JP5728118B1 - Surface-treated copper foil, method for producing the surface-treated copper foil, and copper-clad laminate using the surface-treated copper foil - Google Patents

Abstract

[PROBLEMS] To provide a copper-clad that enables FPC having a bonding property (bonding property between a copper foil and a resin film) equal to or higher than that of the conventional one even when the bonding surface between the copper foil and the resin film is made lower in roughness than the conventional one. Provided are a laminate, a surface-treated copper foil for obtaining the copper-clad laminate, and a method for producing the surface-treated copper foil. A surface-treated copper foil of the present invention is obtained by forming a plurality of coating layers on a surface of a copper raw foil on a side to be bonded to the resin film. The coating layer is a roughened copper plating layer formed of roughened copper crystal grains having a predetermined average particle diameter formed on the copper raw foil, and a rust-proof nickel plating formed on the roughened copper plating layer A small protrusion copper plating layer made of small protrusion copper crystal grains formed on the rust-proof nickel plating layer and having a predetermined average particle diameter, and a zinc plating layer formed on the small protrusion copper plating layer And have. [Selection] Figure 1

Description

  The present invention relates to a technique for a flexible printed wiring board, and more particularly, to a copper-clad laminate suitable for a flexible printed wiring board, a surface-treated copper foil for obtaining the copper-clad laminate, and a method for producing the surface-treated copper foil. Is.

  A flexible printed circuit board (FPC) has a structure in which a flexible base material such as a resin film and a conductive foil are laminated, and because of its thinness and excellent flexibility, the flexibility in the wiring mounting form is high. It has the advantage of being expensive. Therefore, at present, FPC is widely used as a wiring in a movable part of an electronic device, a bent wiring in a narrow space, a wiring material to a liquid crystal member, an IC chip mounting material, and the like.

  As flexible substrates of FPC, resin films (for example, polyimide films) with good thermal, mechanical, and chemical properties are generally used, and various surface treatments are applied to FPC conductor foils. Pure copper foil or copper alloy foil (hereinafter simply referred to as “copper foil” or “surface-treated copper foil”) is generally used. The raw copper foil that is the basis of the surface-treated copper foil is roughly classified into an electrolytic copper foil and a rolled copper foil depending on the difference in the production method.

  The manufacturing process of FPC is roughly as follows: “Process for forming copper clad laminate (CCL) by bonding copper foil for FPC and resin film” and “Process for forming circuit wiring on the CCL (circuit wiring) A step of etching away the copper foil other than the portion). The copper-clad laminate is a three-layer copper-clad laminate in which a resin film and a copper foil are laminated via an adhesive, and a two-layer in which a resin film and a copper foil are directly laminated without using an adhesive. Broadly divided into copper-clad laminates.

  One of the important characteristics required for FPC is excellent bondability between the resin film and the copper foil (for example, peel strength of 0.5 N / mm or more). Therefore, in order to ensure sufficient bondability at the CCL stage, the bonding surface between the resin film and the copper foil (usually the bonding surface on the copper foil side) is usually subjected to a roughening treatment (eg, roughening). A copper plating layer is formed). In general, as the surface roughness of the bonding surface on the copper foil side increases (as the deep unevenness is formed), the bondability with the resin film is improved by the anchor effect (a kind of physical effect). In addition, in order to obtain chemical bonding between the resin film and the copper foil, a silane coupling treatment is often performed on the outermost surface of the copper foil (the outermost surface of the roughened grains).

  In addition, from the viewpoint of preventing discoloration of the copper foil in CCL (for example, discoloration due to the heating process of CCL production or discoloration during storage) and chemical resistance (for example, acid resistance), the surface of the copper foil is usually Rust prevention treatment is applied. In order to achieve both a rust-proofing effect and the above-described bondability, surface-treated copper foils having various structures have been proposed.

  For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-141227) discloses a copper foil for a printed wiring board made of copper or a copper alloy, on one surface of a copper raw foil (adhesion with a substrate for a printed wiring board). A smooth plating layer having an average thickness not less than 1.5 times the surface roughness Rz and not less than the surface roughness Rz of the original foil is formed on the surface, and a roughened copper plating layer is formed on the smooth plating layer. An alloy plating layer mainly composed of nickel and cobalt is formed on the roughened copper plating layer, a zinc plating layer is formed on the alloy plating layer, and a chromate layer is formed on the zinc plating layer, A copper foil for printed wiring board in which a silane coupling layer is formed on a chromate layer is disclosed.

Patent Document 2 (Japanese Patent Laid-Open No. 2005-290519) discloses a three-dimensional surface area A (S) obtained by measuring the surface area of a roughened surface of a copper foil sample S three-dimensionally with a laser microscope, and the three-dimensional surface area. Measured using the area coefficient C (S) defined by A (S) / B (S) from the measurement area B (S), which is the area of the measurement area of A (S), and a stylus profilometer The roughness R _Z (S) of the roughened surface of the copper foil sample S is expressed by the formula “0.5 × R _Z (S) + 0.5 ≦ C (S)” (where R _Z (S) is A copper foil characterized in that the roughness R _Z (S) is 1.0 μm to 3.0 μm.

  In Patent Document 3 (Japanese Patent Application Laid-Open No. 2011-038168), a primary roughened surface subjected to a primary roughening treatment with metallic copper on one surface of an untreated copper foil, and a secondary roughening treatment with metallic copper were performed. A secondary roughened surface, a tertiary treated surface subjected to tertiary treatment with metallic zinc, a chromate rust preventive layer with chromate, and a thin film layer with a silane coupling agent are provided in this order. A heat-resistant copper foil with excellent high-frequency transmission characteristics is disclosed in which the roughness of the secondary roughened surface subjected to the roughening treatment is in the range of 2.0 to 4.0 μm in the Rz value specified in JIS-B-0601. Yes.

  In Patent Document 4 (Japanese Patent Laid-Open No. 2013-147688), roughened particles are formed on the surface of the copper foil by a roughening treatment, and the average roughness Rz of the roughened surface is 0.5 to 1.3 μm. The glossiness is 0.5 to 68, and the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is 2.00 to 2.45. A surface treated copper foil is disclosed.

JP 2010-141227 A JP 2005-290519 A JP 2011-038168 A JP 2013-147688 A

  As described above, the application range of FPC has expanded in recent years, and the characteristics required for FPC (and copper-clad laminate, which is the previous stage of FPC) have become increasingly severe. For example, in FPC, good etching controllability of a conductor foil is required from the viewpoint of finer circuit wiring, and the surface flatness of the conductor foil is required from the viewpoint of electrical high-frequency characteristics. In addition, from the viewpoint of mounting workability of electronic components (for example, liquid crystal components and IC chips), transmission visibility is required in the resin film portion left after the conductive foil is chemically etched away (this is the FPC This is because positioning of electronic components to be mounted is performed with a positioning marker that is visible through the resin film portion). Furthermore, prevention of discoloration of the copper foil is required from the viewpoint of appearance stability.

  Etching controllability of conductor foil, surface flatness, and transmission visibility in the resin film part after removing the conductor foil are required to reduce the roughness of the joint surface in the copper-clad laminate (low roughness of the joint surface). The reduction in the roughness of the joint surface is usually a factor that reduces the bondability between the surface-treated copper foil and the resin film. On the other hand, from the viewpoint of long-term reliability of circuit wiring, there is a demand for bondability equivalent to or better than before (bondability between surface-treated copper foil and resin film, for example, peel strength of 0.8 N / mm or more). That is, these requirements are contradictory requirements in the conventional technical concept, and in order to satisfy the conflicting requirements, further improvements and improvements in the copper-clad laminate are required.

  Therefore, the present invention enables an FPC having a bondability (copper foil and resin film bondability) equal to or higher than that of the conventional one even if the bonding surface between the copper foil and the resin film is made lower than the conventional roughness. An object of the present invention is to provide a copper clad laminate, a surface treated copper foil for obtaining the copper clad laminate, and a method for producing the surface treated copper foil.

