TW201446489A - Copper foil, copper-clad laminated plate, printed wiring board and carrier-attached copper foil for high-frequency circuit, electronic machine and manufacturing method of printed wiring board - Google Patents

Abstract

The present invention provides a copper foil for high-frequency circuit capable of satisfactorily inhibiting transmission loss and also satisfactorily depressing generation of dropped powders on the surface of the copper foil even when it is used for a high-frequency circuit board. In order to provide the copper foil for high-frequency circuit in accordance with the present invention, a primary particle layer of copper is formed on the surface of a copper foil, and then a secondary particle layer of ternary alloy formed by copper, cobalt and nickel is formed on the primary particle layer, thereby forming the copper foil. The unevenness height of a coarsened surface obtained by using a laser microscope has an average value which is greater than 1500.

Description

Copper foil for high-frequency circuit, copper-clad laminate for high-frequency circuit, printed wiring board for high-frequency circuit, copper foil with high-frequency circuit, electronic device, and manufacturing method of printed wiring board

The present invention relates to a copper foil for a high-frequency circuit, a copper-clad laminate for a high-frequency circuit, a printed wiring board for a high-frequency circuit, a copper foil with a carrier for a high-frequency circuit, an electronic device, and a method for producing a printed wiring board.

Printed wiring boards have made great progress in this half century and are now used in almost all electronic machines. In recent years, with the increase in the demand for miniaturization and high performance of electronic equipment, the high-density mounting of components and the high-frequency of signals have been gradually advanced, and high-frequency correspondence is required for printed wiring boards.

In order to ensure the quality of the output signal, the transmission loss of the high frequency substrate is required. The transmission loss mainly includes dielectric loss caused by the resin (substrate side) and conductor loss caused by the conductor (copper foil side). The smaller the dielectric constant and dielectric loss tangent of the resin, the less the dielectric loss. In the high-frequency signal, the main reason for the conductor loss is that the higher the frequency, the more the current flows on the surface of the conductor, and the cross-sectional area of the current flow is reduced and the resistance is improved.

As a technique for reducing the transmission loss of the high-frequency copper foil, for example, Patent Document 1 discloses a metal foil for a high-frequency circuit which is one-sided or double-sided on the surface of the metal foil. A silver or silver alloy is applied to the silver or silver alloy coating layer, and a coating layer other than silver or a silver alloy is applied to the thickness of the silver or silver alloy coating layer. Further, it is described that the metal foil which reduces the loss due to the skin effect even in the ultra-high frequency region used in satellite communication can be provided.

Further, Patent Document 2 discloses a roughened copper foil for roughening a high-frequency circuit, which is characterized in that (200) plane integral obtained by X-ray diffraction on a rolling surface after recrystallization annealing of a rolled copper foil The intensity (I(200)) is the integrated strength (I0(200)) of the (200) plane obtained by X-ray diffraction with respect to the fine powder copper, that is, I(200)/I0(200)>40, the calendering The arithmetic mean roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment by electrolytic plating is 0.02 μm to 0.2 μm, and the ten point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5. Μm, and it is a raw material for a printed circuit board. Further, it is described that a printed circuit board which can be used at a high frequency exceeding 1 GHz can be provided.

Further, Patent Document 3 discloses an electrolytic copper foil characterized in that one of the surfaces of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm composed of nodular protrusions. Further, an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided.

[Patent Document 1] Japanese Patent No. 4161304

[Patent Document 2] Japanese Patent No. 4704025

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-244656

It is known that the conductor loss caused by the conductor (copper foil side) is caused by the skin effect as described above, but the resistance is not only affected by the resistance of the copper foil itself, There is also an influence of the surface treatment layer formed by the roughening treatment of the surface of the copper foil to ensure adhesion to the resin substrate. Specifically, the roughness of the surface of the copper foil is a main factor of the conductor loss, and the roughness The smaller the transmission loss, the smaller.

The inventors further studied the relationship between the roughness of the surface of the copper foil and the transmission loss, and found that the smaller the roughness of the surface of the copper foil, the less the transmission loss is, especially if the roughness of the surface of the copper foil is reduced to To some extent, significant fluctuations in the relationship between the reduction in transmission loss and the roughness of the surface of the copper foil are observed, and it is difficult to reduce the transmission loss well by merely controlling the roughness of the surface of the copper foil.

Further, as a roughening treatment of the surface of the copper foil, it is known to form a cobalt-nickel alloy plating layer, and a copper foil having a cobalt-nickel alloy plating layer formed thereon is formed of a copper-cobalt-nickel alloy plating layer formed on the surface thereof. The shape of the roughened particles is dendritic, and thus there is a problem that peeling off from the upper portion or the root portion of the branch, which is generally called a falling powder phenomenon.

The powder falling phenomenon is a problem of trouble. Although the roughened layer of the copper-cobalt-nickel alloy plating has the characteristics of excellent heat resistance, the particles are easily peeled off due to external force, and the following problem occurs: generation of "friction" by the treatment The peeling caused by the peeling, the dirt caused by the peeling powder, and the etching residue caused by the peeling powder.

Therefore, an object of the present invention is to provide a phenomenon in which a high-frequency circuit substrate can be satisfactorily suppressed from transmission loss, and a phenomenon in which roughened particles formed on a surface of a copper foil are peeled off from the surface is suppressed. The resulting high-frequency circuit is made of copper foil.

The present inventors have found that it is extremely effective for suppressing transmission loss when used for a high-frequency circuit substrate and suppressing powder falling on the surface of a copper foil by forming a specific roughened particle layer on the surface of an extremely thin copper layer of a copper foil with a carrier, and The average value of the uneven height of the surface of the roughened particle layer is controlled.

The present invention is based on the above findings. In one aspect, a copper foil for a high-frequency circuit is formed by forming a primary particle layer of copper on a surface of a copper foil, and forming copper, cobalt, and In the copper foil obtained by the secondary particle layer of the ternary alloy composed of nickel, the average value of the unevenness height of the roughened surface obtained by the laser microscope is 1,500 or more.

In one embodiment, the copper foil for high-frequency circuit of the present invention has an average particle diameter of the primary particle layer of copper of 0.25 to 0.45 μm, and a secondary particle layer formed of a ternary alloy composed of copper, cobalt, and nickel. The average particle diameter is 0.35 μm or less.

In another embodiment of the copper foil for high-frequency circuit of the present invention, the primary particle layer and the secondary particle layer are electroplated layers.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, the secondary particles are one or a plurality of dendritic particles grown on the primary particles or a normal plating layer grown on the primary particles.

In still another embodiment of the copper for high-frequency circuit of the present invention, the average value of the unevenness height of the roughened surface obtained by a laser microscope is 1,500 or more and 2,000 or less.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, the peeling strength of the primary particle layer and the secondary particle layer is 0.80 kg/cm or more.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, the peeling strength of the primary particle layer and the secondary particle layer is 0.90 kg/cm or more.

In still another embodiment, the copper foil for high-frequency circuit of the present invention is formed on the secondary particle layer: (A) is made of Ni and is selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, and P. An alloy layer composed of one or more elements consisting of W, Mn, Sn, As, and Ti, and (B) either or both of the chromate layers.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, (A) Ni and a selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, and Al are sequentially formed on the secondary particle layer. Any one or both of an alloy layer composed of one or more elements of P, W, Mn, Sn, As, and Ti, and (B) a chromate layer, and a decane coupling layer.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, either or both of a Ni-Zn alloy layer and a chromate layer are formed on the secondary particle layer.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, either or both of a Ni-Zn alloy layer and a chromate layer and a decane coupling are sequentially formed on the secondary particle layer. Floor.

In still another embodiment of the copper foil for high-frequency circuit of the present invention, a resin layer is provided on the surface of the secondary particle layer.

In still another embodiment, the copper foil for high-frequency circuit of the present invention comprises Ni and a material selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti. The alloy layer composed of one or more elements, or the chromate layer, or the decane coupling layer, or the surface of the Ni-Zn alloy layer is provided with a resin layer.

In another aspect, the invention is a copper foil with a carrier attached to one side of the carrier or The double-sided layer has an intermediate layer and an extremely thin copper layer, and the ultra-thin copper layer is the copper foil for high-frequency circuits of the present invention.

In one embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultra-thin copper layer on one side of the carrier, and has a roughened layer on the other side of the carrier.

In still another aspect of the invention, a copper-clad laminate for a high-frequency circuit using the copper foil of the invention is used.

In still another aspect of the invention, a printed wiring board for a high-frequency circuit using the copper foil of the invention is used.

In one embodiment of the copper-clad laminate for high-frequency circuits of the present invention, the copper foil is laminated with a polyimide, a liquid crystal polymer or a fluororesin.

In still another aspect of the invention, there is provided a printed wiring board for a high-frequency circuit of the invention, which comprises any one of a polyimide, a liquid crystal polymer or a fluororesin.

In still another aspect of the invention, an electronic apparatus using the printed wiring board of the invention is used.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After laminating the carrier copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified half-addition Any method of forming a circuit forms a circuit.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; a side surface of the ultra-thin copper layer with a carrier copper foil forming a resin layer forming a circuit on the resin layer; after forming a circuit on the resin layer, the carrier is peeled off; and removing the ultra-thin copper layer by peeling off the carrier The circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.

According to the present invention, it is possible to satisfactorily suppress the transmission loss even when used for a high-frequency circuit board, and to suppress the occurrence of the phenomenon that the roughened particles formed on the surface of the copper foil are peeled off from the surface, that is, the so-called "falling powder" The high frequency circuit uses copper foil.

Fig. 1 is a conceptual explanatory view showing a state in which powder is dropped in a case where a roughening treatment by copper-cobalt-nickel alloy plating is performed on a conventional copper foil.

2 is a conceptual illustration of a copper foil-treated layer of a copper foil which is formed by pre-forming a primary particle layer on a copper foil and forming a secondary particle layer composed of a copper-cobalt-nickel alloy plating on the primary particle layer. Figure.

