KR101194320B1 - Copper clad laminate, surface treated copper foil used for manufacturing the same, and printed wiring board manufactured using the same - Google Patents

Abstract

An object of this invention is to provide the flexible printed wiring board which does not produce the undercut phenomenon in the bottom part of a wiring circuit even if it processes with the etching liquid containing sulfuric acid and hydrogen peroxide, and the copper foil which can prevent this phenomenon.

In order to achieve the above object, a transition metal other than zinc capable of having a zinc component and up to three types of ion valences at an interface between the copper layer and the insulated resin layer of the copper foil laminate for manufacturing a printed wiring board in which the copper layer and the insulated resin layer are bonded together. The copper foil laminated board which has the surface treatment layer containing a component, and the surface roughness (Rzjis) of the interface of the said copper layer and the said insulated resin layer is 2.5 micrometers or less is employ | adopted. In addition, in the manufacture of this copper foil laminated sheet, the surface of copper foil 2 contains the transition metal component other than zinc which can have a zinc component and three or less types of ion valences, and the surface roughness (Rzjis) is 2.5 micrometers or less The surface-treated copper foil 1 provided with the processing layer 3 is employ | adopted.

Description

Copper clad laminate, surface treated copper foil used for manufacturing the same, and printed wiring board manufactured using the same}

This invention relates to the copper foil laminated board, the surface-treated copper foil used for manufacture of this copper foil laminated board, and the printed wiring board obtained using this copper foil laminated board. In particular, it is related with the copper foil laminated board used for manufacture of a printed wiring board containing the process of manufacturing a wiring circuit with the etching liquid containing a sulfuric acid and hydrogen peroxide.

In recent years, not only industrial electronic and electrical equipment but also many consumer electronic and electrical equipment have added an information processing function, and such products are naturally equipped with IC components such as CPU and LSI. Representatives of equipment having an information processing function include mobile phones, portable music players, and the like, and are required to be small and highly functional. As a result, the demand for light and thin reduction is increasing in printed wiring boards mounted on these devices such as package substrates on which LSIs and the like are mounted. Therefore, what employ | adopted various processing methods in manufacture of a printed wiring board is proposed, and the copper foil laminated board suitable for each construction method is developed. In particular, a flexible printed wiring board (Flexible 단 Printed Circuit: hereinafter referred to as 'FPC'), which is excellent in flexibility and easily accommodated in a limited narrow case, has been adopted as a printed wiring board suitable for light and short reduction. .

By the way, when the printed wiring board is miniaturized and multilayered for the purpose of further miniaturization and thinning, so-called 'copper', in which electroless plating (electroless copper plating, electroless gold plating, etc.) is deposited between the wiring circuits by narrowing the wiring circuit pitch, A 'plating residual phenomenon' called 'residual' or 'gold residual' is likely to occur. As the wiring circuit pitch of the printed wiring board becomes narrower, this plating residual phenomenon tends to occur, and the repair work for removing metal components between the wiring circuits becomes difficult. In particular, in the manufacture of printed wiring boards such as TCP, a two-layer flexible copper clad laminate (hereinafter referred to as 'FCCL'), which does not provide a bonding agent layer among FPCs, is used. Is almost impossible. Such a product that cannot be repaired is not preferable because it is a waste product and is likely to be disposed of as a waste. As a countermeasure against the occurrence of this "plating residual phenomenon", it has been said that it is effective not to leave a metal component or an ionic inorganic component between wirings after wiring circuit formation.

Moreover, the multilayer FPC provided with the some wiring circuit layer may be manufactured using the said two-layer FCCL. In the manufacturing process of this multilayer FPC, a wiring circuit is formed in FCCL using insulating resin base materials, such as polyimide, multilayered by building up via a bonding sheet, and interlayer conduction means, such as a via hole, are formed and multiple wiring circuit layers Electrically connect between them. By the way, although polyimide resin, aramid resin, etc. which comprise the insulation resin layer of FPC are generally excellent in heat resistance, chemical resistance, especially chemical resistance with respect to alkaline chemicals, may be inadequate, and the process of a printed wiring board is performed. You may be constrained. Therefore, an aqueous solution containing sulfuric acid and hydrogen peroxide and not containing strong acid ions such as chlorine is often used for pretreatment for multilayer stacking and soft etching before via hole formation.

