KR101736537B1 - Copper foil for high frequency circuit, copper clad laminate for high frequency circuit, printed wiring board for high frequency circuit, copper foil attached with carrier for high frequency circuit, electronic device, and method for manufacturing printed wiring board - Google Patents

Abstract

Provided is a copper foil for a high frequency circuit in which transmission loss is suppressed well even when used for a high frequency circuit board and occurrence of dust drop on the surface of the copper foil is satisfactorily suppressed. A copper foil obtained by forming a primary particle layer of copper on the surface of a copper foil and then forming a secondary particle layer of a ternary alloy of copper, cobalt and nickel on the primary particle layer, A copper foil for a high frequency circuit having an average height of unevenness of 1500 or more.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper foil for a high frequency circuit, a copper clad laminate for a high frequency circuit, a printed circuit board for a high frequency circuit, a copper foil with a carrier for a high frequency circuit, CIRCUIT, PRINTED WIRING BOARD FOR HIGH FREQUENCY CIRCUIT, COPPER FOIL ATTACHED WITH CARRIER FOR HIGH FREQUENCY CIRCUIT, ELECTRONIC DEVICE, AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

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

Printed circuit boards have made great strides over the past half century, and today they are used in almost all electronic devices. With recent demands for miniaturization and high performance of electronic apparatuses, mounting of high-density mounting parts and high-frequency signals have progressed, and high-frequency response to printed wiring boards has been demanded.

In order to secure the quality of an output signal, a reduction in transmission loss is required for a high frequency substrate. The transmission loss mainly consists of a dielectric loss caused by a resin (substrate side) and a conductor loss caused by a conductor (copper foil side). The dielectric loss decreases as the dielectric constant and dielectric tangent of the resin become smaller. In the high-frequency signal, the conductor loss is mainly caused by the decrease in the cross-sectional area through which the current flows due to the skin effect that the current does not flow outside the surface of the conductor as the frequency increases.

As a technique for reducing the transmission loss of the high frequency copper foil, for example, Patent Document 1 discloses a technique of coating a silver or silver alloy on one surface or both surfaces of a surface of a metal foil, And a coating layer other than silver or silver alloy is coated thinner than the thickness of the silver or silver alloy coating layer. According to this, it is described that a metal foil having a reduced loss due to the skin effect can be provided even in a very high frequency region used in satellite communication.

Patent Document 2 discloses that the integrated intensity (I (200)) of the (200) plane obtained by X-ray diffraction on the rolled surface after the recrystallization annealing of the rolled copper foil is smaller than the integral intensity (200) / I0 (200) > 40 with respect to the integral intensity (I0 (200)), and the arithmetic average roughness (hereinafter referred to as " roughness ") of the roughened surface after subjected to roughening treatment by electrolytic plating (Hereinafter, referred to as Ra) is 0.02 to 0.2 μm, and 10-point average roughness (hereinafter referred to as Rz) is 0.1 to 1.5 μm, is a material for a printed circuit board. . According to this, it is possible to provide a printed circuit board which can be used under high frequencies exceeding 1 GHz.

Further, Patent Document 3 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is an irregular surface having a surface roughness of 2 탆 to 4 탆, which is formed by a lump-like projection. According to this, it is described that an electrolytic copper foil having excellent high-frequency transmission characteristics can be provided.

Japanese Patent Publication No. 4161304 Japanese Patent Publication No. 4704025 Japanese Patent Application Laid-Open No. 2004-244656

The conductor loss caused by the conductor (copper foil side) is caused by the fact that resistance increases due to the skin effect as described above. However, this resistance is not limited to the resistance of the copper foil itself, It is known that the surface roughness of the surface of the copper foil is a main factor of the conductor loss and that the transmission loss decreases as the roughness becomes smaller.

The present inventors further investigated the relationship between the roughness of the surface of the copper foil and the transmission loss. As a result, it was found that the lower the roughness of the surface of the copper foil, the more the transmission loss was not reduced. , It is found that the relationship between the reduction of the transmission loss and the roughness of the surface of the copper foil shows a remarkable variation and it is difficult to reduce the transmission loss well only by controlling the roughness of the surface of the copper foil.

Although the formation of the cobalt-nickel alloy plating layer is known as the roughening treatment of the surface of the copper foil, the copper foil on which the conventional cobalt-nickel alloy plating layer is formed has the shape of the roughened particles formed of the copper-cobalt- Since the resin is ground, it peels off from the top or the root of the resin, and generally causes a phenomenon called a powder falling phenomenon.

This powder dripping phenomenon is a troublesome problem, and the roughened layer of the copper-cobalt-nickel alloy plating is characterized in that it has excellent heat resistance, but the particles easily fall off due to external force, , Contamination of the roll by the peeling powder, and etching residue due to the peeling powder.

Therefore, it is an object of the present invention to provide a high-frequency circuit device capable of suppressing transmission loss even when used in a high-frequency circuit board, and also capable of suppressing the phenomenon that coarse particles formed on the surface of the copper foil are peeled off from the surface, It is an object of the present invention to provide a copper foil.

The inventors of the present invention found that it is preferable to form a predetermined roughening particle layer on the surface of the extremely thin copper layer of the copper foil with the carrier and to control the average value of the height of the roughened surface of the roughening particle layer, Suppressing the occurrence of cracks on the surfaces of the copper foil, and suppressing the dropping of the powder on the surface of the copper foil.

A primary particle layer of copper is formed on the surface of a copper foil on one side, and then a ternary alloy of copper, cobalt and nickel is formed on the primary particle layer. Wherein the average height of the unevenness of the roughened surface by the laser microscope is 1500 or more.

The copper foil for a high-frequency circuit according to one embodiment of the present invention is characterized in that the average particle diameter of the primary particle layer of the copper is 0.25 to 0.45 mu m and the average particle diameter of the secondary particle layer made of a ternary alloy of copper, cobalt and nickel is 0.35 Mu m or less.

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

The copper foil for a high-frequency circuit of the present invention is a copper foil for a high-frequency circuit according to still another embodiment, wherein the secondary particles are particles of one or a plurality of branches grown on the primary particles or a normal plating layer grown on the primary particles.

In another embodiment of the copper foil for a high frequency circuit according to the present invention, the average value of the unevenness heights of the roughened surface by a laser microscope is 1500 or more and 2000 or less.

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

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

In the copper foil for a high-frequency circuit according to another embodiment of the present invention, on the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn,

(B) a chromate layer

Or both of them are formed.

In the copper foil for a high-frequency circuit according to another embodiment of the present invention, on the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn,

(B) a chromate layer

Or both,

The silane coupling layer

Are formed in this order.

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

In the copper foil for a high-frequency circuit according to another embodiment of the present invention, either one or both of a Ni-Zn alloy layer and a chromate layer and a silane coupling layer are formed in this order on the secondary particle layer .

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

The copper foil for a high-frequency circuit according to the present invention is a copper foil for a high-frequency circuit, wherein the Ni is at least one selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, An alloy layer comprising at least two kinds of elements, or a chromate layer, a silane coupling layer, or a resin layer on the surface of the Ni-Zn alloy layer.

According to another aspect of the present invention, there is provided a copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of a carrier, wherein the ultra- It is a copper foil with a carrier which is a copper foil.

In one embodiment, the copper foil with a carrier according to the present invention has the intermediate layer and the ultra-thin copper layer on one surface of the carrier in this order, and the other surface of the carrier has a roughened treatment layer.

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

In another aspect, the present invention is a printed circuit board for a high frequency circuit using the copper foil of the present invention.

In one embodiment of the copper-clad laminate for high frequency circuit of the present invention, the copper foil and polyimide, liquid crystal polymer or fluorine resin are laminated.

According to another aspect of the present invention, there is provided a printed wiring board for a high frequency circuit using the polyimide, the liquid crystal polymer or the fluorine resin.

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

According to another aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising the steps of preparing a copper foil and an insulating substrate,

A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,

After the step of laminating the copper foil on which the carrier is adhered and the insulating substrate is peeled off from the carrier of the copper foil on which the carrier is adhered to form a copper clad laminate,

And thereafter forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, and a modified semi-additive method.