(I) One aspect of the present invention is a surface-treated copper foil for bonding a resin film to form a copper-clad laminate,
The surface-treated copper foil is obtained by forming a plurality of coating layers on the surface of the copper raw foil on the side to be bonded to the resin film,
The plurality of coating layers are formed on the copper raw foil and a roughened copper plating layer made of roughened copper crystal grains having a predetermined average particle diameter, and an anti-corrosion formed on the roughened copper plating layer. A rust nickel plating layer, a small protrusion copper plating layer made of small protrusion copper crystal grains having a predetermined average particle diameter formed on the rust prevention nickel plating layer, and formed on the small protrusion copper plating layer A surface-treated copper foil having a galvanized layer is provided.

In the surface-treated copper foil (I) according to the present invention described above, the present invention can be improved or changed as follows.
(I) The average grain diameter of the roughened copper crystal grains is 0.1 μm or more and 0.5 μm or less, the average grain diameter of the small protrusion copper crystal grains is 0.03 μm or more, and the average of the roughened copper crystal grains It is 1/2 or less of the particle size.
(Ii) The average thickness of the roughened copper plating layer is 0.07 μm or more and 0.35 μm or less. In the present invention, the average thickness of the plating layer is calculated from the coating amount (mass per unit area) of the plating layer and the theoretical density (mass per unit volume) of the metal constituting the plating layer. It is.
(Iii) The coating amount of the galvanized layer is 0.1 μg / cm ² or more and 3 μg / cm ² or less.
(Iv) The copper raw foil is a rolled copper foil, and the plurality of coating layers further have a base copper plating layer formed between the copper raw foil and the roughened copper plating layer.
(V) The plurality of coating layers further include a chromate treatment layer formed on the zinc plating layer and a silane coupling treatment layer formed on the chromate layer.

(II) Another embodiment of the present invention is a method for producing a surface-treated copper foil in which a plurality of coating layers are formed on at least one surface of a copper raw foil,
A roughened copper plating layer forming step of forming a roughened copper plating layer on the copper raw foil, and a rustproof nickel plating layer forming step of forming a rustproof nickel plating layer on the roughened copper plating layer; Including a small protrusion copper plating layer forming step of forming a small protrusion copper plating layer on the rust-proof nickel plating layer, and a galvanization layer forming step of forming a galvanization layer on the small protrusion copper plating layer,
Provided is a method for producing a surface-treated copper foil in which the small protrusion copper plating layer forming step is performed by electrolytic plating, and the electrolytic plating is performed at a current density that is less than a limit current density.

In the method (II) for producing a surface-treated copper foil according to the present invention, the present invention can be modified or changed as follows.
(Vi) Before the roughening copper plating layer forming step, a base copper plating layer forming step of forming a base copper plating layer between the copper raw foil and the roughing copper plating layer is further included.
(Vii) It further includes a chromate treatment layer forming step of forming a chromate treatment layer on the galvanized layer and a silane coupling treatment layer formation step of forming a silane coupling treatment layer on the chromate treatment layer.

  (III) Still another embodiment of the present invention is a copper clad laminate in which a surface-treated copper foil and a resin film are bonded, wherein the surface-treated copper foil is the surface-treated copper according to the present invention. A copper-clad laminate that is a foil is provided.

The present invention can add the following improvements and changes to the copper clad laminate (III) according to the present invention.
(Viii) The peel strength between the surface-treated copper foil and the resin film is 0.8 N / mm or more.
(Ix) A copper-zinc alloy layer formed by alloying the small projection copper plating layer and the galvanization layer of the plurality of coating layers is formed.

  According to the present invention, even if the bonding surface between the copper foil and the resin film is made to have a lower roughness than before, an FPC having a bonding property (bonding property between the copper foil and the resin film) equal to or higher than the conventional one can be realized. A copper-clad laminate, a surface-treated copper foil for obtaining the copper-clad laminate, and a method for producing the surface-treated copper foil can be provided.

It is the cross-sectional schematic diagram and partial enlarged schematic diagram which show an example of the structure of the surface treatment copper foil which concerns on this invention. It is a flowchart which shows an example of the manufacturing process of the copper clad laminated board which concerns on this invention. It is a SEM observation image of the surface of the roughening copper plating layer in the middle stage of manufacture of the surface treatment copper foil of Example 1 (immediately after a roughening copper plating layer formation process). It is a SEM observation image of the surface by the side of the roughening copper plating layer in the manufacture middle stage (just after a small protrusion copper plating layer formation process) of the surface treatment copper foil of Example 1. FIG. It is a SEM observation image of the surface by the side of the roughening copper plating layer in the manufacture middle stage (just after a small protrusion copper plating layer formation process) of the surface treatment copper foil of Example 2. FIG.

(Basic idea of the present invention)
In order to satisfy the recent requirements for FPC as described above (for example, compatibility between low roughness and high bondability between the resin film and copper foil in CCL), the present inventors have reduced the roughness of the bond surface. The relationship between crystallization and peel strength was investigated in detail.

  In the investigation, the inventors of the present invention reduced the roughness of the joint surface within the range of the prior art, the average of the entire surface unevenness is certainly small, but locally the region with small and large surface unevenness It has been found that there is a tendency to become bipolar, and the variation in peel strength increases (as a result, the product yield of FPC decreases). Therefore, in order to elucidate the cause, a detailed investigation was conducted by going back to the process of forming the roughened copper plating layer.

  In the conventional techniques such as Patent Documents 1 to 4, in any case, the process of forming the roughened copper plating layer is performed by electrolytic plating (so-called burnt plating) with a current density equal to or higher than the limit current density. Note that the limiting current density in electrolytic plating is that the amount of metal ions deposited does not catch up with the amount of precipitation per unit time predicted from Faraday's law (the concentration of the metal ions in the diffusion boundary layer is zero). Defined as the current density. That is, the burnt plating is no longer a steady state electrolytic plating but an electroplating in an unsteady state.

  Physicochemical phenomena in the unsteady state (here, precipitation growth of metal crystal grains by electroplating) are difficult to analyze theoretically because they do not have a steady-state solution, and there are slight fluctuations in fabrication conditions and trace amounts of impurities. Even so, they are easily affected by them. For this reason, the roughened copper plating layer forming step in the prior art is often formed by forming conditions obtained from many studies.

  Here, the present inventors have considered that the conventional process for forming a roughened copper plating layer is burnt plating.

  In the prior art, the roughened copper plating layer is formed directly on the copper base foil or the base copper plating layer. That is, the interface of the roughened copper plating layer / copper raw foil and the interface of the roughened copper plating layer / underlying copper plating layer are almost the same interface (the copper raw foil and the roughened copper plating layer are made of copper alloy). However, in the category of combinations of copper-based alloys, it can be said that the interface is almost the same).

  Considering the precipitation growth of metal crystal grains by electrolytic plating, if a homogeneous growth that forms a homogeneous interface under steady-state growth conditions is performed, a dense and smooth layer is formed due to the principle of high creeping growth. It is considered that it is difficult to form a roughened layer (that is, a plating layer mainly composed of multinuclear three-dimensional growth) that is easily formed and has clear surface irregularities. In other words, in order to realize multinuclear three-dimensional growth in the same kind of growth, it is considered that electroplating (bake plating) in an unsteady state was necessary. However, in electroplating in an unsteady state, the influence of factors that are difficult to control is strong as described above. It is thought that the variation in peel strength appears greatly because the bipolarization becomes obvious when the process is advanced.

  The improvement in bonding strength due to the anchor effect is generally interpreted as being caused by an increase in the bonding interface (bonding area). In order to satisfy the above-mentioned requirements for FPC (and CCL, which is the previous stage of FPC) (coexistence of low roughness of joint surface and high jointability), in principle, the absolute surface roughness due to roughened grains It is considered that it is only necessary to secure a bonding interface (bonding area) equal to or greater than that of the conventional one while reducing the value.

  From the viewpoint of increasing the bonding interface (bonding area), the technique described in Patent Document 3 (forming fine-grained secondary roughened copper particles on the primary roughened copper particles) is helpful. However, in the technique described in Patent Document 3, secondary roughened copper particles are further formed by burnt plating on the primary roughened copper particles formed by burnt plating, which is difficult to control in an unsteady state. Since the electrolytic plating (bake plating) is performed repeatedly, it is considered that ensuring the controllability and reproducibility as a whole is extremely severe, and there is a concern that the product yield may be reduced.