Therefore, in order to solve the problem of the said FPC, the approach for solving the problem in both directions of the copper foil which is a component material, and the insulated resin layer component material was needed. In the copper foil field, the etching characteristics are improved so that metal components and the like do not remain, and the low profile of the bonding surface with the insulating resin layer, the refinement of the roughened particles, the rust prevention component, and the like are examined. come.

For example, Patent Literature 1 discloses a technique related to a copper foil in which production of the above-described FPC is in view. That is, when the resin substrate is laminated on the surface to be bonded of the copper foil to form a copper foil laminated plate, the peel strength between the copper foil and the resin substrate is maintained high, and excellent in heat resistance, chemical resistance, and moisture resistance, and etching during electroless plating. A silane coupling agent, a silicate, and a thiodiglycolic acid are provided on the surface to be bonded of the copper foil for the purpose of providing a copper foil excellent in electroless plating processability in which precipitation of the plated metal to the resin base surface from which the copper foil has been removed is not caused. The manufacturing method of the copper foil for printed wiring boards which has the mixture coating layer which consists of these is disclosed. And according to the manufacturing method of the copper foil disclosed by patent document 1, in providing a roughening process layer and a rust prevention layer in a to-be-joined surface, it is made of a nickel- molybdenum-cobalt alloy layer, an indium zinc alloy layer, and a chromate layer as a rust prevention layer. Forming a layer which consists of is disclosed.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-138394

However, even when using FCCL in which "copper foil in which roughening particle | grains were formed through the composite metal layer containing molybdenum etc. via the antirust layer manufactured by the technique disclosed by patent document 1" was bonded, abnormal undercut phenomenon as shown in FIG. (The point indicated by the arrow at 2 is an undercut portion) tends to occur. When such a phenomenon occurs, even if the wiring circuit has a good circuit width in appearance, the adhesion between the wiring circuit and the insulating resin layer is greatly deteriorated, so that there is a danger that the circuit may be easily peeled off or the circuit may be easily dropped by repeated bending stress. Increases.

For this reason, there has been a demand in the FPC industry for FCCL, in which the undercut phenomenon does not occur at the bottom of the wiring circuit even if treated with an etching solution containing sulfuric acid and hydrogen peroxide, and a copper foil which can prevent the occurrence of this phenomenon.

Therefore, as a result of repeated studies, the inventors of the present invention have shown that if a printed wiring board is manufactured using a copper foil laminate having the characteristics described below, fine wiring can be formed, and the bottom of the wiring circuit can be treated with an etching solution containing sulfuric acid and hydrogen peroxide. The undercut phenomenon did not occur in the part.

Copper foil laminated board which concerns on this invention: The copper foil laminated board which concerns on this invention is a copper foil laminated board used for manufacture of a printed wiring board containing the process of manufacturing a wiring circuit with the etching liquid containing a sulfuric acid and hydrogen peroxide, This copper foil laminated board is a copper layer and an insulating resin layer It is bonded and provided with the surface treatment layer containing the zinc component and transition metal components other than zinc which can have three or less types of ion valence in the interface of the said copper layer and the said insulated resin layer, and the said The surface roughness (Rzjis) of the interface of a copper layer and the said insulated resin layer is 2.5 micrometers or less, It is characterized by the above-mentioned.

In the copper foil laminate according to the present invention, the surface treatment layer preferably has a mass thickness of 40 mg / m 2 or more in terms of the total thickness of zinc and the transition metal component.

It is preferable that the copper foil laminated board which concerns on this invention gives a roughening process to the bonding surface with the insulated resin base material of the said copper layer.

It is preferable to make the copper foil laminated board which concerns on this invention into a flexible copper foil laminated board using the resin film which has flexibility to the said insulated resin base material.

