically, regarding the volume of the micro-protrusions (harmonic particles) that affect transmission characteristics, the micro-tip particle volume is 1.300 μm 3 It was found that excellent transmission characteristics can be realized by making the number of particles less than or equal to 1. In addition, it was found that by making the cut level difference Rdc in measurement conditions reflecting the height of a wide range of textured processing surfaces 0.95 μm or more, high peel strength between the copper foil and the substrate can be realized by utilizing the waviness of the copper foil, even with small textured particles for which peel strength is inherently difficult to secure.

[0058] Although the mechanism by which transmission characteristics can be improved by controlling the volume of micro-tip particles is not necessarily certain, it is thought to be as follows. Here, a schematic cross-sectional view of a protrusion (harmonic particle) with a boundary between the core part and the protruding ridge part is shown in FIG. 9. As shown in FIG. 9, the volume of the combined core part and the protruding ridge part of the protrusion per unit area (the part excluding the lower part of the protrusion corresponding to the protruding ridge part from the entire protrusion) corresponds to Vmp+Vmc. And, since the ridge apex density Spd represents the number of protrusions per unit area, as shown in FIG. 9, Vmp+Vmc divided by Spd (=(Vmp+Vmc) / Spd) corresponds to the volume of micro-tip particles per protrusion. In this regard, when two types of harmonic processing surfaces are assumed where Spd is the same (i.e., the number of protrusions per unit area is the same) and Vmp+Vmc is different, the harmonic processing surface with a smaller Vmp+Vmc has better transmission characteristics because the size of the protrusions becomes smaller. On the other hand, when two types of harmonic processing surfaces are assumed where Vmp+Vmc is the same (i.e., the volume of protrusions per unit area is the same) and Spd is different, the harmonic processing surface with a larger Spd has better transmission characteristics because the same volume is distributed among multiple protrusions, i.e., the size per protrusion becomes smaller. Therefore, it is possible to improve transmission characteristics by controlling the volume of the micro-tip particle to a small value.

[0059] The harmonic particle components and waviness components of the copper foil surface that affect transmission characteristics or peel strength can be distinguished by using the measurement magnification of the laser microscope, S filter and L filter, or cutoff values ​​λs and λc. Specifically, by measuring the harmonic treated surface at a high magnification of 200x, the fine irregularities of the harmonic treated surface that affect transmission characteristics can be accurately evaluated. Furthermore, by measuring under conditions of a cutoff wavelength of 0.3 μm for the S filter and a cutoff wavelength of 5 μm for the L filter, parameters of the harmonic particle components with the influence of the waviness component cut off can be obtained. Therefore, the micro-tip particle volume, Vmp, Vmc, Vmp+Vmc, Spd, and Sdr in the present invention can be said to accurately reflect the parameters of the harmonic particles on the copper foil surface, and transmission characteristics can be accurately evaluated by using these indicators. In contrast, by measuring the harmonized surface at a low magnification of 20x, the height (wavyness) of the entire harmonized surface, which affects adhesion reliability, can be evaluated extensively. Furthermore, by measuring the harmonized surface under conditions of a cutoff wavelength of 320 μm using a cutoff value λc or an L filter, without performing a cutoff using a cutoff value λs or an S filter, parameters of the entire harmonized surface that reflect the influence of both the harmonized particle component and the waviness component can be obtained. Accordingly, Rdc, Sk, and Sxp in the present invention are parameters that reflect not only the harmonized particle component of the copper foil surface but also the waviness component, and by using these indicators, the peel strength can be accurately evaluated.

[0060] The surface of the harmonized copper foil has a cutting level difference Rdc of 0.95 μm or more, preferably 1.10 μm or more and 20.00 μm or less, more preferably 1.15 μm or more and 12.00 μm or less, even more preferably 1.20 μm or more and 6.00 μm or less, and particularly preferably 1.25 μm or more and 4.00 μm or less. If the Rdc is within the above range, excellent transmission characteristics can be secured, and the anchor effect can be effectively exerted to realize high peel strength.

