KR20210090608A - Surface-treated copper foil, copper foil with carrier, copper clad laminate and printed wiring board - Google Patents

Abstract

When used for the SAP method, the etching process of the electroless copper plating layer WHEREIN: The surface-treated copper foil which can provide the surface profile which can suppress effectively generation|occurrence|production of the chipping which may generate|occur|produce in a circuit to a resin base material is provided. This surface-treated copper foil is a surface-treated copper foil having a treated surface on at least one side, thermocompression bonding a resin film to the treated surface, transferring the surface shape of the treated surface to the surface of the resin film, and etching the surface-treated copper foil When , the skewness Ssk measured based on ISO25178 on the surface of the remaining resin film is -0.6 or less.

Description

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

This invention relates to surface-treated copper foil, copper foil with a carrier, a copper clad laminated board, and a printed wiring board.

In recent years, a 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 a very fine circuit, and it is performed using the roughening process copper foil with a carrier as the example. For example, as shown in FIGS. 1 and 2, the ultra-thin copper foil 10 provided with the roughened surface is prepreg on the insulated resin substrate 11 provided with the underlayer circuit 11b in the base material 11a. (12) and the primer layer 13 are pressed to adhere (step (a)), the carrier (not shown) is peeled, and if necessary, via holes 14 are formed by laser drilling ( process (b)). Next, the ultra-thin copper foil is removed by etching to expose the primer layer 13 provided with the roughened surface profile (step (c)). After electroless copper plating 15 is applied to this roughened surface (step (d)), it is masked in a predetermined pattern by exposure and development using a dry film 16 (step (e)), and electrolytic copper plating ( 17) is carried out (step (f)). After the dry film 16 is removed to form the wiring portion 17a (step (g)), unnecessary electroless copper plating 15 between the adjacent wiring portions 17a and 17a is removed by etching (step (g)). (h)), a wiring 18 formed in a predetermined pattern is obtained.

Thus, as for the SAP method using roughening process copper foil, roughening process copper foil itself will be removed by etching after laser drilling (process (c)). And since the uneven|corrugated shape of the roughening process surface of the roughening process copper foil is transcribe|transferred by the laminated body surface from which the roughening process copper foil was removed, in the process after that, the insulating layer (for example, the primer layer 13 or, when there is not it, prep The adhesion between the legs 12) and the plating circuit (eg, the wiring 18) can be ensured. In addition, although the modified semi-additive method (MSAP method) which does not perform the copper foil removal process corresponding to the step (c) is also widely adopted, in the etching step after the dry film removal (corresponding to the step (h)), the copper foil layer and Since two layers of the electroless copper plating layer must be removed by etching, it is necessary to perform etching deeper than the SAP method which ends with the etching removal of one electroless copper plating layer. Therefore, it can be said that the MSAP method is somewhat inferior to the SAP method in the fine circuit formability in that it is necessary to narrow the circuit space to some extent in consideration of a larger etching amount. That is, for the purpose of forming a further fine circuit, the SAP method is advantageous.

By the way, in the etching step (corresponding to step (h)) after the dry film removal, the interface portion between the circuit (for example, the wiring 18) and the insulating layer is etched, and as a result, the circuit is eroded so that the root of the circuit is cut out. A phenomenon called "cutting" may occur. When this shearing generate|occur|produces, the adhesive force of a circuit and an insulating layer will fall, and it will become a cause of circuit peeling.

On the other hand, the roughening process copper foil which controlled the shape of roughening particle|grains is known. For example, in patent document 1 (Japanese Patent No. 6293365), the roughening process copper foil which has a roughening process surface provided with several substantially spheroidal process WHEREIN: The average height of the substantially spheroidal process shall be 2.60 micrometers or less, In addition, by making the ratio b _ave /a _ave of the average maximum diameter b _{ave of the approximately nodules} to the average neck diameter a ave of the approximately nodal projections 1.2 or more, when used in the SAP method, not only excellent adhesion to the plating circuit but also electroless It becomes possible to provide the surface profile excellent also in the etching property with respect to copper plating to a laminated body.

Japanese Patent Publication No. 6293365

In recent years, with the further miniaturization of circuits, adoption of the SAP method advantageous for fine circuit formation is expanding. In this regard, it can be said that, as the circuit pattern width becomes narrow, the allowable cutting width is also relatively reduced. In addition, in the SAP method, in the etching process after dry film removal, since it is enough to etch away only the electroless copper plating layer, not electrolytic copper but the etching liquid which can selectively remove electroless copper can be used. By doing in this way, the thinning of the circuit mainly comprised by electrolytic copper can be suppressed. Accordingly, it can be said that the SAP method is more advantageous than the MSAP method in terms of fine circuit formation properties. On the other hand, since the lowermost part of the circuit formed by the SAP method is comprised with electroless copper, when the said etching liquid is used, it becomes more easy to generate|occur|produce chamfering.

This time, the present inventors give the surface of the resin substrate a unique surface profile defined by skewness Ssk measured in accordance with ISO25178, so that in the etching process of the electroless copper plating layer in the SAP method, it can occur in the circuit. The knowledge that it can effectively suppress the occurrence of chamfering was obtained. Moreover, when it used for the SAP method, the knowledge that the surface-treated copper foil which can provide the said specific surface profile to a resin base material can be provided was also acquired.

Therefore, it is an object of the present invention, when used in the SAP method, in the etching process of the electroless copper plating layer, a surface treatment capable of imparting a surface profile capable of effectively suppressing the occurrence of chipping that may occur in the circuit to the resin substrate. To provide copper foil.

According to one aspect of the present invention, as a surface-treated copper foil having a treatment surface on at least one side,

When a resin film is thermocompression-bonded to the treated surface to transfer the surface shape of the treated surface to the surface of the resin film, and the surface-treated copper foil is removed by etching, in the surface of the resin film remaining, The surface-treated copper foil from which skewness Ssk measured based on ISO25178 will be -0.6 or less is provided.

According to another one aspect|mode of this invention, the copper foil with a carrier provided with a carrier, the peeling layer provided on the said carrier, and the said surface-treated copper foil provided on this peeling layer with the said process surface outward is provided.