Surface-treated copper foil which concerns on this invention: The surface-treated copper foil which concerns on this invention is a surface-treated copper foil used for manufacture of the copper foil laminated board mentioned above, and can have a zinc component and three or less types of ion valence in the bonding surface with an insulated resin base material. It is provided with the surface treatment layer containing the transition metal component other than the presence of zinc, and surface roughness (Rzjis) of the bonding surface with this insulating resin base material is 2.5 micrometers or less, It is characterized by the above-mentioned.

It is preferable that the surface-treated copper foil which concerns on this invention gives a roughening process to the bonding surface with the insulated resin base material of the said surface-treated copper foil.

Printed wiring board which concerns on this invention: The printed wiring board which concerns on this invention is obtained by carrying out an etching process etc. using the copper foil laminated board mentioned above, It is characterized by the above-mentioned.

Further, the printed wiring board according to the present invention is formed at the interface between the wiring and the insulating resin substrate after immersing the wiring circuit in an aqueous solution of 30 ° C. for 30 seconds having a sulfuric acid concentration of 10 to 30% and a hydrogen peroxide concentration of 10 to 20%. The undercut has a characteristic of being 3.0 µm or less from the end surface of the wiring.

The copper foil laminated board which concerns on this invention is used for manufacture of a printed wiring board containing the process of manufacturing a wiring circuit with the etching liquid containing a sulfuric acid and hydrogen peroxide. This copper foil laminated sheet is equipped with the surface treatment layer containing the zinc component and transition metal components other than zinc which may have three or less types of ion valence at the interface of the said copper layer and the said insulated resin layer, and the said copper layer and the said insulating water The surface roughness Rzjis of the interface of the layer is 2.5 µm or less. As a result, an undercut phenomenon does not occur even if it processes with the etching liquid containing a sulfuric acid and hydrogen peroxide, and it exhibits favorable adhesiveness between the wiring circuit obtained by the manufacturing process of a printed wiring board, and an insulating resin layer. Moreover, since the profile of the surface roughness Rzjis of the interface of the said copper layer and the said insulated resin layer is low, formation of the fine pitch circuit required for FPC becomes easy. Therefore, the printed wiring board obtained by processing the copper foil laminated board suitable for manufacture of a printed wiring board, and this copper foil laminated board can be obtained. In addition, the layer structure with which the copper foil laminated board which concerns on this invention is equipped can be manufactured easily by using the surface-treated copper foil which concerns on this invention.

Form of copper foil laminated board which concerns on this invention: The copper foil laminated board which concerns on this invention is a copper foil laminated board used for manufacture of a printed wiring board containing the process of manufacturing a wiring circuit with the etching liquid containing a sulfuric acid and hydrogen peroxide. The copper foil laminated sheet which concerns on this invention has the laminated constitution which the copper layer and the insulated resin layer bonded together, and is a transition other than zinc which can have a zinc component and three or less types of ion valence at the interface of the said copper layer and the said insulated resin layer. A first feature is to include a surface treatment layer containing a metal component. Moreover, the copper foil laminated board which concerns on this invention is a 2nd characteristic that surface roughness (Rzjis) of the interface of the said copper layer and the said insulated resin layer is 2.5 micrometers or less.

First, the first feature will be described. The 1st characteristic is that the surface treatment layer containing a "zinc component" and "a transition metal component other than zinc which may have three or less types of ion valences" is provided in the interface of the said copper layer and the said insulated resin layer. Here, a zinc component is an essential component in a surface treatment layer. This is because even if a metal component other than zinc, a transition metal component other than zinc capable of having three or less ionic valences, is difficult to alloy with copper, zinc and copper tend to be alloyed. This is because good adhesion between the surface treatment layer and the same layer including the zinc component 'and the' transition metal component other than zinc capable of having three or less kinds of ion valences' can be obtained. This is because the zinc component is a component necessary for improving the heat resistance characteristics of the printed wiring board.

In addition, components other than zinc are "transition metal components other than zinc which can have three or less types of ion valences." Generally, as long as the behavior between the metal and the metal ions in the aqueous solution, constant estimation is possible from the ionization tendency. By the way, the various solutions which come into contact when processing a copper foil laminated board with a printed wiring board have many oxidizing powers which melt | dissolve a metal component. When the copper foil laminate comes into contact with such a solution (dilute sulfuric acid, dilute hydrochloric acid, etc.), the metal copper is oxidized while being oxidized and dissolved.