Fig. 3 is a photomicrograph of the surface of a conventional copper foil subjected to roughening treatment by copper-cobalt-nickel alloy plating.

4 is a pre-formed primary particle layer on a copper foil of the present invention, and formed on the primary particle layer A photomicrograph of a layer of a copper foil-treated surface of a secondary particle layer composed of a copper-cobalt-nickel alloy plating.

A to C of Fig. 5 is a schematic view showing a cross section of the wiring board in the step of removing the resist from the plating circuit and the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

FIG. 6 is a cross-sectional view of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening using the specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention. Schematic diagram.

Fig. 7 is a schematic view showing a cross section of the wiring board in the step from the formation of the through-hole filler to the step of peeling off the carrier of the first layer, using a specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention.

Fig. 8 is a schematic view showing a cross section of the wiring board in the step of forming a bump or a copper pillar in a specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention.

Fig. 9 is an image of a computer screen showing the analysis result obtained by the analysis software KVH1A9 of the average value (concave-convex height) of the height histogram of the first embodiment.

Fig. 10 is an example of an operation screen disclosed in "Setting of DISTANCE ‧ PITCH" on page 4-3 of the VK-8500 User's Manual of the KVH1A9 software.

The form of the copper foil substrate which can be used in the present invention is not particularly limited. Typically, the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Usually, an electrolytic copper foil is produced by electrolyzing copper into a drum of titanium or stainless steel by a copper sulfate plating bath, and the rolled copper foil is repeatedly produced by plastic working and heat treatment by a calender roll. For bending In the application, calendered copper foil is used in many cases.

As the material of the copper foil substrate, in addition to high-purity copper such as refined copper or oxygen-free copper which is usually used as a conductor pattern of a printed wiring board, for example, Sn-doped copper, Ag-doped copper, Cr, Zr or Mg added may be used. A copper alloy such as a copper alloy or a Cason copper alloy to which Ni and Si are added. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

Further, the thickness of the copper foil substrate is not particularly limited, and is, for example, 1 to 1000 μm, 1 to 500 μm, 1 to 300 μm, 3 to 100 μm, 5 to 70 μm, 6 to 35 μm, or 9 to 18 μm.

Further, another aspect of the present invention is a copper foil with a carrier which has a carrier, an intermediate layer, and an extremely thin copper layer in this order, and the ultra-thin copper layer is a copper foil for a high-frequency circuit of the present invention. That is, in another aspect of the present invention, a copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order can be used as the copper foil substrate. In the case where the carrier copper foil is used in the present invention, a surface treatment layer such as a roughening treatment layer is provided on the surface of the ultra-thin copper layer. Further, another embodiment of the carrier-attached copper foil is as follows.

Usually, in order to improve the peeling strength of the rough surface of the copper foil and the resin substrate, that is, the copper foil after lamination, the surface of the copper foil after degreasing is subjected to roughening treatment in the form of "nodulation". The electrolytic copper foil has irregularities at the time of production, and the convex portion of the electrolytic copper foil is reinforced by the roughening treatment to further enlarge the unevenness. There are cases where normal copper plating or the like is performed as a pre-roughening treatment, and normal copper plating or the like is performed as a roughening completion treatment to prevent the plating material from falling off.

In the present invention, the "roughening treatment" includes such pre-treatment and completion treatment, and includes a known treatment relating to roughening of copper foil as needed.

The roughening treatment is performed by copper-cobalt-nickel alloy plating (described below) In order to clarify the difference from the previous step, the roughening treatment of the copper-cobalt-nickel alloy plating is referred to as "secondary particle layer", but if copper is formed on the copper foil only as described above - Cobalt-nickel alloy plating causes problems such as falling powder as described above.

A micrograph of the surface of a copper foil on which a copper-cobalt-nickel alloy plating layer was formed on a copper foil is shown in Fig. 3. As shown in Fig. 3, fine particles extending in a dendritic shape can be seen. Generally, the fine particles extending in a dendritic shape as shown in Fig. 3 are produced at a high current density.

When the treatment is carried out at such a high current density, the particle nucleus is prevented from being generated in the initial plating, and a new particle nucleus is formed at the tip end of the particle, so that the elongated particle gradually grows into a dendritic shape.

Therefore, if the current density is lowered and electroplating is performed to prevent such a situation, the tip is reduced, the particles are increased, and the particles having a curved shape grow. However, in this case, the falling powder was also slightly improved, but sufficient peel strength could not be obtained, and the object of the present invention could not be sufficiently achieved.

The case where the powder is dropped in the case of forming a copper-cobalt-nickel alloy plating layer as shown in Fig. 3 is shown in the conceptual diagram of Fig. 1. The reason why the powder is dropped is that the fine particles are formed into a dendritic shape on the copper foil as described above, and the dendritic particles are likely to be partially broken by the external force and fall off from the root portion. The fine dendritic particles are caused by peeling due to "friction" during the treatment, contamination of the roll by the peeling powder, and generation of etching residue by the peeling powder.

In the present invention, after the primary particle layer of copper is formed on the surface of the copper foil, a secondary particle layer formed of a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer. A micrograph of the surface on which the primary particles and secondary particles are formed on the copper foil is shown in Fig. 4 (details are as follows).

Thereby, the peeling caused by the "friction" during the treatment, the dirt of the roller caused by the peeling powder, When the etching residue due to the release powder disappears, the phenomenon called powder falling can be suppressed, and a copper foil for high-frequency circuit which can improve the peel strength and improve the high-frequency characteristics can be obtained.

According to the examples shown below, it is clarified that the optimum conditions for preventing the falling powder are that the average particle diameter of the primary particle layer is 0.25 to 0.45 μm, and the ternary alloy composed of copper, cobalt and nickel is formed. The average particle diameter of the secondary particle layer is set to 0.35 μm or less. The lower limit of the average particle diameter of the primary particle layer is preferably 0.27 μm or more, more preferably 0.29 μm or more, still more preferably 0.30 μm or more, and still more preferably 0.33 μm or more. The upper limit of the average particle diameter of the primary particle layer is preferably 0.44 μm or less, more preferably 0.43 μm or less, still more preferably 0.40 μm or less, still more preferably 0.39 μm or less. Further, the upper limit of the average particle diameter of the secondary particle layer is preferably 0.34 μm or less, more preferably 0.33 μm or less, still more preferably 0.32 μm or less, still more preferably 0.31 μm or less, still more preferably 0.30 μm or less. Further, it is more preferably 0.28 μm or less, and is preferably 0.27 μm or less. Further, the lower limit of the average particle diameter of the secondary particle layer is not particularly limited, and is, for example, 0.001 μm or more, 0.01 μm or more, 0.05 μm or more, 0.09 μm or more, 0.10 μm or more, 0.12 μm or more, or 0.15 μm or more.

The primary particle layer and the secondary particle layer are formed by a plating layer. The secondary particles are characterized by one or a plurality of dendritic particles grown on the primary particles. Or normal plating grown on the above primary particles. In other words, when the term "secondary particle layer" is used in the present specification, a normal plating layer such as coating plating is also included. Further, the secondary particle layer may have one or more layers formed of roughened particles, and may have one or more layers of normal plating, or may have one or more layers of roughened particles and a normal plating layer, respectively.

The peeling strength of the primary particle layer and the secondary particle layer thus formed can be 0.80 kg/cm or more, and the peel strength can be 0.90 kg/cm or more.

In the copper foil in which the primary particle layer and the secondary particle layer are formed, it is more important that the average value of the unevenness height of the roughened surface obtained by the laser microscope is 1,500 or more, preferably 1600 or more, and more preferably It is 1700 or more, more preferably 1800 or more, still more preferably 1900 or more. Further, the upper limit of the average value of the unevenness height of the roughened surface obtained by the laser microscope is not particularly limited, and is, for example, 4,500 or less, 3,500 or less, 3,100 or less, 3,000 or less, 2,900 or less, or 2,800 or less.

The invention is characterized in that a stratified layer having a primary particle layer and a secondary particle layer is formed, and the ideal state of the roughened layer is formed on the first layer of the larger primary particle layer as shown in FIG. 2 The state of the 2 layers of the smaller secondary particle layer. In reality, there are cases where both primary particles and secondary particles cause the particles to overlap into one segment. After forming a complex layer, it is difficult to estimate the height of the layer based on the particle size. As a general tendency, for example, a case where a secondary particle having a size substantially equal to or larger than that of a primary particle is formed on a primary particle, and a small secondary particle which is thickly formed on a primary primary particle is owed. Preferably, it is difficult to specifically control the combination. Therefore, it has been found that in the present invention, by focusing on and controlling the macroscopic object of "the average value of the unevenness height of the roughened surface obtained by the laser microscope", a roughening treatment layer having the following effects can be formed: Even if the detailed structure of the combination of the primary particles and the secondary particles is not controlled, the stable peel strength and the stable powder falling phenomenon can be improved. In addition, the "roughening surface" in the "average value of the height of the unevenness of the roughened surface obtained by the laser microscope" means the surface on the final product, and means that the primary particle layer and the second layer are formed. The outermost surface of the side of the secondary particle layer. Further, when a surface treatment layer such as a heat-resistant layer, a rust-proof layer, or a decane coupling treatment layer is formed on the secondary particle layer, it means the outermost surface of the surface treatment layer. In addition, when forming the following "resin layer", it means that the copper foil except the resin layer has the surface of the primary particle layer and the secondary particle layer. surface.

If the average value of the unevenness height of the roughened surface obtained by the laser microscope is less than 1,500, the copper foil in which the primary particle layer and the secondary particle layer are formed is deposited by the secondary particle layer, and the coarse particles are enlarged. The unevenness of the height becomes small, and the phenomenon of falling powder is likely to occur.