According to another one aspect|mode of this invention, the copper clad laminated board provided with the said surface-treated copper foil or the said copper foil with a carrier is provided.

According to another one aspect|mode of this invention, the printed wiring board obtained using the said surface-treated copper foil or the said copper foil with a carrier is provided.

According to another aspect of the present invention, there is provided a resin substrate in which at least one surface has a skewness Ssk measured in accordance with ISO25178 of -0.6 or less.

BRIEF DESCRIPTION OF THE DRAWINGS It is a process flow chart for demonstrating the SAP method, and is a figure which shows the process (process (a) to process (d)) of the first half.
Fig. 2 is a process flow chart for explaining the SAP method, and is a diagram showing the latter step (step (e) to step (h)).
FIG. 3A is a diagram for explaining skewness Ssk determined based on ISO25178, and is a diagram showing a surface and height distribution thereof when Ssk<0.
3B is a diagram for explaining skewness Ssk determined based on ISO25178, and is a diagram showing a surface and height distribution thereof when Ssk>0.
4 is a diagram for explaining a load curve and a load area ratio determined based on ISO25178.
5 is a view for explaining the load area ratio Smr1 for separating the protruding ridge and the core, and the load area ratio Smr2 for separating the protruding valley and the core, which are determined based on ISO25178.
6 is a diagram for explaining the pole height Sxp determined based on ISO25178.
Fig. 7 is a diagram for explaining the substantial volume Vmc of the core part determined based on ISO25178.
It is a process flowchart which shows an example of circuit formation by the MSAP method, and is a figure for demonstrating that circuit thinning generate|occur|produces.
It is a process flowchart which shows an example of circuit formation by the SAP method, and is a figure for demonstrating that chamfering generate|occur|produces.
Fig. 9A is a schematic cross-sectional view showing a state before and after the occurrence of chipping in a laminate in which circuits are formed on a resin replica having small Ssk and Spc and large Spd and Vmc/Sxp.
Fig. 9B is a schematic cross-sectional view showing a state before and after the occurrence of chipping in a laminate in which circuits are formed on a resin replica having large Ssk and Spc and small Spd and Vmc/Sxp.
Fig. 10A is a view showing that the convex portion of the resin replica in the laminate of Fig. 9A is taken out and then the height of the convex portion is corrected.
Fig. 10B is a view showing that the convex portion of the resin replica in the laminate of Fig. 9B is taken out and then the height of the convex portion is corrected.
11 is a view for explaining a method of measuring the amount of clipping.

Justice

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

In this specification, "skewness Ssk" is a parameter which shows the symmetry of height distribution measured based on ISO25178. When this value is 0, it indicates that the height distribution is vertically symmetrical. Moreover, as shown in FIG. 3A, when this value is smaller than 0, it indicates that it is a surface with many fine troughs. On the other hand, as shown in FIG. 3B, when this value is larger than 0, it indicates that it is a surface with many fine acids. 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 treated surface with a commercially available laser microscope.}

In this specification, "arithmetic mean curve Spc of mountain vertices" is a parameter which shows the arithmetic mean of the principal curvatures of the mountain vertices of a surface measured based on ISO25178. A small value indicates that the point in contact with another object is rounded. On the other hand, a large value indicates that the point in contact with another object is sharp. Put simply, the arithmetic mean curve Spc of the peak of the mountain can be said to be a parameter indicating the degree of roundness of the ridges that can be measured with a laser microscope. The arithmetic mean curve Spc of the peak can be calculated by measuring the surface profile of a predetermined measurement area (for example, ^{a two-dimensional region of 57074.677 µm 2 ) on the treated surface with a commercially available laser microscope.}

In this specification, "the peak density Spd of a mountain" is a parameter which shows the number of mountain peaks per unit area measured based on ISO25178. A large value suggests that the number of contact points with other objects is large. The peak density Spd of the acid can be calculated by measuring the surface profile of a predetermined measurement area (for example, ^{a two-dimensional region of 57074.677 µm 2 ) on the treated surface with a commercially available laser microscope.}

In this specification, the "load curve of a surface" (hereinafter simply referred to as a "load curve") refers to a curve showing the height at which the load area ratio is 0% to 100%, measured in accordance with ISO25178. The load area ratio is a parameter indicating the area of a region having a certain height c or higher, as shown in FIG. 4 . The load area ratio at the height c corresponds to Smr(c) in FIG. 4 . As shown in Fig. 5, the secant line of the load curve drawn with the difference of the load area ratio from 0% to 40% according to the load curve according to the load area ratio is shifted from the load area ratio 0%, and the inclination of the secant line is The most gradual position is called the central part of the load curve. A straight line in which the sum of squares of deviations in the longitudinal direction is minimized with respect to this central portion is called an equivalent straight line. The part included in the range of the height of 0% to 100% of the load area ratio of an equivalent straight line is called a core part. A portion higher than the core portion is referred to as a protruding ridge, and a portion lower than the core portion is referred to as a protruding valley. The core part represents the height of the area in contact with another object after the initial wear is finished.

In this specification, "pole height Sxp" is a parameter which shows the difference between the height of the load area ratio p% and the load area ratio q% measured based on ISO25178, as shown in FIG. Sxp represents the difference between the average surface of the surface and the height of the surface after removing a particularly high acid from the surface. In this specification, Sxp shall represent the difference of the height of 2.5% of a load area ratio and 50% of a load area ratio. 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.}

As used herein, the term “load area ratio Smr1 that separates the protruding ridge and the core” means the load area ratio at the intersection of the height of the upper part of the core and the load curve, measured in accordance with ISO25178, as shown in FIG. 5 . It is a parameter indicating (that is, the load area ratio dividing the core portion and the protruding ridge portion). It means that the ratio occupied by a protrusion ridge part is so large that this value is large. In addition, in this specification, "the load area ratio Smr2 which separates the protruding valley part and the core part" means, as shown in FIG. 5, the load at the intersection of the height of the lower part of the core part and the load curve, which is measured based on ISO25178. It is a parameter representing the area ratio (that is, the load area ratio dividing the core part and the protruding valley part). A larger value means that the proportion of the protruding valleys is larger.