In such a dissolution reaction model, the surface treatment layer contains a transition metal component other than zinc which may have more than three kinds of ionic valences (hereinafter, simply referred to as 'polyhydric metal'). On the other hand, when an etching solution containing sulfuric acid and hydrogen peroxide is used, hydrogen peroxide water serving as an oxygen source exists, so that an irreversible reaction involving a change in the ion valence between the polyvalent metal itself and the plurality of oxides is likely to occur. As a result, the redox state of the polyvalent metal component in the surface treatment layer changes with the change of the redox potential of the etching solution used for the processing of the wiring circuit, and the oxidation state before zinc and copper dissolution are also affected. As a result, it is thought that the variation of the potential difference between the surface treatment layer and the copper layer becomes large and the copper layer preferentially dissolves, resulting in an undercut phenomenon.

In contrast, when the metal contained in the surface treatment layer has three or less ionic valences (for example, when the eluted metal ions are any of monovalent, divalent, and trivalent), sulfuric acid and hydrogen peroxide may be used. Even if the etchant included is used, irreversible reactions involving the change of the ion valence between the metal component and the oxide thereof are unlikely to occur, and thus, the above-described phenomenon does not occur. Since the same behavior as in the case of general copper etching using the PSA is obtained, the shape of the stable wiring circuit is obtained and the undercut phenomenon is less likely to occur. The term "transition metal component other than zinc which may have three or less types of ionic valences" is nickel, chromium, iron, platinum, manganese, copper, or the like. Among these, it is preferable to use the "transition metal component other than zinc which can have two or less types of ion valences." Specifically, the transition metal component other than zinc that may have two or less kinds of ionic valences forms only copper, divalent or trivalent ions forming monovalent ions or divalent ions, and only bivalent ions. It is nickel. On the other hand, even if the above-mentioned "transition metal component other than zinc which can have three or less types of ion valences" elutes and coexists in etching liquid, there is no adverse effect on copper etching at the time of forming a wiring circuit.

Here, in FIG. 1, the copper foil laminated board is manufactured using the surface-treated copper foil which concerns on this invention described below, and micro etching is performed using the etching liquid containing sulfuric acid and hydrogen peroxide after formation of a wiring circuit at the time of manufacture of a printed wiring board using the same. As a result, the layer structure seen from the cross section of the copper layer 2, the surface treatment layer 3, and the insulated resin base material 5 when the undercut phenomenon did not generate | occur | produce in the bottom part of a wiring circuit is shown. This is a case where the copper foil laminated board is manufactured using the surface-treated copper foil which concerns on this invention, and the printed wiring board was manufactured using this. In FIG. 2, as a result of micro-etching using an etching solution containing sulfuric acid and hydrogen peroxide, the undercut portion 6 is formed in a cross section when an undercut phenomenon occurs at the bottom of the wiring circuit (copper layer 2). It is showing. This is the case where a copper foil laminated board is manufactured using the surface-treated copper foil provided with the surface treatment layer containing molybdenum, and the printed wiring board was manufactured using this, and molybdenum has a transition metal component which may have more than three types of ion valences. to be. By comparing FIG. 1 with FIG. 2, three or more ion valences which the metal contained in a surface treatment layer may have (for example, when the eluted metal ion is any of monovalent, divalent, and trivalent) On the back side, it can be understood that the undercut phenomenon does not occur in the micro etching using the etching solution containing sulfuric acid and hydrogen peroxide.

As for the surface treatment layer of the copper foil laminated board which concerns on this invention mentioned above, the mass thickness of the sum total of a zinc component and the transition metal component other than zinc which may have three or less types of ion valences is 40 mg / m <2> or more thickness. It is preferable. In the case where the mass thickness is less than 40 mg / m 2, the tendency of insufficient coverage of the interface by the surface treatment layer is increased, which is preferable because a local variation occurs in the adhesion, heat resistance, and chemical resistance between the copper layer and the insulating resin substrate. Not. Here, the reason which made mass thickness 40 mg / m <2> the lower limit is demonstrated. This mass thickness is an amount which can coat | cover an ideal plane completely flat with the surface treatment layer of thickness about 40 GPa. The alloy component amount covering the ideal plane with a thickness of 40 kPa is roughly the roughened surface in which the finely roughened particles having a small shape deviation are present on the almost smooth surface based on the surface area of the ideal flat surface. It is because it is an amount sufficient to coat | cover almost without missing including the overhang part which a roughening process particle | grains have.

