TW202020233A - Surface-treated copper foil, carrier-attached copper foil, copper-clad laminate, and printed wiring board - Google Patents

Abstract

Provided is a surface-treated copper foil that, in the case of use in the SAP method, can provide a resin substrate with a surface profile that can effectively prevent the generation of deposition that can be produced in a circuit in the step of etching an electroless copper plating layer. The surface-treated copper foil is a surface-treated copper foil that has a treated surface on at least one side thereof. When a resin film is hot-press bonded to the treated surface, the surface shape of the treated surface is transferred to the surface of the resin film, and the surface-treated copper film is then removed by etching, the skewness Ssk for the surface of the remaining resin film, as measured in accordance with ISO 25178, is less than or equal to -0.6.

Description

Surface treated copper foil, copper foil with carrier, copper clad laminate and printed wiring board

The invention relates to surface-treated copper foil, copper foil with carrier, copper-clad laminate and printed wiring board

In recent years, the semi-additive method (SAP method) has been widely adopted as a manufacturing method of a printed wiring board suitable for circuit miniaturization. The SAP method is a method suitable for forming extremely fine circuits, and as an example, it is performed using a roughened copper foil with a carrier. For example, as shown in FIGS. 1 and 2, an ultra-thin copper foil 10 having a roughened surface is applied to an insulating resin substrate 11 provided with a lower circuit 11b on a lower base material 11a using a prepreg 12 and an undercoat layer 13 to apply pressure After making it adhere (engineering (a)) and peeling off the carrier (not shown), through holes 14 are formed by laser perforation as necessary (engineering (b)). Next, the ultra-thin copper foil is removed by etching to expose the undercoat layer 13 that gives the roughened surface profile (process (c)). After applying the electroless copper plating 15 (process (d)) to the roughened surface, it is masked in a predetermined pattern by exposure and development with the dry film 16 (process (e)), and the electroplated copper 17 is applied (process (f)). After removing the dry film 16 to form the wiring part 17a (process (g)), the unnecessary electroless copper plating 15 between adjacent wiring parts 17a and 17a is removed by etching (process (h)) to obtain wiring formed in a predetermined pattern 18.

In this way, the SAP method of roughening copper foil is used, and the roughening copper foil itself is removed by etching after laser perforation (process (c)). Next, on the surface of the laminated body from which the roughened copper foil is removed, the uneven shape of the roughened surface of the roughened copper foil is transferred, and an insulating layer (such as the undercoat layer 13 or no At this time, it is the adhesion between the prepreg 12) and the plated circuit (for example, the wiring 18). In addition, the modified semi-additive method (MSAP method) that does not perform the copper foil removal process equivalent to the process (c) is also widely used, but it is necessary because of the etching process after the dry film removal (equivalent to the process (h)) The two layers of the copper foil layer and the electroless copper plating layer are removed by etching, and deeper etching is required than the SAP method in which only one layer of the electroless copper plating layer is removed by etching. Therefore, because of the necessity of considering more etching to make the circuit space narrower, the MSAP method is a little worse than the SAP method in the formation of fine circuits. That is, the SAP method is more advantageous for the purpose of forming a finer circuit.

In addition, in the etching process (equivalent to process (h)) after the removal of the dry film, the interface between the circuit (for example, wiring 18) and the insulating layer is etched. As a result, the root of the circuit is hollowed out, which is called erosion. The phenomenon called "insertion". If this insertion occurs, the adhesion between the circuit and the insulating layer will decrease, causing the circuit to peel off.

On the other hand, a roughened copper foil for controlling the shape of roughened particles is known. For example, in Patent Document 1 (Patent No. 6293365), in a roughened copper foil having a roughened surface having a plurality of slightly spherical protrusions, the average height of the slightly spherical protrusions is set to 2.60 μm or less, Moreover, the ratio of the average maximum diameter b _ave of the slightly spherical protrusions to the average neck diameter a _ave of the slightly spherical protrusions b _ave /a _{ave is} set to 1.2 or more, which is not only an excellent coating when used in the SAP method The circuit adhesion can also give the laminate a surface profile that is excellent in the etching property of electroless copper plating. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Patent No. 6293365

In recent years, with the further miniaturization of circuits, the adoption of the SAP method, which is advantageous for the formation of fine circuits, has been expanded. In this regard, as the width of the circuit pattern becomes narrower, the allowable insertion width is relatively reduced. In addition, in the SAP method, in the etching process after removal of the dry film, it is sufficient to etch away only the electroless copper plating layer, and it is possible to use non-electrolytic copper but an etching solution that can selectively remove the electroless copper. With this, it is possible to suppress the thinning of most circuits composed of electrolytic copper. Therefore, the SAP method is more advantageous than the MSAP method in terms of the formation of fine circuits. On the other hand, since the bottom part of the circuit formed by the SAP method is made of electroless copper, insertion is more likely to occur when using the above etching solution.

The present inventors have now obtained that by giving the surface profile specified by the skewness Ssk measured in accordance with ISO 25178 on the surface of the resin substrate, it can be effectively used in the etching process of the electroless copper plating layer of the SAP method Insights to suppress the occurrence of insertions generated in the circuit. In addition, when the method is used in the SAP method, it is also possible to provide an insight that a surface-treated copper foil that can impart the above-mentioned unique surface profile to a resin substrate.

Therefore, an object of the present invention is to provide a surface-treated copper foil which, when used in the SAP method, imparts to the resin a surface profile that can effectively suppress the occurrence of circuit insertion in the etching process of electroless copper plating Substrate.

According to one aspect of the present invention, there is provided a surface-treated copper foil having a treated surface on at least one side; When the resin film is thermally pressed on the treated surface and the surface shape of the treated surface is transferred to the surface of the resin film, and the surface-treated copper foil is removed by etching, among the remaining surfaces of the resin film The skewness Ssk measured under ISO25178 is the criterion -0.6 or less.

According to another aspect of the present invention, there is provided a copper foil with a carrier, comprising: a carrier, a peeling layer provided on the carrier, and a surface-treated copper foil provided on the peeling layer with the aforementioned treated surface as an outer side.

According to another aspect of the present invention, there is provided a copper-clad laminate including the surface-treated copper foil or the carrier-attached copper foil.

According to another aspect of the present invention, there is provided a printed wiring board obtained by using the surface-treated copper foil or the carrier-attached copper foil.