According to another aspect of the present invention, there is provided a method for manufacturing a copper-clad laminate, comprising the steps of: forming a circuit on the surface of the copper-

Forming a resin layer on the ultra-thin copper layer side surface of the copper foil on which the carrier is adhered so that the circuit is buried,

A step of forming a circuit on the resin layer,

A step of forming a circuit on the resin layer and thereafter peeling the carrier,

And removing the ultra-thin copper layer after the carrier is peeled to expose a circuit buried in the resin layer formed on the surface of the extremely thin copper layer side.

According to the present invention, it is possible to suppress the occurrence of a phenomenon in which harmful particles formed on the surface of the copper foil are peeled off from the surface of the copper foil, that is, occurrence of so-called " Can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram showing the state of powder dropping when a conventional copper foil is subjected to a roughening treatment of copper-cobalt-nickel alloy plating.
Fig. 2 is a conceptual illustration of a copper-clad treatment layer of the present invention, in which a primary particle layer is formed on a copper foil in advance and a secondary particle layer made of copper-cobalt-nickel alloy plating is formed on the primary particle layer, .
Fig. 3 is a micrograph of the surface of a conventional copper foil subjected to a roughening treatment of copper-cobalt-nickel alloy plating.
Fig. 4 is a graph showing the relationship between the thickness of the copper-cobalt-nickel alloy plating layer and the thickness of the copper-cobalt-nickel alloy layer of the present invention, in which the primary particle layer is previously formed on the copper foil, It is a microscopic photograph.
5A to 5C are schematic views of a wiring board section in a process up to circuit plating and resist removal according to a specific example of a method for manufacturing a printed wiring board using the copper foil with a carrier according to the present invention.
Figs. 6D to 6F are cross-sectional views illustrating a method of manufacturing a printed wiring board using the copper foil with a carrier according to the present invention, It is a schematic diagram.
Figs. 7G to I are schematic views of a wiring board section in a process from a non-appealing formation to a carrier peeling of a first layer, according to a concrete example of a production method of a printed wiring board using the copper foil with a carrier according to the present invention.
Figs. 8J to K are schematic views of a wiring board section in a process from flash etching to bump-copper filler formation, according to a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
9 is an image of a computer screen showing the result of analysis by the analysis software KVH1A9 of the mean value (ruggedness height) of the height histogram of the first embodiment.
10 is an example of the operation screen displayed in "DISTANCE · PITCH setting" on page 4-3 of the VK-8500 Users Manual of analysis software KVH1A9.

The form of the copper foil substrate usable in the present invention is not particularly limited. Typically, the copper foil used in the present invention may be an electrolytic copper foil or a rolled copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Rolled copper foil is often applied to applications requiring flexibility.

As the material of the copper-clad base material, for example, Sn-containing copper, Ag-containing copper, copper alloy containing Cr, Zr or Mg, etc., other than copper of high purity such as tough pitch copper or anaerobic copper commonly used as a conductor pattern of a printed wiring board , A copper alloy such as a Colson type copper alloy to which Ni and Si are added. In the present specification, when the term " copper foil " is used alone, copper alloy foil is also included.

The thickness of the copper foil substrate is not particularly limited, but may be, for example, 1 to 1000 占 퐉, 1 to 500 占 퐉, 1 to 300 占 퐉, 3 to 100 占 퐉, 5 to 70 占 퐉, 35 mu m, or 9 to 18 mu m.

In another aspect of the present invention, there is provided a copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order, the copper foil having a carrier, wherein the ultra-thin copper layer is a copper foil for a high frequency circuit of the present invention. That is, in another aspect of the present invention, a copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order on which a carrier is attached may be used as the copper foil substrate. In the present invention, when a copper foil with a carrier is used, a surface treatment layer such as the following roughening treatment layer is formed on the surface of the ultra-thin copper layer. Further, another embodiment of the copper foil on which the carrier is attached will be described later.

Conventionally, the surface of the copper foil to be adhered to the resin base, that is, the roughened surface, is subjected to a roughening treatment for electrodeposition of " tuck " shape on the surface of the copper foil after degreasing in order to improve the strength . The electrolytic copper foil has irregularities at the time of manufacture, but the convex portions of the electrolytic copper foil are strengthened by the roughening treatment to further increase the irregularities. Conventional copper plating or the like may be applied as a pretreatment before conditioning, and copper plating or the like may be performed in order to prevent electrodeposition from coming off as a post-conditioning finishing treatment.

In the present invention, known processes relating to the copper foil harmonization, including the pretreatment and the finishing process, are referred to as " harmonization process "

In order to clarify the difference from the previous step, the roughening treatment of the copper-cobalt-nickel alloy plating is referred to as " 2 (Hereinafter referred to as " copper particle layer "). As described above, simply forming a copper-cobalt-nickel alloy plating layer on a copper foil causes problems such as powder falling as described above.

FIG. 3 shows a micrograph of the surface of the copper foil having the copper-cobalt-nickel alloy plating layer formed on the copper foil. As shown in Fig. 3, fine particles that have developed to the ground can be seen. In general, fine particles as shown in Fig. 3 and developed to the ground are fabricated at a high current density.

When treated at such a high current density, the nucleation of particles in the initial electrodeposition is inhibited, and nuclei of new particles are formed at the tip of the particles, so that the particles grow gradually and gradually to the ground.

Therefore, in order to prevent this, when the current density is lowered and electroplating is performed, sharp rise is eliminated, particles increase, and rounded particles grow. Even under such circumstances, however, the powder drop is slightly improved, but sufficient fill strength can not be obtained, which is not sufficient to achieve the object of the present invention.

Fig. 3 is a conceptual explanatory view of Fig. 1 showing a state in which the copper-cobalt-nickel alloy plating layer shown in Fig. 3 is formed. The reason for the dropping of the powder is that fine particles are generated on the copper foil on the copper foil as described above. Particles on the branches are likely to be broken by an external force and fall off from the root. This fine grain-like particle causes peeling due to "squeezing" in processing, contamination of the roll due to peeling powder, and etching residue due to peeling powder.

In the present invention, a primary particle layer of copper is formed on the surface of a copper foil in advance, and then a secondary particle layer made of a ternary alloy made of copper, cobalt and nickel is formed on the primary particle layer. A micrograph of the surface of the copper foil on which the primary particles and the secondary particles are formed is shown in Fig. 4 (details will be described later).

Thereby, it is possible to suppress the phenomenon of peeling due to " squeeze " during processing, fouling of rolls due to peeling powder, disappearance of etching residue due to peeling powder, that is, falling of powder, The copper foil for a high frequency circuit can be obtained.

It is preferable that the mean particle diameter of the primary particle layer is 0.25 to 0.45 mu m and the average particle diameter of the secondary particle layer made of a ternary alloy composed of copper, cobalt and nickel is 0.35 mu m or less, It is an optimal condition to prevent falling. The lower limit of the average particle size of the primary particle layer is preferably at least 0.27 탆, preferably at least 0.29 탆, more preferably at least 0.30 탆, and still more preferably at least 0.33 탆. The upper limit of the average particle diameter of the primary particle layer is preferably 0.44 占 퐉 or less, preferably 0.43 占 퐉 or less, preferably 0.40 占 퐉 or less, and preferably 0.39 占 퐉 or less. The upper limit of the average particle size of the secondary particle layer is preferably 0.34 μm or less, preferably 0.33 μm or less, preferably 0.32 μm or less, preferably 0.31 μm or less, preferably 0.30 μm or less, 0.28 mu m or less, preferably 0.27 mu m or less. The lower limit of the average particle diameter of the secondary particle layer is not particularly limited, but may be, for example, 0.001 m or more, or 0.01 m or more, or 0.05 m or more, or 0.09 m or more, or 0.10 m or more, Or 0.15 탆 or more.

