TWI632054B - Copper foil for high-frequency circuits, copper-clad laminated board for high-frequency circuits, printed wiring boards for high-frequency circuits, copper foil with carrier for high-frequency circuits, electronic equipment, and methods for manufacturing printed wiring boards - Google Patents

Abstract

The present invention provides a copper foil for a high-frequency circuit that can satisfactorily suppress transmission loss even when used in a high-frequency circuit substrate, and also can suppress the occurrence of powder falling on the surface of the copper foil. The copper foil for high-frequency circuits of the present invention is formed by forming a primary particle layer of copper on the surface of the copper foil, and then forming a secondary particle layer of a ternary alloy of copper, cobalt, and nickel on the primary particle layer. The average value of the roughness of the roughened surface of the copper foil obtained by a laser microscope was 1500 or more.

Description

Copper foil for high-frequency circuits, copper-clad laminated board for high-frequency circuits, printed wiring boards for high-frequency circuits, copper foil with carrier for high-frequency circuits, electronic equipment, and methods for manufacturing printed wiring boards

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

The printed wiring board has made great progress in this half century, and has been used in almost all electronic machines. In recent years, with the increasing demand for miniaturization and high performance of electronic equipment, high-density mounting of mounted parts or high-frequency of signals has been gradually promoted, and excellent high-frequency response 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 to be reduced. Transmission loss mainly includes dielectric loss caused by resin (substrate side) and conductor loss caused by conductor (copper foil side). The smaller the dielectric constant and the dielectric loss tangent of the resin, the smaller the dielectric loss. In high-frequency signals, the main reason for conductor losses is that the higher the frequency, the more the skin effect of the current flowing only on the surface of the conductor, which reduces the cross-sectional area of current flow and increases the resistance.

As a technology for the purpose of reducing the transmission loss of high-frequency copper foil, for example, Patent Document 1 discloses a metal foil for a high-frequency circuit, which is coated on one or both sides of the surface of the metal foil. A silver or silver alloy coating is applied to the silver or silver alloy coating layer with a coating layer other than silver or a silver alloy thinner than the thickness of the silver or silver alloy coating layer. In addition, it is described that a metal foil that can reduce the loss due to the skin effect even in an ultra-high frequency region such as that used in satellite communications is described.

In addition, Patent Document 2 discloses a roughened rolled copper foil for high-frequency circuits, which is characterized in that the integral of the (200) plane obtained by X-ray diffraction is used on the rolled surface of the rolled copper foil after recrystallization annealing. The intensity (I (200)) is relative to the integrated intensity (I0 (200)) of the (200) plane obtained by X-ray diffraction of fine powder copper, that is, I (200) / I0 (200)> 40. After the surface is roughened by electrolytic plating, the arithmetic average roughness (hereinafter referred to as Ra) of the surface 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. In addition, it is described that a printed circuit board that can be used at a high frequency exceeding 1 GHz is provided.

Furthermore, Patent Document 3 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is a concave-convex surface having a surface roughness of 2 μm to 4 μm formed by nodular protrusions. In addition, it is described that an electrolytic copper foil having excellent 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 Patent Laid-Open No. 2004-244656

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

The inventors further studied the relationship between the roughness of the copper foil surface and transmission loss, and found that the smaller the roughness of the copper foil surface, the lower the transmission loss, especially if the roughness of the copper foil surface is reduced to To a certain extent, obvious fluctuations can be seen in the relationship between the reduction of transmission loss and the roughness of the copper foil surface, and it is difficult to reduce the transmission loss well only by controlling the roughness of the copper foil surface.

In addition, as a roughening treatment of the surface of a copper foil, it is known to form a cobalt-nickel alloy plating layer. As for a conventional copper foil having a cobalt-nickel alloy plating layer formed thereon, a copper-cobalt-nickel alloy plating is formed on the surface. The shape of the roughened particles is dendritic, which causes problems such as peeling off from the upper part or root of the branch, which is commonly referred to as powder falling.

This powder falling phenomenon is a troublesome problem. Although the roughened layer of the copper-cobalt-nickel alloy plating has the characteristics of excellent heat resistance, the particles are liable to fall off due to external forces, so that the following problems occur: "Stripping caused by peeling, roller contamination caused by peeling powder, etching residue caused by peeling powder.

Therefore, an object of the present invention is to provide a so-called "falling powder" that can well suppress transmission loss even when used in a high-frequency circuit board, and that can suppress the phenomenon that coarsened particles formed on the surface of a copper foil are peeled off from the surface. The resulting high-frequency circuit uses copper foil.

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

The present invention was completed based on the above-mentioned findings. In one aspect, it is a copper foil for high-frequency circuits. After forming a primary particle layer of copper on the surface of the copper foil, copper, cobalt and copper are formed on the primary particle layer. The copper foil formed from the secondary particle layer of a ternary alloy made of nickel has an average roughness height of 1500 or more of the roughened surface obtained by a laser microscope.

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

In another embodiment of the copper foil for high-frequency circuits 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 a 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 a high-frequency circuit according to the present invention, the average value of the uneven height of the roughened surface obtained by a laser microscope is 1500 to 2000.

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

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

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

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

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

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

In another aspect, the present invention is a copper foil with a carrier, which is on one side of the carrier or Both sides have an intermediate layer and an ultra-thin copper layer in this order. 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, the ultra-thin copper layer in order on one side of the carrier, and a roughened layer on the other side of the carrier.

In still another aspect, the present invention is a copper-clad laminated board for high-frequency circuits, which uses the copper foil of the present invention.

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

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

This invention is another one aspect. WHEREIN: The printed wiring board for high frequency circuits of this invention uses any one of polyimide, a liquid crystal polymer, or a fluororesin.

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

In yet another aspect, the present invention is a method for manufacturing a printed wiring board, which includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and an insulating substrate; and After laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminated board is formed through the step of peeling the carrier of the copper foil with the carrier, and then the semi-additive method, the subtractive method, the partial additive method, or the modified semi-additive method are used. Either method forms a circuit.

In still another aspect, the present invention is a method for manufacturing a printed wiring board, which includes the following steps: forming a circuit on the ultra-thin copper layer side surface of the copper foil with a carrier of the present invention; and burying the circuit in the circuit. A resin layer is formed on the resin layer side surface of the copper foil with a carrier to form a resin layer on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and the ultra-thin copper layer is removed after the carrier is peeled off. , And the circuit formed on the side surface of the ultra-thin copper layer buried in the resin layer is exposed.

According to the present invention, even if it is used for a high-frequency circuit substrate, it is possible to provide a so-called "falling powder" which can well suppress the phenomenon that the roughened particles formed on the surface of the copper foil are peeled off and peeled off from the surface. Copper foil for high-frequency circuits.

FIG. 1 is a conceptual explanatory diagram showing a case of falling powder when a roughening treatment consisting of copper-cobalt-nickel alloy plating is performed on a conventional copper foil.

FIG. 2 is a conceptual illustration of a non-falling copper foil treatment layer of the present invention in which a primary particle layer is formed in advance on a copper foil, and a secondary particle layer composed of copper-cobalt-nickel alloy plating is formed on the primary particle layer; Illustration.

FIG. 3 is a microscope photograph of a surface when a roughening treatment consisting of copper-cobalt-nickel alloy plating is performed on a conventional copper foil.

FIG. 4 shows a primary particle layer formed in advance on a copper foil according to the present invention, and the primary particle layer is formed on the copper foil. A microscope photograph of a layer of powder-free copper foil treated surface of a secondary particle layer composed of copper-cobalt-nickel alloy plating.

A to C in FIG. 5 are schematic cross-sectional views of a wiring board in steps of plating a circuit and removing a resist in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier of the present invention.

D to F in FIG. 6 are cross-sections of the wiring board in the steps from the self-laminating resin and the second layer of copper foil with the carrier to the laser opening in the specific example of the method for manufacturing a printed wiring board with the carrier copper foil of the present invention Schematic.

G ~ I of FIG. 7 are schematic diagrams of cross-sections of the wiring board in the steps from forming a through-hole filler to peeling off the carrier of the first layer in a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

J ~ K in FIG. 8 are schematic diagrams of a cross-section of a wiring board in a specific example of the method for manufacturing a printed wiring board with a copper foil with a carrier according to the present invention in the steps from rapid etching to formation of bumps and copper pillars.

FIG. 9 is an image of a computer screen showing the analysis result obtained by the analysis software KVH1A9 of the average (height of bumps) of the height histogram in Example 1. FIG.

Fig. 10 is an example of the operation screen disclosed in "Setting DISTANCE · PITCH" on page 4-3 of the VK-8500 user manual of the analysis software KVH1A9.