The measurement method of the average value of the unevenness height of the roughened surface obtained by the laser microscope was set by the following method: For the laser processing using the laser microscope VK8500 manufactured by Keyence Co., Ltd., the magnification was set to 1000 times. As a result of the measurement, the measurement of the effective area was 786432 μm ² (measurement area 100%), and the height of the concavities and convexities was histograms using the analytical software KVH1A9, and the average value was obtained.

It can be formed on the secondary particle layer: (A) consisting of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti Either or both of the alloy layer, and (B) the chromate layer.

Further, (A) one or more groups selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti may be sequentially formed on the secondary particle layer. Either or both of the alloy layer of the element and (B) the chromate layer, and the decane coupling layer.

Further, either or both of the Ni-Zn alloy layer and the chromate layer may be formed on the secondary particle layer.

Further, either or both of the Ni-Zn alloy layer and the chromate layer and the decane coupling layer may be sequentially formed on the secondary particle layer.

According to this configuration, the high-frequency transmission characteristics can be improved while maintaining the peel strength.

[transmission loss]

In the case where the transmission loss is small, the attenuation of the signal when the signal is transmitted at a high frequency can be suppressed, so that the circuit for transmitting the signal at a high frequency can perform stable signal transmission. Therefore, the smaller value of the transmission loss is suitable for circuit use for transmitting signals at high frequencies, and thus is preferable. After the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), a microstrip line was formed by etching to have a characteristic impedance of 50 Ω, and a network manufactured by HP was used. The analyzer HP8720C measures the transmission coefficient and obtains the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz. In this case, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB/10 cm, more preferably less than 4.1 dB/10 cm. Further preferably, it is less than 3.7 dB/10 cm.

The surface-treated copper foil of the present invention can be bonded to the resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber cloth substrate epoxy resin can be used for the rigid PWB. , glass cloth / paper composite substrate epoxy resin, glass cloth / glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., FPC can use polyester film or polyimide film, liquid crystal polymerization (LCP) film, fluororesin, etc. Further, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peeling strength of the film and the surface-treated copper foil tends to be smaller than in the case of using a polyimide film. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, since the copper circuit is coated with a cap layer after the copper circuit is formed, the film and the copper circuit are not easily peeled off, and the peeling strength can be prevented from being lowered. Peeling of the film from the copper circuit.

Further, since the liquid crystal polymer (LCP) film or the fluororesin film has a small dielectric loss tangent, a liquid crystal polymer (LCP) film or a fluororesin film and a copper-clad laminate of the surface-treated copper foil of the present invention are used. Printed wiring boards and printed circuit boards are suitable for use in high-frequency circuits (circuits that transmit signals at high frequencies). Further, the surface-treated copper foil of the present invention has a small surface roughness Rz and a high gloss, so that the surface is smooth and suitable for high-frequency circuit applications.

In the case of the rigid PWB, the method of bonding is prepared by impregnating a resin with a substrate such as a glass cloth to cure the resin to a semi-hardened state. The copper foil can be formed by superposing the surface of the copper foil from the side opposite to the coating layer with the prepreg and heating and pressing. In the case of FPC, a laminate can be produced by laminating a copper foil with a substrate such as a polyimide film via an adhesive or without an adhesive under high temperature and high pressure, or a polyimide precursor. Coating, drying, hardening, and the like.

The laminate of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, it can be applied to single-sided PWB, double-sided PWB, and multilayer PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be applied to rigid PWB, soft PWB (FPC), and soft and hard composite PWB.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.

Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using a printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted.

(plating conditions of primary particles of copper)

An example of the plating conditions of the primary particles of copper is as follows.

Furthermore, the plating conditions only show a preferred example, and the primary particles of copper are formed on the copper foil. The average particle size is responsible for the prevention of falling powder. Therefore, if the average particle diameter is within the range of the present invention, the plating conditions other than those shown below will not cause any hindrance. The present invention encompasses such.

Liquid composition: copper 10~20g/L, sulfuric acid 50~100g/L

Liquid temperature: 25~50°C

Current density: 1~58A/dm ²

Coulomb amount: 4~81As/dm ²

(plating conditions of secondary particles)

Further, similarly to the above, the plating conditions are only a preferred example, and secondary particles are formed on the primary particles, and the average particle diameter acts as a powder falling prevention. Therefore, if the average particle diameter is within the range of the present invention, the plating conditions other than those shown below will not cause any hindrance. The present invention encompasses such.

Liquid composition: copper 10~20g/L, nickel 5~15g/L, cobalt 5~15g/L

pH: 2~3

Liquid temperature: 30~50°C

Current density: 24~50A/dm ²

Coulomb amount: 34~48As/dm ²

(Formation conditions for forming the heat-resistant layer 1) (Co-Ni plating: cobalt-nickel alloy plating)

In the present invention, a heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

(Formation conditions for forming the heat-resistant layer 2) (Ni-Zn plating: nickel-zinc alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 3) (Ni-Cu plating: nickel-copper alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: nickel 2~30g/L, copper 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 4) (Ni-Mo plating: nickel-molybdenum alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: Ni hexahydrate: 45~55g/dm ³ , sodium molybdate dihydrate: 50~70g /dm ³ , sodium citrate: 80~100g/dm ³

Liquid temperature: 20~40°C

Current density: 1~4A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 5) (Ni-Sn plating: nickel-tin alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: nickel 2~30g/L, tin 2~30g/L

pH: 1.5~4.5

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 6) (Ni-P plating: nickel-phosphorus alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

Liquid composition: nickel 30~70g/L, phosphorus 0.2~1.2g/L

pH: 1.5~2.5

Liquid temperature: 30~40°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 7) (Ni-W plating: nickel-tungsten alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. Plating condition table Shown as below.

Liquid composition: nickel 2~30g/L, W0.01~5g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(plating conditions for forming the heat-resistant layer 8) (Ni-Cr plating: nickel-chromium alloy plating)

In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

A nickel-chromium alloy plating layer is formed using a sputtering target having a composition of Ni: 65 to 85 mass% and Cr: 15 to 35 mass%.

Target: Ni: 65~85mass%, Cr: 15~35mass%

Device: Sputtering device manufactured by ULVAC Co., Ltd.

Output: DC50W

Argon pressure: 0.2Pa

(Formation conditions for forming a rustproof layer)

The present invention can further form the following rust preventive layer. This plating condition is shown as follows. The conditions for impregnating the chromate treatment are as follows, and may also be an electrolytic chromate treatment.

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (0A/dm ² is the case of impregnated chromate treatment)

Coulomb amount: 0~2As/dm ² (0As/dm ² is the case of impregnated chromate treatment)

(Type of weather resistant layer (decane coupling layer))

As an example, the application of the diamino decane aqueous solution is mentioned.

In addition, a metal layer such as a heat-resistant layer or a plating layer is provided by dry plating such as sputtering, and a metal layer such as a heat-resistant layer or a plating layer is provided by wet plating, and normal plating (smooth plating) is used. The coating is performed at a current density that does not reach the limit current density, and has a metal layer such as a heat-resistant layer or a plating layer. The metal layer and the plating layer do not affect the shape of the surface of the copper foil.

The limit current density varies depending on the metal concentration, the pH value, the feed rate, the interelectrode distance, and the temperature of the plating solution. In the present invention, the normal plating (the state in which the plated metal is deposited as a layer) is coarse and thick. The current density at the junction of the plating (the state in which the plated metal is crystallized (spherical or needle-like or tree-like), and the unevenness is defined as the limit current density, and the Hall groove test will be used. The current density (visual judgment) which is the limit of normal plating (that is, immediately before baking) is set as the limit current density.

Specifically, the Hall concentration test was performed by setting the metal concentration, the pH value, and the plating solution temperature to the plating production conditions. Then, the formation state of the plating solution and the temperature of the plating solution were investigated (the metal to be plated was precipitated into a layer or formed into a crystal). Then, based on the current density list manufactured by Yamamoto Gold Platter Tester Co., Ltd., the current density at the position of the boundary was obtained from the position of the test piece at the boundary where the normal plating and the rough plating of the test piece exist. Further, the current density at the position of the boundary is defined as the limit current density. Thereby, the current density of the plating solution composition and the plating solution temperature can be known. In general, if the distance between the electrodes is short, the limit current density tends to be high.

The method of the Hall slot test is described, for example, in the "Plating Practice Book" Maruyama Seiji, Nikkan Kogyo The newspaper was published on pages 157 to 160 of June 30, 1983.

Further, in order to perform the plating treatment at a current density lower than the limit current, it is preferable to set the current density during the plating treatment to 20 A/dm ² or less, more preferably 10 A/dm ² or less, and still more preferably Set to 8A/dm ² or less.

Further, since the thickness of the chromate layer and the decane coupling layer is extremely thin, it does not affect the shape of the surface of the copper foil.

As the secondary particle of copper - cobalt - nickel alloy can be deposited by electroless plating and the plating deposition amount of 10 ~ 30mg / dm ² of copper -100 ~ 3000μg / dm ² of cobalt -50 ~ 500μg / dm ² of nickel ter Elemental alloy layer.

When the Co adhesion amount is less than 100 μg/dm ² , the heat resistance is deteriorated, and the etching property is also deteriorated. When the Co adhesion amount exceeds 3000 μg/dm ² , it is necessary to consider the influence of magnetic properties to be inferior, and an etching spot is generated, and the acid resistance and chemical resistance are considered to be deteriorated.

When the Ni adhesion amount is less than 50 μg/dm ² , the heat resistance is deteriorated. On the other hand, when the Ni adhesion amount exceeds 500 μg/dm ² , the etching property is lowered. That is, although there is no etching residue and it is impossible to etch, it is difficult to perform fine patterning. The preferred deposition amount of Co 500 ~ 2000μg / dm ^2, and, the deposited mass of nickel is preferably 50 ~ 300μg / dm ^2.

According to the above, copper - cobalt - nickel alloy plating can be described over the plating deposition amount is 10 ~ 30mg / dm ² of copper -100 ~ 3000μg / dm ² of cobalt -50 ~ 500μg / dm ² of nickel. The adhesion amount of the ternary alloy layer is only an ideal condition, and does not negate the range exceeding the amount.