The primary particle layer and the secondary particle layer are formed by an electroplating layer. This secondary particle is characterized by one or a plurality of branch-like particles grown on the primary particles. Or a normal plating grown on the primary particles. That is, in the present specification, when the term " secondary particle layer " is used, a normal plating layer such as coated plating is also included. The secondary particle layer may be a layer having one or more layers formed by coarsely grained grains, a layer having one or more normal plating layers, or a layer having one or more normal plating layers .

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

More importantly, in the copper foil in which the primary particle layer and the secondary particle layer are formed, the average value of the height of the unevenness of the roughed surface by the laser microscope is 1500 or more, preferably 1,600 or more, preferably 1,700 or more, Or more, and more preferably, 1900 or more. The upper limit of the average value of the concavity and convexity of the roughened surface by the laser microscope is not particularly limited, but is, for example, 4500 or less, or 3500 or less, or 3100 or less, or 3000 or less, or 2900 or less, or 2800 or less.

A feature of the present invention resides in that a harmonized treatment layer in which a primary particle layer and a secondary particle layer are formed is formed. The harmonized treatment layer has a structure in which a small secondary particle layer The state in which one or two layers are formed is in an ideal state. In reality, there are cases where primary particles and secondary particles are stacked in multiple stages, and complex layers are formed, and it is difficult to estimate the height of the layer from the particle diameter. As a general tendency, for example, in the case of forming secondary particles having the same size as or larger than that of the primary particles in a slightly smaller primary particle and forming a slightly smaller secondary particle in a slightly larger primary particle , But it is difficult to specifically control this combination. Thus, in the present invention, it is possible to provide a stable and stable image by controlling the macroscopic index of the average value of the concavity and convexity of the roughened surface by the laser microscope and by controlling this to control the detailed structure of the combination of the primary particle and the secondary particle It is possible to form a roughened treatment layer having an effect of improving the peel strength and preventing the stable powder falling phenomenon. The " roughened surface " in the " average value of the concavity and convexity of the roughened surface by the laser microscope " means the surface of the final product and means the top surface of the side on which the primary particle layer and the secondary particle layer are formed do. When a surface treatment layer such as a heat resistant layer, a rust preventive layer or a silane coupling treatment layer is formed on the secondary particle layer, it means the outermost surface of the surface treated layer. When a " resin layer " to be described later is formed, it means the outermost surface of the primary particle layer and the side on which the secondary particle layer is formed of the copper foil excluding the resin layer.

When the average value of the concavo-convex height of the roughened surface by the laser microscope is less than 1,500, in the copper foil in which the primary particle layer and the secondary particle layer are formed, the secondary particle layer is superimposed, The powder falling phenomenon tends to occur.

The measurement of the average value of the concavo-convex height of the roughened surface by the laser microscope was carried out using a laser microscope VK8500 manufactured by Keith Co., Ltd., with a magnification of 1000 times, and an effective area of 786432 mu m The measurement area 100%), the height of the ruggedness is made into a histogram by using the analysis software KVH1A9, and the setting is performed by a method of obtaining the average value.

On the secondary particle layer,

(A) an alloy layer comprising at least one element selected from the group consisting of Ni and Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti, One or both of the layers may be formed.

(A) an alloy consisting of at least one element selected from the group consisting of Ni, Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti on the secondary particle layer Layer, and (B) the chromate layer, and the silane coupling layer may be formed in this order.

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

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

According to such a configuration, it is possible to improve the high frequency transmission characteristic while maintaining the peel strength.

[Transmission Loss]

When the transmission loss is small, attenuation of the signal at the time of performing signal transmission at a high frequency is suppressed, so that it is possible to perform stable signal transmission in a circuit for transmitting a signal at a high frequency. Therefore, it is preferable that the value of the transmission loss is small because it is suitable for use in a circuit application for transmitting a high-frequency signal. The surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 mu m, manufactured by Kuraray Co., Ltd.), and microstrip lines were formed so as to have a characteristic impedance of 50 ohms by etching. When the transmission coefficient is measured using the network analyzer HP8720C and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is obtained, a transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm, and a transmission loss of 4.1 dB / 10 cm is more preferable, and less than 3.7 dB / 10 cm is even more preferable.

The surface-treated copper foil of the present invention can be laminated on the resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has properties applicable to a printed wiring board and the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber base epoxy resin, a glass cloth, Resin, glass cloth, glass nonwoven fabric composite base epoxy resin, glass cloth base epoxy resin and the like can be used, and polyester film, polyimide film, liquid crystal polymer (LCP) film, fluorine resin and the like can be used for FPC. In addition, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the film strength of the film and the surface-treated copper foil tends to be smaller than that in the case of using a polyimide film. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the copper circuit is covered with the cover layer after the formation of the copper circuit, thereby making it difficult for the film and the copper circuit to peel off, The peeling of the film and the copper circuit can be prevented.

Since the liquid crystal polymer (LCP) film or the fluororesin film has a small dielectric loss tangent, the copper clad laminate, the printed wiring board and the printed circuit board using the liquid crystal polymer (LCP) film or the fluororesin film and the surface- Circuit (a circuit for transmitting a signal at a high frequency). The surface-treated copper foil according to the present invention has a surface roughness Rz of a small value and a high gloss, so that the surface is smooth and suitable for use in a high-frequency circuit.

In the case of the rigid PWB, the prepreg is prepared by impregnating a base material such as glass cloth with resin and hardening the resin to a semi-hardened state. The copper foil is superimposed on the prepreg from the opposite surface side of the coating layer and is heated and pressed. In the case of an FPC, a laminate is produced by applying an adhesive to a substrate such as a polyimide film, or by laminating the laminate to a copper foil under high temperature and high pressure without using an adhesive, or by applying a polyimide precursor, can do.

The laminate of the present invention can be applied to various printed wiring boards (PWB) and is not particularly limited. For example, it can be applied to single-sided PWB, double-sided PWB, multilayer PWB (three or more layers) And is applicable to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of kinds of insulating substrate materials.

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

An electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic device is mounted, and an electronic device may be manufactured using the printed board on which the electronic device is mounted .

(Plating conditions of primary particles of copper)

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

This plating condition is a preferable example only, and the average particle diameter formed on the copper foil of the primary particles of copper plays a role of prevention of fall of the powder. Therefore, if the average particle size falls within the range of the present invention, plating conditions other than those shown below are not inhibited at all. The present invention includes these.

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Liquid temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Culm volume: 4 ~ 81 As / d㎡

(Plating conditions of secondary particles)

In the same manner as described above, this plating condition is a preferable example. Secondary particles are formed on the primary particles, and the average particle diameter plays a role of prevention of dropping of the powder. Therefore, if the average particle size falls within the range of the present invention, plating conditions other than those shown below are not inhibited at all. The present invention includes these.

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Liquid temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Culm volume: 34 ~ 48 As / d㎡

(Plating condition 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 to 20 g / l, cobalt 1 to 8 g / l

pH: 2-3

Liquid temperature: 40 ~ 60 ℃

Current density: 5 to 20 A / dm 2

Culm volume: 10 ~ 20 As / d㎡

(Plating conditions for forming the 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: 2 to 30 g / l of nickel, 2 to 30 g / l of zinc

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Plating condition for forming the heat resistant layer 3) (NiCu 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: 2 to 30 g / l of nickel, 2 to 30 g / l of copper

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(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: sulfuric acid Ni6 hydrate: 45 to 55 g / dm3, sodium molybdate dihydrate: 50 to 70 g / dm3, sodium citrate: 80 to 100 g / dm3

Liquid temperature: 20 ~ 40 ℃

Current density: 1 to 4 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(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 - 30 g / ℓ, Tin 2 - 30 g / ℓ

pH: 1.5 to 4.5

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Plating condition for forming the heat resistant layer 6) (Ni-P plating: Nickel 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: 30 to 70 g / l of nickel, 0.2 to 1.2 g / l of phosphorus

pH: 1.5 to 2.5

Liquid temperature: 30 ~ 40 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Plating condition 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. The plating conditions are shown below.