The form of the copper foil base material that can be used in the present invention is not particularly limited. Typically, the copper foil used in the present invention can be either an electrolytic copper foil or a rolled copper foil. Generally, electrolytic copper foil is produced by electrolyzing copper onto a drum of titanium or stainless steel using a copper sulfate plating bath, and rolled copper foil is produced by repeatedly performing plastic processing and heat treatment using a calender roll. For flexibility In applications, rolled copper foil is used in many cases.

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

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.

Furthermore, another aspect of the present invention is a copper foil with a carrier, which has a carrier, an intermediate layer, and an ultra-thin copper layer in this order. The ultra-thin copper layer is the copper foil for high-frequency circuits 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 ultra-thin copper layer in this order can be used as the copper foil base material. When the copper foil with a carrier is used in the present invention, a surface treatment layer such as the following roughening treatment layer is provided on the surface of the ultra-thin copper layer. In addition, another embodiment of the copper foil with a carrier is as follows.

Generally, in order to improve the peeling strength of the copper foil after laminating the copper foil and the resin substrate, that is, the roughened surface, the surface of the copper foil after degreasing is subjected to a "nodular" plating roughening treatment. The electrolytic copper foil has unevenness at the time of manufacture, and the convex portion of the electrolytic copper foil is enhanced by roughening treatment to further enlarge the unevenness. There are cases where ordinary copper plating and the like are performed as a treatment before the roughening, and in order to prevent the plating material from falling off, ordinary copper plating and the like are performed as a finish treatment after the roughening.

In the present invention, the so-called "roughening treatment" includes such a pretreatment and a finishing treatment, and also includes a known treatment related to the copper foil roughening, if necessary.

This 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 copper-cobalt-nickel alloy plating is called "secondary particle layer"), but as described above, copper is simply formed on the copper foil- Cobalt-nickel alloy plating may cause problems such as falling powder as described above.

A microscope photograph of the surface of a copper foil on which copper-cobalt-nickel alloy plating is formed on the copper foil is shown in FIG. 3. As shown in FIG. 3, fine particles extending into a dendritic shape can be seen. Generally, the fine particles extended into a dendritic shape shown in FIG. 3 are produced with a high current density.

In the case of processing under such a high current density, it is possible to suppress the generation of particle nuclei in the initial plating and to form new particle nuclei at the tip of the particles. Therefore, the elongated particles gradually grow into dendritic shapes.

Therefore, if the current density is reduced and plating is performed in order to prevent this, the tip decreases, the particles increase, and particles with an arc shape grow. However, in this situation, falling powder can also be slightly improved, but sufficient peel strength cannot be obtained, and the purpose of the invention cannot be fully achieved.

The situation of powder falling when the copper-cobalt-nickel alloy plating layer is formed as shown in FIG. 3 is shown in the conceptual explanatory diagram of FIG. 1. The reason for the falling powder is that as described above, fine particles are formed into a dendritic shape on the copper foil, and the dendritic particles easily break a part of the branch due to external force and fall off from the root. The fine dendritic particles are caused by peeling caused by "friction" during processing, contamination of the roller by peeling powder, and etching residues caused by peeling powder.

In the present invention, after a primary particle layer of copper is formed in advance on the surface of a copper foil, a secondary particle layer made of a ternary alloy 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 a copper foil is shown in FIG. 4 (the details are described below).

As a result, peeling caused by "friction" during processing, roller contamination caused by peeling powder, The disappearance of the etching residue caused by the peeling powder can suppress a phenomenon called powder falling, and a copper foil for a high-frequency circuit capable of improving peeling strength and improving high-frequency characteristics can be obtained.

According to the examples shown below, it can be clarified that the optimal conditions for preventing powder fall are the second one in which the average particle diameter of the primary particle layer is set to 0.25 to 0.45 μm, and a ternary alloy composed of copper, cobalt, and nickel is formed. The average particle diameter of the secondary particle layer is 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, 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, more preferably 0.40 μm or less, and still more preferably 0.39 μm or less. 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, and still more preferably 0.30 μm or less. It is more preferably 0.28 μm or less, and more preferably 0.27 μm or less. 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 growing on the primary particles. Or normal plating grown on the primary particles. That is, when the term "secondary particle layer" is used in this specification, normal plating such as coating plating is also included. The secondary particle layer may be one having more than one layer made of roughened particles, one having more than one layer of normal plating, or one having more than one layer of roughened particles and normal plating, respectively.

The peel strength of the primary particle layer and the secondary particle layer thus formed can reach 0.80 kg / cm or more, and further the peel strength can reach 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 further important to set the average value of the unevenness of the roughened surface obtained by a laser microscope to 1,500 or more, preferably 1600 or more, and more preferably It is 1700 or more, more preferably 1800 or more, and still more preferably 1900 or more. In addition, the upper limit of the average value of the unevenness height of the roughened surface obtained by a laser microscope does not need to be specifically set, and is, for example, 4500 or less, 3500 or less, 3100 or less, 3000 or less, 2900 or less, or 2800 or less.

The present invention is characterized in that a layering treatment layer having a primary particle layer and a secondary particle layer is formed. An ideal state of the roughening treatment layer is as shown in FIG. 2. 1 to 1 is formed on a larger primary particle layer. The state of two smaller secondary particle layers. In reality, there are cases where both the primary particles and the secondary particles overlap the particles. After forming a complicated 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 approximately the same as or larger than that of a primary particle is formed on a small primary particle, and a case where a small secondary particle is formed thickly on a large primary particle are both insufficient. It is difficult to specifically control the combination. Therefore, it was found in the present invention that by focusing on the macroscopic target of "the average value of the unevenness of the roughened surface obtained by the laser microscope" and controlling it, a roughened 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 peeling strength can be improved and the stable powder falling phenomenon can be prevented. In addition, the "roughened surface" in the "average of the height of the unevenness of the roughened surface obtained by a laser microscope" means the surface on the final product, and means that a primary particle layer and two The outermost side of the secondary particle layer. When a surface treatment layer such as a heat-resistant layer, a rust prevention layer, or a silane 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 the surface of the copper foil excluding the resin layer on which the primary particle layer and the secondary particle layer are formed. surface.

If the average value of the uneven height of the roughened surface obtained by the laser microscope is less than 1500, the copper foil with the primary particle layer and the secondary particle layer formed will have a large view of the roughened particles due to the accumulation of the secondary particle layer. The unevenness of the height becomes smaller, and the powder falling phenomenon easily occurs.

The measurement method of the average value of the uneven height of the roughened surface obtained by a laser microscope is set by measuring roughening processing by setting the magnification to 1000 times using a laser microscope VK8500 manufactured by Keynes Corporation. The results obtained on the surface were analyzed by measurement and analysis with an effective area of 786,432 μm ² (100% of the measurement area), and the height of the unevenness was converted into a histogram using the analysis software KVH1A9 to obtain an average value.

Can be formed on the secondary particle layer: (A) consists 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 Or (B) one or both of the chromate layer.

Further, (A) Ni and a group 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. Any one or both of an alloy layer composed of element, and (B) a chromate layer, and a silane coupling layer.

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

Furthermore, one or both of a Ni-Zn alloy layer and a chromate layer, and a silane coupling layer can be sequentially formed on the secondary particle layer.

With this configuration, high-frequency transmission characteristics can be improved while maintaining the peeling strength.

[Transmission loss]

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

The surface-treated copper foil of the present invention can be laminated to a resin substrate from the roughened surface side to produce a laminated body. The resin substrate is not particularly limited as long as it has characteristics applicable to printed wiring boards. For example, paper substrate phenol resin, paper substrate epoxy resin, and synthetic fiber cloth substrate epoxy resin can be used for 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. In FPC, polyester film or polyimide film, liquid crystal polymerization can be used. (LCP) film, fluororesin, etc. When a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, in the case of using a liquid crystal polymer (LCP) film or a fluororesin film, since the copper circuit is covered with a cover layer after the copper circuit is formed, the film and the copper circuit are not easily peeled off, which can prevent this due to a decrease in peel strength. Peeling of film from copper circuit.

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

Regarding the bonding method, in the case of a rigid PWB, a prepreg in which a resin is impregnated into a substrate such as glass cloth and the resin is cured to a semi-hardened state is prepared. It can be performed by superimposing a copper foil on a surface on the side opposite to a coating layer and a prepreg, and heating and pressing. In the case of FPC, laminated boards can be manufactured by laminating copper foils at high temperature and pressure on a substrate such as a polyimide film via an adhesive or without using an adhesive, or on a polyimide precursor Coating, drying, curing and the like are performed.