In this specification, "the substantial volume Vmc of a core part" is a parameter which shows the volume of a core part measured based on ISO25178. As shown in FIG. 7, Vmc represents the difference between the substantial volume in the load area ratio Smr2 which separates the protruding valley part and the core part, and the substance volume in the load area ratio Smr1 which separates the protruding ridge part and the core part. The solid volume Vmc of the core portion can be calculated by measuring the surface profile of a predetermined measurement area (for example, ^{a two-dimensional region of 57074.677 µm 2 ) on the treated surface with a commercially available laser microscope.} In this specification, it is assumed that the load area ratio Smr1 that separates the protruding ridge and the core part is designated as 10%, and the load area ratio Smr2 that separates the protruding valley part and the core part is designated as 80%, respectively, to calculate the substantial volume Vmc of the core part.

In this specification, the "electrode surface" of an electrolytic copper foil refers to the surface on the side which was in contact with the negative electrode at the time of electrolytic copper foil preparation.

In this specification, the "precipitation surface" of an electrolytic copper foil refers to the surface on the side where electrolytic copper precipitates at the time of electrolytic copper foil preparation, ie, the surface on the side which does not contact a cathode.

surface treatment copper foil

The copper foil by this invention is surface-treated copper foil. This surface-treated copper foil is a resin film (hereinafter also referred to as a resin replica) left when a resin film is thermocompression-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 foil is removed by etching. The skewness Ssk measured in accordance with ISO25178 on the surface (hereinafter also referred to as transfer surface) of the surface (hereinafter referred to as "transfer surface") is -0.6 or less.

As described above, with the demand for further miniaturization of circuits, the adoption of the SAP method advantageous for fine circuit formation is expanding. In this regard, it can be said that, as the circuit pattern width becomes narrow, the allowable cutting width is also relatively reduced. That is, the cut width allowed for a conventional pattern width (for example, 30 µm) is out of the standard for a finer circuit pattern width (for example, 10 µm), for reasons such as increasing the risk of circuit collapse. cases may arise.

In addition, the SAP method is advantageous compared with other construction methods such as the MSAP method in terms of circuit miniaturization, but there are cases where it is disadvantageous in terms of cutting suppression. From this point, for example, in circuit formation by the MSAP method, as illustrated in FIG. 8A, the rust prevention layer 114 and the electrolytic copper layer 116 derived from copper foil with a carrier on the resin base material 112. The laminate 110 laminated in this order is prepared (step (i)), and the electroless copper plating 118 is formed in the state in which the electrolytic copper layer 116 remains. Next, it is masked in a predetermined pattern with a dry film, and then electroplated with copper to form the wiring portion 120 (step (ii)). As described above, in the MSAP method, since the electrolytic copper layer 116 remains on the resin substrate 112, in the etching removal step of the unnecessary portion between the adjacent wiring portions 120 and 120, the electrolytic copper layer ( 116) and two layers of electroless copper plating 118 must be removed by etching. Therefore, as shown in step (iii) of FIG. 8A , circuit thinning tends to occur in the obtained wiring 122 . On the other hand, in the MSAP method, since the electrolytic copper layer 116 is not completely removed as described above, the rust preventive layer 114 is present between the resin substrate 112 and the wiring 122 , and this rust preventive layer (114) contributes to the prevention of the occurrence of chamfering. In contrast, in the circuit formation by the SAP method, as illustrated in FIG. 8B , the antirust layer 114 and the electrolytic copper layer 116 are sequentially formed on the resin substrate 112 by preparing the laminate 110 ( Step (i)), complete removal of electrolytic copper layer 116 (step (ii)), formation of electroless copper plating 118, masking with dry film, and electrolytic copper plating of wiring portion 120 Formation is performed sequentially (step (iii)). As described above, in the SAP method, since the electrolytic copper layer 116 does not remain on the resin substrate 112, in the etching process of the unnecessary portion between the adjacent wiring portions 120 and 120, electroless copper plating ( It is sufficient to remove only 118 by etching, whereby the circuit thinning of the obtained wiring 122 can be suppressed. Moreover, in the SAP method, since it becomes possible to use the etching liquid which can selectively remove electroless copper instead of electrolytic copper, the thinning of the wiring 122 mostly comprised by electrolytic copper can be suppressed further more effectively. Therefore, with respect to circuit miniaturization, it can be said that the SAP method is advantageous compared with other construction methods such as the MSAP method. However, as shown in step (iv) of Fig. 8B, since the lowermost portion of the wiring 122 formed by the SAP method is composed of the electroless copper plating 118, an etching solution capable of selectively removing electroless copper is used. In this case, the chamfer 124 tends to occur at the interface between the wiring 122 and the resin substrate 112 . From this point, even when the surface-treated copper foil which provided the rust prevention layer 114 on the electrolytic copper layer 116 is used as copper foil for SAP, in the SAP method, the electrolytic copper layer 116 is completely removed by etching. Therefore, the rust-preventing metal is also etched at the time of the etching (refer to step (ii) of Fig. 8B). In addition, in FIGS. 8A and 8B, the thickness of the rust prevention layer 114 is shown large for emphasis, and the ratio of the thickness in an actual laminated body is not necessarily reflected. As described above, in the SAP method, it is not easy to suppress the chipping that may occur in the circuit.

In this regard, by using the surface-treated copper foil of the present invention for the SAP method, the surface of the resin substrate can be provided with a unique surface profile in which skewness Ssk measured in accordance with ISO25178 is -0.6 or less. By doing in this way, in the etching process of an electroless copper plating layer, it becomes possible to suppress effectively generation|occurrence|production of the chipping which may generate|occur|produce in a circuit. Although the mechanism by which the surface of a resin base material can suppress the chipping|wound which arises in a circuit by having the said surface profile is not necessarily clear, the following are mentioned as one factor. That is, the convex portions of the surface of the resin substrate on which the circuit is formed (that is, the transfer surface of the resin replica) function as a barrier to prevent the ingress of the etchant in the etching step of the electroless copper plating in the SAP method. Therefore, it can be said that chipping becomes difficult to occur, so that this protective wall is thick. In this regard, based on the definition of skewness Ssk described above, as shown in Figs. 9A and 9B, the resin replica 20 having a small skewness Ssk (see Fig. 9A) is a resin replica 20 having a large skewness Ssk. ) (refer to Fig. 9B), it can be said that the wall thickness of the convex portion 20a is increased (refer to the circled portion in the drawing). Therefore, by making the skewness Ssk of the resin replica sufficiently small to -0.6 or less, it is considered that the above-mentioned protective wall can be thickened, and therefore it is possible to effectively suppress the chipping generated in the circuit 22 .

