JP5474316B2 - Copper-clad laminate, surface-treated copper foil used for manufacturing the copper-clad laminate, and printed wiring board obtained using the copper-clad laminate - Google Patents

Description

  The present invention relates to a copper-clad laminate, a surface-treated copper foil used for producing the copper-clad laminate, and a printed wiring board obtained using the copper-clad laminate. In particular, the present invention relates to a copper-clad laminate used for manufacturing a printed wiring board including a step of preparing a wiring circuit with an etching solution containing sulfuric acid and hydrogen peroxide.

  In recent years, information processing functions are often added not only to industrial electronics and electrical equipment but also to consumer electronics and electronic equipment. Such products are naturally equipped with IC components such as CPUs and LSIs. ing. Representative examples of the device having the information processing function include a mobile phone and a portable music player, and are required to be small and have high functionality. As a result, there is a strong demand for lighter, thinner, and smaller printed wiring boards incorporated in these devices such as package substrates on which LSIs are mounted. Therefore, in the production of printed wiring boards, products employing a wide variety of processing methods have been proposed, and copper-clad laminates suitable for each method have been developed. For example, a flexible printed circuit board (hereinafter referred to as “FPC”) is adopted in many devices because it can be easily housed in a limited narrow housing because of its good flexibility. ing.

  However, if the printed wiring board is made smaller and multi-layered for the purpose of further miniaturization and thinning, electroless plating (electroless copper plating, electroless gold plating, etc.) is caused between the wiring circuits due to the narrowing of the wiring circuit pitch. The so-called “copper drop” or “gold drop”, which is deposited, tends to occur. And as the wiring circuit pitch of the printed wiring board becomes narrower, this plating-out phenomenon is more likely to occur, and the repair work for removing the metal component between the wiring circuits becomes difficult. In particular, for the production of a printed wiring board such as TCP, a two-layer flexible copper clad laminate (hereinafter referred to as “FCCL”) without an adhesive layer is used in an FPC. Repair work is almost impossible because of the use of layers. A product that cannot be repaired in this way is not preferable because it has a high probability of being discarded as a defective product and wastes resources. As a countermeasure for preventing the occurrence of the “plating-off phenomenon”, it has been said that it is effective to prevent a metal component or an ionic inorganic component from remaining between the wirings after the wiring circuit is formed.

  In addition, a multilayer FPC having a plurality of wiring circuit layers may be manufactured using the two-layer FCCL. In this multi-layer FPC manufacturing process, a wiring circuit is formed on FCCL using an insulating resin base material such as polyimide, and is built up through a bonding sheet to form a multi-layer, thereby forming interlayer conduction means such as via holes. The wiring circuit layers are electrically connected. However, polyimide resin, aramid resin, etc. that constitute the insulating resin layer of FPC are generally excellent in heat resistance, but they may lack chemical resistance, especially chemical resistance to alkaline chemicals. There are cases where the processing steps of the wiring board are restricted. For this reason, an aqueous solution containing sulfuric acid and hydrogen peroxide and not containing strong acid ions such as chlorine is often used for pretreatment for multi-layer lamination and soft etching before forming via holes.

  Therefore, in order to solve the problems of the FPC, an approach to solve the problems from both directions of the copper foil as the constituent material and the insulating resin layer constituent material is necessary. From the field of copper foil, the etching characteristics are improved so that metal components do not remain, etc., low profile of the bonding surface with the insulating resin layer, refinement of the roughened particles, examination of rust prevention components, etc. Has been done.