[0061] The harmonized surface of the harmonized copper foil has a micro-tip particle volume of 1,300㎛ 3 / piece or less, preferably 0.300㎛ 3 / piece or more 1,300㎛ 3 / piece or less, more preferably 0.400㎛ 3 / piece or more 1,300㎛ 3 / piece or less, more preferably 0.500㎛ 3 / piece or more 1,300㎛ 3 / piece or less, particularly preferably 0.500㎛ 3 / piece or more 1,200㎛ 3 / piece or less. If the volume of micro-tip particles is within the above range, high peel strength and excellent transmission characteristics can be realized.

[0062] The glazing surface of the glazing-treated copper foil has a solid volume Vmc of the core per unit area of ​​0.360㎛. 3 / ㎛ 2 It is preferable that it be less than or equal to 0.040 μm, and more preferably 0.040 μm. 3 / ㎛ 2 0.320㎛ or more 3 / ㎛ 2 Below, more preferably 0.070㎛ 3 / ㎛ 2 0.290㎛ or larger 3 / ㎛ 2 Below, particularly preferably 0.100 μm 3 / ㎛ 2 0.260㎛ or larger 3 / ㎛ 2Below, most preferably 0.130㎛ 3 / ㎛ 2 0.230㎛ or larger 3 / ㎛ 2 The following applies. If Vmc is within the above range, it becomes easier to control the micro-tip particle volume within the aforementioned range, and further excellent transmission characteristics can be realized while maintaining high peel strength.

[0063] The harmonized surface of the harmonized copper foil has a sum Vmp+Vmc, which is the sum of the substantial volume Vmp of the protruding peaks and the substantial volume Vmc of the core part, of 0.380㎛ 3 / ㎛ 2 It is preferable that it be less than or equal to 0.050 μm, and more preferably 0.050 μm. 3 / ㎛ 2 0.340㎛ or larger 3 / ㎛ 2 Below, more preferably 0.090㎛ 3 / ㎛ 2 0.310㎛ or more 3 / ㎛ 2 Below, particularly preferably 0.130 μm 3 / ㎛ 2 0.280㎛ or larger 3 / ㎛ 2 Below, most preferably 0.140㎛ 3 / ㎛ 2 0.250㎛ or larger 3 / ㎛ 2 The following applies. If Vmp+Vmc is within the above range, it becomes easier to control the micro-tip particle volume within the aforementioned range, thereby enabling high peel strength and even better transmission characteristics.

[0064] The harmonized surface of the harmonized copper foil has a peak density Spd of 0.12 peaks / ㎛ per unit area. 2 0.46 or more / ㎛ 2 It is preferable that it be less than or equal to 0.13 particles / ㎛, and more preferably 0.13 particles / ㎛ 2 0.44 or more / ㎛ 2 Below, more preferably 0.14 pieces / ㎛ 2 0.37 or more / ㎛ 2Below, particularly preferably 0.15 pieces / ㎛ 2 0.31 or more / ㎛ 2 Below, most preferably 0.16 pieces / ㎛ 2 0.28 or more / ㎛ 2 The following applies. If Spd is within the above range, it becomes easier to control the micro-tip particle volume within the aforementioned range, thereby enabling high peel strength and even better transmission characteristics.

[0065] The surface of the harmonized copper foil is preferably such that the interface development area ratio Sdr is 70% or less, more preferably 5% or more and 65% or less, even more preferably 10% or more and 60% or less, particularly preferably 15% or more and 55% or less, and most preferably 20% or more and 50% or less. If the Sdr is within the above range, it becomes a shape rich in irregularities that is desirable for realizing even better transmission characteristics while securing high peel strength.

[0066] The level difference Sk of the core portion of the harmonized copper foil is preferably 1.50 μm or more, more preferably 1.58 μm or more and 20.00 μm or less, even more preferably 1.65 μm or more and 12.00 μm or less, particularly preferably 1.70 μm or more and 8.00 μm or less, and most preferably 2.00 μm or more and 6.00 μm or less. If the Sk is within the above range, excellent transmission characteristics are achieved, and an anchoring effect is effectively exerted, thereby realizing even higher peel strength.