  The inventors of the present invention have found that the formation of the secondary roughened copper particles on the primary roughened copper particles is caused to uniformly precipitate and grow fine grains having at least a controlled size and shape (in other words, in a steady state). It was considered necessary to perform electroplating mainly for multi-nuclear three-dimensional growth under growth conditions. As a result of detailed investigations, examinations, and considerations, the present inventors have found the possibility of performing precipitation growth of secondary roughened copper particles on different interfaces. By carrying out precipitation growth on different types of interfaces, creeping growth of precipitate grains is suppressed, and electroplating mainly for multi-nuclear three-dimensional growth is possible even under steady growth conditions. The present invention has been completed based on these findings.

  Hereinafter, embodiments according to the present invention will be described with reference to the drawings. It should be noted that the present invention is not limited to the embodiments taken up here, and combinations and improvements can be appropriately made without departing from the technical idea of the invention.

[Structure of surface-treated copper foil]
FIG. 1 is a schematic cross-sectional view and a partially enlarged schematic view showing an example of the structure of a surface-treated copper foil according to the present invention. FIG. 1 also shows a resin film to be bonded so that the configuration of the copper-clad laminate can be easily understood. As shown in FIG. 1, a surface-treated copper foil 10 according to the present invention is a surface-treated copper foil for forming a copper-clad laminate by being bonded to a resin film 11, and is at least one of copper raw foils 1. A plurality of coating layers are formed on the surface (the surface to be bonded to the resin film 11).

  The plurality of coating layers include a base copper plating layer 2 formed on the copper raw foil 1, a rough copper plating layer 3 formed on the base copper plating layer 2, and a rough copper plating layer 3 Anti-corrosion nickel plating layer 4 formed on top, small protrusion copper plating layer 5 formed on anti-corrosion nickel plating layer 4, and zinc plating layer 6 formed on small protrusion copper plating layer 5 And a chromate treatment layer 7 formed on the galvanized layer 6, and a silane coupling treatment layer 8 formed on the chromate treatment layer 7.

  In the present invention, the base copper plating layer 2 is not an indispensable layer, but unwanted irregularities remaining on the surface of the copper raw foil 1 (for example, minute oil pits and scratches generated during the production of the copper raw foil 1) It is preferable to form from a viewpoint of repairing. Further, the chromate treatment layer 7 and the silane coupling treatment layer 8 are not limited to these, and other layers having the effects of rust prevention / corrosion resistance and chemical bondability may be used.

  The other surface of the copper raw foil 1 (the surface opposite to the side bonded to the resin film 11) is the front surface of the FPC circuit wiring. From the viewpoint of rust prevention (moisture resistance), A rust-proof nickel plating layer 4 ′ is formed on top, a galvanization layer 6 ′ is formed on the rust-proof nickel plating layer 4 ′, and a chromate treatment layer 7 ′ is formed on the galvanization layer 6 ′. Is preferred. As described above, the structure is not limited to this structure, and other coating layer structures that can ensure moisture resistance may be used.

  Each configuration will be specifically described below.

(Copper foil)
The copper foil 1 is not particularly limited, and conventional copper foil (rolled copper foil, electrolytic copper foil) can be used. When extremely excellent bending characteristics (for example, bending characteristics of 1 million times or more) are required in FPC, it is preferable to use a rolled copper foil. As materials, pure copper (for example, tough pitch copper (JIS H 3100 C1100), oxygen-free copper (JIS H 3100 C1020)), and copper (Cu) with a small amount of tin (Sn) or silver (Ag) added. Dilute copper alloys are often used. When mechanical strength characteristics are given priority, a copper alloy material (an alloy having an additive element concentration higher than that of a dilute alloy) may be used as the copper raw foil 1.

(Underlying copper plating layer)
The base copper plating layer 2 is formed directly on the raw copper foil 1 and repairs unwanted irregularities remaining on the surface of the raw copper foil 1 (for example, minute oil pits and scratches generated during the production of the raw copper foil 1). It is a layer for. By providing the prescribed base copper plating layer 2, the roughened grain shape (thickness (concave / convex) direction and in-plane direction) of the roughened copper plating layer 3 formed thereon is equalized and stabilized. There is an advantage that can be. The average thickness of the base copper plating layer 2 is preferably 0.1 μm or more and 0.6 μm or less. When the average thickness is less than 0.1 μm, the effect of the base copper plating layer 2 becomes insufficient. If the average thickness exceeds 0.6 μm, the effect is saturated and the process cost is wasted. As a material, the same composition as that of pure copper or copper foil 1 is preferable.

(Roughened copper plating layer)
The roughened copper plating layer 3 is formed immediately above the base copper plating layer 2. The roughened grain shape of the roughened copper plating layer 3 is “bondability between resin film and copper foil (anchor effect)”, “etching controllability of copper foil”, “electric high frequency characteristics of FPC circuit wiring” and The average particle size is preferably 0.1 μm or more and 0.5 μm or less in order to affect the “transparency visibility in the resin film portion after removing the conductor foil”.

  Further, the average thickness of the roughened copper plating layer 3 is preferably 0.07 μm or more and 0.35 μm or less. When the average thickness is less than 0.07 μm, the average particle size of the roughened grains becomes too small, and the anchor effect is hardly obtained, resulting in insufficient bondability. When the average thickness of the roughened copper plating layer 3 exceeds 0.35 μm, the average grain size of the roughened grains tends to exceed 0.5 μm. “High-frequency characteristics” and “transmission visibility in the resin film part after removing the conductive foil” begin to decrease.

(Anti-rust nickel plating layer)
The rust-proof nickel plating layer 4 is formed directly on the roughened copper plating layer 3, and the rust-proof nickel plating layer 4 ′ is formed directly on the opposite surface of the copper raw foil 1. The rust-proof nickel plating layers 4 and 4 'act as a diffusion barrier for Cu atoms and have an effect of suppressing discoloration of the copper foil. It is said that the diffusion of Cu atoms into the resin film deteriorates the bondability, and has the effect of suppressing it.

  Further, the rust-proof nickel plating layer 4 is a layer serving as a base for the small protrusion copper plating layer 5. By providing the prescribed anti-corrosive nickel plating layer 4, the copper plating layer formed thereon suppresses the creeping growth of the precipitated grains, and electroplating mainly for multinuclear three-dimensional growth even under steady growth conditions Is possible. As a result, the formation of secondary roughened copper particles on the primary roughened copper particles can be equalized and stabilized. The combination of the rust-proof nickel plating layer 4 and the small protrusion copper plating layer 5 is the most characteristic point in the surface-treated copper foil 10 of the present invention.

The average thickness of the rust-proof nickel plating layer 4 is preferably 0.005 μm or more and 0.1 μm or less. When the average thickness is less than 0.005 μm, it becomes difficult to uniformly cover the surface of the underlying layer (underlying copper plating layer 3) with the antirust nickel plating layer 4, and the effect of the antirust nickel plating layer 4 Becomes insufficient. If the average thickness exceeds 0.1 μm, the effect is saturated and process costs are wasted. Further, the coating amount of the anticorrosive nickel plating layer 4, 2μg / cm ² or more 20μg / cm ² or less. When the coating amount is less than 2 μg / cm ² , the function as a diffusion barrier is lowered. When the coating amount exceeds 20 μg / cm ² , etching controllability decreases.

  Note that the rust-proof nickel plating layers 4 and 4 ′ in the present invention include a case of a nickel-cobalt alloy plating layer. When the rust-proof nickel plating layers 4 and 4 ′ are nickel-cobalt alloy plating layers, the cobalt content is preferably 40% by mass to 75% by mass with respect to the total coating amount of nickel and cobalt.

(Small protrusion copper plating layer)
The small bump copper plating layer 5 is a layer of fine secondary roughened copper particles formed on the primary roughened copper particles (roughened copper plated layer 3), which is formed immediately above the anticorrosive nickel plated layer 4. is there. As described above, by depositing and growing a copper plating layer on the rust-proof nickel plating layer 4 that forms a heterogeneous interface, the creeping growth of the precipitated grains is suppressed, and multinuclear three-dimensional growth is mainly performed even under steady growth conditions. It becomes possible to perform electrolytic plating.

  The average grain size of the small projection copper crystal grains constituting the small projection copper plating layer 5 is 0.03 μm or more, and 1/2 or less of the average grain diameter of the roughened copper crystal grains constituting the rough copper plating layer 3 It is preferable that When the average particle diameter of the small projection copper crystal grains is less than 0.03 μm, the particles are too small (the unevenness due to each small projection grain is reduced) and the difference from the film-like precipitation is reduced. As a result, it cannot sufficiently contribute to an increase in the bonding interface / bonding area with the resin film, and the effect (improvement of anchor effect) becomes insufficient.