According to another aspect of the present invention, a resin substrate is provided, and the skewness Ssk measured on at least one surface according to ISO 25178 is -0.6 or less.

definition

Definitions of terms and parameters used to specify the present invention are shown below.

In this specification, "skewness Ssk" refers to a parameter indicating the symmetry of the height distribution measured based on ISO25178. When the value is 0, it means that the height distribution is symmetrical. As shown in FIG. 3A, this value is smaller than 0, which indicates a surface with many fine valleys. On the other hand, as shown in FIG. 3B, when the value is greater than 0, it indicates a surface with many fine peaks. The skewness Ssk can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 57074.677 μm ² ) on the processing surface with a commercially available laser microscope.

The "arithmetic mean curvature Spc of the peak apex" in this specification refers to a parameter indicating the arithmetic mean of the main curvature of the peak apex of the surface measured based on ISO25178. The smaller the value, the point of contact with other objects has rounded corners. On the other hand, a larger value indicates that the point of contact with other objects is sharp. Directly speaking, the arithmetic mean curvature Spc of the peak apex can be said to be a parameter indicating convex roundness that can be measured by a laser microscope. The arithmetic mean curvature Spc of the peak apex can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 57074.677 μm ² ) on the treated surface with a commercially available laser microscope.

In this specification, "peak apex density Spd" refers to a parameter indicating the number of peak apexes per unit area measured based on ISO25178. The larger the value, the greater the number of contact points with other objects. The peak top density Spd can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 57074.677 μm ² ) on the treated surface with a commercially available laser microscope.

In this manual, "surface load curve" (hereinafter, simply referred to as "load curve") refers to a curve that shows the height of the load area ratio from 0% to 100% measured based on ISO25178. As shown in FIG. 4, the load area ratio is a parameter indicating the area of a region of a certain height c or more. The load area ratio at height c corresponds to Smr(c) in FIG. 4. As shown in Figure 5, make the load area from 0% along the load curve and set the difference of the load area ratio to 40% minus the secant of the load curve. The position is called the central part of the load curve. With respect to this central portion, a straight line having the smallest quadratic sum of deviations in the longitudinal axis direction is called an equivalent straight line. The portion included in the height range from the equivalent area of the load area ratio of 0% to 100% is called the core portion. The portion higher than the core portion is called a protruding peak portion, and the portion lower than the core portion is called a protruding valley portion. The core part indicates the height of the area in contact with other objects after the initial wear.

"Pole height Sxp" in this specification, as shown in FIG. 6, refers to a parameter indicating the difference between the heights of the load area ratio p% and the load area ratio q% measured based on ISO25178. Sxp represents the difference between the average height of the surface and the height of the surface after removing particularly high peaks from the surface. In this specification, Sxp represents the difference in height between the load area ratio of 2.5% and the load area ratio of 50%. The pole height Sxp can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 57074.677 μm ² ) on the treated surface with a commercially available laser microscope.

In this specification, the "load area ratio Smr1 separating the protruding peak portion and the core portion", as shown in FIG. 5, refers to the load area ratio indicating the intersection of the height of the upper portion of the core portion and the load curve measured based on ISO25178 (That is, the load area ratio separating the core part and the protruding peak part). The larger the value, the greater the proportion of prominent peaks. In addition, as shown in FIG. 5, the “load area ratio Smr2 separating the protruding valley part and the core part” in this specification refers to the load area indicating the intersection of the height of the lower part of the core part and the load curve measured in accordance with ISO25178. The parameter of the rate (that is, the load area ratio separating the core part and the protruding valley part). The larger the value, the greater the proportion of prominent valleys.

In this specification, "the physical volume of the core part Vmc" refers to a parameter indicating the volume of the core part measured based on ISO25178. As shown in FIG. 7, Vmc represents the difference between the physical volume separating the load area ratio Smr2 of the protruding valley and the core, and the physical volume separating the load area ratio Smr1 of the protruding peak and core. The physical volume Vmc of the core portion can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 57074.677 μm ² ) on the treatment surface with a commercially available laser microscope. In this specification, the load area ratio Smr1 separating the peaks and cores is 10%, and the load area ratio Smr2 separating the valleys and cores is 80%, and the physical volume Vmc of the core is calculated.

In this specification, the "electrode surface" of the electrolytic copper foil refers to the surface on the side connected to the cathode when the electrolytic copper foil is produced.

In this specification, the "precipitation surface" of the electrolytic copper foil is the surface on the side where the electrolytic copper precipitates when the electrolytic copper foil is produced, that is, the surface on the side not connected to the cathode.

Surface treatment copper foil The copper foil of the present invention is a surface-treated copper foil. This surface-treated copper foil is a resin film remaining when the resin film is thermally pressed on the treated surface and the surface shape of the treated surface is transferred to the surface of the resin film, and the surface-treated copper foil is removed by etching (hereinafter, also referred to as Is a resin replica) the skewness Ssk of the surface (hereinafter also referred to as the transfer surface) measured according to ISO25178 is -Those below 0.6.

As mentioned above, with the demand for more miniaturized circuits, the adoption of the SAP method that is advantageous for the formation of fine circuits has been expanded. In this regard, as the width of the circuit pattern becomes narrower, the allowable insertion width is relatively reduced. That is, the insertion width allowed in the former pattern width (for example, 30 μm) and the finer circuit pattern width (for example, 10 μm) are likely to cause the specification to be exceeded due to reasons such as increased risk of circuit collapse.