In addition, although an upper limit is not provided in this mass thickness here, depending on the kind of metal which comprises a surface treatment layer, when the metal component exists in a large quantity, there exists a component which is difficult to melt | dissolve when forming a wiring circuit by etching. In such a configuration, the mass thickness of the surface treatment layer is preferably 80 mg / m 2 or less so that the used alloy component does not become an etching residue or the like.

Next, it describes about the 2nd characteristic of the copper foil laminated board which concerns on this invention "surface roughness Rzjis of the interface of the said copper layer and the said insulating resin layer is 2.5 micrometers or less." If the surface roughness (Rzjis) of the interface exceeds 2.5 µm, when the multilayer FPC is manufactured, the insulation reliability between layers becomes poor and formation of a fine pitch wiring circuit becomes difficult. On the other hand, when the surface roughness Rzjis of the interface is 2.5 µm or less, there is little possibility that locally large roughened particles are formed, and insulation reliability between layers can be maintained even when the insulating resin layer is used for the manufacture of a thin multilayer FPC. . In addition, formation of fine pitch wirings in which the line / space of the FPC is 25 µm / 25 µm is facilitated.

And it is also preferable that the copper layer of the copper foil laminated board which concerns on this invention improves adhesiveness of a copper layer and an insulated resin layer by roughening a joint surface with an insulated resin base material. Therefore, the roughening process layer provided between the copper layer and the insulated resin layer of the copper foil laminated board which concerns on this invention, when the diffusion resistance of the cross section of the copper foil laminated board was measured, adhere | attached fine copper particles, etc., and was formed. roughening layer resistance (R _B1) and a bulk layer resistance of the bulk copper layer (R _B2) of the same layer in a different layer, it is preferable that the relationship between the R _B1 <R _B2. It is preferable to have this relationship for the prevention of undercut phenomenon.

In FIG. 3, the result of the measurement of the diffusion resistance of the cross section of the copper foil laminated board used when the undercut phenomenon did not generate | occur | produce in the bottom part of a wiring circuit is shown. In FIG. 4, the result of the measurement of the diffusion resistance of the cross section of the copper foil laminated board used when the undercut phenomenon generate | occur | produced in the bottom part of a wiring circuit is shown. In these figures, the darker the diffusion resistance measurement is, the a) is the diffusion resistance phase of the cross section and b) is the diffusion resistance phase based on the average value of the bulk copper portion (≒ 2 kΩ). . In addition, the upper part of these figures is a joining interface of a copper layer and the insulated resin layer component material, and a surface layer is a roughening process layer which carried out the roughening process. Here, as can be seen by comparing FIG. 3 with FIG. 4, in the case of FIG. 3, the color tone of the vicinity of the bonding surface (harmonized layer) of the insulating resin layer constituent material of the copper layer is bright, and the color tone of the other bulk copper layer is dark. Lost In contrast, in the case of FIG. 4, the color tone of the roughened layer in the vicinity of the bonding interface between the copper layer and the insulating resin layer constituent material and the color tone of the other bulk copper layer cannot be clearly identified. Moreover, when looking at the outermost layer of the bonding interface of the copper layer of the copper foil laminated board of FIG. 3 and FIG. 4 and the insulated resin layer constituent material, the high resistance area is remarkably observed in FIG. 4 compared with FIG. Here, in the wiring circuit which handles the high frequency signal of GHz order, since a signal flows to the joining surface side of copper foil and an insulating resin base material by a skin effect, in order to improve a high frequency transmission characteristic, the insulating resin layer component material of the copper layer of a copper foil laminated board and The lower the resistance of the bonding surface is, the more preferable. Therefore, even from such a viewpoint, it is preferable that the copper foil laminated board which concerns on this invention has a relationship of roughening process layer resistance value _RB1 <bulk layer resistance value _RB2 .