The laminated body of the present invention can be used in 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, multilayer PWB (3 or more layers) ) From the viewpoint of the type of insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and soft-hard composite PWB.

Furthermore, the printed wiring 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.

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

(Plating conditions of copper primary particles)

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

In addition, the plating conditions are merely preferred examples. The primary particles of copper are formed on the copper foil. The average particle diameter plays the role of preventing powder fall. Therefore, if the average particle diameter is within the scope of the present invention, plating conditions other than those shown below will not cause any hindrance. The present invention includes these.

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

Liquid temperature: 25 ~ 50 ℃

Current density: 1 ~ 58A / dm ²

Coulomb volume: 4 ~ 81As / dm ²

(Plating conditions for secondary particles)

In addition, similar to the above, the plating conditions are merely preferred examples, secondary particles are formed on the primary particles, and the average particle diameter is responsible for preventing powder fall. Therefore, if the average particle diameter is within the scope of the present invention, plating conditions other than those shown below will not cause any hindrance. The present invention includes these.

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

pH value: 2 ~ 3

Liquid temperature: 30 ~ 50 ℃

Current density: 24 ~ 50A / dm ²

Coulomb volume: 34 ~ 48As / dm ²

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

The present invention can further form a heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

pH value: 2 ~ 3

Liquid temperature: 40 ~ 60 ℃

Current density: 5 ~ 20A / dm ²

Coulomb volume: 10 ~ 20As / dm ²

(Plating Conditions for Forming Heat-Resistant Layer 2) (Ni-Zn Plating: Nickel-Zinc Alloy Plating)

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

pH value: 3 ~ 4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

pH value: 3 ~ 4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

Liquid temperature: 20 ~ 40 ℃

Current density: 1 ~ 4A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

pH value: 1.5 ~ 4.5

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

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

pH value: 1.5 ~ 2.5

Liquid temperature: 30 ~ 40 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. Table of plating conditions As shown below.

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

pH value: 3 ~ 4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

The present invention can further form the following heat-resistant layer on the secondary particle layer. The plating conditions are shown below.

A nickel-chromium alloy coating is formed using a sputtering target composed 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

(Plating conditions for forming rust preventive layer)

The present invention can further form a rust preventive layer as described below. The plating conditions are shown below. The conditions for immersion chromate treatment are shown below, and electrolytic chromate treatment may also be used.

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

pH value: 3 ~ 4

Liquid temperature: 50 ~ 60 ℃

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

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

(Types of weather-resistant layer (silane coupling layer))

As an example, application of an aqueous diamine silane solution is mentioned.

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

The limiting current density is changed according to the metal concentration, pH value, feeding speed, distance between electrodes, and temperature of the plating solution. In the present invention, the normal plating (the state where the plated metal is deposited in a layered state) and the coarse The current density at the boundary of electroless plating (sintering, precipitation of the plated metal into a crystalline state (spherical or needle-like or tree-like shape, with unevenness)) is defined as the limiting current density, and a Hall groove test is used The current density (visual judgment), which is the limit of normal plating (before the step of baking), is set as the limit current density.

Specifically, the metal concentration, the pH value, and the temperature of the plating solution were set to the manufacturing conditions for plating, and a Hall groove test was performed. Then, the state of the formation of the metal layer (the plated metal was deposited in a layered or crystalline state) at the composition and temperature of the plating solution was investigated. Then, based on the current density list manufactured by Yamamoto Gold Plating Tester Co., Ltd., the current density at the position of the interface was obtained based on the position of the test piece at the interface between the normal plating and rough plating of the test piece. The current density at the boundary is defined as the limit current density. From this, the limiting current density of the composition of the plating solution and the temperature of the plating solution can be known. Generally, if the inter-electrode distance is short, the limiting current density tends to be high.

The method of Hall groove test is described in "Plating Practice Reader" by Kiyoshi Maruyama, Nikkan Kogyo The newspaper was on pages 157 to 160 of June 30, 1983.

In addition, in order to perform the plating treatment at a current density that has not reached the limit, the current density during the plating treatment is preferably set to 20 A / dm ² or less, more preferably to 10 A / dm ² or less, and even more preferably It is set to 8 A / dm ² or less.

In addition, the thickness of the chromate layer and the silane coupling layer is extremely thin, so it does not affect the shape of the surface of the copper foil.

The copper-cobalt-nickel alloy plating as the above secondary particles can be formed by electrolytic plating with an adhesion amount of 10 ~ 30mg / dm ² copper-100 ~ 3000μg / dm ² cobalt-50 ~ 500μg / dm ² nickel. Element system alloy layer.

When the Co adhesion amount is less than 100 μg / dm ² , the heat resistance is deteriorated, and the etchability is also deteriorated. If the Co adhesion amount exceeds 3000 μg / dm ² , it is not good in terms of the influence of magnetic properties, and etch spots will be generated. In addition, acid resistance and chemical resistance may be deteriorated.

When the Ni adhesion amount is less than 50 μg / dm ² , the heat resistance is deteriorated. On the other hand, if the Ni adhesion amount exceeds 500 μg / dm ² , the etching properties are reduced. That is, although it is not a grade where etching residue exists and cannot be etched, it is difficult to perform fine patterning. A preferable Co adhesion amount is 500 to 2000 μg / dm ² , and a preferable nickel adhesion amount is 50 to 300 μg / 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. Each 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" refers to a case where Co remains undissolved when etching with copper chloride, and the term "etching residue" means that Ni does not Dissolved and remaining.

Generally, when forming a circuit, it is performed using the alkali etchant and copper chloride-based etchant described in the following Examples. The etchant and the etching conditions are versatile, but are not limited to these conditions, and it should be understood that they can be arbitrarily selected.

As described above, the present invention can form a cobalt-nickel alloy plating layer on the roughened surface after the formation of the secondary particles (after the roughening treatment).

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

The cobalt-nickel alloy plating must be performed to such an extent that the bonding strength between the copper foil and the substrate is not substantially reduced. If the cobalt adhesion amount is less than 200 μg / dm ² , the heat-resistant peeling strength is reduced, the oxidation resistance and chemical resistance are deteriorated, and the treated surface is reddish, which is not good.

In addition, if the cobalt adhesion amount exceeds 3000 μg / dm ² , it may be necessary to consider the influence of magnetism, so it is not good, and etched spots are generated, and acid resistance and chemical resistance are considered to be deteriorated. A preferable cobalt adhesion amount is 400 to 2500 μg / dm ² .

In addition, if the cobalt adhesion amount is large, it may cause the infiltration of soft etching. 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 soft etching infiltration is a heat-resistant rust-proof layer composed of a zinc-nickel alloy plating layer, but there are also cases where cobalt also causes the infiltration during soft etching, so it is more desirable. The conditions are adjusted as described above.

On the other hand, when the amount of nickel adhered is small, the heat-resistant peel strength is reduced, and the oxidation resistance and chemical resistance are reduced. In addition, when the amount of nickel adhered is too large, alkali etchability is deteriorated, so it is preferably determined in a balance with the above-mentioned cobalt content.

The invention can form a zinc-nickel alloy plating layer on the 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 heat-resistant rust-proof layer. This condition is also only a preferable 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 preferable additional condition.

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

Also, in the conventional technique, a microcircuit having a zinc-nickel alloy plating layer in a two-layer material formed 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. Its discoloration. Nickel has the effect of suppressing the penetration of an etchant (H ₂ SO ₄ : 10 wt%, H ₂ O ₂ : 2 wt% etching aqueous solution) used in soft etching.

As described above, the total amount of the zinc-nickel alloy plating layer is set to 150 to 500 μg / dm ² , the lower limit value of the nickel ratio in the alloy layer is set to 16% by mass, and the upper limit value is set to 40. When the mass content is 50% and the nickel content is 50 μg / dm ² or more, it has the following effects: it has the function of a heat-resistant rust-proof layer, and suppresses the penetration of the etchant used during soft etching, and can prevent the circuit from joining due to corrosion Weakness of intensity.

In addition, if the total amount of zinc-nickel alloy plating is less than 150 μg / dm ² , the heat resistance and rust resistance are reduced, and it is difficult to bear the role of a heat resistant rust prevention layer. If the same total amount exceeds 500 μg / dm ² , the resistance is The tendency of hydrochloric acid to deteriorate.

In addition, if the lower limit value of the nickel ratio in the alloy layer is less than 16% by mass, the penetration amount during soft etching exceeds 9 μm, which is unfavorable. The upper limit of the nickel ratio is 40% by mass because zinc-nickel alloy plating can be formed The technical limit of the layer.