  For example, Patent Document 1 discloses a technique related to copper foil with the view of manufacturing the FPC described above. In other words, when a resin base material is laminated on the adherend surface of the copper foil to form a copper-clad laminate, the peel strength between the copper foil and the resin base material is kept high, and heat resistance, chemical resistance, For the purpose of providing a copper foil excellent in electroless plating processability, which has excellent moisture resistance and does not cause deposition of plating metal on the resin base material surface from which the copper foil has been removed by etching during electroless plating. A method for producing a copper foil for a printed wiring board having a mixture coating layer composed of a silane coupling agent, a silicate, and thiodiglycolic acid on the adherend surface of the copper foil is disclosed. Then, according to the method for producing a copper foil disclosed in Patent Document 1, a nickel-molybdenum-cobalt alloy layer or an indium-zinc alloy layer is used as a rust prevention layer in providing a roughening treatment layer and a rust prevention layer on the adherend surface. And forming a layer consisting of a chromate layer.

JP 10-138394 A

  However, even if FCCL manufactured by the technique disclosed in Patent Document 1 and bonded with “copper foil in which roughened particles are formed through a composite metal layer containing molybdenum or the like in a rust prevention layer” is used, FIG. As shown, there is a tendency that an abnormal undercut phenomenon (the portion indicated by the arrow of reference numeral 2 is an undercut portion) occurs. When such a phenomenon occurs, even if it is a wiring circuit with an apparently good circuit width, the adhesion between the wiring circuit and the insulating resin layer is greatly deteriorated, and circuit peeling easily occurs. The risk of the circuit being easily dropped due to repeated bending stress increases.

  From the above, in the FPC industry, there is a demand for FCCL that does not cause an undercut phenomenon at the bottom of a wiring circuit even when treated with an etching solution containing sulfuric acid and hydrogen peroxide, and a copper foil that can prevent the occurrence of the phenomenon. there were.

  Therefore, as a result of diligent research, the inventors of the present invention can form fine wiring by using a copper-clad laminate having the following characteristics, and include sulfuric acid and hydrogen peroxide. It was conceived that the undercut phenomenon did not occur at the bottom of the wiring circuit even when the etching solution was used.

Copper-clad laminate according to the present invention: copper-clad laminate according to the present invention, all SANYO where the copper layer and the insulating resin layer is laminated, after wiring circuit is formed, sulfuric acid and hydrogen peroxide A copper-clad laminate for use in printed wiring board production including a step of preparing a wiring circuit with an etching solution containing a zinc component and three or less types of ionic valence on a bonding surface of the copper layer with the insulating resin layer look containing a transition metal component other than zinc can take several, with a surface treatment layer containing no transition metal component capable of forming a ionic valence greater than three, and, bonded between the insulating resin layer in the copper layer The surface roughness (Rzjis) of the surface is 2.5 μm or less.

In the copper-clad laminate according to the present invention, it is preferable that the surface treatment layer has a total mass thickness of 40 mg / m ² or more of zinc and the transition metal component.

It is preferable that the copper clad laminated board which concerns on this invention is equipped with a roughening process layer in the bonding surface with the said insulating resin layer in the said copper layer . Further, when the cross-sectional spreading resistance of the copper-clad laminate is measured, the roughening resistance value (R _B1 ) of the roughening treatment layer and the bulk layer resistance value (R _B2 ) of the bulk copper layer of the copper layer are Unlikely, it is preferable to have a relationship of R _B1 <R _B2 .

  The copper clad laminate according to the present invention is preferably a flexible copper clad laminate using a resin film having flexibility on the insulating resin base material.

Surface-treated copper foil according to the present invention: The surface-treated copper foil according to the present invention is a surface-treated copper foil used for the production of the above-described copper-clad laminate, and a zinc component and a bonded surface with an insulating resin substrate A surface treatment layer containing a transition metal component other than zinc that can take three or less ionic valences is provided, and the surface roughness (Rzjis) of the bonding surface with the insulating resin substrate is 2.5 μm or less. It is characterized by this.

The bonding surface between said insulating resin base material of the surface treated copper foil, it is preferable that roughening treatment is applied.

Printed wiring board according to the present invention: The printed wiring board according to the present invention is obtained by etching using the above-described copper-clad laminate.