It is preferable that the said viewpoint to surface-treated copper foil of this invention is used for preparation of the printed wiring board by SAP method. It can also be said that it is preferable to use the surface-treated copper foil of this invention in order to transcribe|transfer an uneven|corrugated shape to the insulating resin layer for printed wiring boards if another expression is made.

The surface-treated copper foil of this invention has a process surface on at least one side. The treated surface is a surface to which a certain surface treatment is given, and is typically a roughened surface. The treated surface is typically provided with a plurality of ridges (eg roughened particles). In any case, a surface-treated copper foil may have a process surface (for example, roughening process surface) on both sides, and may have a process surface only on one side. In the case of having treated surfaces on both sides, when used in the SAP method, the surface on the laser irradiation side (the surface on the opposite side to the surface to be in close contact with the insulating resin) is also surface-treated. can

The surface-treated copper foil of the present invention is the surface of the resin film left when the resin film is thermocompression-bonded to the treated surface to transfer the surface shape of the treated surface to the surface of the resin film, and the surface-treated copper foil is removed by etching (i.e. , the transfer surface of the resin replica) has skewness Ssk of -0.6 or less, preferably -1.7 or more -0.6 or less, more preferably -1.6 or more -0.7 or less, still more preferably -1.5 or more -0.9 or less. , particularly preferably -1.5 or more and -1.1 or less. If it is in the said preferable range, while suppressing generation|occurrence|production of chamfering in the etching process of SAP method further, the protrusion on the processing surface of surface-treated copper foil can be controlled to a suitable shape which is not too thin and long, and, thereby, surface-treated copper Generation|occurrence|production of the powder fall due to the bend|folding, drop-off|omission, etc. of the raised material in foil can be suppressed effectively. A thermosetting resin film is preferable and the form of a prepreg may be sufficient as a resin film. Examples of the thermosetting resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, a phenol resin, and a polyimide resin. Thermocompression bonding may be performed on the conditions which can transfer the uneven|corrugated shape of the process surface of surface-treated copper foil to a resin film, and is not specifically limited. For example, it is preferable to perform thermocompression bonding under the conditions of a pressure of 3.0 MPa or more and 5.0 MPa or less, a temperature of 200 degreeC or more and 240 degrees C or less, and 60 minutes or more and 120 minutes or less.

The surface-treated copper foil of the present invention, (i.e., the transfer surface of the resin replica) surface of the resin film left after the etching, and that the arithmetic mean of the Song Spc acid vertex 5000mm ^{-1 -1} preferably less than 13000mm, more preferably is more than 7000mm 13000mm ^{-1 -1} or less, more preferably more than 9000mm 13000mm ^{-1 -1} or less, and particularly preferably more than 13000mm 10000mm ^{-1 -1} or less. If it is within this range, controlling the bumps on the treated surface of the surface-treated copper foil to an appropriate shape that is not too thin and long, effectively suppressing the occurrence of powder fall due to the bending or dropping of the bumps in the surface-treated copper foil, while SAP It is possible to further suppress the occurrence of chipping in the etching process of the method. The following are mentioned as one factor which can suppress generation|occurrence|production of chamfering. That is, based on the definition of the arithmetic mean song Spc of the mountain vertex described above, as shown in FIGS. 9A and 9B , the resin replica 20 (see FIG. 9A ) having a small arithmetic mean song Spc of the mountain vertex is Compared with the resin replica 20 (refer to Fig. 9B) having a large arithmetic mean grain Spc, the apex of the convex portion 20a becomes flat. As a result, it is thought that it is because the wall thickness of the convex part 20a functioning as a cut|disconnection protection wall becomes thick.

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) has an acid peak density Spd of 1.13 × 10 ⁶ mm ^-2 or more and 1.50 × 10 ⁶ mm ^-2 or less. Preferably, more preferably 1.13×10 ⁶ mm ^-2 or more and 1.40×10 ⁶ mm ^-2 or less, still more preferably 1.14×10 ⁶ mm ^-2 or more and 1.30×10 ⁶ mm ^-2 or less, particularly preferably 1.15 ×10 ⁶ mm ^-2 or more and 1.20×10 ⁶ mm ^-2 or less. If it exists in such a range, generation|occurrence|production of the chamfering in the etching process of SAP method can be suppressed further, controlling the protrusion on the processing surface of surface-treated copper foil to an appropriate number, and suppressing generation|occurrence|production of powder fall effectively. That is, as described above, since chipping of the circuit can be prevented by the convex portions of the resin replica, it can be said that the resin replica in which the convex portions are present at a high frequency can suppress the progress of chamfering. In this regard, based on the definition of the peak density Spd of the mountain described above, as shown in Figs. 9A and 9B, the resin replica 20 (see Fig. 9A) having a large peak density Spd of the mountain has the peak density Spd of the mountain. Compared with the small resin replica 20 (see Fig. 9B), the convex portions 20a are present at a higher frequency. Therefore, it is thought that the progress can be prevented at an early stage even when chamfering generate|occur|produces.

In the surface-treated copper foil of the present invention, the surface of the resin film remaining after the etching (ie, the transfer surface of the resin replica) is the ratio ^{of the substantial volume Vmc (mL/m 2 ) of the core part to the pole height Sxp (μm) Vmc/} Sxp is preferably 0.39 or more and 0.44 or less, more 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 this range, controlling the bumps on the treated surface of the surface-treated copper foil to an appropriate shape that is not too thin and long, effectively suppressing the occurrence of powder fall due to the bending or dropping of the bumps in the surface-treated copper foil, while SAP It is possible to further suppress the occurrence of chipping in the etching process of the method. Moreover, it also becomes possible to increase the adhesive force of a base material and a circuit. That is, as described above, the convex portion of the resin replica functions as a barrier to prevent the intrusion of the etching solution. It can be said that shaving is further suppressed. On the other hand, based on the above-described definitions of the solid volume Vmc and the pole height Sxp of the core part, as shown in FIGS. 10A and 10B, the actual volume Vmc of the core part depends also on the height of the convex part 20a of the resin replica 20. Therefore, by comparing Vmc/Sxp divided by the pole height Sxp, which is a parameter related to the height of the convex part 20a, the size of the convex part 20a can be evaluated as a converted value in which the height of the convex part 20a is uniformly aligned. can Further, by increasing Vmc/Sxp (for example, 0.39 or more), the area of the convex portion 20a of the resin replica 20 introduced into the circuit 22 also increases (that is, the area of the convex portion 20a surrounded by the circuit 22 is maintained. amount of resin increases), so the adhesion between the substrate and the circuit is also increased by the improvement of the anchor effect.