In addition, although the SAP method is advantageous in miniaturization of the circuit compared with other construction methods such as the MSAP method, there are disadvantages in terms of insertion suppression. At this point, for example, in the circuit formation by the MSAP method, as illustrated in FIG. 8A, on the resin substrate 112, a rust prevention layer 114 and an electrolytic copper layer 116 due to a copper foil with a carrier are prepared to be sequentially laminated The laminated body 110 (process (i)) forms electroless copper plating 118 with the electrolytic copper layer 116 remaining. Next, the dry film is masked in a predetermined pattern, and then copper plating is applied to form the wiring portion 120 (process (ii)). Therefore, in the MSAP method, since the electrolytic copper layer 116 remains on the resin substrate 112, it is necessary to remove the electrolytic copper layer 116 and the electroless copper plating 118 in the etching removal process of unnecessary portions between adjacent wiring portions 120, 120 These two layers are removed by etching. Therefore, as shown in step (iii) of FIG. 8A, the obtained wiring 122 is likely to be thinned. On the other hand, in the MSAP method, since the electrolytic copper layer 116 is not completely removed as described above, the rust prevention layer 114 exists between the resin substrate 112 and the wiring 122, which helps prevent the rust prevention layer 114 from being inserted. On the other hand, in the circuit formation by the SAP method, as illustrated in FIG. 8B, the preparation of the laminate 110 formed by sequentially forming the rust prevention layer 114 and the electrolytic copper layer 116 on the resin substrate 112 (process (i )), complete removal of the electrolytic copper layer 116 (process (ii)), the formation of the electroless copper plating 118, the shielding by dry film, and the formation of the wiring part 120 by copper electroplating (process (iii) )). Therefore, in the SAP method, since the electrolytic copper layer 116 is not left on the resin substrate 112, in the etching removal process of unnecessary portions between adjacent wiring portions 120, 120, only the electroless copper layer 118 may be etched and removed. It is possible to suppress the thinning of the circuit of the wiring 122 thus obtained. In addition, in the SAP method, since non-electrolytic copper is used as an etching solution that can selectively remove electroless copper, it is possible to more effectively suppress the thinning of the wiring 122 mainly composed of electrolytic copper. Therefore, regarding the miniaturization of the circuit, the SAP method is more advantageous than other construction methods such as the MSAP method. However, as shown in step (iv) of FIG. 8B, the wiring 122 formed by the SAP method is composed of electroless copper plating 118 at the bottom, and when an etching solution that can selectively remove electroless copper is used, the wiring 122 and The interface 124 of the resin substrate 112 is susceptible to insertion 124. In this regard, the surface treated copper foil provided with the anti-corrosion layer 114 on the electrolytic copper layer 116 is also used as a copper foil for SAP. In the SAP method, the electrolytic copper layer 116 is completely removed by etching. The anti-rust metal was also etched at this time (refer to the engineering (ii) of FIG. 8B). In addition, in FIGS. 8A and 8B, for emphasis, the thickness of the rust prevention layer 114 is exaggerated and does not necessarily reflect the actual thickness ratio in the laminate. Therefore, in the SAP method, it is not easy to suppress insertion that occurs in the circuit.

In this regard, by using the surface-treated copper foil of the present invention for the SAP method, it is possible to impart a unique surface profile with a skewness Ssk of -0.6 or less measured on the surface of the resin base material according to ISO 25178. In this way, in the etching process of the electroless copper plating layer, it is possible to effectively suppress the occurrence of insertion that may occur in the circuit. Although the mechanism by which the surface contour of the resin base material has the above-mentioned surface profile to suppress insertion in the circuit is not necessarily determined, there are the following as a factor. That is, the convex portion on the surface of the resin substrate forming the circuit (that is, the transfer surface of the resin replica) acts as a protective wall to stop the infiltration of the etchant in the etching process of electroless copper plating by the SAP method. Therefore, the thicker the protective wall, the more difficult it is to insert. At this point, based on the definition of the aforementioned skewness Ssk, as shown in FIGS. 9A and 9B, the resin replica 20 with a small skewness Ssk (refer to FIG. 9A) and the resin replica 20 with a large skewness Ssk (refer to FIG. 9B) In contrast, the wall thickness of the convex portion 20a becomes thicker (refer to the position where a circle mark is added in the figure). Therefore, by making the skewness Ssk of the resin replica sufficiently smaller than -0.6 or less, the protective wall can be thickened, and thus the insertion in the circuit 22 can be effectively suppressed.

From the above viewpoint, the surface-treated copper foil of the present invention is preferably used for the production of printed wiring boards by the SAP method. In other aspects, the surface-treated copper foil of the present invention is preferably used for transferring uneven shapes on the insulating resin layer for printed wiring boards.

The surface-treated copper foil of the present invention has a treated surface on at least one side. The treated surface is a surface subjected to any surface treatment, and is typically a roughened surface. The treated surface is typically formed with plural protrusions (for example, roughened particles). In any case, the surface-treated copper foil may have a treated surface (for example, a roughened surface) on both sides, or a treated surface on only one side. When there are treated surfaces on both sides, when used in the SAP method, the surface irradiated by the laser (the surface opposite to the surface adhered to the insulating resin) is also surface-treated. As a result of the improved laser absorption, it is also possible Laser perforation improved.

The surface-treated copper foil of the present invention is to heat-press the resin film on the treated surface and transfer the surface shape of the treated surface to the surface of the resin film. When the surface-treated copper foil is removed by etching, the surface of the remaining resin film ( That is, the skewness Ssk of the resin replica) is -0.6 or less, preferably -1.7 or more -0.6 or less, more preferably -1.6 or more -0.7 or less, and even more preferably -1.5 or more -0.9 or less, Particularly good is -1.5 or more -1.1 or less. Within the above-mentioned preferable range, the occurrence of insertion in the etching process of the SAP method can be further suppressed, and at the same time, the convex portion of the treated surface of the surface-treated copper foil can be suppressed to an appropriate shape that is not too slender, which can effectively It is possible to suppress the occurrence of powder falling caused by bending or falling of the convex portion of the surface-treated copper foil. The resin film is preferably a thermosetting resin film, and the prepreg may be in the form. Examples of thermosetting resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, phenol resins, and polyimide resins. The hot press-bonding is not particularly limited as long as the irregularities of the treated surface of the surface-treated copper foil can be transferred to the resin film under transferable conditions. For example, hot pressing is preferably performed under the conditions of a pressure of 3.0 MPa or more and 5.0 MPa or less, a temperature of 200°C or more and 240°C or less, and between 60 minutes and 120 minutes.