Here, the term "etching spot" means a case where Co is not dissolved and remains in the case of etching with copper chloride, and the term "etching residue" means that Ni is not used in the case of alkali etching with ammonium chloride. Dissolved and remains.

Usually, in the case of forming a circuit, it is carried out using the alkali etching liquid and the copper chloride-based etching liquid described in the following examples. The etching liquid and the etching conditions are versatile, but are not limited to the conditions, and it should be understood that they can be arbitrarily selected.

In the present invention, as described above, a cobalt-nickel alloy plating layer may be formed on the roughened surface after the secondary particles are formed (after the roughening treatment).

The cobalt-nickel alloy plating layer preferably has a cobalt adhesion amount of 200 to 3000 μg/dm ² and a cobalt ratio of 60 to 66 mass%. This treatment can be regarded as a rust-proof treatment in a broad sense.

The cobalt-nickel alloy plating layer must be carried out to such an extent that the strength of the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 μg/dm ² , the heat-resistant peel strength is lowered, the oxidation resistance and chemical resistance are deteriorated, and the treated surface is reddish, which is not preferable.

In addition, when the cobalt adhesion amount exceeds 3000 μg/dm ² , it is necessary to take into consideration the influence of the magnetic properties, so that the etching spot is not preferable, and the acid resistance and the chemical resistance are deteriorated. A preferred amount of cobalt adhesion is 400 to 2500 μg/dm ² .

Moreover, when the amount of cobalt adhesion is large, there is a case where penetration of soft etching occurs. Therefore, it is desirable to set the ratio of cobalt to 60 to 66% by mass.

As described below, the direct and large cause of the infiltration of the soft etching is a heat-resistant rust-preventing layer composed of a zinc-nickel alloy plating layer, but cobalt is also a cause of infiltration during soft etching, and thus it is more preferable. The conditions were adjusted as described above.

On the other hand, when the amount of nickel adhesion is small, the heat-resistant peel strength is lowered, and oxidation resistance and chemical resistance are lowered. Moreover, when the amount of nickel adhesion is too large, the alkali etching property is deteriorated, and therefore it is preferable to determine the balance with the cobalt content.

The present invention can further form a zinc-nickel alloy plating layer on a cobalt-nickel alloy plating. The total amount of the zinc-nickel alloy plating layer is set to 150 to 500 μg/dm ² , and the ratio of nickel is set to 16 to 40% by mass. It has the function of a heat-resistant rust-proof layer. This condition is also only a preferred condition, and other known zinc-nickel alloy plating can be used. In the present invention, the zinc-nickel alloy plating can be understood as a preferred additional condition.

The processing performed in the manufacturing steps of the circuit becomes higher temperature, and after the product is formed, heat is generated when the machine is used. For example, in a so-called two-layer material in which a copper foil is bonded to a resin by thermocompression bonding, heat of 300 ° C or more is received at the time of bonding. In such a situation, it is necessary to prevent a decrease in the bonding strength between the copper foil and the resin substrate, and the zinc-nickel alloy plating is effective.

Further, in the conventional technique, a microcircuit having a zinc-nickel alloy plating layer in a two-layer material obtained by bonding a copper foil to a resin by thermocompression bonding is caused by infiltration at the edge portion of the circuit during soft etching. Discoloration. Nickel has an effect of suppressing penetration of an etchant (H ₂ SO ₄ : 10 wt%, H ₂ O ₂ : 2 wt% of an etching solution) used in soft etching.

As described above, the total amount of the zinc-nickel alloy plating layer is 150 to 500 μg/dm ² , and the lower limit of the nickel ratio in the alloy layer is 16% by mass, and the upper limit is 40. When the content of nickel is 50 μg/dm ² or more, the effect is as follows: the heat-resistant rust-preventing layer is provided, and the penetration of the etchant used in the soft etching is suppressed, and the bonding of the circuit due to corrosion can be prevented. Weakening of strength.

Further, if the total amount of the zinc-nickel alloy plating layer is less than 150 μg/dm ² , the heat-resistant rust-preventing force is lowered, and it is difficult to function as a heat-resistant rust-proof layer, and if the same total amount exceeds 500 μg/dm ² , it is resistant. The tendency of hydrochloric acid to deteriorate.

Further, when the lower limit of the nickel ratio in the alloy layer is less than 16% by mass, the amount of penetration during soft etching exceeds 9 μm, which is not preferable. The upper limit of the nickel ratio is 40% by mass to form a zinc-nickel alloy plating. The technical limit of the layer.

As described above, in the present invention, a cobalt-nickel alloy plating layer and a zinc-nickel alloy plating layer can be sequentially formed on the copper-cobalt-nickel alloy plating layer as the secondary particle layer. It is also possible to adjust the amount of cobalt adhesion and the amount of nickel attached in the total amount of the layers. It is preferable to set the total adhesion amount of cobalt to 300 to 4000 μg/dm ² and the total adhesion amount of nickel to 100 to 1500 μg/dm ² .

When the total amount of adhesion of cobalt is less than 300 μg/dm ² , heat resistance and chemical resistance are lowered. When the total amount of cobalt adheres exceeds 4000 μg/dm ² , an etching spot is generated, and transmission loss is increased. The situation. In addition, when the total amount of adhesion of nickel is less than 100 μg/dm ² , heat resistance and chemical resistance may be lowered. When the total amount of adhesion of nickel exceeds 1,500 μg/dm ² , there is a case where an etching residue is generated, and a transmission loss is increased.

The total deposited mass of cobalt is preferably 300 ~ 3500μg / dm ^2, more preferably 300 ~ 3000μg / dm ^2, and further preferably 300 ~ 2500μg / dm ^2, and further more preferably 300 ~ 2000μg / dm ^2, the total nickel The amount of adhesion is preferably from 100 to 1000 μg/dm ² , more preferably from 100 to 900 μg/dm ² . If the above conditions are satisfied, it is not necessary to be particularly limited to the conditions described in the paragraph.

Thereafter, anti-rust treatment is performed as needed. The preferred rust-preventing treatment in the present invention is a treatment of a chromium oxide alone film or a mixture of chromium oxide and zinc/zinc oxide. The so-called treatment of a mixture of chromium oxide and zinc/zinc oxide refers to zinc-chromium consisting of zinc or zinc oxide and chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. Treatment of the rustproof layer of the base mixture.

As the plating bath, at least one of a dichromate such as K ₂ Cr ₂ O ₇ or Na ₂ Cr ₂ O ₇ or a CrO ₃ or the like, and at least one of a water-soluble zinc salt such as ZnO, ZnSO ₄ -7H ₂ O or the like is used. And a mixed aqueous solution with alkali hydroxide. Representative plating bath compositions and electrolytic conditions are as follows.

The copper foil thus obtained has excellent heat-resistant peel strength, oxidation resistance, and hydrochloric acid resistance. Further, a circuit having a circuit width of 150 μm or less can be etched by a CuCl ₂ etching solution, or an alkali etching can be used. Further, it is possible to suppress penetration into the edge portion of the circuit during soft etching.

As the soft etching liquid, an aqueous solution of H ₂ SO ₄ : 10 wt%, H ₂ O ₂ : 2 wt% can be used. Processing time and temperature can be adjusted arbitrarily.

As the alkali etching solution, for example, a liquid such as NH ₄ OH: 6 mol/liter, NH ₄ Cl: 5 mol/liter, CuCl ₂ : 2 mol/liter (temperature: 50 ° C) is known.

The copper foil obtained in all the above steps has a black to gray color. Black to gray is more meaningful in terms of alignment accuracy and high heat absorption rate. For example, a circuit board including a rigid substrate and a flexible substrate is mounted with an IC, a resistor, a capacitor, or the like in an automatic step. In this case, the wafer is mounted while being read by the sensor. At this time, there is a case where the copper foil-treated surface is aligned by a film such as Kapton. Moreover, the positioning at the time of forming the through holes is also the same.

The closer the processing surface is to black, the better the absorption of light, so the accuracy of positioning is improved. Further, in the case of producing a substrate, in many cases, the copper foil and the film are cured while applying heat. In this case, when heating is performed by using a long wavelength band such as far infrared rays or infrared rays, the heating efficiency of the blackened surface of the treated surface is good.

Finally, the decane treatment of the decane coupling agent is applied to at least the roughened surface of the rustproof layer for the main purpose of improving the adhesion between the copper foil and the resin substrate as needed. The decane coupling agent to be used for the decane treatment may, for example, be an olefin decane, an epoxy decane, an acrylic decane, an amine decane or a decyl decane, and may be appropriately selected and used. Further, in the case where a liquid crystal polymer is used as the resin, it is preferred to use an amino decane (a decane having an amine group) as a decane coupling agent. Further, it is more preferred to use diaminodecane as a decane coupling agent.

The coating method may be any one of blowing by a spray of a decane coupling agent solution, coating by a coater, dipping, casting, or the like. For example, Japanese Patent Publication No. Sho 60-15654 discloses an improvement in the adhesion between a copper foil and a resin substrate by performing a chromate treatment on the rough side of the copper foil and then performing a decane coupling agent treatment. Please refer to this for details. Thereafter, if necessary, annealing treatment is also performed to improve the ductility of the copper foil.

[with carrier copper foil]

The copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an extremely thin copper layer on one side or both sides of the carrier. Further, the ultra-thin copper layer is a copper foil for high-frequency circuit of the embodiment of the present invention.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, for example, a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, an insulating resin film. (Available, for example, in the form of a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like).

As the carrier which can be used in the present invention, copper foil is preferably used. Since the copper foil has a high electrical conductivity, it is easy to form an intermediate layer and an extremely thin copper layer. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath on a drum of titanium or stainless steel, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, or Mg is added, or Ni and Si may be added. A copper alloy such as a copper alloy.