Method for producing surface-treated copper foil

Although an example of the preferable manufacturing method of the surface-treated copper foil by this invention is demonstrated, the surface-treated copper foil by this invention is not limited to the method demonstrated below, As long as it can provide the above-mentioned surface profile to the resin film surface, What was manufactured by any method may be sufficient.

(1) Preparation of copper foil

As copper foil used for manufacture of surface-treated copper foil, use of both electrolytic copper foil and rolled copper foil is possible. Although the thickness of copper foil is not specifically limited, 0.1 micrometer or more and 18 micrometers or less are preferable, More preferably, 0.5 micrometer or more and 10 micrometers or less, More preferably, 0.5 micrometer or more and 7 micrometers or less, Especially preferably, 0.5 micrometer or more 5 μm or less, and most preferably 0.5 μm or more and 3 μm or less. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil may be formed by a wet film forming method such as an electroless copper plating method and an electrolytic copper plating method, a dry film forming method such as sputtering and chemical vapor deposition, or a combination thereof. .

(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 the copper electrolytic solution for a roughening process. This electrolysis is preferably performed through a two- or three-step plating process, and more preferably through a three-stage plating process. In the plating process of the first step, 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) Using a copper sulfate solution containing a concentration of 20 mg/L or more and 80 mg/L or less, a liquid temperature of 20 ° C or more and 40 ° C or less, a current density of 5 A/dm ² or more and 25 A/dm ² or less, and a time of 2 seconds or more and 10 seconds or less It is preferable to perform electrodeposition. Although the plating process of this 1st stage may be performed twice in total using two tanks, it is preferable to complete it once in total. In the plating process of the 2nd step, 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, the liquid temperature is 45°C or more and 55°C or less, and the current density is 1A/ to carry out the electrodeposition in dm ² plating conditions of more than 10A / dm ² or less, the time for 2 seconds or more than 25 seconds is preferred. In the plating process of the 3rd step, 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 or more and 200 mg/L or less It is preferable to use a copper sulfate solution containing the following to perform electrodeposition under plating conditions of a liquid temperature of 20°C or more and 40°C or less, a current density of 10A/dm ² or more and 40A/dm ² or less, and a time of 0.3 seconds or more and 1.0 second or less. In particular, it is preferable that the first-stage plating process be performed using an additive such as 9PA, and the total electric _{quantity of the electric quantity Q 1} in the first-stage plating process and the electric quantity Q _{2 in the second-stage plating process (} Q ₁ +Q ₂ ) is preferably set to be 100C/dm ^{2 or less.} Moreover, it is preferable that the distance between a positive electrode and a negative electrode in the plating process of a 1st stage set it as 45 mm or more and 90 mm or less, More preferably, it is 50 mm or more and 80 mm or less from the point of uniformity of a process and workability|operativity.

(3) Anti-rust treatment

If desired, you may give a rust prevention process to the copper foil after a roughening process. It is preferable that a rust prevention process includes the plating process using zinc. The plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, and Co. As for the Ni/Zn adhesion ratio in zinc-nickel alloy plating, 1.2 or more and 10 or less are preferable in mass ratio, More preferably, they are 2 or more and 7 or less, More preferably, they are 2.7 or more and 4 or less. Moreover, it is preferable that a rust prevention process further includes a chromate process, It is more preferable that this chromate process is performed on the surface of the plating containing zinc after the plating process using zinc. By doing in this way, rust prevention property can further be improved. A particularly preferable antirust treatment is a combination of a zinc-nickel alloy plating treatment and a subsequent chromate treatment.

(4) Silane coupling agent treatment

If desired, a silane coupling agent process may be given to copper foil, and a silane coupling agent layer may be formed. Thereby, moisture resistance, chemical resistance, adhesiveness with an adhesive, etc. can be improved. A silane coupling agent layer can be formed by suitably diluting a silane coupling agent, apply|coating, and drying. Examples of the silane coupling agent include an epoxy functional silane coupling agent such as 4-glycidylbutyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-2 ( Aminoethyl) 3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrime Amino functional silane coupling agent such as toxysilane, or mercapto functional silane coupling agent such as 3-mercaptopropyltrimethoxysilane, or olefin functional silane such as vinyltrimethoxysilane or vinylphenyltrimethoxysilane A coupling agent or an acrylic functional silane coupling agent such as 3-methacryloxypropyltrimethoxysilane, or an imidazole functional silane coupling agent such as imidazole silane, or a triazine functional silane coupling agent such as triazine silane and the like.

Copper foil with carrier

The surface-treated copper foil of this invention can be provided in the form of copper foil with a carrier. In this case, copper foil with a carrier is equipped with a carrier, the peeling layer provided on this carrier, and the surface-treated copper foil of this invention provided on this peeling layer with a process surface (typically a roughening process surface) turned outward. . Above all, as for copper foil with a carrier, a well-known laminated constitution is employable except using the surface-treated copper foil of this invention.

A carrier is a layer (typically foil) for supporting surface-treated copper foil and improving the handling property. As an example of a carrier, aluminum foil, copper foil, the resin film and glass plate etc. which metal-coated the surface with copper etc. are mentioned, Preferably it is copper foil. Any of a rolled copper foil and an electrolytic copper foil may be sufficient as copper foil. The thickness of the carrier is typically 200 µm or less, and preferably 12 µm or more and 35 µm or less.