Surface treated copper foil of the present invention, the surface of the resin film after the etching residue (i.e., resin transfer surface replicas), an arithmetic mean peak point Spc curvature less than 5000mm ^-1 13000mm ^-1 or less more preferred, more preferably more than 7000mm ^-1 13000mm ^-1 or less, more then 9000mm ^-1 a good 13000mm ^-1 or less, and particularly preferably more than 10000mm ^-1 13000mm ^-1 or less. If it is within the above-mentioned preferred range, the convex portion of the surface of the surface-treated copper foil can be suppressed to an appropriate shape that is not too slender, and the bending or falling off of the convex portion of the surface-treated copper foil can be effectively suppressed The occurrence of powder loss also suppresses the occurrence of insertion in the etching process of the SAP method. As a factor that can suppress the occurrence of insertion, the following causes are presumed. That is, based on the definition of the arithmetic mean curvature Spc of the peak apex, as shown in FIGS. 9A and 9B, the resin replica 20 (refer to FIG. 9A) having a small arithmetic mean curvature Spc of the peak apex and the arithmetic mean of the peak apex Compared with the resin replica 20 having a large curvature Spc (refer to FIG. 9B ), the vertex of the convex portion 20a is flat. As a result, the thickness of the convex portion 20a acting as an insertion protection wall becomes thicker.

The surface-treated copper foil of the present invention has a peak apex density Spd of 1.13×10 ⁶ mm ^-2 or more 1.50×10 ⁶ mm on the surface of the resin film remaining after the etching (that is, the transfer surface of the resin replica) ^-2 or less is better, more preferably 1.13×10 ⁶ mm ^-2 or more 1.40×10 ⁶ mm ^-2 or less, more preferably 1.14×10 ⁶ mm ^-2 or more 1.30×10 ⁶ mm ^-2 or less, especially good It is 1.15×10 ⁶ mm ^-2 or more 1.20×10 ⁶ mm ^-2 or less. Within the above-mentioned preferable range, the convex portions of the treated surface of the surface-treated copper foil can be suppressed to an appropriate number to effectively suppress the occurrence of dusting, and the occurrence of insertion in the etching process of the SAP method can be further suppressed. That is, as described above, because the insertion of the circuit is stopped at the convex portion of the resin replica, the resin replica where the convex portion exists at a high frequency can suppress the progress of the insertion. At this point, based on the definition of the peak apex density Spd, as shown in FIGS. 9A and 9B, the resin replica 20 (see FIG. 9A) having a large peak apex density Spd is copied with the resin having a small peak apex density Spd Compared with the product 20 (refer to FIG. 9B), the convex portion 20a exists at a high frequency. Therefore, even when the insertion occurs, the progress can be stopped at an early stage.

In the surface-treated copper foil of the present invention, the surface of the resin film remaining after the etching (that is, the transfer surface of the resin replica), the physical volume of the core part Vmc (mL/m ² ) relative to the pole height Sxp (μm) The ratio Vmc/Sxp is 0.39 or more and 0.44 or less, preferably 0.39 or more and 0.43 or less, still more preferably 0.39 or more and 0.42 or less, particularly preferably 0.39 or more and 0.41 or less, and most preferably 0.39 or more and 0.40 or less. If it is within the above-mentioned preferred range, the convex portion of the surface of the surface-treated copper foil can be suppressed to an appropriate shape that is not too slender, and the bending or falling off of the convex portion of the surface-treated copper foil can be effectively suppressed The occurrence of powder loss also suppresses the occurrence of insertion in the etching process of the SAP method. In addition, the adhesion between the substrate and the circuit can also be increased. That is, as described above, after the convex portion of the resin replica acts as a protective wall to stop the penetration of the etchant, if the solid volume Vmc of the core portion is larger based on the definition of the solid volume Vmc of the core portion, the resin replica The convex portion also becomes larger, and insertion can be more suppressed. On the other hand, if based on the aforementioned definition of the physical volume Vmc of the core portion and the pole height Sxp, as shown in FIGS. 10A and 10B, the physical volume Vmc of the core portion also depends on the height of the convex portion 20a of the resin replica 20, by By comparing Vmc/Sxp, which is the pole height Sxp, which is a parameter related to the height of the convex portion 20a, the size of the convex portion 20a can be evaluated by using the height of the convex portion 20a as a consistent conversion value. Also, by increasing Vmc/Sxp (for example, 0.39 or more), the area of the convex portion 20a of the resin replica 20 that bites into the circuit 22 also becomes larger (that is, the amount of resin that is surrounded and held by the circuit 22 increases) because of the anchor As the fixed effect increases, the adhesion between the substrate and the circuit also increases.

Method for manufacturing surface-treated copper foil Although an example of a preferred method for manufacturing the surface-treated copper foil of the present invention is described, the surface-treated copper foil of the present invention is not limited to the method described below, and can be manufactured by any method as long as the above-mentioned surface profile can be given to the surface of the resin film can.

(1) Preparation of copper foil As the copper foil used for the manufacture of the surface-treated copper foil, both electrolytic copper foil and rolled copper foil can be used. Although the thickness of the copper foil is not particularly limited, it is preferably 0.1 μm or more and 18 μm or less, more preferably 0.5 μm or more and 10 μm or less, more preferably 0.5 μm or more and 7 μm or less, particularly preferably 0.5 μm or more and 5 μm or less, and most preferably 0.5 μm or more and 3μm or less. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil is formed by a wet film forming method such as electroless copper plating and electrolytic copper plating, a dry film forming method such as sputtering and chemical vapor deposition, or a combination of these It can be formed by other methods.

(2) Surface treatment (roughening treatment) At least one surface of the copper foil is roughened using copper particles. This roughening is performed by electrolysis using a copper electrolytic solution for roughening treatment. The electrolysis is preferably performed through a two-stage or three-stage coating process, and more preferably through a three-stage coating process. In the first-stage coating process, copper concentration of 5 g/L or more and 20 g/L or less, sulfuric acid concentration of 30 g/L or more and 200 g/L or less, chlorine concentration of 20 mg/L or more and 100 mg/L or less, and 9-phenylacridine (9PA) Copper sulfate solution with a concentration of 20 mg/L or more and 80 mg/L or less, with a coating temperature of 20°C or more and 40°C or less, current density of 5A/dm ² or more and 25A/dm ² or less, and a time of 2 seconds or more and 10 seconds or less It is better to perform electrodeposition. Although this first-stage coating process can be performed twice using a total of two tanks, it is preferably completed once in total. In the second-stage coating process, a copper sulfate solution containing a copper concentration of 65 g/L or more and 80 g/L or less and a sulfuric acid concentration of 200 g/L or more and 280 g/L or less is used at a liquid temperature of 45°C or higher and 55°C or lower, and a current density of 1A /dm ₂ or more and 10A/dm ₂ or less, and a plating time of 2 to 25 seconds. In the third-stage coating process, copper concentration of 10 g/L or more and 20 g/L or less, sulfuric acid concentration of 30 g/L or more and 130 g/L or less, chlorine concentration of 20 mg/L or more and 100 mg/L or less, and 9PA concentration of 100 mg/L are used. A copper sulfate solution of 200 mg/L or less is preferably electrodeposited under plating conditions of a liquid temperature of 20° C. or more and 40° C. or less, a current density of 10 A/dm ² or more and 40 A/dm ² or less, and a time of 0.3 seconds or more and 1.0 second or less. In particular the first stage coating project using additives like 9PA Preferably, the first stage coating project in _a total charge amount Q ₂ (Q ₁ + Q ₂₎ and the second stage coating project in the amount Q It is preferably set to 100 C/dm ² or less. In addition, from the viewpoint of uniformity of processing and workability, the distance between the positive electrode and the negative electrode in the coating process in the first stage is preferably 45 mm or more and 90 mm or less, and more preferably 50 mm or more and 80 mm or less.