  In the printed wiring board according to the present invention, the wiring circuit is immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% at a liquid temperature of 30 ° C. for 30 seconds. The depth of the undercut formed at the interface with the insulating resin base material has a characteristic of 3.0 μm or less from the end face of the wiring.

  The copper clad laminate according to the present invention is used in printed wiring board manufacture including a step of preparing a wiring circuit with an etching solution containing sulfuric acid and hydrogen peroxide. The copper-clad laminate includes a surface treatment layer containing a zinc component and a transition metal component other than zinc capable of taking an ion valence of three or less at the interface between the copper layer and the insulating resin layer, and The surface roughness (Rzjis) of the interface between the copper layer and the insulating resin layer is 2.5 μm or less. As a result, the undercut phenomenon does not occur even when treated with an etching solution containing sulfuric acid and hydrogen peroxide, so that the circuit between the wiring circuit obtained in the printed wiring board manufacturing process and the insulating resin layer is good. Demonstrate adhesion. Moreover, since the profile of the surface roughness (Rzjis) at the interface between the copper layer and the insulating resin layer is low, the fine pitch circuit required for FPC can be easily formed. Therefore, a copper-clad laminate suitable for printed wiring board production and a printed wiring board obtained by processing the copper-clad laminate are obtained, and the layer configuration of the copper-clad laminate according to the present invention is the present invention. It can manufacture easily by using the surface treatment copper foil which concerns on this.

Form of copper-clad laminate according to the present invention: A copper-clad laminate according to the present invention is a copper-clad laminate used for manufacturing a printed wiring board including a step of preparing a wiring circuit with an etching solution containing sulfuric acid and hydrogen peroxide. It is. The copper clad laminate according to the present invention basically has a layer structure in which a copper layer and an insulating resin layer are bonded together, and at the interface between the copper layer and the insulating resin layer, a zinc component and three or less types A first feature is that a surface treatment layer including a transition metal component other than zinc capable of taking an ionic valence is provided. The copper clad laminate according to the present invention has a second feature that the surface roughness (Rzjis) of the interface between the copper layer and the insulating resin layer is 2.5 μm or less.

  First, the first feature will be described. A first feature is that a surface treatment layer including a “zinc component” and “a transition metal component other than zinc capable of taking three or less ionic valences” is provided at an interface between the copper layer and the insulating resin layer. That is. Here, the “zinc component” is an essential component in the surface treatment layer. Even if this is a metal component other than zinc, for example, "a transition metal component other than zinc that can take three or less ionic valences" is a metal component that is difficult to alloy with copper, Since the zinc and copper are easily alloyed, good adhesion between the surface treatment layer containing the “zinc component” and the “transition metal component other than zinc capable of taking three or less ionic valences” and the copper layer This is because sex can be obtained. Moreover, the zinc component is a component necessary for improving the heat resistance characteristics as a printed wiring board.

  Components other than zinc are “transition metal components other than zinc that can take three or less ionic valences”. In general, if the behavior is between a metal and a metal ion in an aqueous solution, a certain guess can be made from the ionization tendency. However, various solutions that come into contact when processing a copper-clad laminate into a printed wiring board often have an oxidizing power that dissolves metal components. When the copper-clad laminate comes into contact with such a solution (dilute sulfuric acid, dilute hydrochloric acid, etc.), the copper metal is oxidized and dissolved as copper ions.

  In such a dissolution reaction model, the surface treatment layer contains “a transition metal component other than zinc capable of taking an ion valence exceeding three types (hereinafter simply referred to as“ multivalent metal ”)”. On the other hand, when an etching solution containing sulfuric acid and hydrogen peroxide is used, since there is hydrogen peroxide water as an oxygen supply source, between the multivalent metal itself and its oxides, Irreversible reactions with changes in ionic valence are likely to occur. As a result, the redox state of the polyvalent metal component in the surface treatment layer changes according to the change in the redox potential of the etching solution used for the processing of the wiring circuit, and the oxidation before elution of zinc and copper is performed. The state will also be affected. As a result, the potential difference fluctuation between the surface treatment layer and the copper layer is increased, and a phenomenon in which the copper layer is preferentially dissolved occurs, and an undercut phenomenon appears.