[0067] The surface of the harmonized copper foil preferably has a pole height Sxp of 1.10 μm or more, more preferably 1.20 μm or more and 20.00 μm or less, even more preferably 1.30 μm or more and 12.00 μm or less, particularly preferably 1.40 μm or more and 8.00 μm or less, and most preferably 1.70 μm or more and 6.00 μm or less. If the pole height Sxp is within the above range, excellent transmission characteristics are achieved, and an anchoring effect is effectively exerted, thereby realizing even higher peel strength.

[0068] The thickness of the copper foil treated with shaping is not particularly limited, but is preferably 0.1 μm or more and 210 μm or less, and more preferably 0.3 μm or more and 105 μm or less. In addition, the copper foil treated with shaping according to the present invention is not limited to a copper foil surface treated with shaping, but may also be a copper foil surface treated with shaping or fine shaping of a copper foil provided with a carrier.

[0069] An example of the harmonized copper foil of the present invention is illustrated in FIG. 10. As illustrated in FIG. 10, the harmonized copper foil of the present invention can be preferably manufactured by forming fine harmonized particles by performing a harmonization treatment under desired low harmonization conditions on a copper foil surface having a predetermined degree of wavyness (e.g., the precipitation surface of an electrolytic copper foil). Accordingly, according to a preferred embodiment of the present invention, the harmonized copper foil is an electrolytic copper foil, and the harmonized surface is located on the precipitation surface side of the electrolytic copper foil. Furthermore, the harmonized copper foil may have harmonized surfaces on both sides or may have a harmonized surface on only one side. The harmonized surface is typically formed by a plurality of harmonized particles, and it is preferable that each of these plurality of harmonized particles is composed of copper particles. The copper particles may be made of metallic copper or may be made of a copper alloy.

[0070] The roughening treatment for forming a roughened surface can preferably be performed by forming roughening particles of copper or a copper alloy on the copper foil. The copper foil prior to the roughening treatment may be an unroughened copper foil or may have undergone preliminary roughening. The surface of the copper foil to be roughened preferably has a 10-point average roughness Rz measured in accordance with JIS B0601-1994 of 1.50 μm or more and 20.00 μm or less, and more preferably 2.00 μm or more and 10.00 μm or less. Within the above range, it becomes easier to impart the surface profile required for the roughened copper foil of the present invention to the roughened surface.

[0071] The harmonization treatment is, for example, in a copper sulfate solution containing a copper concentration of 7 g / L or more and 17 g / L or less and a sulfuric acid concentration of 50 g / L or more and 200 g / L or less, at a temperature of 20°C or more and 40°C or less, at 10 A / dm 2 50A / dm or more 2 It is preferable to perform electrolytic deposition as follows. It is preferable that this electrolytic deposition be performed for 0.5 seconds or more and 30 seconds or less, more preferable that it be performed for 1 second or more and 30 seconds or less, and even more preferable that it be performed for 1 second or more and 3 seconds or less. However, the copper foil treated with enamel according to the present invention may be manufactured by various methods, not limited to the above method.

[0072] When the above electrolytic precipitation occurs, the following formula:

[0073] R L =L / D C

[0074] (during food, R L Silver is the liquid resistance index (mm·L / mol), L is the distance between the anode and cathode (mm), and D C is the charge carrier density (mol / L)

[0075] Liquid resistance index R defined by LIt is preferable to set it to 9.0 mm·L / mol or more and 20.0 mm·L / mol or less, and more preferable to set it to 11.0 mm·L / mol or more and 17.0 mm·L / mol or less. In this way, the liquid resistance index R L By increasing , the voltage across the entire system increases, and the voltage during the protrusion formation reaction also increases. As a result of this affecting the shape of the protrusion, it is possible to preferably form protrusions of a shape suitable for imparting the surface profile required for the harmonized copper foil of the present invention. Furthermore, the charge carrier density D C It can be calculated by summing the products of the respective ion concentration and the valence for all ions present in the plating solution. For example, when a copper sulfate solution is used as the plating solution, the charge carrier density D C is, the following formula:

[0076] Dc=[H + ]×1+[Cu 2 + ]×2+[SO4 2- ]×2

[0077] (In the food, [H + ] is the hydrogen ion concentration in the solution (mol / L), [Cu 2 + ] is the copper ion concentration in solution (mol / L), [SO4 2- ] is the sulfate ion concentration (mol / L) in the solution)

[0078] It is produced by.