(3) Anti-rust treatment If necessary, the copper foil after the roughening treatment may be subjected to rust prevention treatment. The rust prevention treatment is preferably a plating treatment containing zinc. The coating treatment using zinc may be any of zinc coating treatment and zinc alloy coating treatment. The zinc alloy coating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be at least a plating treatment containing Ni and Zn, or may contain other elements such as Sn, Cr, and Co. The Ni/Zn adhesion to the zinc-nickel alloy plating film is preferably a mass ratio of 1.2 or more and 10 or less, more preferably 2 or more and 7 or less, and even more preferably 2.7 or more and 4 or less. In addition, the rust prevention treatment preferably further contains a chromate treatment, which is preferably performed on the surface of the zinc-containing plating film after the zinc-containing plating film treatment. This can further improve the rust resistance. In particular, the preferred anti-rust treatment is a combination of chromate treatment after zinc-nickel alloy coating treatment.

(4) Silane coupling agent treatment If necessary, a silane coupling agent may be applied to the copper foil to form a silane coupling agent layer. This can improve moisture resistance, chemical resistance and adhesion to adhesives. The silane coupling agent layer can be formed by appropriately diluting and coating the silane coupling agent and drying it. Examples of silane coupling agents include epoxy functional silane coupling agents such as 4-glycidyl ether trimethyl, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltriethoxy Amino functional silane coupling agent such as silane, N-phenyl-3-aminopropyl triethoxy silane, or mercapto functional silane coupling agent such as 3-aminopropyl triethoxy silane, or vinyl trimethoxy Alkene functional silane coupling agent such as silane, vinylphenyl trimethoxy silane, etc., acrylic functional silane coupling agent such as 3-methacryl propyl propyl trimethoxy silane, or imidazole such as imidazole silane Functional silane coupling agent, triazine functional silane coupling agent such as triazine silane, etc.

Copper foil with carrier The surface-treated copper foil of the present invention can be provided in the form of a copper foil with a carrier. At this time, the copper foil with a carrier includes a carrier, a peeling layer provided on the carrier, and the surface-treated copper foil of the present invention provided with a treated surface (typically a roughened surface) on the peeled layer as an outer side. Moreover, in addition to using the surface-treated copper foil of this invention, the copper foil with a carrier can also use a well-known layer structure.

The carrier is a layer (typically a foil) for supporting the surface-treated copper foil and improving its handleability. Examples of the carrier include aluminum foil, copper foil, a metal-coated resin film coated with copper or the like on the surface, a glass plate, etc., preferably copper foil. The copper foil can be either rolled copper foil or electrolytic copper foil. The thickness of the carrier is typically 200 μm or less, preferably 12 μm or more and 35 μm or less.

The surface on the release layer side of the carrier preferably has a ten-point surface roughness Rz of 0.5 μm or more and 1.5 μm or less, more preferably 0.6 μm or more and 1.0 μm or less. Rz can be determined based on JIS B 0601-1994. By giving this ten-point surface roughness Rz to the surface of the carrier on the peeling layer side in advance, the surface-treated copper foil of the present invention produced thereon via the peeling layer can easily give the desired surface profile.

The peeling layer is a layer having a function of weakening the peeling strength of the carrier foil, guaranteeing the stability of the strength, and suppressing mutual diffusion between the carrier and the copper foil that is easily caused during high-temperature embossing. The release layer is generally formed on one side of the carrier foil, but may be formed on both sides. The peeling layer may be an organic peeling layer or an inorganic peeling layer. Examples of organic components used in the organic peeling layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Examples of nitrogen-containing organic compounds include triazole compounds, imidazole compounds, and the like. Among them, the triazole compounds are preferred from the standpoint of peelability stability. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4- Triazole, and 3-amino-1H-1,2,4-triazole, etc. Examples of sulfur-containing organic compounds include mercaptobenzene, thiocyanuric acid, and 2-benzimidazole mercaptan. Examples of carboxylic acids include monocarboxylic acids and dicarboxylic acids. On the other hand, examples of the inorganic components used in the inorganic peeling layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and chromate-treated films. In addition, the formation of the peeling layer may be performed by contacting the peeling layer component-containing solution on at least one surface of the carrier, and fixing the peeling layer component to the surface of the carrier foil. The contact of the carrier to the peeling layer component-containing solution may be performed by immersion into the peeling layer component-containing solution, spraying of the peeling layer component-containing solution, or flow-down of the peeling layer component-containing solution. In addition, the fixation of the peeling layer component to the surface of the carrier may be performed by adsorption and drying of the peeling layer component-containing solution, and the electrodeposition of the peeling layer component-containing solution of the peeling layer component. The thickness of the peeling layer is typically 1 nm or more and 1 μm or less, preferably 5 nm or more and 500 nm or less.

As the surface-treated copper foil, the above-described surface-treated copper foil of the present invention is used. Although the roughening treatment of the present invention is applied to a roughener using copper particles, the copper layer is first formed on the surface of the peeling layer as a copper foil in order, and then at least roughening may be performed. The details of the roughening are as described above. In addition, in order to make use of the advantages of the copper foil as a copper foil with a carrier, it is preferable that it is configured in the form of an ultra-thin copper foil. The preferred thickness of the ultra-thin copper foil is 0.1 μm or more and 7 μm or less, more preferably 0.5 μm or more and 5 μm or less, and still more preferably 0.5 μm or more and 3 μm or less.