  On the other hand, when the average grain size of the small protrusion copper crystal grains exceeds 1/2 of that of the roughened copper crystal grains, the number of small protrusion copper crystal grains precipitated per one roughened copper crystal grain decreases, In general, the roughened grains become coarse. As a result, the device for reducing the roughness of the joint surface is offset, and the effect achieved by the reduction in roughness becomes insufficient.

  In addition to the above-described effects, the small protrusion copper plating layer 5 is alloyed with the zinc plating layer 6 through a heat treatment in a subsequent CCL manufacturing process to form a copper-zinc alloy layer. It also has the effect of improving chemical properties (corrosion resistance). From the viewpoint of this effect (improves chemical resistance of the galvanized layer), the present invention may form a small protrusion copper plated layer on the rust-proof nickel plated layer 4 '.

(Zinc plating layer)
The zinc (Zn) plating layer 6 is formed immediately above the small protrusion copper plating layer 5, and the zinc (Zn) plating layer 6 ′ is formed directly above the rust-proof nickel plating layer 4 ′. The galvanized layers 6, 6 ′ are layers that serve as foundations for the formation of the chromate treatment layers 7, 7 ′ and the formation of the silane coupling treatment layer 8. The coating amount of the galvanized layers 6 and 6 ′ is preferably 0.1 μg / cm ² or more and 3 μg / cm ² or less. When the coating amount is less than 0.1 μg / cm ² , the effect of the galvanized layers 6 and 6 ′ becomes insufficient. When the coating amount exceeds 3 μg / cm ² , chemical resistance (for example, acid resistance) decreases.

(Chromate treatment layer)
The chromate treatment layers 7 and 7 ′ are formed directly on the galvanized layers 6 and 6 ′, respectively. The chromate treatment layers 7 and 7 ′ are layers mainly responsible for ensuring rust prevention and corrosion resistance in the surface-treated copper foil 10. There is no particular limitation on the chromate treatment layers 7 and 7 ′, and conventional techniques can be used, but a trivalent chromate treatment layer is preferable from the viewpoint of environmental protection. The coating amount of the chromate treatment layers 7 and 7 ′ is preferably 0.1 μg / cm ² or more and 1 μg / cm ² or less as the chromium amount. When the coating amount is less than 0.1 μg / cm ² , the rust prevention and corrosion resistance effects are insufficient. When the coating amount exceeds 1 μg / cm ² , the chromate treatment layer itself becomes thick and brittle, and the peel strength decreases.

(Silane coupling treatment layer)
The silane coupling treatment layer 8 is formed immediately above the chromate treatment layer 7. The silane coupling treatment layer 8 is a layer responsible for a chemical bonding action with the resin film 11 in CCL. The silane coupling treatment layer 8 is not particularly limited, and a conventional technique can be used.

[Manufacturing method of copper clad laminate]
The manufacturing method of the copper clad laminated board which concerns on this invention is demonstrated using FIG. FIG. 2 is a flowchart showing an example of a manufacturing process of the copper clad laminate according to the present invention. In addition, below, description of a washing | cleaning process and a drying process may be abbreviate | omitted, However, It is preferable that these processes are suitably performed as needed.

(S10) Copper raw foil preparation process In this process, the copper raw foil 1 is prepared. As described above, there is no particular limitation on the raw copper foil 1 itself, and since a conventional rolled copper foil or electrolytic copper foil can be used, the copper foil preparation method is not particularly limited, and the conventional method is used. be able to.

(S20) Base copper plating layer forming step In this step, the base copper plating layer 2 is formed immediately above the copper foil 1. As described above, this step is not an essential step, but is preferably performed from the viewpoint of repairing unwanted irregularities remaining on the surface of the copper raw foil 1.

Before forming the base copper plating layer 2, it is preferable to clean the surface of the copper raw foil 1 by performing electrolytic degreasing treatment and pickling treatment. The electrolytic degreasing process is a process of performing cathodic electrolytic degreasing by immersing the copper raw foil 1 in an alkaline aqueous solution. As the alkaline aqueous solution, for example, an aqueous solution containing sodium hydroxide (NaOH) at 20 g / L to 60 g / L and sodium carbonate (Na ₂ CO ₃ ) at 10 g / L to 30 g / L is used. Can do.

The pickling treatment is a treatment in which the copper foil 1 subjected to electrolytic degreasing treatment is immersed in an acidic aqueous solution to neutralize the alkali component remaining on the surface of the copper foil 1 and remove the copper oxide film. As the acidic aqueous solution, for example, an aqueous solution containing sulfuric acid (H ₂ SO ₄ ) of 120 g / L or more and 180 g / L or less, a citric acid (C ₆ H ₈ O ₇ ) aqueous solution, a copper etching solution, or the like can be used. .

The formation of the base copper plating layer 2 is performed by an electrolytic treatment using the copper base foil 1 as a cathode in an acidic copper plating bath mainly composed of copper sulfate and sulfuric acid. The liquid composition, liquid temperature, electrolysis conditions, and average thickness of the base copper plating layer of the acidic copper plating bath are preferably selected from the following ranges, for example.
Copper sulfate pentahydrate: 20 g / L or more and 300 g / L or less (preferably 50 g / L or more and 300 g / L or less)
Sulfuric acid: 10 g / L or more and 200 g / L or less (more preferably 30 g / L or more and 200 g / L or less)
Additive: Add specified organic additive Additive temperature: 15 ° C or more and 50 ° C or less Current density: 2 A / dm ² or more and 15 A / dm ² or less
Treatment time: 1 second or more and 30 seconds or less Average thickness: 0.1 μm or more and 0.6 μm or less.

  Examples of the predetermined organic additive include a compound having a mercapto group (for example, 3-mercapto-1-sulfonic acid (MPS), bis (3-sulfopropyl) disulfide (SPS)), a surfactant (for example, Additives combining polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyalkylene ether), leveling agents (eg diallyldialkylammonium alkyl sulfate), and aqueous solutions containing chloride ions (eg aqueous hydrochloric acid) Is used.

  Such an additive can be prepared by blending a predetermined amount of constituent reagents (commercially available products). Also, plating chemicals that are pre-mixed with components (for example, plating chemicals containing a compound having a mercapto group, plating chemicals containing a surfactant, and plating containing a leveling agent) It is also possible to use a mixture of medicinal solution). Furthermore, it is also possible to mix and use a chemical solution for plating in which constituent components are mixed in advance and a constituent reagent (commercial product).

  More specifically, as the concentration of the compound having a mercapto group in the base copper plating bath, for example, in the case of SPS, 10 mg / L or more and 60 mg / L or less is preferable, 10 mg / L or more and 45 mg / L or less Is more preferable, and 10 mg / L or more and 30 mg / L or less is still more preferable. If the SPS concentration is less than 10 mg / L, the effect of adding this additive cannot be sufficiently obtained. On the other hand, when the concentration of SPS exceeds 60 mg / L, the effect of the additive is saturated and wasteful material costs are generated.

  As the surfactant, for example, a CU-BRITE TH-R III (registered trademark) series surfactant chemical solution manufactured by Ebara Eugelite Co., Ltd. can be used. In this case, the addition concentration in the base copper plating bath is preferably 1 mL / L or more and 5 mL / L or less.

  As the leveling agent, for example, a leveling agent chemical solution mainly composed of CU-BRITE TH-R III (registered trademark) series polymer hydrocarbons manufactured by Ebara Eugelite Co., Ltd. can be used. In this case, the addition concentration in the base copper plating bath is preferably 3 mL / L or more and 10 mL / L or less.

  As an aqueous solution containing chloride ions, for example, commercially available hydrochloric acid (hydrogen chloride concentration: 35% to 37%) can be used. In this case, the addition concentration in the base copper plating bath is preferably 0.05 mL / L or more and 0.3 mL / L or less.