It is preferable to make the copper foil laminated board which concerns on this invention into a flexible copper foil laminated board using the resin film which has flexibility to the said insulated resin base material. The resin film which has flexibility here is a polyimide resin film, an aramid resin film, a PET resin film, a liquid crystal polymer resin film, etc., and there is no special limitation in a film material, a film thickness, etc.

Surface-treated copper foil which concerns on this invention: The surface-treated copper foil which concerns on this invention is surface-treated copper foil used for manufacture of the copper foil laminated board mentioned above. Therefore, the surface treatment layer containing the zinc component and the transition metal component other than zinc which may have three or less types of ion valences in the joint surface with an insulated resin base material, and also the surface roughness of the joint surface with this insulated resin base material (Rzjis) needs to be 2.5 micrometers or less. By bonding this surface-treated copper foil to the insulated resin layer constitution material, the copper foil laminated board which concerns on this invention mentioned above is obtained. Therefore, since description regarding the "surface treatment layer" and "surface roughness (Rzjis) of a joining surface is 2.5 micrometers or less" required as description of this surface-treated copper foil overlaps, description here is abbreviate | omitted. The surface-treated copper foil 1 which concerns on this invention at this time is comprised from the copper foil (bulk copper layer) 2 and the surface treatment layer 3, This layer structure was shown by the schematic cross section in FIG. On the other hand, in the case of the surface-treated copper foil which concerns on this invention, you may provide a silane coupling agent treatment layer further on the surface of a surface treatment layer as a means of further improving adhesiveness with the insulated resin layer constitution material.

And it is preferable that the surface-treated copper foil which concerns on this invention gives a roughening process to the bonding surface with the insulated resin base material of the said surface-treated copper foil. In the case of the surface-treated copper foil 1 which concerns on this invention, the roughening process surface 4 is formed by roughening on the bonding surface of the copper foil 2, and the surface treatment layer 3 is made on the roughening process surface 4 It is common to form and to set it as the layer structure shown in FIG. In the case of using the technique of attaching the roughened particles to the formation of the roughened surface 4, when the fine copper particles made of metal copper are used, etching removal of the roughened particles is possible by copper etching when forming the wiring circuit. Since it is not necessary to take large over-etching time for removing roughened particles, the etching factor of the wiring circuit becomes good. In addition, the mutual diffusion of copper occurs at the adhesion interface between copper bulk (copper foil side) and fine copper particles (harmonized particles) due to the heat history added in the manufacturing process of the copper foil laminated plate, so that the adhesion of the roughened particles to copper bulk is more enhanced. It is preferable because it becomes solid.

Form of printed wiring board which concerns on this invention: The printed wiring board which concerns on this invention is obtained by performing an etching process etc. using the above-mentioned copper foil laminated board, It is characterized by the above-mentioned. As mentioned above, even if a wiring circuit is immersed in various chemicals in the manufacturing process of a multilayer printed wiring board, undercut does not generate | occur | produce in the wiring cross section, and it is a printed wiring board excellent in electrical characteristics and connection reliability.

In addition, the printed wiring board according to the present invention is an interface between the wiring and the insulating resin substrate after immersing the wiring circuit in an aqueous solution of 30 ° C. having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% for 30 seconds. The depth of the undercut formed in the film is 3.0 µm or less from the end surface of the wiring. That is, undercutting does not occur even when an etching solution containing sulfuric acid and hydrogen peroxide is used during flash etching, micro etching, and copper circuit etching. Therefore, it is suitable for the use of the flexible printed wiring board which requires formation of a fine pitch circuit among printed wiring boards.