It is also possible to provide another functional layer between the peeling layer and the carrier and/or copper foil. As an example of such another functional layer, for example, an auxiliary metal layer may be used. The auxiliary metal layer is preferably composed of nickel and/or cobalt. The thickness of the auxiliary metal layer is preferably 0.001 μm or more and 3 μm or less.

Copper clad laminate The surface-treated copper foil to the carrier-attached copper foil of the present invention are preferably used for the production of copper-clad laminates for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate having the above-mentioned surface-treated copper foil or the above-mentioned carrier-attached copper foil. By using the surface-treated copper foil of the present invention to a copper foil with a carrier, a copper-clad laminate that is particularly suitable for the SAP method can be provided. The copper-clad laminate is provided with the surface-treated copper foil of the present invention and a resin layer densely provided on the roughened surface of the surface-treated copper foil, or with the copper foil with carrier of the present invention, and the copper with carrier Surface treatment of the foil The roughened surface of the copper foil is made of densely arranged resin layers. The surface-treated copper foil or the copper foil with carrier may be provided on one side or both sides of the resin layer. The resin layer contains resin, preferably insulating resin. The resin layer is preferably a prepreg and/or resin sheet. The prepreg is a general term for composite materials in which synthetic resin plates, glass plates, glass woven fabrics, glass non-woven fabrics, paper and other substrates are impregnated with synthetic resin. Preferred examples of the insulating resin include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. In addition, examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester fiber resin. In addition, from the viewpoint of improving the insulation of the resin layer and the like, filler particles made of various inorganic particles such as silica and alumina may be contained. Although the thickness of the resin layer is not particularly limited, it is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and still more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of a plurality of layers. The resin layer such as a prepreg and/or a resin sheet may be provided between the surface-treated copper foil and the carrier-attached copper foil via an undercoat resin layer previously coated on the roughened surface of the surface-treated copper foil.

Printed wiring board The surface-treated copper foil of the present invention to the carrier-attached copper foil are preferably used for the production of printed wiring boards, and particularly preferably produced by a semi-additive method (SAP). That is, according to a preferred aspect of the present invention, there is provided a method for manufacturing a printed wiring board using the aforementioned surface-treated copper foil or the aforementioned copper foil with a carrier, or the aforementioned surface-treated copper foil or the aforementioned copper-clad layer The printed wiring board obtained from the board. By using the surface-treated copper foil of the present invention to a copper foil with a carrier, the above-mentioned surface profile can be given to the laminate, and insertion can be effectively suppressed in an etching process which is a process of printed wiring board manufacturing. The printed wiring board of this aspect includes a layer structure in which a resin layer and a copper layer are laminated. In the case of the SAP method, the surface-treated copper foil of the present invention is removed in the process (c) of FIG. 1, and the printed wiring board produced by the SAP method does not already contain the surface-treated copper foil of the present invention, only from the surface The surface profile transferred from the roughened surface of the treated copper foil remains. In addition, the resin layer is the same as described above for the copper-clad laminate. In any case, the printed wiring board may adopt a well-known layer structure. As a specific example of the printed wiring board, there is a single-sided or double-sided printed wiring that forms a circuit after bonding the surface-treated copper foil of the present invention on one or both sides of the prepreg and hardening the laminate of the copper foil with carrier Board, or a multilayer printed wiring board in which it is multilayered. In addition, as other specific examples, a flexible printed circuit wiring board, a COF, a TAB tape, or the like formed by forming a surface-treated copper foil and a copper foil with a carrier of the present invention on a resin film to form a circuit. As another specific example, a resin-coated copper foil (RCC) coated with the resin layer is formed on the surface-treated copper foil of the present invention to a copper foil with a carrier, and the resin layer is laminated on the printed circuit board as an insulating adhesive layer After that, the surface-treated copper foil is used as all or part of the wiring layer to form a circuit-layered wiring board by a modified semi-additive (MSAP) method, a subtractive process method, or the like, or the surface-treated copper foil is removed for semi-additive (SAP ) Method to form a circuit's laminated wiring board, alternately repeating the lamination of resin-coated copper foil onto the semiconductor integrated circuit, direct lamination of the circuit formation on the wafer, etc. As a more specific example of development, there are an antenna element in which a copper foil with resin is laminated on a substrate to form a circuit, and an electronic material or window for panel display formed by laminating a pattern on a glass or resin film with an adhesive layer An electronic material for glass, an electromagnetic wave shielding film coated with a conductive adhesive on the surface-treated copper foil of the present invention, and the like. In particular, the surface-treated copper foil of the present invention to the copper foil with carrier is suitable for the SAP method. For example, when the circuit is formed by the SAP method, the configuration shown in FIGS. 1 and 2 can be adopted.

Resin substrate According to a preferred aspect of the present invention, a resin substrate is provided, and the skewness Ssk measured on at least one surface according to ISO 25178 is -0.6 or less. This resin substrate corresponds to a resin replica that transfers the surface shape of the surface-treated copper foil of the present invention. Therefore, the preferred form of the resin replica that transfers the surface shape of the surface-treated copper foil (skewness Ssk, arithmetic mean curvature Spc of the peak apex, peak apex density Spd, and core volume Vmc relative to the pole The parameters of the height Sxp ratio Vmc/Sxp) can also be applied to the resin substrate of this aspect. The resin base material includes a resin, preferably an insulating resin. The resin substrate is preferably a prepreg and/or resin sheet. The prepreg is a general term for composite materials in which synthetic resin plates, glass plates, glass woven fabrics, glass non-woven fabrics, paper and other substrates are impregnated with synthetic resin. Preferred examples of the insulating resin include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. In addition, examples of the insulating resin constituting the resin base material include insulating resins such as epoxy resin, polyimide resin, and polyester fiber resin. In addition, from the viewpoint of improving the insulating properties of the resin substrate, etc., filler particles made of various inorganic particles such as silica and alumina may be contained. The thickness of the resin substrate 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 still more preferably 3 μm or more and 200 μm or less. The resin base material may be composed of a plurality of layers. The resin substrate of the present invention can be preferably used as a starting material and an intermediate product in the production of a printed wiring board by the SAP method. [Example]

The present invention will be described more specifically by the following examples.