The thickness of the carrier which can be used in the present invention is also not particularly limited as long as it is used as a The carrier may be appropriately adjusted to a suitable thickness, and may be, for example, 5 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

Further, a roughened layer may be provided on the surface opposite to the surface on the side of the ultra-thin copper layer on which the carrier is provided. The roughening treatment layer can be provided by a known method, or can be set by the above-described roughening treatment. The case where the roughened layer is provided on the surface opposite to the surface on the side where the ultra-thin copper layer side of the carrier is provided has the advantage that when the carrier is laminated on the surface of the resin substrate or the like from the surface side having the roughened layer, the carrier It is not easily peeled off from the resin substrate.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and the step of laminating the insulating substrate is performed. The rear ultra-thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or more of the group consisting of such oxides and organic substances. Also, the intermediate layer may be a plurality of layers.

Further, for example, the intermediate layer may be configured by forming a single one composed of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a metal layer or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, formed thereon a layer composed of one or more elements of a group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an oxide or an organic substance, or selected from Cr , Ni, Co, a single metal layer composed of an element consisting of Fe, Mo, Ti, W, P, Cu, Al, and Zn, or selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, An alloy layer composed of one or two or more elements of an element group of Al and Zn.

In the case where the intermediate layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the surface opposite to the carrier. Further, in the case where the intermediate layer is provided by chromate treatment or zinc chromate treatment or plating treatment, it is considered that a part of the metal to which the chromium or zinc adheres is a hydrate or an oxide.

Further, for example, the intermediate layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, and chromium on a carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin copper layer. Adhesion amount of the intermediate layer of nickel, preferably 100μg / dm ² or more 40000μg / dm ² or less, more preferably 100μg / dm ² or more 4000μg / dm ² or less, and further preferably 100μg / dm ² or more 2500μg / dm ² or less More preferably, it is 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and is used in the form of a usual electrolytic copper foil to form at a high current density. In terms of copper foil, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, and is typically 1.5 to 5 μm, and is typically 2 to 5 μm. Furthermore, it can also be provided on both sides of the carrier. Set a very thin copper layer.

A carrier-attached copper foil having a carrier, an intermediate layer laminated on the carrier, and an extremely thin copper layer laminated on the intermediate layer was produced in this manner. The method of using the copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, or a glass. After the cloth/paper composite substrate epoxy resin, the glass cloth/glass non-woven composite substrate epoxy resin, the glass cloth substrate epoxy resin, the polyester film, the polyimide film, and the like, and is thermocompression bonded, The peeling carrier is used to form a copper clad laminate, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

Further, the carrier-attached copper foil including a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer may have a roughened layer on the ultra-thin copper layer on the roughened layer There is provided one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate (treatment) layer, and a decane coupling (treatment) layer.

[resin layer]

A resin layer may be formed on the surface of the secondary particle layer of the copper foil for high-frequency circuit of the present invention (including the case where the copper foil for high-frequency circuit is a very thin copper layer with a carrier copper foil). Further, the resin layer may be formed of Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, respectively, formed on the secondary particle layer of the high-frequency circuit copper foil. The surface of the alloy layer composed of one or more elements of the composition of As and Ti may be formed on the surface of the chromate layer, may be formed on the surface of the decane coupling layer, or may be formed on the surface of the Ni-Zn alloy layer. Further, the resin layer is more preferably formed on the outermost surface of the copper foil for high-frequency circuits. Further, the copper foil with a carrier may be provided with a resin layer on the roughened layer or the heat-resistant layer, the rustproof layer, the chromate (treatment) layer, or the decane coupling (treatment) layer. The above resin layer may also be an insulating resin layer.

The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer is superimposed and stored even if the surface is touched with a finger, and the heat-treated reaction is caused by the heat treatment.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type thereof is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polyvinyl acetal resin. A resin such as an amine ester resin.

The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (a dielectric containing an inorganic compound and/or an organic compound, or a dielectric containing a metal oxide may be used. Electrochemical), reaction catalyst, crosslinking agent, polymer, prepreg, framework material, and the like. Further, as the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) can be used. And/or a method for forming a resin layer, and a device for forming the same: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. 11-5828, Japanese Patent Laid-Open No. 11-140281 Japanese Patent No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Application No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, and Japanese Patent Laid-Open No. 2004-349654 Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070 No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Special Open 2008- No. 111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017 , International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

The resin is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin liquid, which is applied onto the copper foil or the ultra-thin copper layer by, for example, a roll coating method. Or the heat-resistant layer, the rust-preventive layer, or the chromate film layer or the decane coupling agent layer, and then heat-dried as needed to remove the solvent to be in a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

A copper foil for a high-frequency circuit (a copper foil for a high-frequency circuit with a resin) having the above-mentioned resin layer is formed by laminating a resin layer and a base material, and then thermally bonding the entire resin layer to thermally cure the resin layer, and then copper is used. The foil is used in the form of a specific wiring pattern.

Further, the carrier-attached copper foil (resin-attached copper foil with resin) having the resin layer is formed by laminating a resin layer and a base material, and then thermally bonding the entire resin layer to thermally cure the resin layer, and then peeling off the carrier to expose The ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) is thus used in the form of forming a specific wiring pattern.

When the copper foil for a high-frequency circuit with a resin or a copper foil with a resin attached thereto is used, the number of sheets of the prepreg material used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer is set to ensure the thickness of the interlayer insulation, or the copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: only prepreg is manufactured. The thickness of the multilayer printed wiring board of the thickness of the bulk material is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 80 μm.

When the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesion is lowered, and it is difficult to ensure that the resin-attached copper foil with a resin is laminated on the substrate having the inner layer material without passing through the prepreg material. The interlayer insulation between the inner layer and the circuit.

On the other hand, when the thickness of the resin layer is thicker than 80 μm, it is difficult to form a resin layer having a target thickness by one application step, and an unnecessary material cost and number of steps are required, which is economically disadvantageous. Further, since the resin layer formed is inferior in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow is caused when thermocompression bonding to the inner layer material, and it is difficult to smoothly laminate. .

Further, as another product form of the copper foil with a resin attached thereto, a resin layer may be coated on the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromate layer or the decane described above. On the coupling layer, after being in a semi-hardened state, the carrier is subsequently peeled off, and it is produced in the form of a resin-attached copper foil (very thin copper layer) in which no carrier is present.

Here, the following is an example of a manufacturing procedure of a plurality of printed wiring boards using the copper foil with a carrier of the present invention.

An embodiment of the method for producing a printed wiring board according to the present invention comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; and insulating the side of the ultra-thin copper layer After the substrate is laminated, the copper foil with the carrier and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then the semi-additive method and the modified semi-additive method are used. Any method of partial addition and subtraction forms a circuit. The insulating substrate can also be set as an inner layer circuit inlet.

In the present invention, the term "semi-additive method" refers to a method of performing electroless plating on an insulating substrate or a copper foil seed layer, forming a pattern of a plating resist, and then performing electroplating and plating. The resist is removed and etched, thereby forming a conductor pattern.

In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening the circuit forming portion by electrolytic plating. After the copper is thick, the resist is removed, and the metal foil other than the circuit formation portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.

In the present invention, the partial addition method refers to a method of manufacturing a printed wiring board by a method in which a substrate having a conductor layer is formed, and a hole for a through hole or an auxiliary hole is formed as needed. A catalyst core is applied to the substrate, and a conductor circuit is formed by etching. If a solder resist or a plating resist is provided as needed, the via hole or the auxiliary hole or the like is thickened on the conductor circuit by electroless plating.

In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like.

Further, in the present invention, a known method can be used as a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. Further, in the present invention, in the semi-additive method, the modified semi-additive method, the partial addition method, and the subtractive method, through holes or/and blind holes may be provided in the insulating substrate or the like.

Here, a specific example of a method of manufacturing a printed wiring board using a carrier-attached copper foil of the present invention will be described in detail with reference to the drawings.

First, as shown in Fig. 5-A, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed thereon is prepared.

Next, as shown in FIG. 5-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape.

Next, as shown in FIG. 5-C, after the plating for forming the circuit, the resist is removed, thereby forming a circuit plating of a specific shape.

Next, as shown in FIG. 6-D, a resin layer is laminated on the ultra-thin copper layer by plating the coated circuit (by plating the buried circuit), and then the resin layer is laminated on the side of the ultra-thin copper layer. Another carrier copper foil (layer 2).

Next, as shown in Fig. 6-E, the carrier is peeled off from the carrier copper foil of the second layer.

Next, as shown in Fig. 6-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating to form a blind hole.

Next, as shown in Fig. 7-G, copper is buried in the blind via to form a via fill.

Next, as shown in Fig. 7-H, circuit plating is formed on the via fill in the manner of Fig. 5-B and Fig. 5-C described above.

Next, as shown in Fig. 7-I, the carrier is peeled off from the carrier copper foil of the first layer.

Next, as shown in Fig. 8-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating in the resin layer.

Next, as shown in Fig. 8-K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier copper foil (second layer) can be used with the copper foil with a carrier of the present invention, and a conventional copper foil with a carrier can be used, and a usual copper foil can also be used. Further, a layer 1 or a plurality of layers may be further formed on the circuit of the second layer shown in FIG. 7-H, and may be subjected to a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method forms the circuits.

According to the manufacturing method of the printed wiring board as described above, the structure in which the circuit plating is embedded in the resin layer is formed. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in, for example, FIG. 8-J, the resin layer is protected. The circuit is plated and maintained in shape, whereby it is easy to form a fine circuit. Moreover, since the resin layer protection circuit is plated, the electron mobility resistance is improved, and the wiring of the circuit can be satisfactorily suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 8-J and FIG. 8-K, the exposed surface of the circuit plating becomes a shape recessed from the resin layer, so that it is easy to form a convex on the circuit plating. The block, which in turn forms a copper pillar thereon, improves manufacturing efficiency.