[0079] Liquid resistance index R L The relationship between overvoltage and voltage is explained as follows. First, according to Ohm's law, the following equation:

[0080] V=ρ×L×I / S

[0081] (In the equation, V is voltage, ρ is resistivity, L is the distance between poles, I is the current, and S is the cross-sectional area between poles)

[0082] ...is derived. That is, voltage V is proportional to resistivity ρ, inter-electrode distance L, and current density (=I / S). And, resistivity ρ is the aforementioned charge carrier density D C It is inversely proportional to. For this reason, when the current density is constant, (proportional to the inter-electrode distance L and charge carrier density D C By increasing the liquid resistance index (which is inversely proportional to), the voltage also increases. Therefore, the liquid resistance index can be considered an indicator related to the resistance of the solution.

[0083] Depending on the preference, the copper foil treated with rust may be subjected to anti-rust treatment to form an anti-rust treatment layer. The anti-rust treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and among the zinc alloy plating treatments, a zinc-nickel alloy treatment is particularly preferred. The zinc-nickel alloy treatment should be a plating treatment containing at least Ni and Zn, and may additionally include other elements such as Sn, Cr, Co, and Mo. For example, by including Mo in addition to Ni and Zn in the anti-rust treatment layer, the treated surface of the copper foil treated with rust exhibits superior adhesion to the resin, chemical resistance, and heat resistance, and is also less likely to leave etching residue. In the zinc-nickel alloy plating, the Ni / Zn adhesion ratio is preferably 1.2 or more and 10 or less by mass, more preferably 2 or more and 7 or less, and even more preferably 2.7 or more and 4 or less. In addition, it is desirable for the anti-corrosion treatment to further include a chromate treatment, and it is more desirable for this chromate treatment to be performed on the surface of the zinc-containing plating after a zinc plating treatment. By doing so, the anti-corrosion properties can be further improved. A particularly desirable anti-corrosion treatment is a combination of a zinc-nickel alloy plating treatment and a subsequent chromate treatment.

[0084] Depending on the preference, the harmonized copper foil may be treated with a silane coupling agent on its surface to form a silane coupling agent treatment layer. This can improve moisture resistance, chemical resistance, and adhesion to adhesives, etc. The silane coupling agent treatment layer can be formed by applying a silane coupling agent that has been appropriately diluted, and then drying it. Examples of silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, or amino-functional silane coupling agents such as 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane, or olefin-functional silane coupling agents such as vinyltrimethoxysilane and vinylphenyltrimethoxysilane, or acrylic-functional silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane, or imidazolesilane, etc. Examples include imidazole functional silane coupling agents, or triazine functional silane coupling agents such as triazine silanes.

[0085] For the reasons stated above, it is preferable that the rust-treated copper foil further comprises an anti-corrosion treatment layer and / or a silane coupling agent treatment layer on the rust-treated surface, and more preferably, comprises both the anti-corrosion treatment layer and the silane coupling agent treatment layer. The anti-corrosion treatment layer and the silane coupling agent treatment layer may be formed not only on the rust-treated surface side of the rust-treated copper foil but also on the side where the rust-treated surface is not formed.

[0086] Dongjang laminated board

[0087] The harmonized copper foil of the present invention is preferably used in the manufacture of copper-clad laminates for printed circuit boards. That is, according to a preferred embodiment of the present invention, a copper-clad laminate having the harmonized copper foil is provided. By using the harmonized copper foil of the present invention, excellent transmission characteristics and high peel strength can be achieved in the copper-clad laminate. The copper-clad laminate comprises the harmonized copper foil of the present invention and a resin layer provided in close contact with the harmonized surface of the harmonized copper foil. The harmonized copper foil may be provided on one side of the resin layer or on both sides. The resin layer comprises a resin, preferably an insulating resin. The resin layer is preferably a prepreg and / or a resin sheet. Prepreg is a general term for a composite material in which a synthetic resin is impregnated into a substrate such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, or paper. Preferred examples of insulating resins include epoxy resin, cyanate resin, bis-maleimide triazine resin (BT resin), polyphenylene ether resin, phenolic resin, etc. In addition, examples of insulating resins constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester resin. Furthermore, the resin layer may contain filler particles composed of various inorganic particles such as silica and alumina to improve insulation properties. The thickness of the resin layer is not particularly limited, but it is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and even more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of multiple layers. The resin layer, such as prepreg and / or resin sheet, may be provided in a copper foil treated with a primer resin layer that is applied to the surface of the copper foil in advance.