Example 1～6 The production and evaluation of the copper foil with carrier and the resin replica were performed in the following manner.

(1) Preparation of carrier As a cathode, a titanium electrode with a surface polished with a #2000 polishing cloth was prepared. As an anode, DSA (Dimensional Stability Anode) was prepared. These electrodes were immersed in a copper sulfate solution with a copper concentration of 80 g/L and a sulfuric acid concentration of 260 g/L, electrolyzed at a solution temperature of 45° C. and a current density of 55 A/dm ² , and obtained by using an electrolytic copper foil with a thickness of 18 μm as a carrier.

(2) Formation of peeling layer The electrode surface side of the carrier after pickling treatment was carried out in a CBTA aqueous solution with a CBTA (carboxybenzotriazole) concentration of 1 g/L, a sulfuric acid concentration of 150 g/L, and a copper concentration of 10 g/L at a liquid temperature of 30° C. for 30 seconds The impregnation of CBTA makes the components of CBTA adsorb to the electrode surface of the carrier. By this, the CBTA layer is formed as an organic peeling layer on the surface of the electrode surface of the carrier.

(3) Formation of auxiliary metal layer The carrier forming the organic peeling layer is immersed in a nickel concentration solution made of nickel sulfate at a concentration of 20 g/L, and the thickness is adjusted under the conditions of a liquid temperature of 45° C., pH 3, and a current density of 5 A/dm ² . Nickel with an equivalent amount of 0.001 μm adhered to the organic peeling layer. With this, a nickel layer is formed as an auxiliary metal layer on the organic peeling layer.

(4) The ultra-thin copper foil is formed into a carrier that will form the auxiliary metal layer, immersed in a copper sulfate solution with a copper concentration of 60 g/L and a sulfuric acid concentration of 200 g/L, at a solution temperature of 50° C. and a current density of 5 A/dm ² or more and 30 A/ Electrolysis of dm ² or less forms an ultra-thin copper foil with a thickness of 1.2 μm on the auxiliary metal layer.

(5) Roughening treatment The precipitation surface of the ultra-thin copper foil is roughened. This roughening treatment is performed twice in the first-stage plating. In each stage of the coating process, a copper sulfate solution having the copper concentration, sulfuric acid concentration, chlorine concentration, and 9-phenylacridine (9PA) concentration shown in Table 1 was used. The liquid temperature shown in Table 1 and Table 2 were used. The current density and time shown are electrodeposited. The distance between the positive electrode and the negative electrode in the first-stage coating process is 50 mm or more and 80 mm or less. In this way, six types of roughened copper foils from Examples 1 to 6 were produced.

(6) Anti-rust treatment The surface of the roughened layer of the obtained copper foil with carrier was subjected to anti-rust treatment consisting of zinc-nickel alloy plating treatment and chromate treatment. First, using an electrolyte solution with a zinc concentration of 0.2 g/L, a nickel concentration of 2 g/L, and a potassium pyrroline concentration of 300 g/L, at a temperature of 40° C. and a current density of 0.5 A/dm ² , the roughened layer and The surface of the carrier is coated with zinc-nickel alloy. Next, the surface of the zinc-nickel alloy plating treatment was subjected to chromate treatment using an aqueous solution having a chromic acid concentration of 1 g/L under the conditions of pH 11, liquid temperature of 25° C., and current density of 1 A/dm ² .

(7) Silane coupling agent treatment An aqueous solution containing 3 g/L of 3-aminopropyltriethoxysilane was adsorbed on the surface of the copper foil side of the copper foil with carrier, the water was evaporated by an electric heater, and a silane coupling agent treatment was performed. At this time, the silane coupling agent treatment was not performed on the carrier side.

(8) Manufacture of copper clad laminate Use copper foil with carrier to make copper clad laminate. First, on the surface of the inner substrate, an ultra-thin copper foil with a carrier copper foil was laminated as a resin film with a BT resin prepreg (GHPL-830NS manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.1 mm thick) at a pressure of 4.0 After hot pressing at MPa and 220 degrees for 90 minutes, the carrier foil was peeled off to produce a copper-clad laminate.

(9) Production of resin replicas The copper foil on the surface of the copper-clad laminate was completely removed with a sulfuric acid/hydrogen peroxide-based etching solution to obtain a resin replica.

(10) Measurement of the surface profile of the resin replicas The surface of the resin replica (transferred to the surface curve of the roughened surface) is analyzed by surface roughness analysis of a laser microscope (manufactured by Keynes Co., Ltd., VK-X100) The measurement is based on ISO25178. Specifically, the surface profile of the area of 57074.677 μm ² of the transfer surface of the resin replica was measured by the above-mentioned laser microscope at an objective lens magnification of 50 times. The surface contour of the transfer surface of the obtained resin replica was corrected by surface inclination (automatic) as a pre-processing, and analyzed by the laser method to calculate each parameter (the physical volume of the core part Vmc relative to the skewness Ssk, peak apex The arithmetic mean curvature Spc, the peak apex density Spd, and the pole height Sxp ratio Vmc/Sxp). At this time, neither the S filter nor the L filter is used to measure the value. The above operation was performed three times for each case, and the average value was used as the value of each parameter in each case. The results are shown in Table 3.

(11) Production of laminates for SAP evaluation The resin replica is subjected to degreasing, Pd-based catalyst application, and activation treatment. Electroless copper plating (thickness: 1 μm) was performed on the activated surface to obtain a laminate (hereinafter referred to as a laminate for SAP evaluation) before laminating a dry film in the SAP method. Such works are carried out in accordance with the known conditions of the SAP law.

(12) Evaluation of laminates for SAP evaluation Regarding the SAP evaluation price obtained above, the evaluation of various characteristics was performed as follows.