(S30) Roughened copper plating layer forming step In this step, the roughened copper plating layer 3 is formed immediately above the base copper plating layer 2. The roughened copper plating layer 3 is formed by electrolytic treatment using copper raw foil 1 as a cathode in an acidic copper plating bath mainly composed of copper sulfate and sulfuric acid, and the roughened grains are formed on the surface of the underlying copper plating layer 2. Precipitate and grow. The liquid composition, liquid temperature, electrolysis conditions, and average thickness of the roughened copper plating layer of the acidic copper plating bath are preferably selected from the following ranges, for example.
Copper sulfate pentahydrate: 20 g / L or more and 300 g / L or less Sulfuric acid: 10 g / L or more and 200 g / L or less Other components: One or more selected from Fe, Mo, Ni, Co, Cr, Zn, W Liquid temperature: 15 ° C or higher and 50 ° C or lower Current density: 20 A / dm ² or higher and 100 A / dm ² or lower (exceeding the limit current density)
Treatment time: 0.1 seconds or more and less than 5 seconds Average thickness: 0.07 μm or more and 0.35 μm or less.

  Since the formation of the roughened copper plating layer 3 is performed by plating with a current density exceeding the limit current density (so-called burnt plating), it is necessary to add Fe to the plating bath so that the coarsening grains that precipitate and grow do not become excessively large. It is preferable to add at least one sulfate selected from Mo, Ni, Co, Cr, Zn and W. For example, iron sulfate heptahydrate is added to the plating bath in the range of 10 g / L to 30 g / L. This facilitates control of the roughened shape. The roughened shape is not particularly limited as long as each roughened grain is uniformly deposited and grown in the uneven direction and the in-plane direction.

(S40) Rust-proof nickel plating layer forming step In this step, the rust-proof nickel plating layer 4 is formed directly on the roughened copper plating layer 3. The formation of the rust-proof nickel plating layer 4 is preferably selected from the following plating conditions, for example.
Nickel sulfate hexahydrate: 280 g / L or more and 320 g / L or less Nickel chloride: 40 g / L or more and 50 g / L or less Boric acid: 40 g / L or more and 60 g / L or less Other components: Other metal elements ( For example, Co) may be added to form a Ni alloy plating layer Liquid temperature: 30 ° C to 60 ° C Current density: 0.5 A / dm ^{2 to} 10 A / dm ²
Treatment time: 1 second or more and 10 seconds or less Average thickness: 0.005 μm or more and 0.1 μm or less Coating amount: 2 μg / cm ² or more and 20 μg / cm ² or less.

Further, when nickel-cobalt alloy plating is performed as the rust-proof nickel plating layer 4, for example, it is preferable to use a plating bath containing the following components.
Nickel sulfate hexahydrate: 150 g / L or more and 250 g / L or less Cobalt sulfate heptahydrate: 5 g / L or more and 50 g / L or less Trisodium citrate: 5 g / L or more and 50 g / L or less.

(S50) Small protrusion copper plating layer forming step In this step, the small protrusion copper plating layer 5 is formed immediately above the rust-proof nickel plating layer 4. The small protrusion copper plating layer 5 is formed by electrolytic treatment using copper raw foil 1 as a cathode in an acidic copper plating bath mainly composed of copper sulfate and sulfuric acid, and fine grains (small protrusion grains) are plated with rust-proof nickel. It is deposited and grown on the surface of the layer 4. The liquid composition, liquid temperature, electrolysis conditions, and average particle diameter of the small protrusion copper crystal grains of the acidic copper plating bath are preferably selected from the following ranges, for example.
Copper sulfate pentahydrate: 20 g / L or more and 300 g / L or less (preferably 50 g / L or more and 300 g / L or less)
Sulfuric acid: 10 g / L or more and 200 g / L or less (more preferably 30 g / L or more and 200 g / L or less)
Other components and additives: None in particular Liquid temperature: 15 ° C to 50 ° C Current density: 2 A / dm ^{2 to} 15 A / dm ² (3 A / dm ^{2 to} 10 A / dm ² or less is more preferable)
Processing time: 0.1 seconds to 25 seconds.

  The small protrusion copper plating layer forming step in the present invention has a great feature in that it is performed by ordinary electroplating less than the limit current density, unlike that of the prior art. In addition, there is a feature that a simple plating bath consisting only of a copper component can be used without adding other components and additives to the plating bath for the shape control of the roughened grains that precipitate and grow as in the prior art. . From these characteristics (electrolytic plating below limit current density, use of simple plating bath), this small bump copper plating layer formation process is easy to perform theoretical analysis based on Faraday's law and nucleation theory. The coating amount and the shape / average particle size of the small protrusion copper crystal grains can be accurately controlled. From the viewpoint of controllability of the nucleation frequency, the current density of electrolytic plating is more preferably 1/5 or more and 2/3 or less of the limit current density. In addition, this small protrusion copper plating layer formation process does not deny adding another component and an additive to a plating bath.

(S60) Zinc plating layer forming step In this step, the zinc plating layer 6 is formed immediately above the small protrusion copper plating layer 5. The formation of the galvanized layer 6 is preferably selected from the following plating conditions, for example.
Zinc sulfate: 80 g / L or more and 120 g / L or less Sodium sulfate: 60 g / L or more and 80 g / L or less Liquid temperature: 15 ° C or more and 35 ° C or less Current density: 0.1 A / dm ² or more and 10 A / dm ² or less (Limited to the current density limit)
Treatment time: 0.2 second to 10 seconds Coating amount: 0.1 μg / cm ^{2 to} 3 μg / cm ²

(S70) Chromate treatment layer forming step In this step, the chromate treatment layer 7 is formed immediately above the galvanized layer 6. The formation of the chromate treatment layer 7 is preferably selected from the following treatment conditions, for example.
Treatment liquid: Trivalent chromium reactive chromate liquid (trivalent chromium ion concentration: 70 mg / L or more and less than 500 mg / L in terms of metallic chromium. There is no particular limitation on the source of trivalent chromium ions. For example, nitric acid Chromium, chromium sulfate, chromium chloride)
Liquid temperature: 15 ° C. or more and 40 ° C. or less Processing time: 3 seconds or more and 30 seconds or less Coating amount: Chromium amount is 0.1 μg / cm ² or more and 1 μg / cm ² or less.

(S80) Silane coupling treatment layer forming step In this step, the silane coupling treatment layer 8 is formed immediately above the chromate treatment layer 7. The formation of the silane coupling treatment layer 8 is preferably selected from the following treatment conditions, for example.
Treatment liquid: Silane coupling liquid (Select one suitable for the flexible base material to be laminated. For example, when the flexible base material is made of polyimide, the main material is aminosilane or aminopropyltrimethoxysilane. Preferably selected)
Liquid temperature: 15 to 35 ° C Treatment time: 3 to 40 seconds Drying temperature: 100 to 200 ° C Drying time: 5 to 35 seconds Thickness: Molecular layer level.

  As described above, the surface-treated copper foil 10 (surface-treated copper foil for copper-clad laminate) according to the present invention is completed by the steps S10 to S80.

  When forming the antirust nickel plating layer 4 ′, the zinc plating layer 6 ′, and the chromate treatment layer 7 ′ on the other surface of the copper raw foil 1, the anticorrosion nickel plating layer 4 and the zinc plating described above are formed, respectively. The layer 6 and the chromate treatment layer 7 can be formed by the same method. The formation of the rust-proof nickel plating layer 4 ′, the zinc plating layer 6 ′, and the chromate treatment layer 7 ′ may be performed simultaneously with the formation of the rust-proof nickel plating layer 4, the zinc plating layer 6 and the chromate treatment layer 7. May be performed separately.

(S90) Flexible base material laminating step In this step, the surface-treated copper foil 10 and the resin film 11 are laminated. In the case of a two-layer copper-clad laminate, the surface-treated copper foil 10 and the resin film 11 are directly laminated by being heated and pressed without going through the resin adhesive layer. The heating / pressing conditions are appropriately set depending on the properties of the resin film 11, but are preferably selected from the following ranges, for example.
Temperature: 150 ° C to 350 ° C Pressure: 0.5 MPa to 30 MPa Holding time: 5 minutes to 60 minutes

  By this step, the copper clad laminate according to the present invention is completed.

  When a rolled copper foil is used as the copper raw foil 1, the heated copper foil is recrystallized and tempered into a cubic texture by heating in this step, and the bending characteristics (that is, the final copper foil) FPC's bending characteristics) are dramatically improved. Moreover, in order to prevent undesired deformation (elongation, wrinkle, breakage, etc.) of the surface-treated copper foil 10 during handling in this step, the surface-treated copper foil 10 (at least the copper raw foil 1) used in this step is It is preferable that the recrystallized structure is not tempered (at least not annealed).