As described above, the present invention can sequentially form a cobalt-nickel alloy plating layer and a zinc-nickel alloy plating layer on the copper-cobalt-nickel alloy plating layer as the secondary particle layer as needed. The total amount of cobalt and nickel in these layers can also be adjusted. It is desirable 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 .

If the total adhesion amount of cobalt does not reach 300 μg / dm ² , the heat resistance and chemical resistance will decrease. If the total adhesion amount of cobalt exceeds 4000 μg / dm ² , etching spots may occur, and transmission loss may increase. Situation. In addition, if the total adhesion amount of nickel is less than 100 μg / dm ² , heat resistance and chemical resistance may be reduced. If the total adhesion amount of nickel exceeds 1500 μg / dm ² , etching residues may be generated, and transmission loss may be 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 adhesion amount is preferably 100 to 1000 μg / dm ² , and more preferably 100 to 900 μg / dm ² . If the above conditions are satisfied, there is no particular limitation on the conditions described in this paragraph.

Thereafter, an anti-rust treatment is performed as necessary. The preferred antirust treatment in the present invention is a coating treatment of chromium oxide alone or a coating treatment of a mixture of chromium oxide and zinc / zinc oxide. The so-called chromium oxide and zinc / zinc oxide mixture coating treatment refers to using a plating bath containing zinc salt or zinc oxide and chromate to coat zinc-chromium composed of zinc or zinc oxide and chromium oxide by electroplating Treatment of rust-proof layer of base mixture.

As the plating bath, at least one of dichromates such as K ₂ Cr ₂ O ₇ and Na ₂ Cr ₂ O ₇ or CrO ₃ and the like, and at least one of water-soluble zinc salts such as ZnO and ZnSO ₄ -7H ₂ O are typically used. A mixed aqueous solution with alkali hydroxide. Examples of typical 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. In addition, a circuit having a pitch width of 150 μm or less can be etched by using a CuCl ₂ etching solution, and can also be set to alkali etching. In addition, infiltration into the circuit edge portion during soft etching can be suppressed.

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

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

The copper foil obtained in all the above steps has black to gray. Black to gray are more significant in terms of alignment accuracy and high heat absorption. For example, a circuit board including a rigid substrate and a flexible substrate is mounted with ICs, resistors, capacitors, and other components in automatic steps. At this time, the chip is mounted while reading the circuit with a sensor. At this time, the copper foil-treated surface may be aligned with a film such as Kapton. The positioning is also the same when the through hole is formed.

The closer the processing surface is to black, the better the absorption of light, so the positioning accuracy improves. Furthermore, when a substrate is produced, in many cases, it is cured while applying heat to the copper foil and the film, and then it is cured. At this time, in the case of heating by using a long-wavelength band such as far-infrared rays or infrared rays, the processing surface has a better heating efficiency than a black one.

Finally, if necessary, with the main purpose of improving the adhesion between the copper foil and the resin substrate, a silane treatment with a silane coupling agent coated on at least the roughened surface of the rust preventive layer is performed. Examples of the silane coupling agent used in the silane treatment include olefin-based silanes, epoxy-based silanes, acrylic-based silanes, amino-based silanes, and mercapto-based silanes, and these can be appropriately selected and used. When a liquid crystal polymer is used as the resin, it is preferable to use an amine-based silane (a silane having an amine group) as the silane coupling agent. It is more preferable to use a diamine silane as the silane coupling agent.

The coating method may be any one of spray coating using a silane coupling agent solution, coating using a coating machine, dipping, casting, and the like. For example, Japanese Patent Publication No. 60-15654 describes that the adhesion between a copper foil and a resin substrate is improved by performing a silane coupling agent treatment after performing a chromate treatment on the rough side of the copper foil. For details, please refer to this. Thereafter, if necessary, annealing treatment may be performed in order to improve the ductility of the copper foil.

[Copper foil with carrier]

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

<Carrier>

The carrier that can be used in the present invention is typically a metal foil or a resin film, for example, copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin film (For example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyimide film, a polyester film, a fluororesin film, etc.) are provided.

As a carrier usable in the present invention, copper foil is preferably used. Due to the high electrical conductivity of copper foil, it is easy to form subsequent intermediate layers and extremely thin copper layers. Typically, the carrier is provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath on a titanium or stainless steel drum, and rolled copper foil is produced by repeating plastic processing and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as fine copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, copper alloys to which Cr, Zr, or Mg is added, and Ni and Si to which it is added can be used. Carson is a copper alloy such as a copper alloy.

The thickness of the carrier that can be used in the present invention is not particularly limited as long as it functions as The thickness of the carrier may be appropriately adjusted for the function of the carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost increases, and therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, and more typically 18 to 35 μm.

Furthermore, a roughening treatment layer may be provided on the surface on the side opposite to the surface on the side where the ultra-thin copper layer of the carrier is provided. This roughening treatment layer can be set using a known method, and can also be set by the above roughening treatment. When the roughening treatment layer is provided on the surface opposite to the surface on which the ultra-thin copper layer side of the carrier is provided, there is an advantage that when the carrier is laminated on a support such as a resin substrate from the surface side having the roughening treatment layer, the carrier It is not easy to peel from the resin substrate.

<Middle layer>

An intermediate layer is provided on the carrier. Other layers may 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 has the following structure: before the step of laminating the copper foil with a carrier onto the insulating substrate, the extremely thin copper layer is not easy to peel off from the carrier; on the other hand, in the step of laminating the insulating substrate The rear extremely thin copper layer can be peeled from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may also contain a material selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloys, these hydrates, One or two or more groups of these oxides and organic substances. The intermediate layer may be a plurality of layers.

In addition, for example, the intermediate layer may be constituted by forming a unit composed of one 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, on which an optional layer is formed. A layer composed of one or more hydrates, oxides, or organics of an element group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or a layer selected from the group consisting of Cr , Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn A single metal layer composed of one element, or a single metal layer 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 types of element group consisting of Al and Zn.

When an intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When an intermediate layer is provided by a chromate treatment, a zinc chromate treatment, or a plating treatment, it may be considered that a part of the attached metal such as chromium or zinc becomes a hydrate or an oxide.

In addition, for example, the intermediate layer may be formed by sequentially stacking nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, and chromium on a carrier. The adhesion force between nickel and copper is higher than the adhesion force between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, it is peeled off at the interface between the ultra-thin copper layer and chromium. In addition, a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin copper layer is expected for the nickel in the intermediate 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 It is more preferably 100 μg / dm ² or more and less than 1000 μg / dm ² , and the chromium adhesion amount in the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less.

<Ultra-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 with electrolytic baths such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and it can be used in the form of ordinary electrolytic copper foil, which can be formed at 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 generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, further typically 1.5 to 5 μm, and further typically 2 to 5 μm. Furthermore, it can be set on both sides of the carrier. Place a very thin copper layer.

In this way, a copper foil with a carrier including a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer was manufactured. The method of using the copper foil with a carrier itself is well known to the industry. For example, the surface of an 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, and glass. Cloth / paper composite substrate epoxy resin, glass cloth / glass non-woven fabric composite substrate epoxy resin, glass cloth substrate epoxy resin, polyester film, polyimide film and other insulating substrates The carrier is peeled to make a copper-clad laminated board, and the ultra-thin copper layer on the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

Moreover, the copper foil with a carrier provided with a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer may be provided with a roughening treatment layer on the ultra-thin copper layer, and on the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate (treatment) layer, and a silane coupling (treatment) layer.

[Resin layer]

A resin layer may also be formed on the surface of the secondary particle layer of the copper foil for high-frequency circuits of the present invention (including the case where the copper foil for high-frequency circuits is an ultra-thin copper layer with a carrier copper foil). In addition, the resin layer may be formed on the secondary particle layer of the copper foil for high-frequency circuits, each made of Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, The surface of the alloy layer composed of more than one element of the group consisting of As and Ti may be formed on the surface of the chromate layer, the surface of the silane coupling layer, or the surface of the Ni-Zn alloy layer. The resin layer is more preferably formed on the outermost surface of the copper foil for high-frequency circuits. Moreover, the said copper foil with a carrier may be provided with the resin layer on the said roughening process layer, or the said heat-resistant layer, a rust prevention layer, a chromate (treatment) layer, or a silane coupling (treatment) layer. The resin layer may be an insulating resin layer.

The resin layer may be an adhesive or an insulating resin layer in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no stickiness even if the surface is touched with a finger, and the insulating resin layer can be stacked and stored, and further heat treatment will cause a hardening reaction.

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The type is not particularly limited, and preferred examples include epoxy resins, polyimide resins, polyfunctional cyanate compounds, maleimide compounds, and polyvinyl acetal resins. , Amine ester resin, etc.