Further, a well-known resin or prepreg can be used as the resin (Resin). For example, BT (bis-s-butylene diimide III) can be used. A resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, as the above-mentioned embedded resin (Resin), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

Further, regarding the above-mentioned copper foil with a carrier for the first layer, the copper foil with the carrier The surface may have a substrate or a resin layer. The copper foil with a carrier used for the first layer having the substrate or the resin layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, as long as the substrate or the resin layer has an effect of supporting the above-described carrier-attached copper foil for the first layer, all of the substrate or the resin layer can be used. For example, a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, or a plate of an organic compound, which are described in the present specification, may be used. A foil of an organic compound is used as the above substrate or resin layer.

[Examples]

Hereinafter, description will be made based on examples and comparative examples. Furthermore, this embodiment is only an example and is not limited to this example. That is, other aspects or modifications included in the present invention are included. Further, the original foils of the following Examples 1 to 6, 11 to 15, and Comparative Examples 1 to 5 were made of a standard rolled copper foil TPC (fine copper of JIS H3100 C1100, manufactured by JX Nippon Mining & Metals) of 18 μm.

Further, the original foils of Examples 7 to 10 used the carrier-attached copper foil produced by the following method.

In Examples 7 to 10, an electrolytic copper foil (JTC foil manufactured by JX Nippon Mining & Metals) having a thickness of 18 μm was prepared as a carrier, and in Example 12, a standard rolled copper foil TPC having a thickness of 18 μm was prepared as a carrier. Further, an intermediate layer was formed on the surface of the carrier under the following conditions, and an extremely thin copper layer was formed on the surface of the intermediate layer. Further, in the case where the carrier is an electrolytic copper foil, an intermediate layer is formed on the shiny side (S surface).

‧Example 7 <intermediate layer>

(1) Ni layer (Ni plating)

The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Ni layer having an adhesion amount of 1000 μg/dm ² . The specific plating conditions are described below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and then, on the roll-to-roll type connection plating line, the Cr layer of 11 μg/dm ² is electrolyzed by the following conditions. The chromate is treated to adhere to the Ni layer.

Potassium dichromate 1~10g/L, zinc 0g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

<very thin copper layer>

Next, the surface of the Cr layer formed in (2) is washed with water and pickled, and then formed on a roll-to-roll type connection plating line by plating an extremely thin copper layer having a thickness of 1.5 μm under the following conditions. On the Cr layer, a copper foil with a carrier was produced.

Copper concentration: 90~110g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

Further, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R _{2 are} selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

‧Example 8 <intermediate layer>

(1) Ni-Mo layer (nickel-molybdenum alloy plating)

The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Ni-Mo layer having an adhesion amount of 3000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Ni hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 7 except that the thickness of the ultra-thin copper layer was set to 2 μm.

‧Example 9 <intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 7.

(2) Organic layer (organic layer formation treatment)

Next, after washing and pickling the surface of the Ni layer formed in (1), the surface of the Ni layer is showered and sprayed with a carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L under the following conditions. The aqueous solution having a liquid temperature of 40 ° C and a pH of 5 was allowed to form an organic layer for 20 to 120 seconds.

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 7 except that the thickness of the ultra-thin copper layer was changed to 3 μm.

‧Example 10 <intermediate layer>

(1) Co-Mo layer (cobalt-molybdenum alloy plating)

The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Co-Mo layer having an adhesion amount of 4000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Co: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 7 except that the thickness of the ultra-thin copper layer was set to 5 μm.

(Examples 1 to 15)

Forming a primary particle layer (Cu) on the surface of the ultra-thin copper layer (Examples 7 to 10) of the rolled copper foil (Examples 1 to 6, 11 to 15) or the copper foil with a carrier, in the range of conditions shown below, Secondary particle layer (copper-cobalt-nickel alloy plating).

The bath composition and plating conditions used are as follows.

[Bath composition and plating conditions]

(A) Formation of primary particle layer (Cu plating)

Liquid composition: copper 15g / L, sulfuric acid 75g / L

Liquid temperature: 25~30°C

Current density: 1~70A/dm ²

Coulomb amount: 2~90As/dm ²

(B) Formation of secondary particle layer (Cu-Co-Ni alloy plating)

Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L

pH: 2

Liquid temperature: 40 ° C

Current density: 10~50A/dm ²

Coulomb amount: 10~80As/dm ²

The conditions of the formation of the primary particle layer (Cu plating) and the formation of the secondary particle layer (Cu-Co-Ni alloy plating) were adjusted, and the average height of the unevenness of the roughened surface obtained by the laser microscope was 1,500. the above. The measurement of the surface area uses a measurement using the above-described laser microscope.

(Comparative examples 1 to 5)

In the comparative examples, the bath composition and plating conditions used were as follows.

[Bath composition and plating conditions]

(A) Formation of primary particle layer (copper plating)

Liquid composition: copper 15g / L, sulfuric acid 75g / L

Liquid temperature: 25~35°C

Current density: 1~70A/dm ²

Coulomb amount: 2~90As/dm ²

(B) Formation of secondary particle layer (Cu-Co-Ni alloy plating conditions)

Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L

pH: 2

Liquid temperature: 40 ° C

Current density: 20~50A/dm ²

Coulomb amount: 30~80As/dm ²

<surface treatment layer other than primary particle layer and secondary particle layer>

After forming the primary particle layer and the secondary particle layer, a part of the examples and comparative examples were subjected to a surface treatment layer under the following conditions.

(Examples 3, 4, 8, and 9, Comparative Examples 1 to 4)

‧Co-Ni plating: cobalt-nickel alloy plating

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

(Examples 5 and 10)

‧Ni-Zn plating: nickel-zinc alloy plating

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

Further, Examples 5 and 10 were subjected to electrolytic chromate treatment and decane coupling treatment using diamine decane after Ni-Zn plating.

(Example 6)

‧Ni-Cu plating: nickel-copper alloy plating

Liquid composition: nickel 2~30g/L, copper 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(Example 11)

‧Ni-Mo plating: nickel-molybdenum alloy plating

Liquid composition: Ni hexahydrate: 45~55g/dm ³ , sodium molybdate dihydrate: 50~70g/dm ³ , sodium citrate: 80~100g/dm ³

Liquid temperature: 20~40°C

Current density: 1~4A/dm ²

Coulomb amount: 1~2As/dm ²

Further, Example 11 was subjected to electrolytic chromate treatment after Ni-Mo plating.

(Embodiment 12)

‧Ni-Sn plating: nickel-tin alloy plating

Liquid composition: nickel 2~30g/L, tin 2~30g/L

pH: 1.5~4.5

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

Further, in Example 12, after Ni-Sn plating, a decane coupling treatment using diamine decane was carried out.

(Example 13)

‧Ni-P plating: nickel-phosphorus alloy plating

Liquid composition: nickel 30~70g/L, phosphorus 0.2~1.2g/L

pH: 1.5~2.5

Liquid temperature: 30~40°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

(Example 14)

‧Ni-W plating: nickel-tungsten alloy plating

Liquid composition: nickel 2~30g/L, W0.01~5g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

Further, in Example 14, after Ni-W plating, electrolytic chromate treatment and decane coupling treatment using diamino decane were carried out.

(Example 15)

‧Ni-Cr plating: nickel-chromium alloy plating

A nickel-chromium alloy plating layer was formed using a sputtering target having a composition of Ni: 80 mass% and Cr: 20 mass%.

Target: Ni: 80 mass%, Cr: 20 mass%

Device: Sputtering device manufactured by ULVAC Co., Ltd.

Output: DC50W

Argon pressure: 0.2Pa

The average particle diameter of the primary particles and the secondary particles in the case of forming the primary particle layer (Cu plating) and the secondary particle layer (Cu-Co-Ni alloy plating) on the copper foil formed by the above embodiment The average particle diameter, the falling powder, the peel strength, the heat resistance, and the average value (height height) of the height histogram of a certain region of the roughened surface were measured, and the results are shown in Table 1. Here, the measured "roughening surface" is the outermost surface on which the primary particle layer and the secondary particle layer side are formed. Further, a Co-Ni plating, a Ni-Zn plating, a chromate layer, a decane coupling layer, or the like is formed on the secondary particle layer, and a surface treatment layer other than the primary particle layer and the secondary particle layer is formed. The surface of the outermost layer of the layers was measured as a roughened surface (i.e., the surface of the primary particle layer and the secondary particle layer side after the entire surface treatment layer of the copper foil was formed).

The average particle diameter of the primary particles and the secondary particles on the roughened surface was observed by a S4700 (scanning electron microscope) manufactured by Hitachi High-Technologies Co., Ltd. at a magnification of 30,000 times, and photographs were taken based on the photographs obtained. The particle diameter was measured for each of the primary particles and the secondary particles. Then, the arithmetic mean of the particle diameters of the obtained primary particles and secondary particles is defined as the average particle diameter of the primary particles and the average particle diameter of the secondary particles. Further, in the case where a straight line is drawn on the particles of the scanning electron microscope photograph, the length of the longest portion of the straight line transverse to the particle is defined as the particle diameter of the particle. Further, the size of the measurement field of view was set to 13.44 μm ² (=4.2 μm × 3.2 μm) per one field of view, and one field of view was measured. In addition, when observed by a scanning electron microscope photograph, particles which are superimposed on the side of the copper foil (below) and particles which are not overlapped are judged as primary particles, and are superposed and existed on other particles. The particles are determined to be secondary particles.

Average of the height histogram of the roughened surface obtained with a laser microscope (Bump height) The measurement method is a laser microscope VK8500 manufactured by Keyence Co., Ltd., and the magnification is set to 1000 times. After the copper foil as a measurement object is loaded on the stage of the laser microscope, the focus is adjusted by the focus handle. At the position of the stage, after the focus of the lens of the laser microscope is aligned with the roughened surface of the copper foil, the following "DISTANCE ‧ PITCH setting" is performed, and then the roughened surface of the copper foil is measured.