  In the above description, the case where the pre-molded resin film 11 is used as the flexible base material has been described, but the present invention is not limited thereto. For example, by a lamination method (manufacture of a two-layer copper-clad laminate by a casting method) in which a varnish to be polyimide is applied to the joint surface of the surface-treated copper foil 10 and the varnish is cured by heat treatment to form a flexible substrate There may be. Further, the copper clad laminate of the present invention may be a two-layer single-sided copper clad laminate in which the surface-treated copper foil 10 is laminated on one side of the resin film 11, or the surface-treated copper foil on both sides of the resin film 11. It may be a two-layer double-sided copper-clad laminate in which 10 is laminated.

[FPC manufacturing method]
FPC is manufactured by performing the formation process of a circuit wiring with respect to the copper clad laminated board obtained above. The step of forming the circuit wiring is usually performed by chemically removing a part of the surface-treated copper foil 10 of the copper clad laminate.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these.

[Production of surface-treated copper foil of Example 1]
The surface-treated copper foil 10 of Example 1 was produced by the following procedure. First, a rolled copper foil (thickness 11 μm) made of oxygen-free copper was prepared as the copper raw foil 1. Next, electrolytic degreasing treatment and pickling treatment were performed on the copper foil 1 under the following conditions, respectively, to clean the surface of the copper foil 1. After the pickling treatment, the copper raw foil 1 was washed with water.

(Electrolytic degreasing)
Solution: Aqueous solution containing 40 g / L sodium hydroxide and 20 g / L sodium carbonate Temperature: 40 ° C
Charge density: 100 C / dm ² (10 A / dm ² × 10 s).

(Pickling treatment)
Solution: Aqueous solution containing 150 g / L sulfuric acid Liquid temperature: Room temperature (25 ° C)
Processing time: 10 seconds.

Next, a base copper plating layer 2 was formed on one surface of the raw copper foil 1 under the following plating conditions, and then washed with water.
(Base copper plating layer formation process)
Copper sulfate pentahydrate: 170 g / L
Sulfuric acid: 70 g / L
Additive 1: SPS 30 mg / L as an organic sulfur compound
Additive 2: CU-BRITE TH-R III manufactured by Sugawara Eugene Corporation as a surfactant
Series of surfactant chemicals 3 mL / L
Additive 3: CU-BRITE TH-R III manufactured by Sugawara Eugene Corporation as a leveling agent
Leveling chemicals based on high-molecular-weight hydrocarbons of the series 5 mL / L
Additive 4: Hydrochloric acid reagent stock solution as an aqueous solution containing chloride ions 0.15 mL / L
Liquid temperature: 35 ℃
Charge density: 210 C / dm ² (7 A / dm ² × 30 s)
Average thickness: 0.3 μm.

Next, a roughened copper plating layer 3 was formed on the base copper plating layer 2 under the following plating conditions, and then washed with water.
(Roughening copper plating layer forming process)
Copper sulfate pentahydrate: 100 g / L
Sulfuric acid: 150 g / L
Other ingredients: Iron sulfate heptahydrate 20 g / L
Liquid temperature: 30 ℃
Charge density: 120 C / dm ² (60 A / dm ² × 2 s)
Average thickness: 0.2 μm.

Next, on both surfaces of the copper raw foil 1 on which the roughened copper plating layer 3 is formed (on the roughened copper plating layer 3 and the other surface of the copper raw foil 1), the rust-proof nickel plating layer 4 is applied according to the following plating conditions. , 4 'was formed, and then washed with water. Here, nickel-cobalt alloy plating was performed as rust-proof nickel plating.
(Rust-proof nickel plating layer formation process)
Nickel sulfate hexahydrate: 200 g / L
Cobalt sulfate heptahydrate: 30 g / L
Trisodium citrate: 30 g / L
Liquid temperature: 50 ℃
Charge density: 14 C / dm ² (2 A / dm ² × 7 s)
Coating amount: 20 μg / cm ² (average thickness: 0.025 μm).

Next, a small protrusion copper plating layer 5 was formed on the rust-proof nickel plating layer 4 under the following plating conditions, and then washed with water.
(Small protrusion copper plating layer forming process)
Copper sulfate pentahydrate: 170 g / L
Sulfuric acid: 70 g / L
Liquid temperature: 40 ℃
Charge density: 0.55 C / dm ² (5.5 A / dm ² × 0.1 s)
Average thickness: 0.001 μm.

Next, the zinc plating layers 6 and 6 ′ were formed on the small protrusion copper plating layer 5 and the rust-proof nickel plating layer 4 ′ under the following plating conditions, and then washed with water.
(Zinc plating layer forming process)
Zinc sulfate: 90 g / L
Sodium sulfate: 70 g / L
Liquid temperature: 30 ℃
Charge density: 1.5 C / dm ² (1.5 A / dm ² × 1 s)
Coating amount: 1.2 μg / cm ² (average thickness: 0.0017 μm).

Next, chromate treatment layers 7 and 7 ′ were formed on the galvanized layers 6 and 6 ′ under the following treatment conditions.
(Chromate treatment layer formation process)
Treatment solution: Trivalent chromium reactive chromate solution using chromium nitrate as the source of trivalent chromium ions (Trivalent chromium ion concentration: 300 mg / L in terms of metallic chromium)
Liquid temperature: 30 ℃
Processing time: 5 seconds Coating amount: 0.7 μg / cm ² .

Next, a silane coupling treatment layer 8 was formed on the chromate treatment layer 7 under the following treatment conditions.
(Silane coupling treatment layer formation process)
Treatment liquid: Silane coupling liquid containing 5% 3-aminopropyltrimethoxysilane Liquid temperature: Room temperature (25 ° C)
Treatment time: 5 seconds Heat drying: 200 ° C, 15 seconds.

[Production of surface-treated copper foil of Example 2]
The surface-treated copper foil 10 of Example 2 changes the precipitation growth form of the small protrusion copper plating layer 5 by setting the charge density in the small protrusion copper plating layer forming step to 15 C / dm ² (5 A / dm ² × 3 s). Except for the above, it was produced under the same conditions as the surface-treated copper foil 10 of Example 1 described above.

[Production of surface-treated copper foil of Example 3]
In the surface-treated copper foil 10 of Example 3, the concentration of copper sulfate pentahydrate in the small protrusion copper plating layer forming step was 250 g / L, and the charge density was 0.68 C / dm ² (6.8 A / dm ² × 0.1 As s), the precipitation growth form of the small protrusion copper plating layer 5 was changed. Other than that, it produced on the conditions similar to the surface-treated copper foil 10 of above-mentioned Example 1. FIG.

[Production of surface-treated copper foil of Example 4]
The surface-treated copper foil 10 of Example 4 changes the precipitation growth form of the roughened copper plating layer 4 by setting the charge density in the roughened copper plating layer forming step to 4.4 C / dm ² (22 A / dm ² × 0.2 s). Except for the above, it was produced under the same conditions as the surface-treated copper foil 10 of Example 1 described above.

[Production of surface-treated copper foil of Example 5]
The surface-treated copper foil 10 of Example 5 changes the precipitation growth form of the roughened copper plating layer 4 by setting the charge density in the roughened copper plating layer forming step to 210 C / dm ² (60 A / dm ² × 3.5 s). Except for the above, it was produced under the same conditions as the surface-treated copper foil 10 of Example 1 described above.

[Production of surface-treated copper foil of Example 6]
The surface-treated copper foil 10 of Example 6 changes the precipitation growth form of the small protrusion copper plating layer 5 by setting the charge density in the small protrusion copper plating layer forming step to 70 C / dm ² (7 A / dm ² × 10 s). The surface treatment copper foil 10 of Example 5 was prepared under the same conditions as those described above.

[Production of surface-treated copper foil of Example 7]
The surface-treated copper foil 10 of Example 7 was produced under the same conditions as the surface-treated copper foil 10 of Example 1 described above, except that the rust-proof nickel-plated layers 4 and 4 ′ were pure nickel-plated layers. The plating conditions for the pure nickel plating layer are as follows.
(Rust-proof nickel plating layer formation process)
Nickel sulfate hexahydrate: 300 g / L
Nickel chloride: 45 g / L
Boric acid: 50 g / L
Liquid temperature: 50 ℃
Charge density: 10 C / dm ² (2 A / dm ² × 5 s)
Coating amount: 15 μg / cm ² (average thickness: 0.02 μm).