The resin layer may contain any of a known resin, a resin hardener, a compound, a hardening accelerator, and a dielectric (a dielectric including an inorganic compound and / or an organic compound, a dielectric including a metal oxide, or the like) may be used. (Electric body), reaction catalyst, cross-linking agent, polymer, prepreg, framework material, etc. The resin layer may be, for example, those described in the following documents (resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, cross-linking agent, polymer, prepreg, skeleton material, etc.) And / or resin layer forming method and device: International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, Japanese Patent Laid-Open No. 11-5828, Japanese Patent Laid-Open No. 11-140281 , Japanese Patent No. 3184485, 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 Laid-Open 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, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070 No., Japanese Patent Laid-Open 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 Patent Laid-Open No. 2008- 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 Application Publication 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.

These resins are dissolved in a solvent such as methyl ethyl ketone (MEK), toluene, etc. to prepare a resin liquid, and the resin is applied to the above-mentioned copper foil or an extremely thin copper layer by, for example, a roll coating method. Or the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane coupling agent layer, and then, if necessary, heat-dried to remove the solvent and become a B-stage state. The drying can be performed using, for example, a hot-air drying furnace, and the drying temperature can be 100 to 250 ° C, preferably 130 to 200 ° C.

The copper foil for high-frequency circuits provided with the resin layer (copper foil for high-frequency circuits with a resin) is made by laminating the resin layer and the substrate, and then thermocompression-bonding the entirety of the resin layer, and then copper The foil is used in the form of a specific wiring pattern.

Moreover, the copper foil with a carrier provided with the said resin layer (copper foil with a carrier with a resin) overlaps the resin layer and a base material, and heat-compresses the whole resin by thermocompression, and the carrier is peeled and exposed. The ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), so it is used in the form of forming a specific wiring pattern.

If the copper foil for high-frequency circuits with a resin or the copper foil with a carrier with a resin is used, the number of prepreg materials used in manufacturing a multilayer printed wiring board can be reduced. In addition, the thickness of the resin layer is set to a thickness capable of ensuring interlayer insulation, or a copper-clad laminated board can be manufactured without using a prepreg material at all. At this time, the surface of the substrate may be primed with an insulating resin to further improve the surface smoothness.

Furthermore, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step becomes simplified, so it is economically advantageous, and it has the following advantages: only the prepreg is manufactured The thickness of the multilayer printed wiring board having a thickness of approximately the bulk material can be reduced, and an extremely thin multilayer printed wiring board having a thickness of 100 μm or less can be manufactured.

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

If the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesive force is reduced and it is difficult to ensure that the resin-coated copper foil with a carrier is laminated on a substrate provided with an inner layer material without passing through the prepreg material. Interlayer insulation between the inner layer and the circuit.

On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer of a target thickness in one coating step, and an excessive material cost and number of steps are required, which is disadvantageous economically. Furthermore, the formed resin layer has poor flexibility, so there are cases where cracks and the like are easy to occur during operation, and excessive resin flow is caused during thermal compression bonding to the inner layer material, which makes it difficult to laminate smoothly. .

Furthermore, as another product form of the copper foil with a carrier and a resin attached thereto, a resin layer may be coated on the extremely thin copper layer, or the heat-resistant layer, rust-proof layer, or the chromate layer, or the silane After the coupling layer is in a semi-hardened state, the carrier is peeled off, and manufactured in the form of a copper foil (ultra-thin copper layer) with resin without a carrier.

Here, some examples of the manufacturing steps of the printed wiring board using the copper foil with a carrier of this invention are shown below.

One embodiment of the method for manufacturing a printed wiring board of the present invention includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; and insulating the ultra-thin copper layer side from the insulation. After the copper foil with a carrier and an insulating substrate are laminated in a substrate facing manner, a copper-clad laminated board is formed through a step of peeling the carrier of the copper foil with a carrier, and then a semi-additive method and an improved semi-additive method are used. Either the partial addition method or the subtraction method forms a circuit. The insulating substrate can also be used as an inner circuit entrance.

In the present invention, the so-called semi-additive method refers to a method including the following cases: thin electroless plating on an insulating substrate or a copper foil seed layer to form a pattern of a plating resist, and then plating and plating The resist is removed and etched to form a conductor pattern.

In the present invention, the so-called improved semi-additive method refers to a method including: laminating a metal foil on an insulating layer, protecting a non-circuit forming portion with 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 forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.

In the present invention, the so-called partial addition method refers to a method for manufacturing a printed wiring board by a method including a substrate formed by providing a conductor layer and passing through holes for through holes or auxiliary holes as necessary. A catalyst core is provided on the substrate, and a conductor circuit is formed by etching. If necessary, a solder resist or a plating resist is provided, and then through holes or auxiliary holes are thickened by the electroless plating process on the conductor circuit.

In the present invention, the so-called subtractive method refers to a method including a case where a conductor pattern is formed by selectively removing unnecessary portions of a copper foil on a copper-clad laminate by etching or the like.

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.

First, as shown in FIG. 5-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened layer formed on the surface is prepared.

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

Secondly, as shown in FIG. 5-C, after forming the circuit plating, 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 covering the circuit plating method (by the buried circuit plating method), and then the resin layer is laminated from the ultra-thin copper layer side. Another copper foil with carrier (layer 2).

Next, as shown in FIG. 6-E, the carrier is peeled from the copper foil with a carrier in the second layer.

Secondly, as shown in FIG. 6-F, laser drilling is performed at a specific position of the resin layer to expose the circuit plating and form a blind hole.

Secondly, as shown in FIG. 7-G, copper is buried in the blind holes to form through-hole filling materials.

Next, as shown in FIG. 7-H, a circuit plating is formed on the through-hole filler in the manner of FIGS. 5-B and 5-C described above.

Next, as shown in FIG. 7-I, the carrier is peeled from the copper foil with a carrier in the first layer.

Secondly, as shown in FIG. 8-J, the ultra-thin copper layers on both surfaces are removed by rapid etching, so that the surface of the circuit plating in the resin layer is exposed.

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. In this way, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The other copper foil with a carrier (second layer) described above may use the copper foil with a carrier of the present invention, a conventional copper foil with a carrier may be used, and a general copper foil may also be used. In addition, one or multiple layers of circuits can be formed on the second layer of the circuit shown in Figure 7-H. Any of the semi-additive method, subtractive method, partial additive method, or modified semi-additive method can be used. One way to form such circuits.

According to the manufacturing method of the printed wiring board as described above, a structure is formed in which the circuit plating is buried in the resin layer. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 8-J, the resin layer is used for protection. The circuit is plated and its shape is maintained, whereby a fine circuit can be easily formed. In addition, since the circuit plating is protected by the resin layer, the electron migration resistance is improved, and the conduction of the wiring of the circuit can be suppressed well. Therefore, it is easy to form a fine circuit. In addition, when the ultra-thin copper layer is removed by rapid etching as shown in FIGS. 8-J and 8-K, the exposed surface of the circuit plating becomes a shape recessed from the resin layer, so it is easy to form a protrusion on the circuit plating. Blocks, and copper pillars are formed thereon, thereby improving manufacturing efficiency.

Further, as the embedded resin (Resin), a known resin or prepreg can be used. For example, BT (bis-cis-butene difluorene imine tri ) Resin or glass cloth impregnated with BT resin is prepreg, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. As the embedded resin (Resin), a resin layer and / or a resin and / or a prepreg described in this specification can be used.

Also, regarding the copper foil with a carrier for the first layer described above, The surface may have a substrate or a resin layer. By having the substrate or the resin layer, the copper foil with a carrier for the first layer is supported, so that wrinkles are not easily generated, and therefore there is an advantage of improving productivity. Furthermore, as long as the substrate or the resin layer has the effect of supporting the copper foil with a carrier for the first layer described above, all the substrates or the resin layer may 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 plate of an inorganic compound, a plate of an organic compound, or the like described in the specification of the present case can be used. An organic compound foil is used as the substrate or resin layer.

[Example]

Hereinafter, it demonstrates based on an Example and a comparative example. 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. The original foils of the following Examples 1 to 6, 11 to 15, and Comparative Examples 1 to 5 used a standard rolled copper foil TPC (fine copper based on JIS H3100 C1100, manufactured by JX Nippon Mining & Metals) of 18 μm.

In addition, as the original foils of Examples 7 to 10, a copper foil with a carrier manufactured by the following method was used.