It is preferable that the surface by the side of the peeling layer of a carrier has 10-point surface roughness Rz of 0.5 micrometer or more and 1.5 micrometers or less, More preferably, they are 0.6 micrometer or more and 1.0 micrometer or less. Rz can be determined based on JIS B 0601-1994. By providing such 10-point surface roughness Rz to the surface by the side of the peeling layer of a carrier, it can be made easy to provide a preferable surface profile to the surface-treated copper foil of this invention produced through a peeling layer on it.

The release layer is a layer having a function of weakening the peel strength of the carrier, guaranteeing the stability of the strength, and further suppressing the interdiffusion that may occur between the carrier and the copper foil during press molding at high temperatures. The release layer is generally formed on one side of the carrier, but may be formed on both sides. The release layer may be either an organic release layer or an inorganic release layer. Examples of the organic component used for the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. A triazole compound, an imidazole compound, etc. are mentioned as an example of a nitrogen-containing organic compound, Among them, a triazole compound is preferable at the point which peelability is easy to stabilize. Examples of the triazole compound include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino -1H-1,2,4-triazole and the like. Examples of the sulfur-containing organic compound include mercaptobenzothiazole, thiocyanuric acid, and 2-benzimidazolethiol. Monocarboxylic acid, dicarboxylic acid, etc. are mentioned as an example of carboxylic acid. On the other hand, as an example of the inorganic component used for an inorganic peeling layer, Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, a chromate-treated film, etc. are mentioned. The release layer may be formed by, for example, bringing the release layer component-containing solution into contact with at least one surface of the carrier and fixing the release layer component to the surface of the carrier. The carrier may be brought into contact with the release layer component-containing solution by immersion in the release layer component-containing solution, spraying the release layer component-containing solution, flowing down the release layer component-containing solution, or the like. The release layer component may be fixed to the carrier surface by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like. The thickness of the release layer is typically 1 nm or more and 1 µm or less, and preferably 5 nm or more and 500 nm or less.

As surface-treated copper foil, the surface-treated copper foil of this invention mentioned above is used. Although the roughening process using a copper particle was performed, the roughening process of this invention forms a copper layer as copper foil on the surface of a peeling layer first as a procedure, What is necessary is just to roughen at least after that. The details of harmony are the same as described above. Moreover, in order that copper foil may make use of the advantage as copper foil with a carrier, it is preferable to be comprised in the form of ultra-thin copper foil. Preferred thickness as an ultra-thin copper foil is 0.1 micrometer or more and 7 micrometers or less, More preferably, they are 0.5 micrometer or more and 5 micrometers or less, More preferably, they are 0.5 micrometer or more and 3 micrometers or less.

You may provide another functional layer between a peeling layer and a carrier and/or copper foil. An example of such another functional layer is an auxiliary metal layer. The auxiliary metal layer preferably includes 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

It is preferable that the surface-treated copper foil thru|or copper foil with a carrier of this invention is used for preparation of the copper clad laminated board for printed wiring boards. That is, according to the preferable aspect of this invention, the copper clad laminated board provided with the said surface-treated copper foil or the said copper foil with a carrier is provided. By using the surface-treated copper foil thru|or copper foil with a carrier of this invention, the copper clad laminated board suitable especially for SAP method can be provided. This copper clad laminated board is provided with the surface-treated copper foil of this invention, and the resin layer provided in close contact with the roughening process surface of this surface-treated copper foil, Or the copper foil with a carrier of this invention, and this copper with a carrier A resin layer provided in close contact with the roughened surface of the surface-treated copper foil in foil is provided. Surface-treated copper foil or copper foil with a carrier may be provided in the single side|surface of a resin layer, and may be provided in both surfaces. The resin layer comprises a resin, preferably an insulating resin. The resin layer is preferably a prepreg and/or a resin sheet. A prepreg is a generic term for composite materials in which a synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, and paper. Preferred examples of the insulating resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, and a phenol resin. Moreover, as an example of insulating resin which comprises a resin sheet, insulating resin, such as an epoxy resin, a polyimide resin, and a polyester resin, is mentioned. Moreover, the filler particle etc. containing various inorganic particles, such as a silica and an alumina, from a viewpoint of improving insulation etc. may be contained in a resin layer. Although the thickness of a resin layer is not specifically limited, 1 micrometer or more and 1000 micrometers or less are preferable, More preferably, they are 2 micrometers or more and 400 micrometers or less, More preferably, they are 3 micrometers or more and 200 micrometers or less. The resin layer may be constituted by a plurality of layers. Resin layers, such as a prepreg and/or a resin sheet, may be provided in the surface-treated copper foil thru|or copper foil with a carrier via the primer resin layer previously apply|coated to the roughening process surface of surface-treated copper foil.

printed wiring board

It is preferable that the surface-treated copper foil thru|or copper foil with a carrier of this invention is used for manufacture of a printed wiring board, Especially preferably, it is used for manufacture of the printed wiring board by a semi-additive method (SAP). That is, according to a preferred aspect of the present invention, a printed wiring board is manufactured using the above-described surface-treated copper foil or the copper foil with a carrier, a method for manufacturing a printed wiring board, or the above-mentioned surface-treated copper foil or the above The printed wiring board obtained using copper foil with a carrier is provided. By using the surface-treated copper foil thru|or copper foil with a carrier of this invention, the above-mentioned surface profile can be provided to a laminated body, and the etching process which is one process of printed wiring board manufacture WHEREIN: It becomes possible to suppress chamfering effectively. The printed wiring board by this aspect consists of the laminated constitution in which the resin layer and the copper layer were laminated|stacked. In the case of the SAP method, since the surface-treated copper foil of the present invention is removed in the step (c) of Fig. 1, the printed wiring board produced by the SAP method no longer contains the surface-treated copper foil of the present invention, and the surface-treated copper Only the surface profile transferred from the roughened surface of the foil remains. In addition, about a resin layer, it is as above-mentioned about a copper clad laminated board. In any case, as for a printed wiring board, a well-known layer structure is employable. Specific examples of the printed wiring board include a single-sided or double-sided printed wiring board in which a circuit is formed after bonding the surface-treated copper foil or copper foil with a carrier of the present invention to one or both sides of the prepreg to obtain a cured laminate, and a multilayered printed circuit board with these A wiring board etc. are mentioned. Moreover, as another specific example, the flexible printed wiring board, COF, TAB tape, etc. which form the surface-treated copper foil of this invention thru|or the copper foil with a carrier on a resin film to form a circuit are mentioned. As another specific example, a copper foil with resin (RCC) in which the above-described resin layer is applied to the surface-treated copper foil or copper foil with a carrier of the present invention is formed, and the resin layer is laminated on the above-described printed circuit board as an insulating adhesive layer. Then, a build-up wiring board in which a circuit is formed by a modified semi-additive (MSAP) method, a subtractive method, etc. as all or a part of the surface-treated copper foil as a wiring layer, or a semi-additive by removing the surface-treated copper foil A buildup wiring board in which a circuit is formed by the (SAP) method, and a direct buildup on a wafer in which lamination of a copper foil with resin and circuit formation are alternately repeated on a semiconductor integrated circuit. As a more advanced specific example, an antenna element formed by laminating the copper foil with resin on a substrate to form a circuit, an electronic material for panel/display electronic material or window glass electronic material in which a pattern is formed by laminating on glass or a resin film through an adhesive layer , the electromagnetic shielding film etc. which apply|coated the conductive adhesive to the surface-treated copper foil of this invention are also mentioned. In particular, the surface-treated copper foil of this invention thru|or the copper foil with a carrier is suitable for SAP method. For example, when a circuit is formed by the SAP method, the structure as shown in FIGS. 1 and 2 is employable.