  On the other hand, if the ionic valence that can be taken by the metal contained in the surface treatment layer is within 3 types (for example, when the eluted metal ion is monovalent, divalent, or trivalent), sulfuric acid and Even when an etching solution containing hydrogen peroxide is used, an irreversible reaction accompanied by a change in ionic valence between the metal component and its oxide hardly occurs, and the above phenomenon is not exhibited. Since a behavior similar to that of general copper etching using a ferric copper etchant, a cupric chloride etchant, or the like is exhibited, a stable wiring circuit shape can be obtained and an undercut phenomenon is hardly caused. The “transition metal component other than zinc capable of taking three or less types of ionic valence” as used herein is nickel, chromium, iron, platinum, manganese, copper, or the like. Among these, it is more preferable to use “a transition metal component other than zinc capable of taking two or less ionic valences”. Specifically speaking, transition metal components other than zinc that can take two or less kinds of ionic valences include copper that forms monovalent ions or divalent ions, iron that forms divalent ions or trivalent ions, and divalent ions. Nickel that forms only ions. In addition, even if the above-described “transition metal components other than zinc capable of taking three or less ionic valences” are eluted and coexist in the etching solution, the copper etching for forming the wiring circuit, There is no adverse effect.

  Here, in FIG. 1, a copper-clad laminate is manufactured using the surface-treated copper foil according to the present invention described below, and in the production of a printed wiring board using the same, sulfuric acid and hydrogen peroxide are formed after the wiring circuit is formed. As a result of microetching using an etchant containing copper, the layer structure seen from the cross section of the copper layer 2, the surface treatment layer 3, and the insulating resin substrate 5 when no undercut phenomenon occurs at the bottom of the wiring circuit Is shown. This is a case where a copper-clad laminate is manufactured using the surface-treated copper foil according to the present invention, and a printed wiring board is manufactured using this. FIG. 2 shows an undercut portion from a cross section when an undercut phenomenon occurs at the bottom of the wiring circuit (copper layer 2) as a result of microetching using an etching solution containing sulfuric acid and hydrogen peroxide. 6 is shown. This is a case where a copper-clad laminate is manufactured using a surface-treated copper foil having a surface treatment layer containing molybdenum, and a printed wiring board is manufactured using the copper-clad laminate. It is a transition metal component that can take a valence. Since FIG. 1 and FIG. 2 are compared, the ionic valence that can be taken by the metal contained in the surface treatment layer is within 3 types (for example, the eluted metal ion is either monovalent, bivalent, or trivalent). In this case, it can be understood that the undercut phenomenon does not occur in microetching using an etching solution containing sulfuric acid and hydrogen peroxide.

The surface treatment layer of the copper clad laminate according to the present invention described above has a total mass thickness of 40 mg of “zinc component” and “transition metal component other than zinc capable of taking three or less ionic valences”. / M ² or more is preferable. When the mass thickness is less than 40 mg / m ² , there is a strong tendency to have a portion where the interface is not sufficiently covered with the surface treatment layer, and the adhesion between the copper layer and the insulating resin substrate is increased. This is not preferable because there is a local variation in heat resistance and chemical resistance. Here, the reason why the mass thickness of 40 mg / m ² is set as the lower limit will be described. The mass thickness is an amount that can cover a completely flat ideal plane with the surface treatment layer having a thickness of about 40 mm. The amount of the alloy component covering the ideal plane with a thickness of 40 mm is a roughened surface having fine roughened particles having small shape variations on a substantially smooth surface on the basis of the surface area of the ideal plane. However, if the surface area ratio is around 2, it is an amount sufficient to cover the entire surface including the overhang portion of the roughened particles.