The copper foil laminated sheet which concerns on this invention is used in manufacture of the printed wiring board containing the process of manufacturing a wiring circuit with the etching liquid containing a sulfuric acid and hydrogen peroxide. By using this copper foil laminated sheet, undercut phenomenon does not occur even if etching liquid containing sulfuric acid and hydrogen peroxide is used for flash etching, micro etching, and copper circuit etching. Moreover, since the profile of the surface roughness Rzjis of the interface of the said copper layer and the said insulated resin layer is low, formation of the fine pitch circuit required for FPC becomes easy. In particular, the copper foil laminate according to the present invention satisfies the required properties required for the flexible printed wiring board. Moreover, the copper foil laminated board which concerns on this invention can be manufactured easily by laminating | processing with the resin sheet, prepreg, etc. which comprise an insulating resin layer by using the surface-treated copper foil which concerns on this invention.

BRIEF DESCRIPTION OF THE DRAWINGS It is an optical microscope observation image which shows the state seen from the cross section when undercut phenomenon does not generate | occur | produce in the bottom part of a wiring circuit.

It is an optical microscope observation image which shows the state seen from the cross section when the undercut phenomenon generate | occur | produces in the bottom part of a wiring circuit.

It is a result of the measurement of the diffusion resistance of the cross section of the bulk copper layer of the surface-treated copper foil used when the undercut phenomenon did not generate | occur | produce in the bottom part of a wiring circuit.

It is the result of the measurement of the diffusion resistance of the cross section of the bulk copper layer of the surface-treated copper foil used when the undercut phenomenon generate | occur | produced in the bottom part of a wiring circuit.

It is a schematic cross section for demonstrating the laminated constitution of the surface-treated copper foil which concerns on this invention.

It is a schematic cross section for demonstrating the laminated constitution of the surface-treated copper foil containing the roughening process layer which concerns on this invention.

[Description of Symbols]

One… Surface treatment copper foil

2… Copper foil (bulk copper floor)

3 ... Surface treatment layer

4… Roughened layer (harmonized particles, fine copper particles)

5 ... Insulation resin layer

6... Under cut part

Claims (8)

As a copper foil laminated board used for manufacture of a printed wiring board containing the process of manufacturing a wiring circuit with the etching solution containing a sulfuric acid and hydrogen peroxide, The said copper foil laminated board is a thing in which the copper layer and the insulated resin layer were joined, A surface treatment layer containing a zinc component and a transition metal component other than zinc which may have three or less kinds of ion valences at an interface between the copper layer and the insulated resin layer, The surface roughness (Rzjis) of the interface of the said copper layer and the said insulated resin layer is 2.5 micrometers or less, In addition, the copper layer was roughened on the bonding surface between the copper layer and the insulating resin substrate, and the roughened treatment layer resistance value (R _B1 ) <bulk layer resistance value of the bulk copper layer (R _B2 ) The copper foil laminated sheet characterized by having a relationship. The method of claim 1, The said surface treatment layer is a copper foil laminated board whose mass thickness of the sum total of zinc and the said transition metal component is 40 mg / m <2> or more. delete The method according to any one of claims 1 to 2, The copper foil laminated board which is a flexible copper foil laminated board obtained using the resin film which has flexibility to the said insulated resin layer. As a surface-treated copper foil used for manufacture of the copper foil laminated board of any one of Claims 1-2, A surface treatment layer containing a zinc component and a transition metal component other than zinc which may have three or less kinds of ionic valences at a bonding surface with the insulating resin substrate, The surface roughness (Rzjis) of the bonding surface with the said insulated resin base material is 2.5 micrometers or less, In addition, the said surface-treated copper foil was roughened on the bonding surface with the insulated resin base material of the said surface-treated copper foil, and the said roughened process layer resistance value R _B1 <bulk layer resistance value of a bulk copper layer ( It has a relationship of R _B2 ), The surface-treated copper foil characterized by the above-mentioned. delete The wiring circuit was formed using the copper foil laminated board of Claim 4. The printed wiring board characterized by the above-mentioned. The method of claim 7, wherein The depth of the undercut formed at the interface between the wiring and the insulating resin substrate after immersing the wiring circuit in an aqueous solution at 30 ° C. with a sulfuric acid concentration of 10 to 30% and a hydrogen peroxide concentration of 10 to 20% for 30 seconds is increased. The printed wiring board which is 3.0 micrometers or less from an end surface.

Images