[Production of surface-treated copper foil of Comparative Example 1]
The surface-treated copper foil of Comparative Example 1 is a sample that is obtained by reducing the roughness of a roughened copper plating layer in the category of the prior art, and is a standard for the prior art. As a specific production method, the base copper plating layer 2 was formed without adding a predetermined organic additive in the base copper plating layer forming step, and the small protrusion copper plating layer 5 of the present invention was not formed. Other than that, it produced on the conditions similar to the surface-treated copper foil 10 of above-mentioned Example 1. FIG.

[Production of surface-treated copper foil of Comparative Example 2]
In the surface-treated copper foil of Comparative Example 2, an attempt was made to form a small protrusion copper plating layer 5 immediately above the roughened copper plating layer 3 under the same plating conditions as in Example 1, and a protective layer was formed immediately above the small protrusion copper plating layer 5. A rust nickel plating layer 4 was formed. Other than that, it produced on the conditions similar to the surface-treated copper foil 10 of above-mentioned Example 1. FIG.

[Production of surface-treated copper foil of Comparative Example 3]
The surface-treated copper foil of Comparative Example 3 had a copper sulfate pentahydrate concentration of 25 g / L and an iron sulfate heptahydrate concentration of 5 g / L in the roughened copper plating layer forming step, and a charge density. Was changed to 0.55 C / dm ² (5.5 A / dm ² × 0.1 s), and the precipitation growth form of the roughened copper plating layer 4 was changed. Also, in the small bump copper plating layer formation process, the copper sulfate pentahydrate concentration is 250 g / L, and the charge density is 0.2 C / dm ² (2 A / dm ² × 0.1 s). The precipitation growth mode was changed. Other than that, it produced on the conditions similar to the surface-treated copper foil 10 of above-mentioned Example 1. FIG.

[Production of surface-treated copper foil of Comparative Example 4]
In the surface-treated copper foil of Comparative Example 4, the precipitation growth form of the roughened copper plating layer 4 was changed by setting the charge density in the roughened copper plating layer forming step to 252 C / dm ² (60 A / dm ² × 4.2 s). Except for this, it was produced under the same conditions as the surface-treated copper foil 10 of Example 2 described above.

[Production of surface-treated copper foil of Comparative Example 5]
The surface-treated copper foil of Comparative Example 5 has a copper sulfate pentahydrate concentration of 250 g / L and a charge density of 0.2 C / dm ² (2 A / dm ² × 0.1 s) in the small protrusion copper plating layer forming step. ) Except that the precipitation growth form of the small protrusion copper plating layer 5 was changed under the same conditions as the surface-treated copper foil 10 of Example 1 described above.

[Production of surface-treated copper foil of Comparative Example 6]
In the surface-treated copper foil of Comparative Example 6, the precipitation growth form of the small protrusion copper plating layer 5 was changed by setting the charge density in the small protrusion copper plating layer forming step to 70 C / dm ² (7 A / dm ² × 10 s). Except for this, it was produced under the same conditions as the surface-treated copper foil 10 of Example 1 described above.

[Preparation of copper-clad laminate]
Using the surface-treated copper foils of Examples 1 to 7 and Comparative Examples 1 to 6, copper-clad laminates (CCL) of Examples 1 to 7 and Comparative Examples 1 to 6 were produced under the following conditions. In addition, as CCL, the roughened surface of the surface-treated copper foil (the surface on the side on which the roughened copper plating layer 3 is formed) is opposed to the resin film, and the two layers of the surface-treated copper foil are laminated on one surface of the resin film A single-sided copper-clad laminate was produced.
Resin film: Polyimide film (thickness 25 μm, Kaneka Corporation, Pixio)
Temperature: 300 ° C
Pressure: 5 MPa
Retention time: 15 minutes.

[FPC sample preparation]
FPC simulation sample in which circuit wiring (line width: 1 mm) was formed by chemically etching a part of the surface-treated copper foil to the copper clad laminates of Examples 1 to 7 and Comparative Examples 1 to 6 (Example) 1-7 and Comparative Examples 1-6) were produced. Chemical etching removal was performed by ferric chloride spray etching.

[Survey of properties of surface-treated copper foil and FPC simulation sample]
(1) Surface microstructure observation of surface-treated copper foil Using a scanning electron microscope (SEM) to prevent the samples in the middle of production of the surface-treated copper foils of Examples 1 to 7 and Comparative Examples 1 to 6 The microstructures of the surface of the rust nickel plating layer 4 and the surface of the small protrusion copper plating layer 5 were observed (observed from two directions, a vertical direction and an oblique direction with respect to the sample surface). Moreover, image analysis was performed on the SEM image observed from the direction perpendicular to the sample surface, and the average particle diameters of the roughened grains and the small protrusion grains were obtained. Specifically, for each grain in the acquired SEM observation image, the diameter of a circle (equivalent circle) having an area equivalent to the area of the grain was obtained, and the average value was taken as the average grain size. The average particle size results are shown in Table 1 below.

(2) Peel strength measurement in FPC simulated sample For circuit wiring (part where surface treated copper foil remains) in FPC simulated sample of Examples 1-7 and Comparative Examples 1-6, in accordance with JIS C6481 The peel strength was measured and the average value of 10 samples was obtained. Recently, peel strength of 0.8 N / mm or more has been demanded as an index of bondability between a resin film and a copper foil, and the pass / fail judgment criterion here was also set to 0.8 N / mm. The results are also shown in Table 1.

(3) Light transmittance measurement in exposed polyimide film part For the exposed polyimide film part in the FPC simulated samples of Examples 1-7 and Comparative Examples 1-6, a haze meter (BYK Gardner-Haze-Guard Plus, stock) The total light transmittance T _t and diffuse transmittance T _d of the polyimide film were measured using a company Toyo Seiki Seisakusho, and the haze H (T _d / T _t × 100%) was calculated. From the viewpoint of transmission visibility in the resin film part after the conductor foil is removed, the haze H of 60% or less is considered as one of the indicators, so the pass / fail judgment criterion here is also “H ≦ 60% " The results are also shown in Table 1.

  FIG. 3A is an SEM observation image of the surface of the roughened copper plating layer in the course of manufacturing the surface-treated copper foil of Example 1 (immediately after the roughened copper plating layer forming step). FIG. 3B is an SEM observation image of the surface on the side of the roughened copper plating layer in the middle stage of production of the surface-treated copper foil of Example 1 (immediately after the small protrusion copper plating layer forming step). FIG. 3C is an SEM observation image of the surface on the side of the roughened copper plating layer in the middle stage of production of the surface-treated copper foil of Example 2 (immediately after the small protrusion copper plating layer forming step). 3A to 3C are SEM images observed from an oblique direction with respect to the sample surface so that the morphology of roughened grains and small protrusion grains can be easily understood.

  As can be confirmed from FIGS. 3A to 3C, the average grain size of the roughened grains in Example 1 was measured to be 0.3 μm (see Table 1), and the average grain size of the small protrusion grains in Example 1 was 0.05 μm. It was measured (see Table 1), and the average particle size of the small protrusion grains in Example 2 was measured to be 0.15 μm (see Table 1). Further, as shown in FIGS. 3B and 3C, small projection grains are uniformly distributed along the surface of the roughened grains (strictly, along the surface of the rust-proof nickel plating layer formed on the roughened grain surface). Has been confirmed to be growing multi-dimensional three-dimensional.

  As shown in Table 1, in Examples 1 to 7, in the peel strength measurement, the average strength achieved 0.8 N / mm or more, and it was also confirmed that variations in individual measurements were small. Further, it was confirmed in the light transmittance measurement that a haze of 60% or less was achieved.

  On the other hand, in Comparative Example 1, which is a reference sample of the prior art, the average strength was less than 0.8 N / mm due to large variations in individual measurements in peel strength measurement. This was thought to be due to the large variation in local thickness of the roughened copper plating layer. However, since the average particle diameter of the roughened grains was small, the haze in the light transmission measurement was less than 60%.