Liquid composition: nickel 2 to 30 g / l, W 0.01 to 5 g / l

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Plating condition 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 plating layer was formed using a sputtering target having a composition of Ni: 65 to 85 mass% and Cr: 15 to 35 mass%.

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

Apparatus: Sputtering apparatus manufactured by Erica Co., Ltd.

Output: DC50W

Argon pressure: 0.2 Pa

(Plating conditions for forming a rust preventive layer)

The present invention can further form the following rust preventive layer. The plating conditions are shown below. In the following, the conditions of the immersion chromate treatment are shown, but electrolytic chromate treatment may also be employed.

Liquid composition: Potassium dichromate 1 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Liquid temperature: 50 ~ 60 ℃

Current density: 0 to 2 A / dm 2 (0 A / dm 2 is for immersion chromate treatment)

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

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

As an example, application of an aqueous solution of diaminosilane can be mentioned.

Further, when a metal layer such as a heat resistant layer, a plating layer formed by dry plating such as sputtering, and a metal layer such as a heat resistant layer or a plating layer formed by wet plating, a metal layer such as a heat resistant layer, In the case of normal plating (smoothing plating, that is, plating performed at a current density less than the critical current density), the metal layer and the plating layer do not affect the shape of the surface of the copper foil.

The limiting current density varies depending on the metal concentration, the pH, the liquid supply speed, the distance between the electrodes, and the temperature of the plating solution. In the present invention, the normal plating (the state in which the plated metal is deposited in layers) and the plating (baking plating, The current density at the boundary of the crystalline phase (the state of being precipitated in spherical, needle-like, or ice-tree), irregularities) is defined as the limiting current density. (Visual judgment) of the current density is defined as the limiting current density.

More specifically, the metal concentration, the pH, and the plating solution temperature are set as plating conditions, and the hullell test is performed. Then, the composition of the plating solution and the state of metal layer formation at the plating solution temperature (whether the plated metal is deposited in a layer or in a crystal phase) are examined. Based on the current density chart of the Yamamoto plating tester manufactured by the corporation, the current density at the position of the boundary of the test piece is obtained from the position of the test piece at the boundary between the normal plating and the plating plating of the test piece. Then, the current density at the position of the boundary is defined as the limiting current density. Thus, the composition of the plating solution and the critical current density at the plating solution temperature can be found. Generally, when the inter-pole distance is short, the threshold current density tends to increase.

The method of the Hulcel test is described in, for example, "Practice of Plating Practice", Kiyoshi Maruyama, Journal of Industrial Daily Newspaper, June 30, 1983, pp. 157-160.

In order to perform the plating treatment at a current density lower than the critical current density, the current density at the plating treatment is preferably 20 A / dm 2 or less, more preferably 10 A / dm 2 or less, more preferably 8 A / Or less.

Further, the chromate layer and the silane coupling layer have an extremely small thickness, so that the shape of the surface of the copper foil is not affected.

The copper-cobalt-nickel alloy plating as the secondary particles may be formed by electrolytic plating in an amount of 10 to 30 mg / dm 2 of copper-100 to 3000 μg / dm 2 of cobalt-50 to 500 μg / An alloy layer can be formed.

When the Co deposition amount is less than 100 占 퐂 / dm2, the heat resistance is deteriorated and the etching property is also deteriorated. When the Co deposition amount exceeds 3,000 占 퐂 / dm2, it is not preferable when the effect of magnetism must be taken into consideration. Etching unevenness occurs and deterioration of acid resistance and chemical resistance can be considered.

When the Ni adhesion amount is less than 50 占 퐂 / dm2, the heat resistance is deteriorated. On the other hand, if the Ni deposition amount exceeds 500 / / dm 2, the etching property is lowered. That is, etching residues are formed and the etching is not at a level that can not be performed, but fine patterning becomes difficult. The preferable Co deposition amount is 500 to 2000 占 퐂 / dm2, and the preferable nickel deposition amount is 50 to 300 占 퐂 / dm2.

From the above, it can be said that the adhesion amount of the copper-cobalt-nickel alloy plating is preferably 10 to 30 mg / dm 2 copper-100 to 3000 μg / dm 2 cobalt-50 to 500 μg / dm 2 nickel. The deposition amount of the ternary alloy layer is a preferable condition, and the range exceeding this amount is not denied.

Here, the term "etching unevenness" means that when Co is etched with copper chloride, Co remains unmelted, and the etching residue means that Ni remains unmelted when subjected to alkali etching with ammonium chloride.

In general, when a circuit is formed, an alkaline etching solution and a copper chloride etching solution described in the following embodiments are used. Although the etchant and the etching conditions are versatile, it is to be understood that they are not limited to these conditions and can be arbitrarily selected.

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

In this cobalt-nickel alloy plating layer, the adhesion amount of cobalt is 200 to 3000 占 퐂 / dm2, and the ratio of cobalt is preferably 60 to 66 mass%. This treatment can be seen as a kind of rust treatment in a broad sense.

This cobalt-nickel alloy plating layer needs to be carried out to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 占 퐂 / dm2, the heat peel strength is lowered, the oxidation resistance and the chemical resistance are deteriorated, and the treated surface becomes reddish.

When the amount of cobalt adhered exceeds 3000 占 퐂 / dm2, it is not preferable when the effect of magnetic property must be taken into consideration, and etching unevenness is caused, and acid resistance and chemical resistance deteriorate. The preferred cobalt deposition amount is 400 to 2500 占 퐂 / dm2.

In addition, if the amount of cobalt adhered is large, the soft etching may cause blurring. In this respect, it can be said that the ratio of cobalt is preferably 60 to 66 mass%.

As described later, a direct cause of occurrence of smearing of soft etching is a heat-resistant anticorrosion layer made of a zinc-nickel alloy plating layer, but there is also a case where cobalt causes blurring at the time of soft etching. Is more preferable.

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

The present invention can further form a zinc-nickel alloy plating layer on the cobalt-nickel alloy plating. The total amount of the zinc-nickel alloy plating layer is 150 to 500 占 퐂 / dm 2, and the proportion of nickel is 16 to 40% by mass. This has a role of a heat-resistant rust-preventive layer. This condition is also a preferable condition, and other known zinc-nickel alloy platings can be used. It will be understood that this zinc-nickel alloy plating is a preferable additional condition in the present invention.

The processing performed in the circuit manufacturing process becomes higher in temperature, and there is heat generation during use of the device after the product becomes a product. For example, in a so-called two-layer material in which a copper foil is bonded to a resin by thermocompression bonding, heat is applied at 300 占 폚 or more at the time of bonding. In such a situation, it is necessary to prevent the lowering of the bonding force between the copper foil and the resin substrate, and the zinc-nickel alloy plating is effective.

In the conventional technique, in a minute circuit including a zinc-nickel alloy plating layer in a two-layer material in which a copper foil is bonded to a resin by thermocompression bonding, discoloration due to smearing occurs at the edge of the circuit during soft etching do. Nickel has an effect of suppressing the bleeding of an etching agent (H ₂ SO ₄ : 10 wt%, H ₂ O ₂ : 2 wt% of an etching aqueous solution) used in soft etching.

As described above, the total amount of the zinc-nickel alloy plating layer is 150 to 500 占 퐂 / dm2, the lower limit of the nickel content in the alloy layer is 16 mass%, the upper limit is 40 mass% When the content is set to 50 占 퐂 / dm2 or more, it has a role as a heat-resistant anticorrosion layer and also suppresses the bleeding of the etching agent used in soft etching and prevents the weakening of the bonding strength of the circuit due to corrosion Effect.

When the total amount of the zinc-nickel alloy plating layer is less than 150 mu g / dm < 2 >, the heat resistance deteriorates and it is difficult to play a role as a heat resistant rust preventive layer. There is a tendency to get worse.

When the lower limit of the nickel percentage in the alloy layer is less than 16 mass%, the amount of bleeding during soft etching exceeds 9 占 퐉, which is not preferable. The upper limit of the nickel content of 40% by mass is a technical limit for forming a zinc-nickel alloy plating layer.