<insert evaluation> A dry film is attached to the surface of the SAP evaluation laminate, and exposure, dry film removal, electrolytic plating, etc. are performed to form a circuit with a circuit width of 22 μm, a height of 22 μm, and a length of 150 μm (at this stage, the lower part of each circuit is State of electrical connection of electroless copper plating). The obtained circuit was treated with an etching solution (manufactured by JCU Corporation, SAC-700W3C), and the electroless copper plating layer remaining between the circuits was dissolved and removed to insulate each circuit. At this time, the etching rate of the copper foil was measured in advance, and then etched again by a so-called appropriate amount of etching to the equivalent of 4 μm, under the condition of so-called over-etching. After the etching process, the circuit is washed with water and dried. Observe the cross section of the circuit with an optical microscope to determine the insertion amount. Specifically, as shown in FIG. 11, the upper width x (μm) and the lower width y (μm) of the circuit 22 formed on the resin replica 20 are measured, and the difference (x-y) is taken as the insertion amount (μm). For each case, the measurement was performed with two fields of view, and the average value was used as the insertion amount of each case. The results are shown in Table 3.

<Adhesion of coated circuit (peel strength)> A dry film was attached to the laminate for SAP evaluation, and exposure and development were performed. After the laminated body covered by the developed dry film was subjected to copper plating by pattern plating, the dry film was peeled off. The electroless copper plating exposed by the etching liquid (made by JCU Corporation, SAC-700W3C) was removed, and the sample for peeling strength measurement of 20 micrometers in height and 10 mm in width was produced. Based on JIS C 6481 (1996), the peel strength when peeling the copper layer from the sample for evaluation was measured. The results are shown in Table 3.

As can be seen from Table 3, in Example 5, no matter how large the value of Vmc/Sxp, the peel strength did not increase significantly. The reason should be "dropping powder" as a factor. That is, if dusting occurs, the anchoring effect will no longer be obtained, and the peel strength will tend to decrease, but if Vmc/Sxp is too large, it will cause powdering. Example 5 stopped at a slightly low peel strength because of slight powder loss.

10: Ultra-thin copper foil 11a: Underground substrate 11b: Lower layer circuit 11: Insulating resin substrate 12: prepreg 13: Undercoat 14: through hole 15: Electroless copper plating 16: Dry film 17: Copper electroplating 17a: wiring part 18: Wiring 112: resin substrate 114: Anti-rust layer 116: electrolytic copper layer 110: laminate 118: Electroless copper plating 120: wiring part 122: Wiring 124: Insert 20: resin replica 20a: convex part 22: Circuit

[Figure 1] A flow chart for explaining the SAP method, showing the first half of the project (from project (a) to project (d)). [Figure 2] A flow chart for explaining the SAP method, showing the second half of the project (from project (e) to project (h)). [FIG. 3A] A diagram for explaining the skewness Ssk determined based on ISO25178, and a diagram showing the surface and its height distribution when Ssk<0. [FIG. 3B] A diagram for explaining the skewness Ssk determined based on ISO25178, and a diagram showing the surface and its height distribution when Ssk>0. [Figure 4] A diagram for explaining the load curve and load area ratio determined based on ISO25178. [Fig. 5] A diagram for explaining the separation of the load area ratio Smr1 of the protruding peak portion and the core portion determined based on ISO25178 and the separation of the load area ratio Smr2 of the protruding valley portion and the core portion. [Figure 6] A diagram for explaining the pole height Sxp determined based on ISO25178. [Fig. 7] A diagram for explaining the physical volume Vmc of the core determined according to ISO 25178. [FIG. 8A] An engineering flow chart showing an example of circuit formation by the MSAP method, and is used to explain a detailed diagram of the generation circuit. [FIG. 8B] An engineering flow chart showing an example of circuit formation by the SAP method, and is used to explain the generation of insertion diagrams. [Fig. 9A] Fig. 9A is a schematic cross-sectional view showing a state before and after insertion occurs in a laminate in which a circuit is formed on a resin replica where Ssk and Spc are small and Spd and Vmc/Sxp are large. [FIG. 9B] A schematic cross-sectional view showing the state before and after insertion occurs in a laminate in which a circuit is formed on a resin replica in which Ssk and Spc are large, and Spd and Vmc/Sxp are small. [FIG. 10A] A diagram showing that the height of the convex portion is corrected after the convex portion of the resin replica of the laminate of FIG. 9A is extracted. [FIG. 10B] A diagram showing that the height of the convex portion is corrected after the convex portion of the resin replica of the laminate of FIG. 9B is extracted. [Fig. 11] A diagram for explaining the method of measuring the insertion amount.

Claims (11)

A surface-treated copper foil having a treated surface on at least one side; When the resin film is thermally pressed on the treated surface and the surface shape of the treated surface is transferred to the surface of the resin film, and the surface-treated copper foil is removed by etching, among the remaining surfaces of the resin film The skewness Ssk measured under ISO25178 is the criterion -0.6 or less. The surface-treated copper foil according to claim 1, wherein the skewness Ssk is -1.7 or more and -0.6 or less. Item 1 A surface treated copper foil described in the request, wherein the surface of the resin film remaining after the etch, according to ISO25178 whichever peak point Spc arithmetic mean curvature of 5000mm ^-1 measured less than 13000mm ^-1. The surface-treated copper foil according to claim 1, wherein the peak density Spd of the peak measured on the basis of ISO25178 of the surface of the resin film remaining after the etching is 1.13×10 ⁶ mm ^-2 or more 1.50×10 ⁶ mm ^-2 or less. The surface-treated copper foil according to claim 1, wherein the solid volume Vmc of the core portion measured in accordance with ISO25178 is relative to the pole height Sxp measured in accordance with ISO25178 based on the surface of the resin film remaining after the etching The ratio, Vmc/Sxp, is 0.39 or more and 0.44 or less. The surface-treated copper foil as described in claim 1 is used to transfer the uneven shape to the insulating resin layer for printed wiring boards. The surface-treated copper foil as described in claim 1 is used for the production of printed wiring boards by the semi-additive method (SAP). A copper foil with a carrier, comprising: a carrier, a peeling layer provided on the carrier, and the surface-treated copper foil according to any one of claims 1 to 7 provided with the aforementioned treated surface on the peeling layer. A copper-clad laminate comprising: the surface-treated copper foil according to any one of claims 1 to 7 or the copper foil with a carrier according to claim 8. A printed wiring board obtained by using the surface-treated copper foil according to any one of claims 1 to 7 or the copper foil with a carrier according to claim 8. A method of manufacturing a printed wiring board is to use a surface-treated copper foil as described in any one of claims 1 to 7 or a copper foil with a carrier as described in claim 8 to manufacture a printed wiring board.

Images