In Examples 7 to 10, an electrolytic copper foil (JTC foil manufactured by JX Nippon Mining & Metals) with a thickness of 18 μm was prepared as a carrier, and in Example 12, the standard rolled copper foil TPC with a thickness of 18 μm was prepared as a carrier. In addition, 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. When the carrier is an electrolytic copper foil, an intermediate layer is formed on the glossy surface (S surface).

‧Example 7 <Middle layer>

(1) Ni layer (Ni plating)

Under the following conditions, the carrier was electroplated using a roll-to-roll connection plating line, thereby forming a Ni layer having an adhesion amount of 1000 μg / dm ² . 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

Luster: Saccharin, butynediol, etc.

Sodium lauryl sulfate: 55 ~ 75ppm

pH value: 4 ~ 6

Bath temperature: 55 ~ 65 ℃

Current density: 10A / dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) was washed with water and pickled, and then, on a roll-to-roll connection plating line, the Cr layer with an adhesion amount of 11 μg / dm ² was electrolyzed under the following conditions: The chromate treatment adheres to the Ni layer.

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

pH value: 7 ~ 10

Liquid temperature: 40 ~ 60 ℃

Current density: 2A / dm ²

<Ultra-thin copper layer>

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

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

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 ℃

Current density: 100A / dm ²

Linear speed of electrolyte: 1.5 ~ 5m / sec

‧Example 8 <Middle layer>

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

Under the following conditions, the carrier was electroplated using a roll-to-roll connection plating line, thereby forming a Ni-Mo layer with an adhesion amount of 3000 μg / dm ² . Specific plating conditions are described below.

(Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³

(Liquid temperature) 30 ℃

(Current density) 1 ~ 4A / dm ²

(Power-on time) 3 ~ 25 seconds

<Ultra-thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An ultra-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 <Middle layer>

(1) Ni layer (Ni plating)

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

(2) Organic layer (organic layer forming treatment)

Next, after the surface of the Ni layer formed in (1) was washed with water and acid, the surface of the Ni layer was showered under the following conditions and sprayed with a carboxybenzotriazole (CBTA) containing 1-30 g / L An aqueous solution having a liquid temperature of 40 ° C and a pH value of 20 for 20 to 120 seconds forms an organic layer.

<Ultra-thin copper layer>

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

‧Example 10 <Middle layer>

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

Under the following conditions, the carrier was plated with a roll-to-roll connection plating line, thereby forming a Co-Mo layer with an adhesion amount of 4000 μg / dm ² . Specific plating conditions are described below.

(Liquid composition) Co sulfate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³

(Liquid temperature) 30 ℃

(Current density) 1 ~ 4A / dm ²

(Power-on time) 3 ~ 25 seconds

<Ultra-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 extremely thin copper layer was set to 5 μm.

(Examples 1 to 15)

The primary particle layer (Cu) was formed on the surface of the rolled copper foil (Examples 1 to 6, 11 to 15) or the extremely thin copper layer of the copper foil with a carrier (Examples 7 to 10) within 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 ℃

Current density: 1 ~ 70A / dm ²

Coulomb volume: 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 ℃

Current density: 10 ~ 50A / dm ²

Coulomb volume: 10 ~ 80As / dm ²

The conditions for 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 value of the roughness height of the roughened surface obtained by a laser microscope was 1500. the above. The surface area is measured using a measurement method using the above-mentioned laser microscope.

(Comparative Examples 1 to 5)

In the comparative example, the bath composition and plating conditions used are 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 ℃

Current density: 1 ~ 70A / dm ²

Coulomb volume: 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 ℃

Current density: 20 ~ 50A / dm ²

Coulomb volume: 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 using the following conditions.

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

‧Co-Ni plating: cobalt-nickel alloy plating

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

pH value: 2 ~ 3

Liquid temperature: 40 ~ 60 ℃

Current density 5 ~ 20A / dm ²

Coulomb volume: 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 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

In addition, Examples 5 and 10 were subjected to electrolytic chromate treatment and silane coupling treatment using diaminosilane after Ni-Zn plating.

(Example 6)

‧Ni-Cu plating: nickel-copper alloy plating

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

pH value: 3 ~ 4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

(Example 11)

‧Ni-Mo plating: nickel-molybdenum alloy plating

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

Liquid temperature: 20 ~ 40 ℃

Current density: 1 ~ 4A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

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

(Example 12)

‧Ni-Sn plating: nickel-tin alloy plating

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

pH value: 1.5 ~ 4.5

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

In addition, Example 12 was subjected to a silane coupling treatment using diamine silane after Ni-Sn plating.

(Example 13)

‧Ni-P plating: nickel-phosphorus alloy plating

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

pH value: 1.5 ~ 2.5

Liquid temperature: 30 ~ 40 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

(Example 14)

‧Ni-W plating: nickel-tungsten alloy plating

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

pH value: 3 ~ 4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 ~ 2A / dm ²

Coulomb volume: 1 ~ 2As / dm ²

In addition, Example 14 was subjected to electrolytic chromate treatment and silane coupling treatment using diamine silane after Ni-W plating.

(Example 15)

‧Ni-Cr plating: nickel-chromium alloy plating

A nickel-chromium alloy coating was formed using a sputtering target composed of Ni: 80mass% and Cr: 20mass%.

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

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

Output: DC50W

Argon pressure: 0.2Pa

When forming the primary particle layer (Cu plating) and the secondary particle layer (Cu-Co-Ni alloy plating) on the copper foil formed in the above examples, the average particle diameter of the primary particles and the secondary particles The average particle diameter, falling powder, peeling strength, heat resistance, and the average value of the height histogram (concave and convex height) of a certain area of the roughened surface were measured. The measured results are shown in Table 1. Here, the "roughened surface" measured is the outermost surface on which the primary particle layer and the secondary particle layer are formed. Further, Co-Ni plating, Ni-Zn plating, chromate layer, silane coupling layer, etc. are formed on the secondary particle layer, and those having a surface treatment layer other than the primary particle layer and the secondary particle layer will be The surface of the outermost layer among these layers is measured as a roughened surface (that is, the surface of the primary particle layer and the secondary particle layer side after the entire surface treatment layer of the copper foil is formed is measured).

The average particle diameters of the primary particles and secondary particles of the roughened surface are measured by using S4700 (scanning electron microscope) manufactured by Hitachi High-tech Co., Ltd. at a magnification of 30,000 times. The particle diameter was measured for each primary particle and secondary particle. Then, the arithmetic mean value of the particle diameters of each of the obtained primary particles and secondary particles is taken as the value of the average particle diameter of the primary particles and the average particle diameter of the secondary particles. When a straight line is drawn on a particle in a scanning electron microscope photograph, the length of the particle having the longest straight line length across the particle is taken as the particle diameter of the particle. The size of the measurement field of view is 13.44 μm ² (= 4.2 μm × 3.2 μm) per one field of view, and the measurement is performed for one field of view. In addition, when observing with a scanning electron microscope photograph, particles that are visible overlapping and existing on the copper foil side (below) and non-overlapping particles are determined as primary particles, and those that are visible overlapping and exist on other particles The particles were determined as secondary particles.

Average of height histogram of roughened surface obtained by laser microscope The measurement method of (concave and convex height) is to use a laser microscope VK8500 manufactured by Keynes Co., Ltd., set the magnification to 1000 times, load the copper foil as the measurement object on the laser microscope stage, and adjust the focus with the focus handle. After the position of the stage is aligned with the focal point of the lens of the laser microscope and 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 Setting" is based on the description on page 4-3 of the VK-8500 user manual. The PITCH system is set to 0.1 μm. In addition, as a reference, an example of the operation screen disclosed in "DISTANCE · PITCH Setting" on page 4-3 of this VK-8500 user manual is shown in FIG. 10.

In addition, "Click the 1 [▲] (Lens Position Move) button to move the lens up to the out of focus position of the image" in the VK-8500 User's Manual, page 4-3. ”Set the height of the lens as a self-visible image. Click the [▲] (lens position movement) button to slowly increase the height of the lens, and keep the lens away from the object (roughened surface), so that the roughened processing is performed. The image on the surface can be seen in a clearly blurred position.

Also, in the VK-8500 User Manual, page 4-3, click the "3 [▼] (Lens Position Move)" button to move the lens down to the out-of-focus position of the image. ”Set the height of the lens as a self-visible image. Click the [▼] (Lens Position Move) button to slowly reduce the height of the lens, make the lens close to the roughened surface, and make the image on the roughened surface visible. Obviously blurred location. In addition, the above-mentioned "setting of DISTANCE · PITCH" and the adjustment of the position of the table of the laser microscope were performed in each of Examples and Comparative Examples.