In addition, although there is no upper limit on the mass thickness here, depending on the type of metal constituting the surface treatment layer, if a large amount of the metal component exists, it is difficult to dissolve when forming a wiring circuit by etching. There are various ingredients. Even in such a configuration, the mass thickness of the surface treatment layer is preferably 80 mg / m ² or less so that the alloy component used does not become an etching residue.

  Next, the second feature of the copper clad laminate according to the present invention, “the surface roughness (Rzjis) of the interface between the copper layer and the insulating resin layer is 2.5 μm or less” will be described. If the surface roughness (Rzjis) of the interface exceeds 2.5 μm, it becomes difficult to form insulation reliability between layers and fine pitch wiring circuit when a multilayer FPC is manufactured. On the other hand, if the surface roughness (Rzjis) of this interface is 2.5 μm or less, there is almost no possibility of forming locally roughened particles, and the multilayer FPC with a thin insulating resin layer is eliminated. Even if it is used for manufacturing, the insulation reliability between layers can be maintained. In addition, it becomes easy to form fine pitch wiring with 25 μm / 25 μm FPC line / space.

And it is also preferable that the copper layer of the copper clad laminated board which concerns on this invention provides a roughening process to the bonding surface with an insulating resin base material, and improves the adhesiveness of a copper layer and an insulating resin layer. Therefore, the roughening treatment layer provided between the copper layer and the insulating resin layer of the copper clad laminate according to the present invention adheres fine copper grains when the cross-sectional spreading resistance of the copper clad laminate is measured. The roughening treatment layer resistance value (R _B1 ) of the roughening treatment layer formed in this way is different from the bulk layer resistance value (R _B2 ) of the bulk copper layer of the copper layer, and has a relationship of R _B1 <R _B2 Is preferred. It is preferable to have this relationship for preventing the undercut phenomenon.

FIG. 3 shows the results of measuring the resistance of the cross section of the copper clad laminate used when the undercut phenomenon does not occur at the bottom of the wiring circuit. FIG. 4 shows the results of measuring the resistance of the cross section of the copper-clad laminate used when an undercut phenomenon occurs at the bottom of the wiring circuit. In these drawings, the darker the portion, the higher the spread resistance measurement value is, the a) in each figure is the cross-sectional spread resistance image, and b) is the average value of the bulk copper part (≈2 kΩ). It is a spread resistance image based on. Moreover, the upper part of these drawings is a bonding interface between the copper layer and the insulating resin layer constituent material, and the surface layer is a roughened layer subjected to a roughening process. Here, as apparent from the comparison between FIG. 3 and FIG. 4, in the case of FIG. 3, the color tone in the vicinity (roughening layer) of the bonding surface of the copper layer to the insulating resin layer constituent material is It is bright and the color of other bulk copper layers is dark. On the other hand, in the case of FIG. 4, the difference between the color tone of the roughened layer near the bonding interface between the copper layer and the insulating resin layer constituting material and the color tone of the other bulk copper layer cannot be clearly confirmed. is there. Further, when the outermost layer of the bonded interface between the copper layer and the insulating resin layer constituting material of the copper clad laminate of FIGS. 3 and 4 is observed, the high resistance region of FIG. 4 is significantly observed compared to FIG. Has been. Here, in a wiring circuit that handles high-frequency signals in the order of GHz, the signal flows on the bonding surface side of the copper foil and the insulating resin base material due to the skin effect, so in order to improve high-frequency transmission characteristics, The lower the resistance of the bonding surface between the copper-clad laminate and the insulating resin layer constituting material of the copper layer, the better. Therefore, also from this viewpoint, it is preferable that the copper-clad laminate according to the present invention has a relation of roughening treatment layer resistance value (R _B1 ) <bulk layer resistance value (R _B2 ).