As described above, in the present invention, a cobalt-nickel alloy plating layer, and further, a zinc-nickel alloy plating layer can be sequentially formed on a copper-cobalt-nickel alloy plating layer as a secondary particle layer. The total amount of cobalt and nickel deposited on these layers may be adjusted. Cobalt is 300 to 4000 占 퐂 / dm2, and the total amount of nickel is 100 to 1,500 占 퐂 / dm2.

If the total adhesion amount of cobalt is less than 300 占 퐂 / dm2, heat resistance and chemical resistance are lowered. If the total adhesion amount of cobalt exceeds 4000 占 퐂 / dm2, etching unevenness may occur and transmission loss may increase . When the total amount of nickel deposited is less than 100 占 퐂 / dm2, heat resistance and chemical resistance may be lowered. If the total deposition amount of nickel exceeds 1500 占 퐂 / dm2, etching residues may be generated and the transmission loss may increase.

Preferably, the total deposition amount of cobalt is 300 to 3500 占 퐂 / dm2, more preferably 300 to 3000 占 퐂 / dm2, more preferably 300 to 2500 占 퐂 / dm2, still more preferably 300 to 2000 占 퐂 / dm < 2 >, and the total deposition amount of nickel is preferably 100 to 1,000 mu g / dm < 2 >, more preferably 100 to 900 mu g / dm & If the above conditions are satisfied, it is not particularly limited to the conditions described in this paragraph.

Thereafter, rust-preventive treatment is carried out, if necessary. The rust-preventive treatment preferable in the present invention is a film treatment of chromium oxide alone or a treatment of a mixture of chromium oxide and zinc / zinc oxide. The treatment of the mixture of chromium oxide and zinc / zinc oxide is a treatment of zinc or a rust-preventive layer of a zinc-chromium group mixture composed of zinc oxide and chromium oxide by electroplating using a zinc salt or a plating bath containing zinc oxide and chromate .

Representative examples of the plating bath include K ₂ Cr ₂ O ₇ , Na ₂ Cr ₂ O ₇ Such as dichromate or CrO ₃ And at least one water-soluble zinc salt such as ZnO, ZnSO ₄ .7H ₂ O, and an alkali hydroxide is used. Typical examples of plating bath composition and electrolysis conditions are as follows.

The thus obtained copper foil has excellent heat resistance peel strength, oxidation resistance and hydrochloric acid resistance. In addition, a circuit with a circuit width of 150 μm pitch or less can be etched with a CuCl ₂ etchant, and alkali etching can be performed. In addition, it is possible to suppress the blur on the circuit edge portion at the time of soft etching.

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

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

The copper foil obtained in the whole process has black to gray. Black to gray are meaningful in terms of high alignment accuracy and high heat absorption rate. For example, a circuit board including a rigid board and a flexible board mounts components such as ICs, resistors, and capacitors in an automatic process, and chip mounting is carried out while a circuit is being read by the sensor. At this time, there is a case where alignment is performed on the copper foil-processed surface through a film such as a capton. The positioning in the formation of the through holes is also the same.

The closer the processing surface is to black, the better the absorption of light, and hence the higher the accuracy of positioning. Further, in the case of manufacturing a substrate, the copper foil and the film are often cured while adhering to heat. At this time, when heating is performed by using long-wave such as far-infrared ray or infrared ray, the color tone of the processed surface is black, and the heating efficiency is improved.

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

The application method may be spraying by spraying a silane coupling agent solution, coating with a coater, dipping, or pouring. For example, Japanese Patent Laid-Open No. 60-15654 discloses that the adhesion between a copper foil and a resin substrate is improved by performing a chromate treatment on the roughened surface side of the copper foil and then performing a silane coupling agent treatment. See this for details. Thereafter, if necessary, annealing may be performed for the purpose of improving the ductility of the copper foil.

[Copper with carrier attached]

The copper foil with the carrier, which is another embodiment of the present invention, has an intermediate layer and an ultra-thin copper layer in this order on one surface of the carrier or on both surfaces thereof. The ultra-thin copper layer is a copper foil for a high-frequency circuit, which is one embodiment of the present invention described above.

<Carrier>

The carrier that can be used in the present invention is typically a metal foil or a resin film and may be a metal foil or a resin film such as a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, a steel foil, an iron alloy foil, a stainless steel foil, And is provided in the form of a film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film or the like).

As the carrier usable in the present invention, it is preferable to use a copper foil. This is because the copper foil has a high electrical conductivity, which facilitates formation of the intermediate layer and the extremely thin copper layer thereafter. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Examples of the material of the copper foil include copper of high purity such as tough pitch copper and oxygen free copper, copper such as Sn-containing copper, Ag-containing copper, copper alloy containing Cr, Zr or Mg, Copper alloys such as alloys may also be used.

The thickness of the carrier which can be used in the present invention is not particularly limited, but it may be suitably adjusted to a suitable thickness for fulfilling its role as a carrier, for example, 5 mu m or more. However, if it is too thick, the production cost becomes high, and therefore, it is generally preferable to be 35 mu m or less. Thus, the thickness of the carrier is typically 12 to 70 占 퐉, and more typically 18 to 35 占 퐉.

The roughening treatment layer may be formed on the surface of the carrier opposite to the surface on which the extremely thin copper layer is formed. The roughening treatment layer may be formed using a known method, or may be formed by the roughening treatment described above. The roughening treatment layer is formed on the surface of the carrier opposite to the surface on which the extremely thin copper layer is formed because when the carrier is laminated on a support such as a resin substrate from the surface side having the roughened treatment layer, It has an advantage that it becomes difficult to peel off.

<Middle layer>

An intermediate layer is formed on the carrier. Another layer may be formed between the carrier and the intermediate layer. The intermediate layer used in the present invention is a structure in which the ultra-thin copper layer is difficult to peel off from the carrier before the step of laminating the copper foil with the carrier to the insulating substrate, while the ultra-thin copper layer is peelable from the carrier after the laminating step to the insulating substrate Is not particularly limited. For example, the intermediate layer of the copper foil with the carrier of the present invention may contain at least one selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, Or one or more selected from the group consisting of The intermediate layer may be a plurality of layers.

For example, the intermediate layer may be a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, A layer made of a hydrate, an oxide or an organic material of one or more elements selected from the group consisting of Mo, Ti, W, P, Cu, Al and Zn; A single metal layer composed of one element selected from the group consisting of W, P, Cu, Al and Zn or a single metal layer composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, And an alloy layer composed of one or more elements selected from the group of elements.

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

In addition, for example, the intermediate layer can be formed by stacking nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium in this order on a carrier. Since the adhesive force between nickel and copper is higher than the adhesion force between chrome and copper, it is peeled from the interface between the ultra-thin copper layer and chromium when the ultra-thin copper layer is peeled off. In addition, a barrier effect for preventing the copper component from diffusing from the carrier into the ultra-thin copper layer is expected for nickel in the intermediate layer. The adhesion amount of nickel in the intermediate layer is preferably 100 μg / dm 2 to 40000 μg / dm 2, more preferably 100 μg / dm 2 to 4000 μg / dm 2, and still more preferably 100 μg / Dm 2 or more, more preferably 100 μg / dm 2 or more and less than 1000 μg / dm 2, and the adhesion amount of chromium in the intermediate layer is preferably 5 μg / dm 2 or more and 100 μg / dm 2 or less.

<Ultra-thin copper layer>

And an ultra-thin copper layer is formed on the intermediate layer. Another layer may be formed between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and can be used as a general electrolytic copper foil. In addition, copper foil can be formed at a high current density, . The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 占 퐉 or less. Typically from 0.5 to 12 占 퐉, more typically from 1 to 5 占 퐉, more typically from 1.5 to 5 占 퐉, and more typically from 2 to 5 占 퐉. In addition, a very thin copper layer may be formed on both sides of the carrier.