In addition, the obtained results were analyzed by measurement and analysis with an effective area of 786432 μm ² (100% of the measurement area), and the rugged height histogram was analyzed using the analysis software KVH1A9 to obtain the average value. Specifically, the screen of "Histogram details (dark and light features)" is displayed, and "height" is selected as "display data", and "histogram" is selected as "display form". The value of "average" is rounded down to the decimal point of the read value, and the obtained value is set to "the average value of the unevenness of the roughened surface obtained by the laser microscope". The analysis software KVH1A9 is configured using a laser microscope VK8500 manufactured by Keynes Corporation.

The powder-falling property is obtained by attaching a transparent invisible tape on the roughened surface of the copper foil, and peeling the roughened particles attached to the adhesive surface of the tape when the tape is peeled off, thereby changing the color of the tape. That is, when the color of the tape is not discolored or very small, it is set to be OK (falling powder), and when the color of the tape is changed to gray, it is set to be powder fall (NG). The normal peeling strength is that a copper-clad laminated board is produced by laminating a copper foil roughened surface and a FR4 resin substrate by hot pressing. A common copper chloride circuit etching solution is used to make a 10mm circuit. The 10mm circuit copper foil is peeled from the substrate. The normal peeling strength was measured while pulling in the 90 ° direction.

(Measurement of transmission loss)

A resin substrate (LCP: liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), polyimide: 50 μm manufactured by Kaneka, and a fluororesin thickness 50 μm were bonded to each sample having a thickness of 18 μm: After Dupont), a microstrip line was formed by etching so that the characteristic impedance became 50Ω. The transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss was calculated at a frequency of 20 GHz and a frequency of 40 GHz. In addition, 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, the carrier was peeled off, and then copper plating was performed to form an ultra-thin copper layer After the total thickness with copper plating was set to 18 μm, the same transmission loss measurement was performed as described above. As a frequency of 20GHz The evaluation of transmission loss is set to ◎ for less than 3.7dB / 10cm, ○ for 3.7dB / 10cm or more and less than 4.1dB / 10cm, and △ for 4.1dB / 10cm or more and less than 5.0dB / 10cm. Let × be 5.0dB / 10cm or more.

Moreover, as a comparative example, the same result is shown in Table 1.

In addition, the example in which two current conditions and the coulomb amount are listed in the primary particle current condition column of Table 1 means that after plating is performed under the conditions described on the left, further plating is performed under the conditions described on the right. For example, when "(65A / dm ² , 80As / dm ² ) + (20A / dm ² , 30As / dm ² )" is described in the column for the condition of the primary particle current in Example 1, it means that the primary particle 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.

The results of the embodiments of the present invention according to Table 1 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 It was set to 28 A / dm ² , and the coulomb amount was set to 20 As / dm ² .

In addition, the current density and the coulomb amount forming the primary particles are in two stages. When the primary particles are usually formed, two-stage plating is necessary. That is, the plating conditions for the formation of the nuclear particles in the first stage and the plating for the growth of the nuclear particles in the second stage.

The initial plating conditions are plating conditions for the formation of nuclear-forming particles in the first stage, and the next plating conditions are plating conditions for the growth of nuclear particles in the second stage. The following examples and comparative examples are also the same, so descriptions are 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 uneven height of the roughened surface obtained by the laser microscope was 2689, which satisfies the conditions of the present invention.

As a result, it has the following characteristics: less falling powder, higher normal peeling strength of 1.16 kg / cm, and heat resistance degradation rate (after normal peeling measurement, the peeling strength after heating at 180 ° C for 48 hours is measured, and the difference is (Deterioration rate) is less than 30%.

The heat resistance degradation rate was determined by the following formula.

Thermal degradation rate (%) = (normal peeling strength (kg / cm)-peeling strength (kg / cm) after heating at 180 ° C for 48 hours) / normal peeling strength (kg / cm) × 100

Example 2 is as follows: the current density of the primary particles is set to 65A / dm ² and 2A / dm ² , the coulomb amount is 80As / dm ² and 4As / dm ² , and the current density of the secondary particles is set. It was set to 25 A / dm ² , and the coulomb amount was set 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 of the roughened surface obtained by the laser microscope was 1556, which satisfies 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, heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set (Deterioration rate) is less than 30%.

Example 3 is the case where the current density of forming 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 forming secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 uneven height obtained by the laser microscope on the roughened surface was 1809, which satisfies the conditions of the present invention.

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

Example 4 is the case where the current density of primary particles is set to 55A / dm ² and 1A / dm ² , the coulomb amount is set to 75As / dm ² and 5As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1862, which satisfies the conditions of the present invention.

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

Example 5 is the case where the current density of primary particles is set to 50A / dm ² and 5A / dm ² , the coulomb amount is 70As / dm ² and 10As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1857, which satisfies the conditions of the present invention. Has the following characteristics: no falling powder, normal peel strength is 0.94kg / cm, heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate ) Is less than 30%.

Example 6 is a case where the current density of 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 (secondary Particle layer) The current density was set to 20 A / dm ² , and the Coulomb amount was set to 60 As / dm ² to perform plating (normal plating), and then the current density was set to 20 A / dm ² , and the Coulomb amount was set to 20As / dm ² to form particles.

As a result, the average particle diameter of the primary particles was 0.35 μm, and the secondary particles had a two-stage structure of a coated (normal) plating state (particle diameter less than 0.1 μm) and an average particle diameter of 0.15 μm. The average value of the uneven height of the chemically treated surface is 1752, which satisfies the conditions of the present invention. Has the following characteristics: no falling powder, normal peel strength is 0.83kg / cm, heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate ) Is less than 30%.

Example 7 is the case where the current density of forming primary particles is set to 65A / dm ² and 2A / dm ² , the coulomb amount is set to 80As / dm ² and 4As / dm ² , and the current density of forming secondary particles is set. It was set to 25 A / dm ² , and the coulomb amount was set 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 of the roughened surface obtained by the laser microscope was 1560, which satisfied the conditions of the present invention.

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

Example 8 is the case where the current density of primary particles is set to 60A / dm ² and 10A / dm ² , the coulomb amount is set to 80As / dm ² and 20As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 uneven height obtained by the laser microscope on the roughened surface was 1814, which satisfies the conditions of the present invention.

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

Example 9 is the case where the current density of primary particles is set to 55A / dm ² and 1A / dm ² , the coulomb amount is set to 75As / dm ² and 5As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1866, which was satisfied. Conditions of the invention of this case.

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

Example 10 is a case where the current density of primary particles is set to 50A / dm ² and 5A / dm ² , the coulomb amount is set to 70As / dm ² and 10As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1858, which satisfies the conditions of the present invention. Has the following characteristics: no falling powder, normal peel strength is 0.94kg / cm, heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate ) Is less than 30%.

Example 11 is a case where the current density of 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 secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 uneven height obtained by the laser microscope on the roughened surface was 1808, which satisfies the conditions of the present invention.

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

Example 12 is a case where the current density of primary particles is set to 55A / dm ² and 1A / dm ² , the coulomb amount is set to 75As / dm ² and 5As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1861, which satisfies the conditions of the present invention.

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

Example 13 is the case where the current density of primary particles is set to 50A / dm ² and 5A / dm ² , the coulomb amount is 70As / dm ² and 10As / dm ² , and the current density of secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 using a laser microscope was 1858, which satisfies the conditions of the present invention. Has the following characteristics: no falling powder, normal peel strength is 0.94kg / cm, heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate ) Is less than 30%.

Example 14 is a case where the current density of primary particles is set to 60A / dm ² and 15A / dm ² , the coulomb amount is set to 80As / dm ² and 20As / dm ² , and secondary particles are formed (secondary Particle layer) The current density was set to 20 A / dm ² , and the Coulomb amount was set to 60 As / dm ² to perform plating (normal plating), and then the current density was set to 20 A / dm ² , and the Coulomb amount was set to 20As / dm ² to form particles.

As a result, the average particle diameter of the primary particles was 0.35 μm, and the secondary particles became coated (normal). The two-stage configuration of the plating state (particle diameter is less than 0.1 μm) and the average particle diameter of 0.15 μm. The average value of the uneven height of the roughened surface obtained by a laser microscope is 1751, which satisfies the conditions of the present invention. It has the following characteristics: no falling powder, normal peel strength is 0.84kg / cm, heat resistance degradation rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate ) Is less than 30%.

Example 15 is a case where the current density of forming 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 forming secondary particles is set. It was set to 25 A / dm ² and the coulomb amount was set 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 uneven height obtained by the laser microscope on the roughened surface was 1805, which satisfies the conditions of the present invention.

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

In contrast, the comparative example has the following results.