[0088] Print wiring board

[0089] The harmonized copper foil of the present invention is preferably used in the manufacture of printed circuit boards. That is, according to a preferred embodiment of the present invention, a printed circuit board equipped with the harmonized copper foil is provided. By using the harmonized copper foil of the present invention, excellent transmission characteristics and high peel strength can be achieved in a printed circuit board. A printed circuit board according to the present embodiment comprises a layered structure in which a resin layer and a copper layer are laminated. The copper layer is a layer derived from the harmonized copper foil of the present invention. Furthermore, regarding the resin layer, it is as described above regarding copper-clad laminates. In any case, known layered structures may be adopted for the printed circuit board. Specific examples regarding the printed circuit board include a single-sided or double-sided printed circuit board in which a circuit is formed after forming a laminate by adhering the harmonized copper foil of the present invention to one or both sides of a prepreg and curing it, or a multilayer printed circuit board formed by multilayering these. Furthermore, other specific examples include a flexible printed circuit board, COF, TAB tape, etc., in which a circuit is formed by forming the harmonized copper foil of the present invention on a resin film. As another specific example, a resin-equipped copper foil (RCC) is formed by applying the resin layer described above to the copper foil treated with the present invention, and the resin layer is laminated onto the printed circuit board described above as an insulating adhesive layer, and then a circuit is formed using the modified semi-additive method (MSAP), subtractive method, etc., with the copper foil treated with the present invention as all or part of the wiring layer, or a build-up wiring board in which the copper foil treated with the present invention is removed and a circuit is formed using the semi-additive method (SAP), or a direct build-up-on-wafer in which the lamination of the resin-equipped copper foil and the formation of a circuit are alternately repeated on a semiconductor integrated circuit.

[0090] Examples

[0091] The present invention will be explained in more detail by the following examples.

[0092] Examples 1 to 15

[0093] The copper foil of the present invention was manufactured as follows.

[0094] (1) Manufacturing of electrolytic copper foil

[0095] For Examples 1 to 9 and 11 to 15, a sulfate acidic copper sulfate solution having the composition shown below was used as the copper electrolyte, a titanium electrode was used as the cathode, and a DSA (dimension-stable anode) was used as the anode, with a solution temperature of 45°C and a current density of 55 A / dm² 2 Electrolytic copper foil A with the thickness shown in Table 1 was obtained by electrolysis. At this time, as the cathode, an electrode with a surface roughness adjusted by polishing the surface with a #1000 buff was used.

[0096] <Composition of Acidic Copper Sulfate Solution>

[0097] - Copper concentration: 80 g / L

[0098] - Sulfuric acid concentration: 300g / L

[0099] - Glue concentration: 5 mg / L

[0100] - Chlorine concentration: 30 mg / L

[0101] Meanwhile, for Example 10, an acidic copper sulfate solution with the composition shown below was used as the copper electrolyte to obtain an electrolytic copper foil B with the thickness shown in Table 1. At this time, conditions other than the composition of the acidic copper sulfate solution were the same as those for electrolytic copper foil A.

[0102] <Composition of Acidic Copper Sulfate Solution>

[0103] - Copper concentration: 80 g / L

[0104] - Sulfuric acid concentration: 260 g / L

[0105] - Bis(3-sulfopropyl)disulfide concentration: 30 mg / L

[0106] - Diallyldimethylammonium chloride polymer concentration: 50 mg / L

[0107] - Chlorine concentration: 40 mg / L

[0108] (2) Harmonization

[0109] Among the electrode surface and deposition surface of the electrolytic copper foil described above, a roughening treatment was performed on the deposition surface side for Examples 1 to 6, 10, and 12 to 15, and on the electrode surface side for Examples 7 to 9 and 11. In addition, the 10-point average roughness Rz measured in accordance with JIS B0601-1994 using a contact-type surface roughness meter on the deposition surface of the electrolytic copper foil used in Examples 1 to 6, 10, and 12 to 15, and on the electrode surface of the electrolytic copper foil used in Examples 7 to 9 and 11, was as shown in Table 1.