Thus, a copper foil having a carrier, an intermediate layer laminated on the carrier, and a carrier having the ultra-thin copper layer laminated on the intermediate layer is produced. For example, the surface of the ultra-thin copper layer may be coated with a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth epoxy resin, a glass cloth / paper composite epoxy resin, Glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film or the like, peeling the carrier after thermocompression to form a copper clad laminate, The printed wiring board can be finally manufactured.

Further, the copper foil having the carrier and the carrier having the ultra-thin copper layer laminated on the carrier and the intermediate layer laminated on the intermediate layer has the coarsened layer on the extremely thin copper layer, At least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate (treatment) layer and a silane coupling (treatment) layer may be provided.

[Resin Layer]

The resin layer may be formed on the surface of the secondary particle layer of the copper foil for a high-frequency circuit of the present invention (the copper foil for a high-frequency circuit includes an ultra-thin copper layer of a copper foil having a carrier). In addition, the resin layer is composed of a group consisting of Ni, Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti formed on the secondary particle layer of the high- Or may be formed on the surface of the chromate layer, on the surface of the silane coupling layer, or on the surface of the Ni-Zn alloy layer. It is more preferable that the resin layer is formed on the outermost surface of the copper foil for a high-frequency circuit. The copper foil on which the carrier is adhered may be provided with a resin layer on the roughening treatment layer or on the heat resistant layer, rust preventive layer, or chromate (treatment) layer or 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-cured state (B-stage state) for bonding. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface is touched with a finger, and a curing reaction occurs when subjected to heat treatment.

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The kind thereof is not particularly limited. Preferable resins include, for example, an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin and the like.

The resin layer may be formed of any of known resins, resin curing agents, compounds, curing accelerators, dielectrics (dielectrics including inorganic compounds and / or organic compounds, dielectrics including metal oxides), reaction catalysts, A polymer, a prepreg, a skeleton material, and the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, International Publication Nos. WO2009 / 084533, JP-A 11-5828, Japanese Patent Publication No. 3184485, International Publication Nos. WO97 / 02728, 3676375, 2000-43188, 3612594, 2002-179772, 2002-359444, Japan Japanese Patent Application Laid-Open Nos. 2003-304068, 3992225, 2003-249739, 4136509, 2004-82687, 4025177, 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open Publication No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open Publication No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid- -257153, JP-A-2007-326923 Japanese Patent Laid-Open Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication Nos. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication Nos. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Patent Application Laid-Open No. 2009-173017, International Publication Nos. WO2007 / 105635, Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication No. WO2009 / A resin, a curing accelerator, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, and the like described in International Publication No. WO2009 / 145179, International Publication Nos. WO2011 / 068157 and 2013-19056, A skeletal material, etc.) and / or a method of forming a resin layer and a forming apparatus.

These resins are dissolved in, for example, a solvent such as methyl ethyl ketone (MEK) or toluene to form a resin solution, which is then coated on the copper foil or ultra thin copper layer, or on the heat resistant layer, rust preventive layer, The silane coupling layer is coated by, for example, a roll coater method, and then, if necessary, heated and dried to remove the solvent to obtain a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

The copper foil for a high-frequency circuit (copper foil for a high-frequency circuit with a resin) having the resin layer is obtained by superimposing the resin layer on a substrate and then thermally bonding the whole to thermally cure the resin layer, To form a pattern.

Further, the copper foil having the carrier layer with the resin layer (the copper foil with the carrier with the resin attached thereto) is superimposed on the base material, and the whole is thermally bonded to thermally cure the resin layer, Is peeled off to expose an extremely thin copper layer (of course, the exposed surface is the surface of the intermediate layer side of the extremely thin copper layer), and a predetermined wiring pattern is formed thereon.

The use of a copper foil for a high frequency circuit with the resin or a copper foil with a carrier to which a resin is attached can reduce the number of prepreg materials used in the production of a multilayer printed wiring board. In addition, the copper clad laminate can be produced even if the thickness of the resin layer is set to a thickness sufficient for ensuring interlayer insulation or the prepreg material is not used at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is also simplified, which is economically advantageous. Moreover, the thickness of the multilayer printed wiring board produced by the thickness of the prepreg material is It is possible to produce an ultra-thin multilayer printed circuit board having a thickness of 100 m or less in one layer.

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

When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered. When the copper foil with the carrier on which the resin with the resin is adhered is laminated on the base material having the inner layer material without interposing the prepreg material, It may be difficult to secure the interlayer insulation of the semiconductor device.

On the other hand, if the thickness of the resin layer is made thicker than 80 占 퐉, it becomes difficult to form a resin layer having a target thickness in one coating step, resulting in economical disadvantage because extra material cost and number of steps are involved. Further, since the formed resin layer is inferior in flexibility, cracks and the like are liable to occur at the time of handling, and excessive resin flow occurs at the time of thermocompression bonding with the inner layer material, which may make it difficult to smoothly laminate the resin layer.

Further, as another product type of the copper foil to which the resin with the resin adhered is adhered, a resin layer is coated on the extremely thin copper layer or on the heat resistant layer, the anticorrosive layer, or the chromate layer or the silane coupling layer , It is possible to manufacture the copper foil in the form of a copper foil (a very thin copper layer) to which a resin free from carriers is adhered by peeling the carrier after it is brought into a semi-cured state.

Hereinafter, some examples of the manufacturing process of the printed wiring board using the copper foil with the carrier according to the present invention are shown.

In one embodiment of the method for producing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier according to the present invention; laminating the copper foil with the carrier and the insulating substrate; A step of peeling the carrier of the copper foil on which the carrier is adhered to form a copper clad laminate after the laminated copper foil and the insulating substrate are laminated so that the extremely thin copper layer side faces the insulating substrate, A semi-additive process, a partly additive process, and a subtractive process. It is also possible that the insulating substrate has an inner layer circuit.

In the present invention, the semi-additive method is a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer to form a plating resist pattern, and then electroplating, removal of the plating resist and etching are performed, Or the like.

In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, a copper thickness is formed in the circuit forming portion by electrolytic plating, , And removing the metal foil other than the circuit forming portion by (flash) etching to form a circuit on the insulating layer.

In the present invention, the term "partly additive method" refers to a method in which a catalyst layer is formed on a substrate on which a conductor layer is formed and, if necessary, a catalyst core is formed on a substrate formed by punching holes for a through hole or a via hole, Refers to a method for producing a printed wiring board by a method including forming a solder resist or a plating resist as necessary and then carrying out thickness formation by electroless plating on the conductor circuit, through holes, via holes, and the like.

In the present invention, the subtractive method refers to a method including a step of selectively removing an unnecessary portion of a copper foil on a copper clad laminate by etching or the like to form a conductor pattern.

In the present invention, known methods such as a semi-additive method, a modified semi-additive method, a partly additive method and a subtractive method can be used. In the present invention, through-holes and / or blind vias may be formed on an insulating substrate in the semi-additive method, the modified semi-additive method, the partly additive method and the subtractive method described above.

Here, specific examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings.

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

Next, as shown in Fig. 5-B, a resist is coated on the roughened layer of the ultra-thin copper layer, exposure and development are performed, and the resist is etched into a predetermined shape.

Next, as shown in Fig. 5-C, a circuit plating for a circuit is formed, and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in Fig. 6-D, a resin layer is formed on the ultra-thin copper layer so as to cover the circuit plating (so that the circuit plating is buried) to laminate the resin layers and then the copper foil 2 Layer) is adhered from the ultra-thin copper layer side.

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

Next, as shown in FIG. 6-F, a laser hole is formed at a predetermined position of the resin layer, and the circuit plating is exposed to form a blind via.

Next, as shown in FIG. 7-G, copper is buried in the blind via to form a non-appeal.

Next, as shown in FIG. 7-H, circuit plating is formed on the non-appealing surface as shown in FIGS. 5-B and 5-C.

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

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

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

The copper foil with the carrier according to the present invention may be used as the copper foil with the other carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, the circuit may be formed as a single layer or a plurality of layers on the second layer circuit shown in Fig. 7-H, and their circuit formation may be formed by a semiadditive method, a subtractive method, a partly additive method, And a semi-additive method.