"DISTANCE‧PITCH Settings" is based on the description in page 4-3 of the VK-8500 User's Manual. The PITCH system was set to 0.1 μm. Further, for reference, an example of an operation screen disclosed in "Setting of DISTANCE ‧ PITCH" on page 4-3 of the VK-8500 User's Manual is shown in FIG.

Also, the VK-8500 User's Manual, page 4-3, "Click the 1[▲] (Lens Position Move) button to move the lens up to the position where the focus of the image is out of alignment" ”Set the [▲] (lens position movement) button from the height of the lens of the visible image to increase the height of the lens slowly, so that the lens is away from the object (roughening surface), so that the roughening process The image of the face shows a clearly blurred position.

Also, the VK-8500 User's Manual, page 4-3, "Click the 3[▼] (Lens Position Move) button to move the lens down to the focus misalignment position of the image" Set the height of the lens from the visible image to select the [▼] (lens position shift) button, so that the height of the lens is slowly lowered, so that the lens is close to the roughened surface, so that the image of the roughened surface is visible. Obviously blurred position. In addition, the adjustment of the position of the "DISTANCE ‧ PITCH" and the position of the stage of the laser microscope was performed in each of the examples and the comparative examples.

Further, the obtained results were analyzed by measurement of an effective area of 786432 μm ² (measurement area 100%), and the height of the concavity and convexity was histograms using the analytical software KVH1A9, and the average value was obtained. Specifically, the screen of "Histogram Detail (Shade Feature)" is displayed, "Height" is selected as "Display Data", "Histogram" is selected as "Display Form", and "Item of Concentration Measurement" is read. The value of the average value is rounded off to the decimal point of the read value, and the obtained value is set to "the average value of the unevenness height of the roughened surface obtained by the laser microscope". Further, the analysis software KVH1A9 was arranged using a laser microscope VK8500 manufactured by Keynes Co., Ltd.

In the powder falling property, a transparent invisible tape was attached to the roughened surface of the copper foil, and when the tape was peeled off, the peeled coarse particles adhered to the adhesive surface of the tape and the tape was discolored, and according to this, the powder falling characteristics were evaluated. That is, in the case where the tape is not discolored or extremely small, it is set to be good in powdering (OK), and when the tape is discolored to gray, it is set as a powder falling defect (NG). The normal peel strength is to form a copper-clad laminate by hot-pressing a copper foil roughened surface and an FR4 resin substrate, and a 10 mm circuit is formed using a normal copper chloride circuit etching solution, and a 10 mm copper foil is peeled off from the substrate. The normal peel strength was measured while stretching in the 90° direction.

(Measurement of transmission loss)

The resin substrate described in Table 1 (LCP: liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), polyimine: Kaneka thickness 50 μm, and fluororesin thickness 50 μm were bonded to each sample having a thickness of 18 μm: After the manufacture of Dupont, the microstrip line was formed by etching with a characteristic impedance of 50 Ω, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. Further, in Examples 7 to 10, the surface of the ultra-thin copper layer side of the copper foil with a carrier was bonded to the resin substrate described in Table 1, and then the carrier was peeled off, followed by copper plating to form an extremely thin copper layer. After the total thickness of the copper plating was set to 18 μm, the measurement of the same transmission loss as described above was performed. As the frequency is 20GHz The evaluation of the transmission loss is set to ◎ of 3.7 dB/10 cm, 3.7 dB/10 cm or more and less than 4.1 dB/10 cm, and 4.1 dB/10 cm or less and less than 5.0 dB/10 cm. , set 5.0dB/10cm or more to ×.

Further, as a comparative example, the same results are shown in Table 1.

In addition, in the primary particle current condition table of Table 1, the description of the two current conditions and the Coulomb amount means that the plating is performed under the conditions described on the left side, and further, the plating is performed under the conditions described on the right side. For example, when the column of primary particle current conditions in the first embodiment is described as "(65A/dm ² , 80As/dm ² ) + (20A/dm ² , 30As/dm ² )", it means that primary particles will be formed. after the current density was 65A / dm ^2, the coulomb amount to 80As / dm ² and plating, thus forming primary particles of the current density is set to 20A / dm ^2, the coulomb amount to 30As / dm ² and for Plating.

According to Table 1, the results of the examples of the present invention are as follows.

Example 1 based the following: the formation of the primary particles of the current density is set to 65A / dm ² to 20A / dm ^2, the coulomb amount to 80As / dm ² and 30As / dm ^2, the current density and the formation of secondary particles Set to 28 A/dm ² and set the coulomb amount to 20 As/dm ² .

Further, the current density and the coulomb amount of the primary particles are formed into two stages, and in the case where the primary particles are usually formed, two-stage plating is necessary. That is, the plating conditions for the formation of the core particles in the first stage and the growth of the core particles in the second stage are performed.

The initial plating conditions are the plating conditions for the formation of the core-forming particles in the first stage, and the next plating conditions are the plating conditions for the growth of the core particles in the second stage. The following examples and comparative examples are also the same, and thus the description thereof is omitted.

As a result, the average particle diameter of the primary particles was 0.45 μm, the average particle diameter of the secondary particles was 0.30 μm, and the average value of the unevenness height of the roughened surface obtained by the laser microscope was 2,689, which satisfied the conditions of the present invention.

As a result, the powder has a small amount of falling powder, and the normal peel strength is 1.16 kg/cm, and the heat resistance deterioration rate (after the normal peeling measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

In addition, the heat deterioration rate is obtained by the following formula.

Heat deterioration rate (%) = (normal peel strength (kg/cm) - peel strength (kg/cm) after heating at 180 ° C for 48 hours) / normal peel strength (kg / cm) × 100

Example 2 based the following: the current density of the primary particles forming the set to 65A / dm ² and 2A / dm ^2, the coulomb amount to 80As / dm ² and 4As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 15 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.40 μm, the average particle diameter of the secondary particles was 0.15 μm, and the average value of the unevenness height of the roughened surface obtained by the laser microscope was 1,556, which satisfied the conditions of the present invention.

As a result, it has the following characteristics: no powder falling, normal peel strength is 1.08 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

Example 3 is a case where the current density of the primary particles is set to 60 A/dm ² and 10 A/dm ² , the coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and the current density of the secondary particles is formed. Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average value of the unevenness height obtained by the laser microscope on the roughened surface was 1809, which satisfied the conditions of the present invention.

It has the following characteristics: no powder; normal peel strength is 0.92 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

Example 4 based the following: the formation of the primary particles of the current density is set to 55A / dm ² and 1A / dm ^2, the coulomb amount to 75As / dm ² and 5As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average height of the roughened surface obtained by the laser microscope was 1862, which satisfied the conditions of the present invention.

Has the following characteristics: no falling powder, normal peel strength is higher 0.94kg / cm, heat resistance The deterioration rate (after the normal peel measurement, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) was 30% or less.

Example 5 based the following: the current density of the primary particles forming the set to 50A / dm ² and 5A / dm ^2, the coulomb amount to 70As / dm ² and 10As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average height of the roughened surface obtained by the laser microscope was 1857, which satisfied the conditions of the present invention. It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 6 is a case where the current density of forming primary particles is set to 60 A/dm ² and 15 A/dm ² , the coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and secondary particles are formed (secondary The current density of the particle layer is 20 A/dm ² , and the coulomb amount is 60 As/dm ^{2 ,} and after coating plating (normal plating), the current density is 20 A/dm ² , and the coulomb amount is set to 20As/dm ² forms particles.

As a result, the average particle diameter of the primary particles was 0.35 μm, and the secondary particles were formed in a two-stage coating (normal) plating state (particle diameter of less than 0.1 μm) and an average particle diameter of 0.15 μm, and the coarse particles were obtained by a laser microscope. The average height of the unevenness of the treated surface was 1752, which satisfied the conditions of the invention of the present invention. It has the following characteristics: no falling powder, normal peel strength is 0.83 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 7 Series following: the formation of the primary particles of the current density is set to 65A / dm ² and 2A / dm ^2, the coulomb amount to 80As / dm ² and 4As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 15 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.41 μm, the average particle diameter of the secondary particles was 0.16 μm, and the average value of the unevenness height of the roughened surface obtained by the laser microscope was 1,560, which satisfied the conditions of the present invention.

As a result, it has the following characteristics: no falling powder, normal peel strength is 1.09 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

Example 8 is a case where the current density of the primary particles is set to 60 A/dm ² and 10 A/dm ² , the Coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and the current density of the secondary particles is formed. Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.31 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average value of the unevenness height obtained by the laser microscope on the roughened surface was 1814, which satisfied the conditions of the present invention.

It has the following characteristics: no powder; normal peel strength is 0.93kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

Example 9 based the following: the formation of the primary particles of the current density is set to 55A / dm ² and 1A / dm ^2, the coulomb amount to 75As / dm ² and 5As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.26 μm, and the average height of the roughened surface obtained by the laser microscope was 1866, which satisfied The conditions of the invention of the present invention.

It has the following characteristics: no falling powder, normal peel strength is 0.95 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 10 lines the following: the current density of the primary particles forming the set to 50A / dm ² and 5A / dm ^2, the coulomb amount to 70As / dm ² and 10As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average height of the roughened surface obtained by the laser microscope was 1858, which satisfied the conditions of the present invention. It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 11 is a case where the current density of the primary particles is set to 60 A/dm ² and 10 A/dm ² , the Coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and the current density of the secondary particles is formed. Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average value of the unevenness height obtained by the laser microscope on the roughened surface was 1808, which satisfied the conditions of the present invention.

It has the following characteristics: no powder; normal peel strength is 0.93kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

Example 12 lines the following: the current density of the primary particles forming the set to 55A / dm ² and 1A / dm ^2, the coulomb amount to 75As / dm ² and 5As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average height of the roughened surface obtained by the laser microscope was 1861, which satisfied the conditions of the present invention.