[0110] For Examples 1 to 8, the tamping treatment (first tamping treatment) described below was performed. This tamping treatment was carried out by electrolyzing in a copper electrolytic solution for tamping treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30℃) under the conditions of liquid resistance index, current density, and time shown in Table 1 for each example, and by washing with water.

[0111] For Examples 9 to 15, the first harmonic treatment, the second harmonic treatment, and the third harmonic treatment shown below were performed in this order.

[0112] - The first tamping treatment was performed by electrolyzing in a copper electrolytic solution for tamping treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30℃) under the conditions of liquid resistance index, current density, and time shown in Table 1, and by washing with water.

[0113] - The second harmonization treatment was performed by electrolyzing in a copper electrolytic solution for harmonization treatment of the same composition as the first harmonization treatment under the conditions of liquid resistance index, current density, and time shown in Table 1, and then washing with water.

[0114] - The third harmonization treatment was performed by electrolyzing in a copper electrolytic solution for harmonization treatment (copper concentration: 65 g / L or more and 80 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 45℃) under the conditions of liquid resistance index, current density, and time shown in Table 1, and by washing with water.

[0115] (3) Anti-corrosion treatment

[0116] The anti-corrosion treatment shown in Table 1 was performed on the electrolytic copper foil after the thawing treatment. As for this anti-corrosion treatment, for Examples 1 to 5, 7, and 8, a pyrophosphate bath was used on the thawing-treated surface of the electrolytic copper foil, with a potassium pyrophosphate concentration of 100 g / L, a zinc concentration of 1 g / L, a nickel concentration of 2 g / L, a molybdenum concentration of 1 g / L, a liquid temperature of 40°C, and a current density of 0.5 A / dm² 2 Zinc-nickel-molybdenum-based anti-corrosion treatment was performed. In addition, on the surface of the electrolytic copper foil that was not treated, a pyrophosphate bath was used with a potassium pyrophosphate concentration of 80 g / L, a zinc concentration of 0.2 g / L, a nickel concentration of 2 g / L, a liquid temperature of 40℃, and a current density of 0.5 A / dm². 2 Zinc-nickel anti-corrosion treatment was performed in this manner. Meanwhile, for Examples 6 and 9 to 15, zinc-nickel anti-corrosion treatment was performed on both sides of the electrolytic copper foil under the same conditions as the sides of the electrolytic copper foil in Examples 1 to 5, 7, and 8 that were not treated.

[0117] (4) Chromate treatment

[0118] Chromate treatment was performed on both sides of the electrolytic copper foil treated with the above-mentioned anti-corrosion treatment to form a chromate layer on the anti-corrosion treatment layer. This chromate treatment was performed at a chromic acid concentration of 1 g / L, pH 11, liquid temperature of 25°C, and current density of 1 A / dm². 2 It was performed under the conditions of.

[0119] (5) Silane coupling agent treatment

[0120] The copper foil subjected to the above chromate treatment was washed with water, and then immediately treated with a silane coupling agent to adsorb the silane coupling agent onto the chromate layer of the glazing treatment surface. This silane coupling agent treatment was performed by spraying a solution of the silane coupling agent, using pure water as a solvent, onto the glazing treatment surface via a shower and adsorbing it. As the silane coupling agent, 3-aminopropyltrimethoxysilane was used in Examples 1 and 3 to 8, and 3-glycidoxypropyltrimethoxysilane was used in Examples 2 and 9 to 15. The concentration of the silane coupling agent was set to 3 g / L in all cases. After the adsorption of the silane coupling agent, the moisture was finally evaporated using an electric heater to obtain a glazing-treated copper foil of a predetermined thickness.

[0121]

[0122] evaluation

[0123] Various evaluations as shown below were performed on the manufactured copper foil treated with harmonization.