According to the above-described method for producing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in, for example, The circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit is well suppressed. Therefore, formation of a fine circuit is facilitated. As shown in Figs. 8-J and 8-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes a recessed shape from the resin layer, , And the copper filler is more easily formed thereon, thereby improving the manufacturing efficiency.

Known resins and prepregs can be used for the buried resin (resin). For example, glass cloth prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in this specification can be used for the above-mentioned embedding resin (resin).

The copper foil with the carrier used in the first layer may have a substrate or a resin layer on the surface of the copper foil on which the carrier is adhered. By having the substrate or the resin layer, the copper foil with the carrier used for the first layer is supported, and wrinkles are less likely to be generated, which is advantageous in that the productivity is improved. Further, any substrate or resin layer may be used for the substrate or resin layer as long as it has the effect of supporting the copper foil with the carrier used for the first layer. For example, the substrate or the resin layer may be a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, A foil of an organic compound can be used.

Example

The following is a description based on examples and comparative examples. Note that this embodiment is merely an example, and is not limited to this example. That is, the present invention includes other aspects or modifications included in the present invention. 18 탆 of standard rolled copper foil TPC (tough pitch copper standardized by JIS H3100 C1100, manufactured by JX Nikko Japan Petroleum Metals Co., Ltd.) was used for the original foils of Examples 1 to 6, 11 to 15 and Comparative Examples 1 to 5 below did.

In the examples 7 to 10, a copper foil having a carrier prepared by the following method was used.

In Examples 7 to 10, an electrolytic copper foil having a thickness of 18 占 퐉 (JTC Nippon Petrochemical JTC foil made by JX Nikko Corp.) was prepared as a carrier, and in Example 12, the aforementioned standard rolled copper foil TPC having a thickness of 18 占 퐉 was prepared as a carrier . Under the following conditions, an intermediate layer was formed on the surface of the carrier, and a very 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 side (S side).

Example 7

<Middle layer>

(1) Ni layer (Ni plating)

The carrier was subjected to electroplating with a roll-to-roll type continuous plating line under the following conditions to form an Ni layer having an adhesion amount of 1000 占 퐂 / dm2. Specific plating conditions will be described below.

Nickel sulfate: 270 to 280 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Boric acid: 30 to 40 g / l

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 55 to 75 ppm

pH: 4 to 6

Bath temperature: 55 ~ 65 ℃

Current density: 10 A / dm 2

(2) Cr layer (electrolytic chromate treatment)

Next, after rinsing and pickling the surface of the Ni layer formed in (1), a Cr layer having an adhesion amount of 11 占 퐂 / dm2 was formed on the Ni layer on a continuous roll line-to-roll type plating line under the following conditions Followed by electrolytic chromate treatment.

1 to 10 g / l potassium dichromate, 0 g / l zinc

pH: 7 ~ 10

Liquid temperature: 40 ~ 60 ℃

Current density: 2 A / dm 2

<Ultra-thin copper layer>

Subsequently, the surface of the Cr layer formed in (2) was washed with water and pickled, and then an ultra-thin copper layer having a thickness of 1.5 탆 was formed on the Cr layer on a continuous roll- To prepare a copper foil with a carrier.

Copper concentration: 90 ~ 110 g / ℓ

Sulfuric acid concentration: 90 to 110 g / l

Chloride ion concentration: 50 to 90 ppm

Leveling first (bis (3-sulfopropyl) disulfide): 10 to 30 ppm

Leveling second (amine compound): 10 to 30 ppm

In addition, the following amine compounds were used as the leveling agent 2.

[Chemical Formula 1]

(Wherein R &lt; ₁ &gt; and R &lt; _{2 &} Is 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: 100 A / dm 2

Electrolyte flux: 1.5 to 5 m / sec

Example 8

<Middle layer>

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

The carrier was electroplated with a roll-to-roll type continuous plating line under the following conditions to form an Ni-Mo layer having an adhesion amount of 3000 占 퐂 / dm2. Specific plating conditions will be described below.

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

(Liquid temperature) 30 DEG C

(Current density) 1 to 4 A / dm 2

(Energization time) 3 to 25 seconds

<Ultra-thin copper layer>

An ultra-thin copper layer was formed on the Ni-Mo layer formed in (1). A very thin copper layer was formed under the same conditions as in Example 7 except that the thickness of the extremely thin copper layer was 2 占 퐉.

Example 9

<Middle layer>

(1) Ni layer (Ni plating)

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

(2) Organic material layer (organic material layer formation treatment)

Next, after the surface of the Ni layer formed in (1) was washed with water and pickled, a solution containing a carboxybenzotriazole (CBTA) with a concentration of 1 to 30 g / An aqueous solution having a temperature of 40 占 폚 and a pH of 5 was sprayed by showering for 20 to 120 seconds to form an organic material layer.

<Ultra-thin copper layer>

An ultra-thin copper layer was formed on the organic material layer formed in (2). The 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 占 퐉.

Example 10

<Middle layer>

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

The carrier was subjected to electroplating with a roll-to-roll type continuous plating line under the following conditions to form a Co-Mo layer having an adhesion amount of 4000 / / dm 2. Specific plating conditions will be described below.

(Liquid composition) Sulfuric acid Co: 50 g / dm 3, Sodium molybdate dihydrate: 60 g / dm 3, Sodium citrate: 90 g / d 3

(Liquid temperature) 30 DEG C

(Current density) 1 to 4 A / dm 2

(Energization time) 3 to 25 seconds

<Ultra-thin copper layer>

An ultra-thin copper layer was formed on the Co-Mo layer formed in (1). The 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 changed to 5 占 퐉 in Example 7.

(Examples 1 to 15)

(Cu), the secondary particle layer (Cu) and the secondary particle layer (Cu) were laminated on the surface of the ultra-thin copper layer (Examples 7 to 10) of the rolled copper foil (Examples 1 to 6 and 11 to 15) (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 15 g / l, sulfuric acid 75 g / l

Liquid temperature: 25 ~ 30 ℃

Current density: 1 to 70 A / dm 2

Culm volume: 2 ~ 90 As / d㎡

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

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

pH: 2

Liquid temperature: 40 ℃

Current density: 10 to 50 A / dm 2

Culm volume: 10 ~ 80 As / d㎡

The conditions of the formation of the primary particle layer (Cu plating) and the formation of the secondary particle layer (Cu-Co-Ni alloy plating) were adjusted so that the average value of the concavo-convex height of the roughened surface by the laser microscope was 1500 or more . The measurement of the surface area was performed by the 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 15 g / l, sulfuric acid 75 g / l

Liquid temperature: 25 ~ 35 ℃

Current density: 1 to 70 A / dm 2

Culm volume: 2 ~ 90 As / d㎡

(B) Formation of Secondary Particle Layer (Cu-Co-Ni alloy plating condition)

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

pH: 2

Liquid temperature: 40 ℃

Current density: 20 to 50 A / dm 2

Culm volume: 30 ~ 80 As / d㎡

&Lt; Surface treatment layer other than primary particle layer and secondary particle layer &gt;

After the formation of the primary particle layer and the secondary particle layer, for some of the examples and comparative examples, the surface treatment layer was formed under 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 to 20 g / l, cobalt 1 to 8 g / l

pH: 2-3

Liquid temperature: 40 ~ 60 ℃

Current density: 5 to 20 A / dm 2

Culm volume: 10 ~ 20 As / d㎡

(Examples 5 and 10)

· Ni-Zn plating: Nickel zinc alloy plating

Liquid composition: 2 to 30 g / l of nickel, 2 to 30 g / l of zinc

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

In Examples 5 and 10, after the Ni-Zn plating, an electrolytic chromate treatment and a silane coupling treatment using diaminosilane were carried out.