It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 13 lines the following: the current density of the primary particles forming the set to 50A / dm ² and 5A / dm ^2, the coulomb amount to 70As / dm ² and 10As / dm ^2, the current density and the formation of secondary particles Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average height of the roughened surface obtained by the laser microscope was 1858, which satisfied the conditions of the present invention. It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 14 is a case where the current density of forming primary particles is set to 60 A/dm ² and 15 A/dm ² , the coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and secondary particles are formed (secondary The current density of the particle layer is 20 A/dm ² , and the coulomb amount is 60 As/dm ^{2 ,} and after coating plating (normal plating), the current density is 20 A/dm ² , and the coulomb amount is set to 20As/dm ² forms particles.

As a result, the average particle diameter of the primary particles was 0.35 μm, and the secondary particles became coated (normal). In the plating state (the particle diameter was less than 0.1 μm) and the average particle diameter of 0.15 μm, the average value of the unevenness height of the roughened surface obtained by the laser microscope was 1,751, which satisfied the conditions of the present invention. It has the following characteristics: no falling powder, normal peel strength is 0.84 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

Example 15 is a case where the current density of the primary particles is set to 60 A/dm ² and 10 A/dm ² , the Coulomb amount is set to 80 As/dm ² and 20 As/dm ² , and the current density of the secondary particles is formed. Set to 25 A/dm ² and set the coulomb amount to 30 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the average value of the unevenness height obtained by the laser microscope on the roughened surface was 1805, which satisfied the conditions of the present invention.

It has the following characteristics: no powder; normal peel strength is 0.93kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

On the other hand, the comparative example is as follows.

In Comparative Example 1, the current density of the primary particles was set to 63 A/dm ² and 10 A/dm ² , and the Coulomb amount was set to 80 As/dm ² and 30 As/dm ² , and secondary particles were not formed. As a result, the average particle diameter of the primary particles was 0.50 μm, and the average value of the unevenness height obtained by the laser microscope on the roughened surface was 2001, which satisfied the conditions of the present invention. In the absence of powder, the normal peel strength was 1.38 kg/cm, which is the grade of the example. However, the heat deterioration rate (the peel strength after the normal peeling measurement was measured at 180 ° C for 48 hours, and the difference was the deterioration rate) was 60%, which was remarkably inferior. The evaluation of the copper foil for the entire high-frequency circuit was poor.

Comparative Example 2 shows a conventional example in which only the primary particle diameter is present and only the secondary particle layer is present. That is, the current density of the secondary particles was set to 50 A/dm ² and the coulomb amount was set to 30 As/dm ² .

As a result, the average particle diameter of the secondary particles was 0.30 μm, and the average height of the roughened surface obtained by the laser microscope was 294, which did not satisfy the conditions of the present invention.

The coarsened particles produce a large amount of falling powder. The normal peel strength is 1.25 kg/cm, and the heat resistance deterioration rate (after the normal peel measurement is measured, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 30% or less. , for the example level. As described above, there is a problem that a large amount of falling powder is generated, and thus the overall evaluation of the copper foil for the high-frequency circuit is poor.

Comparative Example 3 is a case where the current density of the primary particles is set to 63 A/dm ² and 1 A/dm ² , the coulomb amount is set to 80 As/dm ² and ² As/dm ² , and the current density of the secondary particles is formed. Set to 28 A/dm ² and set the coulomb amount to 73 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.60 μm, and the average value of the unevenness height of the roughened surface obtained by the laser microscope was 1298, which did not satisfy the conditions of the present invention. Produce a lot of falling powder. The normal peel strength is 1.42 kg/cm, and the heat resistance deterioration rate (after the normal peel measurement is measured, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 30% or less. , for the example grade, but produced a lot of falling powder. The evaluation of the copper foil for the entire high-frequency circuit was poor.

Comparative Example 4 is a case where the current density of the primary particles is set to 63 A/dn ² and 1 A/dm ² , the coulomb amount is set to 80 As/dm ² and ² As/dm ² , and the current density of the secondary particles is formed. Set to 31 A/dm ² and set the coulomb amount to 40 As/dm ² .

As a result, the average particle diameter of the primary particles is 0.35 μm, and the average particle diameter of the secondary particles is 0.40 μm, the average height of the roughened surface obtained by the laser microscope was 1227, which did not satisfy the conditions of the present invention.

The normal peel strength is 1.37 kg/cm, and the heat resistance deterioration rate (after the normal peel measurement is measured, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 30% or less. , for the example grade, but produced a lot of falling powder. The evaluation of the copper foil for the entire high-frequency circuit was poor.

Comparative Example 5 is a case where the current density of the primary particles is set to 40 A/dm ² and 1 A/dm ² , the Coulomb amount is set to 40 As/dm ² and ² As/dm ² , and the current density of the secondary particles is formed. Set to 20 A/dm ² and set the coulomb amount to 20 As/dm ² .

As a result, the average particle diameter of the primary particles was 0.15 μm, the average particle diameter of the secondary particles was 0.15 μm, and the average value of the unevenness height of the roughened surface obtained by the laser microscope was 1,367, which did not satisfy the conditions of the present invention. Falling powder did not occur. Further, the normal peel strength was 0.71 kg/cm, and the heat resistance deterioration rate (the peel strength after heating at 180 ° C for 48 hours after the normal peel measurement was measured, and the difference was the deterioration rate) was 35%.

According to the comparison between the above embodiment and the comparative example, after forming a primary particle layer of copper on the surface of the copper foil (original foil), a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer. In the case of the formation of the secondary particle layer, in the measurement analysis obtained by the laser microscope in a certain region of the roughened surface, the average value of the unevenness height of the roughened surface is 1500 or more. The excellent effect called the phenomenon of falling powder is stably suppressed, and further, the peel strength is improved and the high frequency characteristics are improved.

In addition, the average particle diameter of the primary particle layer is 0.25 to 0.45 μm, and the average particle diameter of the secondary particle layer formed of the ternary alloy composed of copper, cobalt, and nickel is 0.35 μm or less. The effect is described and is further effective.

Further, when the heat-resistant treatment layer contains Co, the transmission loss tends to increase.

Fig. 9 is a view showing an image of a computer screen showing the analysis result obtained by the analysis software KVH1A9 of the average value (concave-convex height) of the height histogram of the first embodiment. In Fig. 9, the average value (bump height) of the height histogram is obtained by reading the item "average" (herein, 2688.98) of the upper right table (concentration measurement).

Claims (22)

A copper foil for a high-frequency circuit is a copper foil formed by forming a primary particle layer of copper on a surface of a copper foil, and forming a secondary particle layer of a ternary alloy composed of copper, cobalt, and nickel on the primary particle layer. The average height of the unevenness of the roughened surface obtained by the laser microscope is 1,500 or more. The copper foil for a high-frequency circuit according to the first aspect of the invention, wherein the primary particle layer of the copper has an average particle diameter of 0.25 to 0.45 μm, and the secondary particles formed of a ternary alloy composed of copper, cobalt and nickel The average particle diameter of the layer is 0.35 μm or less. The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer are electroplated layers. The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the secondary particles are one or a plurality of dendritic particles grown on the primary particles or a normal plating layer grown on the primary particles. The copper foil for high-frequency circuits according to claim 1, wherein an average value of the unevenness height of the roughened surface obtained by a laser microscope is 1,500 or more and 2,000 or less. The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer have a peeling strength of 0.80 kg/cm or more. The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer have a peel strength of 0.90 kg/cm or more. The copper foil for high-frequency circuit according to the first aspect of the invention, wherein the secondary particle layer is formed with: (A) Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P , W, Mn, Any one or both of an alloy layer composed of one or more elements of Sn, As, and Ti, and (B) a chromate layer. The copper foil for high-frequency circuit according to claim 1, wherein the secondary particle layer is sequentially formed with: (A) Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, and Al. Any one or both of an alloy layer composed of one or more elements of P, W, Mn, Sn, As, and Ti, and (B) a chromate layer, and a decane coupling layer. The copper foil for high-frequency circuits according to claim 1, wherein either or both of a Ni-Zn alloy layer and a chromate layer are formed on the secondary particle layer. The copper foil for high-frequency circuits according to claim 1, wherein one or both of a Ni-Zn alloy layer and a chromate layer and a decane coupling are sequentially formed on the secondary particle layer. Floor. A copper foil for a high-frequency circuit according to the first aspect of the invention, wherein a resin layer is provided on a surface of the secondary particle layer. The copper foil for high-frequency circuit of claim 8, wherein the composition consisting of Ni and Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti The alloy layer composed of one or more elements, or the chromate layer, or the decane coupling layer, or the surface of the Ni-Zn alloy layer is provided with a resin layer. A copper foil with a carrier is a copper layer for a high-frequency circuit according to any one of claims 1 to 13 of the invention, which has an intermediate layer or an ultra-thin copper layer on one side or both sides of the carrier. Foil. The carrier-attached copper foil according to claim 14, wherein the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other side of the carrier. A copper-clad laminate for a high-frequency circuit, which uses the copper foil of any one of claims 1 to 15. A printed wiring board for a high-frequency circuit using the copper foil according to any one of claims 1 to 15. The copper-clad laminate for high-frequency circuits of claim 16 is laminated with the copper foil and polyimide, liquid crystal polymer or fluororesin. A printed wiring board for a high-frequency circuit according to the seventeenth aspect of the invention is the use of any of a polyimide, a liquid crystal polymer or a fluororesin. An electronic machine using the printed wiring board of claim 17 or 19. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of claim 14 or 15; laminating the copper foil with the insulating substrate; and forming a copper foil with the carrier After laminating with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified semi-additive method One method forms a circuit. A manufacturing method of a printed wiring board comprising the following steps: the side surface of the ultra-thin copper layer of the copper foil with carrier of claim 14 or 15 Forming a circuit; forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with the carrier by burying the circuit; forming a circuit on the resin layer; peeling off the carrier after forming a circuit on the resin layer; After the carrier is peeled off, the ultra-thin copper layer is removed, and the circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.