resin substrate

According to a preferred aspect of the present invention, there is provided a resin substrate in which at least one surface has a skewness Ssk measured in accordance with ISO25178 of -0.6 or less. This resin base material corresponds to the resin replica to which the surface shape of the surface-treated copper foil of this invention was transcribe|transferred. Therefore, the preferred form of the resin replica to which the surface shape of the surface-treated copper foil is transferred (skewness Ssk, the arithmetic mean grain Spc of the peaks, the density of the peaks of the peaks Spd, and the ratio of the actual volume Vmc of the core part to the height of the poles Sxp) Each parameter of Vmc/Sxp) is suitable as it is also for the resin base material of this form. The resin substrate comprises a resin, preferably an insulating resin. The resin substrate is preferably a prepreg and/or a resin sheet. A prepreg is a generic term for composite materials in which a synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, and paper. Preferred examples of the insulating resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, and a phenol resin. Moreover, as an example of insulating resin which comprises a resin base material, insulating resins, such as an epoxy resin, a polyimide resin, and a polyester resin, are mentioned. Moreover, the filler particle etc. containing various inorganic particles, such as a silica and an alumina, from a viewpoint of improving insulation etc. may be contained in the resin base material. Although the thickness of a resin base material is not specifically limited, 1 micrometer or more and 1000 micrometers or less are preferable, More preferably, they are 2 micrometers or more and 400 micrometers or less, More preferably, they are 3 micrometers or more and 200 micrometers or less. The resin substrate may be constituted by a plurality of layers. The resin substrate of the present invention can be preferably used as a starting material or an intermediate product in the production of a printed wiring board by the SAP method.

Example

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

Examples 1 to 6

Preparation and evaluation of copper foil with a carrier and a resin replica were performed as follows.

(1) Preparation of carrier

As a cathode, an electrode made of titanium whose surface was polished with a #2000 buff was prepared. In addition, DSA (dimensionally stable positive electrode) was prepared as the positive electrode. These electrodes were immersed in a copper sulfate solution having a copper concentration of 80 g/L and a sulfuric acid concentration of 260 g/L, and electrolysis was performed at a solution temperature of 45° C. and a current density of 55 A/dm ² to obtain an electrolytic copper foil having a thickness of 18 μm as a carrier. .

(2) Formation of a release layer

The electrode surface side of the carrier subjected to pickling is immersed in a CBTA aqueous solution having 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, and the CBTA component is added to the carrier adsorbed to the electrode surface of In this way, a CBTA layer was formed as an organic peeling layer on the surface of the electrode surface of the carrier.

(3) Formation of auxiliary metal layer

The carrier on which the organic release layer was formed was immersed in a solution having a nickel concentration of 20 g/L prepared using nickel sulfate, and ^{under the conditions of a liquid temperature of 45° C., pH 3, and a current density of 5 A/dm 2} , an adhesion amount corresponding to a thickness of 0.001 μm Nickel was deposited on the organic release layer. In this way, a nickel layer was formed as an auxiliary metal layer on the organic release layer.

(4) Formation of ultra-thin copper foil

The carrier on which the auxiliary metal layer is formed is immersed in a copper sulfate solution having a copper concentration of 60 g/L and a sulfuric acid concentration of 200 g/L, and electrolyzed at a solution temperature of 50° C. and a current density of 5 A/dm ² or more and 30 A/dm ² or less, and has a thickness of 1.2 μm. An ultra-thin copper foil was formed on the auxiliary metal layer.

(5) Harmonization processing

The roughening process was performed with respect to the precipitation surface of the ultra-thin copper foil mentioned above. In this roughening process, the plating of the 1st stage divided into 2 times, and was performed. In the plating process of each step, a copper sulfate solution having the copper concentration, sulfuric acid concentration, chlorine concentration, and 9-phenylacridine (9PA) concentration shown in Table 1 is used, and at the liquid temperature shown in Table 1, the current shown in Table 2 Electrodeposition was done at density and time. The distance between the positive electrode and the negative electrode in the plating process of the 1st stage was made into 50 mm or more and 80 mm or less. In this way, six types of roughening process copper foil from Example 1 to Example 6 were produced.

(6) Anti-rust treatment

The surface of the roughening process layer of the obtained copper foil with a carrier was given the rust prevention process containing a zinc- nickel alloy plating process and a chromate process. First, an electrolytic solution having a zinc concentration of 0.2 g/L, a nickel concentration of 2 g/L, and a potassium pyrophosphate concentration of 300 g/L is used, and ^{under the conditions of a liquid temperature of 40° C. and a current density of 0.5 A/dm 2} , the roughening treatment layer and the surface of the carrier was subjected to zinc-nickel alloy plating treatment. Next, using a 1 g/L aqueous solution of chromic acid, chromate treatment was performed on the zinc-nickel alloy plating surface under the conditions of pH 11, liquid temperature 25° C., and current density 1 A/dm ^{2 .}

(7) Silane coupling agent treatment

The silane coupling agent process was performed by making the aqueous solution containing 3 g/L of 3-aminopropyl trimethoxysilane adsorb|suck to the copper foil side surface of copper foil with a carrier, and evaporating water|moisture content with an electric heater. At this time, the silane coupling agent process was not performed on the carrier side.