  The copper clad laminate according to the present invention is preferably a flexible copper clad laminate using a resin film having flexibility on the insulating resin base material. Here, the resin film having flexibility is a polyimide resin film, an aramid resin film, a PET resin film, a liquid crystal polymer resin film, or the like, and there is no particular limitation on the film material, the film thickness, and the like.

Surface-treated copper foil according to the present invention: The surface-treated copper foil according to the present invention is a surface-treated copper foil used for producing the above-described copper-clad laminate. Accordingly, a surface treatment layer containing a zinc component and a transition metal component other than zinc capable of taking three or less ionic valences is provided on the surface to be bonded to the insulating resin base material, and the surface is bonded to the insulating resin base material. The surface roughness (Rzjis) of the surface needs to be 2.5 μm or less. By bonding this surface-treated copper foil to the insulating resin layer constituent material, the above-described copper-clad laminate according to the present invention can be obtained. Therefore, the description regarding the “surface treatment layer” and “the surface roughness (Rzjis) of the bonded surface is 2.5 μm or less” required as the description of the surface-treated copper foil will be duplicated, and the description here is omitted. To do. The surface-treated copper foil 1 according to the present invention at this time is composed of a copper foil (bulk copper layer) 2 and a surface-treated layer 3, and this layer structure is shown as a schematic sectional view in FIG. In the case of the surface-treated copper foil according to the present invention, as a means for further improving the adhesion with the insulating resin layer constituting material, a silane coupling agent treatment layer may be further provided on the surface of the surface treatment layer. I do not care.

  And it is preferable that the surface treatment copper foil which concerns on this invention provides a roughening process in the bonding surface with the insulating resin base material of the said surface treatment copper foil. In the case of the surface-treated copper foil 1 according to the present invention, a roughened surface is formed on the bonded surface of the copper foil 2 to form a roughened surface 4, and the surface-treated layer 3 is formed on the roughened surface 4. In general, the layer structure shown in FIG. 6 is used. In the case of using the method of attaching the roughening treatment particles to the formation of the roughening treatment surface 4, if the fine copper particles made of metallic copper are used, the roughening treatment particles are formed by copper etching when forming the wiring circuit. The etching factor of the wiring circuit is improved because it is not necessary to take a long over-etching time for removing the roughening particles. In addition, due to the thermal history added in the manufacturing process of the copper clad laminate, the mutual diffusion of copper occurs at the adhesion interface between the copper bulk (copper foil side) and the fine copper particles (roughened particles). This is preferable because the adhesion of the roughened particles to the bulk becomes stronger.

Form of Printed Wiring Board According to Present Invention: The printed wiring board according to the present invention is obtained by etching or the like using the above-described copper-clad laminate. As described above, even if the wiring circuit is immersed in various chemicals in the manufacturing process of the multilayer printed wiring board, the printed wiring board is excellent in electrical characteristics and connection reliability without causing an undercut on the wiring end surface.

  In the printed wiring board according to the present invention, the wiring circuit is immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% at a liquid temperature of 30 ° C. for 30 seconds. The depth of the undercut formed at the interface with the insulating resin base material has a characteristic of 3.0 μm or less from the end face of the wiring. That is, under flash etching, micro etching, and copper circuit etching, even if an etching solution containing sulfuric acid and hydrogen peroxide is used, the undercut phenomenon does not occur. Therefore, among printed wiring boards, it is suitable for flexible printed wiring board applications that require the formation of fine pitch circuits.

  The copper clad laminate according to the present invention is used in printed wiring board manufacture including a step of preparing a wiring circuit with an etching solution containing sulfuric acid and hydrogen peroxide. By using this copper clad laminate, even if an etching solution containing sulfuric acid and hydrogen peroxide is used for flash etching, micro etching, and copper circuit etching, the undercut phenomenon does not occur. Moreover, since the profile of the surface roughness (Rzjis) at the interface between the copper layer and the insulating resin layer is low, the fine pitch circuit required for the FPC can be easily formed. In particular, the copper clad laminate according to the present invention satisfies the required characteristics required for a flexible printed wiring board. Moreover, the copper clad laminated board which concerns on this invention can be easily manufactured by carrying out a lamination process with the resin sheet, prepreg, etc. which comprise an insulating resin layer by using the surface treatment copper foil which concerns on this invention.