[0124] (a) Surface properties of the harmonized surface

[0125] Measurements of the surface roughness of the roughened copper foil were performed in accordance with ISO 25178 or JIS B0601-2013 by surface roughness analysis using a laser microscope (Olympus Co., Ltd., OLS-5000). At this time, for Spd, Vmp, Vmc, and Sdr, measurements were performed at a magnification of 200x (objective lens magnification 100x × optical zoom 2x) as shown in Table 2, and for Rdc, Sk, and Sxp, measurements were performed at a magnification of 20x (objective lens magnification 20x) as shown in Table 3. Other specific measurement conditions were as shown in Tables 2 and 3. The surface profile of the obtained roughened surface was analyzed according to the conditions shown in Tables 2 and 3 to calculate Spd, Vmp, Vmc, Sdr, Rdc, Sk, and Sxp. In addition, based on the obtained values ​​of Spd, Vmp, and Vmc, Vmp+Vmc and the micro-tip particle volume (=(Vmp+Vmc) / Spd) were calculated. The results were as shown in Table 4.

[0126]

[0127]

[0128] (b) Peel strength between copper foil and substrate

[0129] To evaluate the adhesion of the copper foil treated with a heating process under ambient temperature and high humidity conditions to the insulating substrate, the state peel strength and moisture peel strength were measured as follows.

[0130] (b-1) Condition peel strength

[0131] As insulating substrates, two prepregs (thickness 100 μm) composed mainly of polyphenylene ether, trialyl isocyanurate, and bismaleimide resin were prepared and laminated. A surface-treated copper foil was laminated onto the laminated prepreg so that its surface treatment side was in contact with the prepreg, and a copper-clad laminate was manufactured by pressing at 32 kgf / ㎠ and 205°C for 120 minutes. Next, a circuit was formed on the copper-clad laminate by an etching method to manufacture a test board having a straight circuit with a width of 3 mm. In addition, for Examples 1, 2, and 12, copper plating was performed on the copper foil side surface of the copper-clad laminate before circuit formation until the thickness of the copper foil reached 18 μm. In addition, for Examples 4 to 6, 14, and 15, etching was performed on the copper foil-side surface of the copper-clad laminate before circuit formation until the thickness of the copper foil reached 18 μm. The straight circuit obtained in this way was peeled from the insulating substrate in accordance with Method A (90° peeling) of JIS C 5016-1994, and the state peel strength (kgf / cm) was measured. The quality of the obtained state peel strength was evaluated according to the following criteria. The results were as shown in Table 4.

[0132] <Criteria for Evaluating Condition Peel Strength>

[0133] - Good: Condition, peel strength of 0.40 kgf / cm or higher

[0134] - Defective: Condition where peel strength is less than 0.40 kgf / cm

[0135] (b-2) Moisture peel strength

[0136] Prior to measuring the peel strength, the moisture-resistant peel strength (kgf / cm) was measured in the same procedure as the peel strength in the above-described state, except that a test substrate equipped with a straight circuit was immersed in boiling water for 2 hours. The quality of the obtained moisture-resistant peel strength was evaluated according to the following criteria. The results were as shown in Table 4.

[0137] Moisture Peel Strength Evaluation Criteria

[0138] - Good: Moisture peel strength of 0.40 kgf / cm or higher

[0139] - Defective: Moisture peel strength less than 0.40 kgf / cm

[0140] (c) Transmission characteristics

[0141] A high-frequency substrate (Panasonic, MEGTRON 6N) was prepared as an insulating resin substrate. Copper foil with a tangling treatment was laminated on both sides of this insulating resin substrate so that the tangling surfaces were in contact with the insulating resin substrate. Using a vacuum press, the layers were laminated under conditions of a temperature of 190°C and a pressing time of 120 minutes to obtain a copper-clad laminate with an insulating thickness of 136 μm. Subsequently, an etching process was performed on the copper-clad laminate to form microstrip lines such that the characteristic impedance was 50 Ω, thereby obtaining a substrate for measuring transmission loss. For the obtained substrate for measuring transmission loss, the transmission loss (dB / cm) at 28 GHz was measured using a network analyzer (Keysight Technologies, N5225B). The quality of the obtained transmission loss was evaluated according to the following criteria. The results were as shown in Table 4.