(8) Production of copper clad laminate

A copper clad laminate was produced using copper foil with a carrier. First, an ultra-thin copper foil of copper foil with a carrier is laminated on the surface of the inner layer substrate via a BT resin prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd., GHPL-830NS, thickness 0.1 mm) as a resin film, and a pressure of 4.0 After thermocompression bonding at MPa and a temperature of 220°C for 90 minutes, the carrier was peeled off to prepare a copper clad laminate.

(9) Preparation of resin replicas

All the copper foils on the surface of the copper clad laminate were removed with a sulfuric acid/hydrogen peroxide-based etchant to obtain a resin replica.

(10) Measurement of the surface profile of the resin replica

By surface roughness analysis using a laser microscope (manufactured by Keyence Corporation, VK-X100), the transfer surface (surface profile of the roughened surface transferred) of the resin replica was measured in accordance with ISO25178. Specifically, the surface profile of a region having an area of 57074.677 µm ² on the transfer surface of the resin replica was measured with the above laser microscope at an objective lens magnification of 50 times. The surface profile of the transferred surface of the obtained resin replica is subjected to surface inclination correction (automatic) as a pretreatment, and then analyzed by the laser method, and each parameter (skewness Ssk, arithmetic mean curve of the peaks Spc, and peak density of the peaks Spd) , the ratio of the solid volume Vmc of the core to the height of the pole Sxp (Vmc/Sxp) was calculated. At this time, numerical values were measured without using either the S filter or the L filter. The above operation was performed 3 times with respect to each example, and the average value was made into the value of each parameter in each example. The results were as shown in Table 3.

(11) Production of a laminate for SAP evaluation

The resin replica was subjected to degreasing, Pd-based catalyst application and activation treatment. In this way, electroless copper plating (thickness: 1 µm) was applied to the activated surface to obtain a laminate (hereinafter, referred to as a laminate for SAP evaluation) just before laminating the dry film in the SAP method. These steps were performed according to the well-known conditions of the SAP method.

(12) Evaluation of the laminate for SAP evaluation

About the obtained laminated body for SAP evaluation, evaluation of various characteristics was performed as follows.

<Evaluation of cutting>

A circuit having 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 formed by attaching a dry film to the surface of the laminate for SAP evaluation, performing exposure, dry film removal, electrolytic plating, etc.) is in a state electrically connected by an electroless copper plating layer) was formed. By treating the obtained circuit with an etchant (SAC-700W3C, manufactured by Ebara Yujirite Co., Ltd.), the electroless copper plating layer remaining between circuits was dissolved and removed to insulate each circuit. The etching amount at this time measured the etching rate of copper foil beforehand, and performed on the conditions of what is called overetching which etches 4 micrometers equivalent further rather than what is called just etching. After etching, the circuit was washed with water and dried. The cross section of the circuit was observed using an optical microscope, and the amount of cut was calculated. 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 xy is subtracted from the cut amount. (μm). Measurement was performed in two fields of view about each example, and the average value was made into the amount of shaving of each example. The results were as shown in Table 3.

<Plating circuit adhesion (peel strength)>

The dry film was stuck to the laminated body for SAP evaluation, and exposure and image development were performed. After depositing a copper layer by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The electroless copper plating exposed with the etching solution (Evara Yujirite Co., Ltd. make, 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 peeling strength at the time of peeling a copper layer from the sample for evaluation was measured. The results were as shown in Table 3.

As can be seen from Table 3, in Example 5, although the value of Vmc/Sxp was large, the peel strength did not rise that much. As for this reason, "powder fall" is considered to be one factor. That is, when powder falling occurs, the anchor effect is no longer obtained and the peel strength tends to decrease, but powder falling occurs when Vmc/Sxp is too large. Example 5 is thought to remain at a slightly lower peel strength because slight powder drop occurred.

Claims (11)

A surface-treated copper foil having a treatment surface on at least one side,
When a resin film is thermocompression-bonded to the treated surface to transfer the surface shape of the treated surface to the surface of the resin film, and the surface-treated copper foil is removed by etching, in the surface of the resin film remaining, Surface-treated copper foil from which skewness Ssk measured based on ISO25178 will be -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. The method of claim 1 or claim 2, wherein the surface of the resin film left after the etching, is in accordance with ISO25178 arithmetic mean of the Song Spc mountain peak, measured over 5000mm ^-1 13000mm ^-1 or less, surface-treated copper foil. The surface of the resin film remaining after the etching has an acid peak density Spd of 1.13×10 ⁶ mm ^-2 or more, ^{measured in accordance with ISO25178, of 1.50×10 6 .} mm ^-2 or less, surface-treated copper foil. The solid volume Vmc of the core part measured according to ISO25178 with respect to the pole height Sxp measured according to ISO25178, with respect to the said surface of the said resin film left after the said etching, The surface-treated copper foil whose ratio Vmc/Sxp is 0.39 or more and 0.44 or less. The surface-treated copper foil as described in any one of Claims 1-5 used in order to transcribe|transfer an uneven|corrugated shape to the insulating resin layer for printed wiring boards. The surface-treated copper foil according to any one of claims 1 to 6, which is used for production of a printed wiring board by a semi-additive method (SAP). Copper foil with carrier provided with a carrier, the peeling layer provided on this carrier, and the surface-treated copper foil in any one of Claims 1-7 provided on this peeling layer with the said process surface outward. . The copper clad laminated board provided with the surface-treated copper foil of any one of Claims 1-7, or the copper foil with a carrier of Claim 8. The printed wiring board obtained using the surface-treated copper foil in any one of Claims 1-7, or the copper foil with a carrier of Claim 8. A printed wiring board is manufactured using the surface-treated copper foil in any one of Claims 1-7, or the copper foil with a carrier of Claim 8, The manufacturing method of the printed wiring board characterized by the above-mentioned.

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