It is an optical microscope observation image which shows a mode seen from the cross section when the undercut phenomenon has not generate | occur | produced in the bottom part of a wiring circuit. It is an optical microscope observation image which shows a mode seen from the cross section when the undercut phenomenon has generate | occur | produced in the bottom part of a wiring circuit. It is a spread resistance measurement result of the cross section of the bulk copper layer of the surface treatment copper foil used when the undercut phenomenon does not occur at the bottom of the wiring circuit. It is a spread resistance measurement result of the cross section of the bulk copper layer of the surface treatment copper foil used when the undercut phenomenon generate | occur | produced in the bottom part of the wiring circuit. It is a schematic cross section for demonstrating the layer structure of the surface treatment copper foil which concerns on this invention. It is a schematic cross section for demonstrating the layer structure of the surface treatment copper foil containing the roughening process layer which concerns on this invention.

Explanation of symbols

1 Surface treated copper foil 2 Copper foil (bulk copper layer)
3 Surface treatment layer 4 Roughening treatment layer (Roughening treatment particle, fine copper particle)
5 Insulating resin layer 6 Undercut part

Claims (9)

All SANYO where the copper layer and the insulating resin layer is laminated, after wiring circuit is formed, used in printed wiring board manufacture comprising a step of preparing a printed circuit with an etching solution containing sulfuric acid and hydrogen peroxide A copper clad laminate,
The bonding surface between the insulating resin layer in the copper layer, viewed contains a transition metal component other than zinc can take ionic valence of less zinc component and three, a transition metal capable of forming a ionic valence greater than three Provided with a surface treatment layer that does not contain ingredients ,
And the copper-clad laminated board characterized by surface roughness (Rzjis) of the bonding surface with the said insulating resin layer in the said copper layer being 2.5 micrometers or less. ^2. The copper clad laminate according to claim 1, wherein the surface treatment layer has a total mass thickness of 40 mg / m ² or more of zinc and the transition metal component. The copper clad laminate according to claim 1, wherein a roughening layer is provided on a surface of the copper layer that is bonded to the insulating resin layer. When the cross-sectional spreading resistance of the copper-clad laminate is measured, the roughening resistance value (R _B1 ) of the roughening treatment layer is different from the bulk layer resistance value (R _B2 ) of the bulk copper layer of the copper layer , The copper clad laminate according to claim 3, comprising a relationship of R _B1 <R _B2 . The copper-clad laminate according to any one of claims 1 to 4 , which is a flexible copper-clad laminate obtained by using a resin film having flexibility for the insulating resin layer. It is the surface treatment copper foil used for manufacture of the copper clad laminated board in any one of Claims 1-5 ,
Provided with a surface treatment layer containing a zinc component and a transition metal component other than zinc capable of taking three or less ionic valences on the bonding surface with the insulating resin base material, and the surface of the bonding surface with the insulating resin base material A surface-treated copper foil having a surface roughness (Rzjis) of 2.5 μm or less.   The surface-treated copper foil according to claim 6, wherein the surface of the surface-treated copper foil bonded to the insulating resin base material is subjected to a roughening treatment. A printed wiring board, wherein a wiring circuit is formed using the copper-clad laminate according to claim 5 . The wiring circuit is formed at the interface between the wiring and the insulating resin substrate after being immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% at a liquid temperature of 30 ° C. for 30 seconds. The printed wiring board according to claim 8 , wherein a depth of the undercut is 3.0 μm or less from an end face of the wiring.