  In Comparative Example 2, the order of the rust-proof nickel plating layer 4 and the small protrusion copper plating layer 5 was changed to form the small protrusion copper plating layer 5 immediately above the roughened copper plating layer 3. Since the electroplating is performed on the same kind of interface, the precipitation growth of the small protrusion grain shape itself did not occur under the condition of less than the limit current density. Therefore, the same property results as in Comparative Example 1 were obtained.

  In Comparative Example 3, the average peel strength was less than 0.8 N / mm because the average grain size of the roughened grains was too small. Moreover, the variation of each measurement was also large. In Comparative Example 4, since the average grain size of the roughened grains was too large, the haze in the light transmission measurement exceeded 60%, and it can be said that the low roughness of the joint surface itself was not achieved. From the results of Comparative Examples 3 and 4 and Examples 4 and 5, it can be said that the average particle diameter of the roughened grains is preferably 0.1 μm or more and 0.5 μm or less.

  In Comparative Example 5, the average peel strength was less than 0.8 N / mm because the average particle size of the small protrusion grains was too small. In Comparative Example 6, since the average particle size of the small protrusion grains was too large, the haze in the light transmission measurement exceeded 60%. From the results of Comparative Examples 5 and 6 and Examples 2 and 3, it can be said that the average particle diameter of the small protrusion grains is 0.03 μm or more and preferably 1/2 or less of the average grain diameter of the roughened grains.

(Investigation of alloying reaction between small protrusion copper plating layer and zinc plating layer)
In addition to the above-described property investigation, the CCL of the present invention is used to determine whether or not an alloying reaction between the small protrusion copper plating layer 5 and the zinc plating layer 6 occurs due to the heat treatment in the CCL manufacturing process (production of a copper-zinc alloy layer). The presence or absence of

  However, since the surface-treated copper foil of the example produced above has a very small coating amount of the small protrusion copper plating layer 5 and the zinc plating layer 6, even if X-ray diffraction measurement is performed on the sample as it is, Therefore, it is difficult to detect and detect the alloying reaction between the small protrusion copper plating layer 5 and the zinc plating layer 6. Therefore, in order to confirm the alloying reaction between the small protrusion copper plating layer 5 and the zinc plating layer 6 by heat treatment in the CCL manufacturing process, a surface-treated copper foil sample for X-ray diffraction measurement was separately prepared.

  Specifically, based on the production conditions of Example 6, the sum of the average thicknesses of both layers is about 1 μm while maintaining the average thickness ratio of the small protrusion copper plating layer 5 and the zinc plating layer 6. Thus, a small projection copper plating layer 5 and a zinc plating layer 6 were formed so as to form a sample for X-ray diffraction measurement in which the chromate treatment layer 7 and the silane coupling treatment layer 8 were not formed. Next, in order to simulate the heat treatment in the CCL manufacturing process, the X-ray diffraction measurement sample was heated to 300 ° C. and held for a predetermined time. The predetermined time is calculated backward from the thickness of the formed plating layer so that the degree of alloying reaction of copper and zinc (degree of mutual diffusion) in the X-ray diffraction measurement sample is equivalent to that in Example 6 above. Set.

  XRD measurement was performed on the surface of the original galvanized layer 6 of the sample for X-ray diffraction measurement produced above using an X-ray diffractometer (Rigaku Corporation, model: Ultima IV). The XRD measurement conditions were as follows: target: Cu, tube voltage: 40 kV, tube current: 40 mA, measurement mode: 2θ / θ, scan speed: 1 deg / min, scan step: 0.01 °.

  As a result of XRD measurement, a peak of the copper-zinc alloy phase was detected from the sample for X-ray diffraction measurement. From this, it is confirmed that the CCL of the present invention causes an alloying reaction between the small projection copper plating layer 5 and the zinc plating layer 6 by the heat treatment in the CCL manufacturing process, and a copper-zinc alloy layer is generated. It was done. As a result, it can be said that the CCL of the present invention has higher chemical resistance (corrosion resistance) than the conventional CCL as in Comparative Example 1.

  The above-described embodiments and examples are described in order to facilitate understanding of the present invention, and the present invention is not limited to the specific configurations described. For example, a part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment. That is, according to the present invention, a part of the configurations of the embodiments and examples of the present specification can be deleted, replaced with other configurations, and added with other configurations.

10 ... Surface treated copper foil, 11 ... Resin film,
1 ... Raw copper foil, 2 ... Under copper plating layer, 3 ... Roughened copper plating layer,
4, 4 '... anticorrosive nickel plating layer, 5 ... small protrusion copper plating layer, 6, 6' ... zinc plating layer,
7,7 '... chromate treatment layer, 8 ... silane coupling treatment layer.

Claims (12)

A surface-treated copper foil for forming a copper-clad laminate by laminating with a resin film,
The surface-treated copper foil is obtained by forming a plurality of coating layers on the surface of the copper raw foil on the side to be bonded to the resin film,
The plurality of coating layers are formed on the copper raw foil and a roughened copper plating layer made of roughened copper crystal grains having a predetermined average particle diameter, and an anti-corrosion formed on the roughened copper plating layer. A rust nickel plating layer, a small protrusion copper plating layer made of small protrusion copper crystal grains having a predetermined average particle diameter formed on the rust prevention nickel plating layer, and formed on the small protrusion copper plating layer A surface-treated copper foil comprising a galvanized layer. In the surface-treated copper foil of Claim 1,
The roughened copper crystal grains have an average particle size of 0.1 μm or more and 0.5 μm or less,
The surface-treated copper foil, wherein the average particle diameter of the small protrusion copper crystal grains is 0.03 μm or more and 1/2 or less of the average particle diameter of the roughened copper crystal grains. In the surface-treated copper foil of Claim 1 or Claim 2,
An average thickness of the roughened copper plating layer is 0.07 μm or more and 0.35 μm or less. In the surface-treated copper foil in any one of Claims 1 thru | or 3,
The surface-treated copper foil, wherein the coating amount of the galvanized layer is 0.1 μg / cm ² or more and 3 μg / cm ² or less. In the surface-treated copper foil in any one of Claims 1 thru | or 4,
The copper raw foil is a rolled copper foil,
The surface-treated copper foil, wherein the plurality of coating layers further include a base copper plating layer formed between the copper raw foil and the roughened copper plating layer. In the surface-treated copper foil in any one of Claims 1 thru | or 5,
The surface-treated copper foil, wherein the plurality of coating layers further include a chromate treatment layer formed on the zinc plating layer and a silane coupling treatment layer formed on the chromate layer. A method for producing a surface-treated copper foil in which a plurality of coating layers are formed on at least one surface of a copper raw foil,
A roughened copper plating layer forming step of forming a roughened copper plating layer on the copper raw foil;
A rust-proof nickel plating layer forming step of forming a rust-proof nickel plating layer on the roughened copper plating layer;
A small protrusion copper plating layer forming step of forming a small protrusion copper plating layer on the rust-proof nickel plating layer;
Including a galvanized layer forming step of forming a galvanized layer on the small protrusion copper plated layer,

The method for producing a surface-treated copper foil, wherein the small protrusion copper plating layer forming step is performed by electrolytic plating, and the electrolytic plating is performed at a current density less than a limit current density. In the manufacturing method of the surface-treated copper foil of Claim 7,
A surface treatment characterized by further comprising a base copper plating layer forming step of forming a base copper plating layer between the raw copper foil and the rough copper plating layer before the roughing copper plating layer forming step. A method for producing copper foil. In the manufacturing method of the surface-treated copper foil of Claim 7 or Claim 8,
A chromate treatment layer forming step of forming a chromate treatment layer on the galvanized layer;
A method for producing a surface-treated copper foil, further comprising a silane coupling treatment layer forming step of forming a silane coupling treatment layer on the chromate treatment layer. A copper clad laminate in which a surface-treated copper foil and a resin film are bonded together,
The said surface-treated copper foil is the surface-treated copper foil in any one of Claims 1 thru | or 6. The copper clad laminated board characterized by the above-mentioned. The copper clad laminate according to claim 10,
A copper clad laminate, wherein a peel strength between the surface-treated copper foil and the resin film is 0.8 N / mm or more. In the copper clad laminate according to claim 10 or 11,
A copper-clad laminate having a copper-zinc alloy layer formed by alloying the small projection copper plating layer and the zinc plating layer of the plurality of coating layers.

Images