[0142] <Transmission Loss Evaluation Criteria>

[0143] -Good: Transmission loss of -0.33dB / cm or higher

[0144] -Poor: Transmission loss less than -0.33 dB / cm

[0145]

Claims

Claim 1 A harmonized copper foil having a harmonized surface on at least one side, wherein the harmonized surface has a substantial volume Vmp (μm) of protruding peaks per unit area. 3 / ㎛ 2 ), actual volume of the core per unit area Vmc (㎛ 3 / ㎛ 2 ), and peak density of mountains per unit area Spd (pieces / ㎛) 2 Based on ), the micro-tip particle volume calculated by the formula (Vmp+Vmc) / Spd is 1.300㎛ 3 A copper foil with a roughness treatment, wherein the number of pieces is less than or equal to 1, and the cutting level difference Rdc is 0.95 μm or greater, and the above Vmp, Vmc, and Spd are values ​​measured under conditions of a magnification of 200x, a cutoff wavelength of 0.3 μm by an S filter, and a cutoff wavelength of 5 μm by an L filter in accordance with ISO 25178, and the above Rdc is a value obtained as the difference in the height direction cutting level c (c(Rmr1)-c(Rmr2)) at a load length ratio (Rmr1) of 20% and a load length ratio (Rmr2) of 80% in a roughness curve measured under conditions of a magnification of 20x, without performing a cutoff by a cutoff value λs, and a cutoff wavelength of 320 μm by a cutoff value λc in accordance with JIS B0601-2013. Claim 2 In claim 1, the harmonized treated surface is a harmonized treated copper foil having a cutting level difference Rdc of 1.10㎛ or more and 20.00㎛ or less. Claim 3 In claim 1 or 2, the harmonized treated surface has a substantial volume Vmc of the core part per unit area of ​​0.360 μm 3 / ㎛ 2 Lee Ha-in, harmony-treated copper foil. Claim 4 In claim 1 or 2, the harmonized treated surface has a sum Vmp+Vmc, which is the sum of the actual volume Vmp of the protruding peak and the actual volume Vmc of the core part, of 0.380 μm 3 / ㎛ 2 Lee Ha-in, harmony-treated copper foil. Claim 5 A harmonized copper foil according to claim 1 or 2, wherein the harmonized treated surface has an interface development area ratio Sdr of 70% or less, and the Sdr is a value measured under conditions of a magnification of 200x, a cutoff wavelength of 0.3㎛ by an S filter, and a cutoff wavelength of 5㎛ by an L filter in accordance with ISO 25178. Claim 6 A harmonized copper foil according to claim 1 or 2, wherein the harmonized treated surface has a level difference Sk of 1.50 μm or more of the core portion, and the Sk is a value measured under conditions of a magnification of 20x, without cutting off by an S filter, and a cutoff wavelength of 320 μm by an L filter in accordance with ISO 25178. Claim 7 A harmonized copper foil according to claim 1 or 2, wherein the harmonized treated surface has a pole height Sxp of 1.10 μm or more, and the Sxp is a value measured under conditions of a magnification of 20x, without cutting off by an S filter, and a cutoff wavelength of 320 μm by an L filter in accordance with ISO 25178. Claim 8 In claim 1 or 2, the harmonic treatment surface has a peak density Spd of the mountain per unit area of ​​0.12 / ㎛ 2 0.46 or more / ㎛ 2 Lee Ha-in, harmony-treated copper foil. Claim 9 A copper foil treated with a rust-prevention treatment layer and / or a silane coupling agent treatment layer further provided on the harmonized surface in accordance with claim 1 or 2. Claim 10 A copper foil treated with a harmonizing process according to claim 1 or 2, wherein the copper foil treated with a harmonizing process is an electrolytic copper foil, and the surface treated with a harmonizing process is located on the precipitation surface side of the electrolytic copper foil. Claim 11 Copper-clad laminate having the copper foil treated with harmonization as described in paragraph 1 or 2. Claim 12 A printed circuit board having the copper foil treated with harmonization as described in paragraph 1 or 2.

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