Comparative Example 1 is a case where the current density of 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 no secondary particles were formed. As a result, the average particle diameter of the primary particles was 0.50 μm, and the average value of the uneven height obtained by the laser microscope on the roughened surface was 2001, which satisfies the conditions of the present invention. There is no powder falling, and the normal peeling strength is 1.38 kg / cm, which is an example level. However, the deterioration rate of heat resistance (after the normal peeling measurement, the peel strength after heating at 180 ° C. for 48 hours was measured, and the difference was set as the deterioration rate) was 60%, which was significantly inferior. The overall evaluation of copper foil for high-frequency circuits was poor.

Comparative Example 2 shows a conventional example in which there is no primary particle size and only a secondary particle layer. That is, it is a case where the current density for forming secondary particles is 50 A / dm ² and the coulomb amount is 30 As / dm ² .

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

Coarse particles produce a large amount of falling powder. Normal peel strength is 1.25 kg / cm, and heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate) is less than 30% Is the embodiment level. As described above, there is a problem that a large amount of powder falls, so the overall evaluation of the copper foil for high-frequency circuits as a whole is poor.

Comparative Example 3 is a case where the current density of primary particles is set to 63A / dm ² and 1A / dm ² , the coulomb amount is 80As / dm ² and 2As / dm ² , and the current density of secondary particles is set. It was set to 28 A / dm ² , and the coulomb amount was set 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 of the roughened surface obtained by the laser microscope was 1298, which did not satisfy the conditions of the present invention. Generates a large amount of falling powder. Normal peel strength is 1.42 kg / cm, and heat resistance degradation rate (after normal peel measurement, peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate) is less than 30% , Which is the example level, but generates a large amount of falling powder. The overall evaluation of copper foil for high-frequency circuits was poor.

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

As a result, the average particle diameter of the primary particles was 0.35 μm, and the average particle diameter of the secondary particles was 0.40 μm, the average height of the roughened surface obtained by a 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 degradation rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is the degradation rate) is less than 30% , Which is the example level, but generates a large amount of falling powder. The overall evaluation of copper foil for high-frequency circuits was poor.

Comparative Example 5 is a case where the current density of primary particles is set to 40A / dm ² and 1A / dm ² , the coulomb amount is set to 40As / dm ² and 2As / dm ² , and the current density of secondary particles is set. It was set to 20 A / dm ² , and the coulomb amount was set 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 uneven height of the roughened surface obtained by the laser microscope was 1367, which did not satisfy the conditions of the present invention. Falling powder did not occur. The normal peel strength was 0.71 kg / cm, and the heat resistance degradation rate (the peel strength after heating at 180 ° C. for 48 hours after the normal peel measurement was measured, and the difference was set as the degradation rate) was 35%.

According to the comparison between the above examples and comparative examples, it can be revealed that after a primary particle layer of copper is formed on the surface of a 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 formed secondary particle layer, in a measurement analysis obtained by a laser microscope in a certain region of the roughened surface, the average value of the height of the unevenness of the roughened surface is set to 1500 or more. The excellent effect of stably suppressing the phenomenon called powder falling is further improved, and the peeling strength is improved and the high-frequency characteristics are improved.

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 made of a ternary alloy made of copper, cobalt, and nickel is 0.35 μm or less. Said effect, and further effective.

When Co is contained in the heat-resistant treatment layer, the transmission loss tends to increase.

FIG. 9 shows an image of a computer screen showing the analysis result obtained by the analysis software KVH1A9, which is the average value (convex height) of the height histogram of Example 1. FIG. In FIG. 9, the average value (concave-convex height) of the height histogram is obtained by reading the item “average” (here, expressed as 2688.98) in the upper right table (concentration measurement).

Claims (22)

A copper foil for high-frequency circuits is formed by forming a primary particle layer of copper on the surface of the copper foil, and then forming a secondary particle layer of a ternary alloy of copper, cobalt, and nickel on the primary particle layer. The average value of the uneven height of the roughened surface obtained by the laser microscope measured by the following method is 1500 or more, and the average value of the uneven height of the roughened surface obtained by the laser microscope is determined by the following method The method was set up. For a result obtained by measuring a roughened surface using a laser microscope VK8500 manufactured by Keynes Corporation with a magnification of 1000 times, the measurement analysis of an effective area of 786432 μm ² (100% of the measurement area) was performed. The height of the unevenness was converted into a histogram using the analysis software KVH1A9, and the average value was calculated. For example, the copper foil for high-frequency circuits in the first patent application range, wherein the average particle diameter of the primary particle layer of the copper is 0.25 to 0.45 μm, and the secondary particles are formed of a ternary alloy composed of copper, cobalt, and nickel. The average particle diameter of the layer is 0.35 μm or less. For example, the copper foil for high-frequency circuits in the first item of the patent application scope, wherein the primary particle layer and the secondary particle layer are electroplated layers. For example, the copper foil for high-frequency circuits of the first patent application scope, 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. For example, the copper foil for high-frequency circuits in the first item of the patent application scope, wherein the average value of the uneven height of the roughened surface obtained by a laser microscope is 1500 to 2000. For example, the copper foil for high-frequency circuits in the first patent application range, wherein the peel strength of the primary particle layer and the secondary particle layer is 0.80 kg / cm or more. For example, the copper foil for high-frequency circuits in the first item of the patent application range, wherein the peel strength of the primary particle layer and the secondary particle layer is 0.90 kg / cm or more. For example, the copper foil for high-frequency circuits in the scope of patent application No. 1 is formed on the secondary particle layer: (A) made of Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, and P An alloy layer composed of one or more elements of the group consisting of,, W, Mn, Sn, As, and Ti, and (B) any one or both of a chromate layer. For example, the copper foil for high-frequency circuits in the scope of patent application No. 1 is formed on the secondary particle layer in order: (A) from Ni and selected from Fe, Cr, Mo, Zn, Ta, Cu, Al An alloy layer composed of one or more elements consisting of P, W, Mn, Sn, As, and Ti, and (B) one or both of a chromate layer, and a silane coupling layer. For example, the copper foil for a high-frequency circuit according to item 1 of the application, wherein either or both of a Ni-Zn alloy layer and a chromate layer are formed on the secondary particle layer. For example, the copper foil for high-frequency circuits in the scope of the first patent application, wherein one or both of a Ni-Zn alloy layer and a chromate layer, and a silane coupling are sequentially formed on the secondary particle layer. Floor. For example, the copper foil for a high-frequency circuit according to item 1 of the patent application scope includes a resin layer on the surface of the secondary particle layer. For example, the copper foil for high-frequency circuits according to any one of claims 8 to 11, wherein Ni is selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, A resin layer is provided on the surface of an alloy layer composed of one or more elements consisting of Sn, As, and Ti, or the chromate layer, the silane coupling layer, or the Ni-Zn alloy layer. A copper foil with a carrier, which has an intermediate layer and an ultra-thin copper layer in order on one or both sides of the carrier. The ultra-thin copper layer is copper for high-frequency circuits in any one of the scope of patent applications 1 to 13. Foil. For example, the copper foil with a carrier in the scope of application for patent No. 14 has the intermediate layer, the ultra-thin copper layer in order on one side of the carrier, and the roughening layer on the other side of the carrier. A copper-clad laminated board for a high-frequency circuit uses a copper foil according to any one of claims 1 to 15 of a patent application scope. For example, the copper-clad laminated board for high-frequency circuits of the scope of application for the patent No. 16 is laminated with the copper foil and polyimide, liquid crystal polymer or fluororesin. A printed wiring board for a high-frequency circuit using a copper foil according to any one of claims 1 to 15 of a patent application. For example, the printed wiring board for high-frequency circuits in the scope of application for item 18 uses any one of polyacrylamide, liquid crystal polymer, or fluororesin. An electronic device using a printed wiring board with a scope of patent application No. 18 or 19. A method for manufacturing a printed wiring board includes the following steps: preparing a copper foil with a carrier and an insulating substrate for applying for a patent application item No. 14 or 15; laminating the copper foil with a carrier and an insulating substrate; and After laminating with the insulating substrate, the copper-clad laminated board is formed through the step of peeling the carrier with the copper foil with the carrier, and then any of the semi-additive method, subtractive method, partial additive method, or modified semi-additive method is used. One way to form a circuit. A method for manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier and a copper foil with a carrier; and burying the circuit in the copper foil with a carrier A resin layer is formed on the side surface of the ultra-thin copper layer; a circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and the ultra-thin copper layer is removed after peeling off the carrier, so that The circuit formed on the side surface of the ultra-thin copper layer and buried in the resin layer is exposed.