(Example 6)

· NiCu plating: Nickel copper alloy plating

Liquid composition: 2 to 30 g / l of nickel, 2 to 30 g / l of copper

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Example 11)

· Ni-Mo plating: Nickel molybdenum alloy plating

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

Liquid temperature: 20 ~ 40 ℃

Current density: 1 to 4 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

In Example 11, electrolytic chromate treatment was performed after Ni-Mo plating.

(Example 12)

· Ni-Sn plating: Nickel tin alloy plating

Liquid composition: Nickel 2 - 30 g / ℓ, Tin 2 - 30 g / ℓ

pH: 1.5 to 4.5

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

In Example 12, after Ni-Sn plating, a silane coupling treatment using diaminosilane was performed.

(Example 13)

· Ni-P plating: nickel-phosphorus alloy plating

Liquid composition: 30 to 70 g / l of nickel, 0.2 to 1.2 g / l of phosphorus

pH: 1.5 to 2.5

Liquid temperature: 30 ~ 40 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

(Example 14)

· Ni-W plating: Nickel tungsten alloy plating

Liquid composition: nickel 2 to 30 g / l, W 0.01 to 5 g / l

pH: 3-4

Liquid temperature: 30 ~ 50 ℃

Current density: 1 to 2 A / dm 2

Culm volume: 1 ~ 2 As / d㎡

In Example 14, after Ni-W plating, an electrolytic chromate treatment and a silane coupling treatment using diaminosilane were carried out.

(Example 15)

· Ni-Cr plating: Nickel chrome alloy plating

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

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

Apparatus: Sputtering apparatus manufactured by Erica Co., Ltd.

Output: DC50W

Argon pressure: 0.2 Pa

The average particle diameter of the primary particles, the average particle diameter of the secondary particles, the average particle diameter of the powder (Cu-Co-Ni alloy plating) in the case of forming the primary particle layer (Cu plating) and the secondary particle layer (Height of concavity and convexity) of a height histogram in a certain region of the surface of the roughened surface are shown in Table 1. The results are shown in Table 1. Here, the "coarsened surface" measured was the outermost surface on the side where the primary particle layer and the secondary particle layer were formed. The reason why the surface treatment layer other than the primary particle layer and the secondary particle layer such as Co-Ni plating, Ni-Zn plating, chromate layer and silane coupling layer is formed on the secondary particle layer is that the outermost layer (I.e., the surface on the side where the primary particle layer and the secondary particle layer exist after all the surface treatment layers of the copper foil are formed) were measured.

The average particle diameter of the primary particles and the secondary particles on the roughened surface was observed with a magnification of 30,000 times and photographed using S4700 (scanning electron microscope) manufactured by Hitachi High-Technologies Corporation, The particle diameters of the respective primary particles and secondary particles were measured. The arithmetic average value of the particle diameters of the obtained primary particles and secondary particles was defined as the average particle diameter of the primary particles and the average particle diameter of the secondary particles. Further, in the case of drawing a straight line on the particle of the scanning electron microscopic photograph, the particle length of the longest portion of the straight line traversing the particle was determined as the particle diameter of the particle. In addition, the measurement field size was set at 13.44 mu m per field of view (= 4.2 mu m x 3.2 mu m), and the measurement was performed for 1 field of view. In addition, when observed with a scanning electron microscope photograph, particles existing on the copper foil side (lower side) and non-overlapping particles as primary particles and particles existing on other particles as overlapping particles It was judged as secondary particles.

Height of Harmonized Surface by Laser Microscope The average value (uneven height) of the histogram was measured using a laser microscope VK8500 manufactured by Keyens Co., Ltd., and the magnification was set at 1000 times. After the copper foil to be measured was placed on the stage of the laser microscope, After the position of the stage is adjusted by the focusing handle and the focus of the lens of the laser microscope is made to match the roughened surface of the copper foil, the following "DISTANCE · PITCH setting" is carried out, .

"DISTANCE · PITCH setting" was performed based on the description on page 4-3 of VK-8500 Users Manual. PITCH was set to 0.1 mu m. For reference, FIG. 10 shows an example of the operation screen displayed in "Setting of DISTANCE PITCH" on page 4-3 of this VK-8500 Users Manual.

Also, please refer to "VK-8500 User's Manual" on page 4-3 "1 [▲] (Lens shift)" button to move the lens up to the position where the image is out of focus. (Lens position shift) button is clicked from the height of the lens where the image is displayed, the height of the lens is gradually raised, the lens is moved away from the object (blurring processing surface), and the blurring process The image of the face was clearly in a dimly visible position.

Also, please click "3 [▼] (Lens shift) button" on page 4-3 of the VK-8500 User's Manual to move the lens down to the position where the image is out of focus. The position of the lens is shifted from the height of the lens in which the image is displayed, by lowering the height of the lens gradually by clicking the [▼] (lens position shift) button, I decided to look clearly faint. In addition, the above-mentioned "setting of DISTANCE · PITCH" and the adjustment of the position of the stage of the laser microscope were carried out for each of the examples and comparative examples.

Then, with respect to the obtained results, the height of the concavities and convexities was measured by the measurement analysis at an effective area of 786432 mu m (measurement area 100%), and the height of the concavities and convexities was converted into a histogram by using the analysis software KVH1A9. More specifically, the screen of the "histogram details (shading feature)" is displayed, the "height" is selected as the "display data", the "histogram" is selected as the "display format" : Average &quot; was read out, and a value obtained by rounding off the decimal point of the readout value was defined as &quot; average value of concavo-convex height of the coarsened surface by laser microscope &quot;. In addition, the analysis software KVH1A9 described above was provided on a laser microscope VK8500 manufactured by Keith Corporation.

The powder dropping property was evaluated by attaching a transparent mending tape on the roughened surface of the copper foil, and detaching loose characteristics from the state where the tape was discolored by the decolorized grains adhering to the tape sticking surface when the tape was peeled off. That is, when there is no discoloration of the tape, or when the tape is slight, it is OK to drop the powder, and when the tape is discolored to gray, the discoloration is NG. The state (normal) fill strength was obtained by a copper clad laminate prepared by bonding a copper foil-roughened surface and an FR4 resin substrate with a hot press, fabricating a 10 mm circuit using a general copper chloride circuit etchant, Peeled, and pulled in the direction of 90 DEG to measure the state peel strength.

(Measurement of transmission loss)

(LCP: liquid crystal polymer resin (Vecstar CTZ-50 占 퐉 manufactured by Kuraray Co., Ltd.), polyimide: Kaneka thickness: 50 占 퐉, fluorine resin thickness: 50 占 퐉: DuPont The microstrip line was formed so as to have a characteristic impedance of 50 OMEGA by etching. The transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz Respectively. In Examples 7 to 10, the surface of the copper foil on the carrier-coated copper foil side was laminated with the resin substrate described in Table 1. Then, the carrier was peeled off, then copper plating was performed, Was made to be 18 占 퐉, and then the same measurement of the transmission loss as above was carried out. The evaluation of the transmission loss at 20 GHz is ◎, less than 3.7 dB / 10 cm, less than 4.1 dB / 10 cm, less than 4.1 dB / 10 cm, less than 5.0 dB / 10 cm , And 5.0 dB / 10 cm or more was rated as &quot; C &quot;.

Table 1 shows the same results as Comparative Examples.

An example in which two current conditions and two amounts of Clemm are described in the primary particle current condition column in Table 1 means that the plating is performed under the conditions described on the left side and then the plating is again performed under the conditions described on the right side . For example, in the primary particle current condition column of Example 1, "(65 A / dm 2, 80 As / dm 2) + (20 A / dm 2, 30 As / dm 2) The current density for forming the primary particles was set to 65 A / dm 2 and the amount of Clemm was set to 80 As / dm 2. Thereafter, the current density for forming the primary particles was set to 20 A / dm 2, dm &lt; 2 &gt;.

As apparent from Table 1, the results of the embodiment of the present invention are as follows.

Example 1 is a case where the current density for forming primary particles is 65 A / dm 2 and 20 A / dm 2, the amount of Clemm is 80 As / dm 2 and 30 As / dm 2, Is 28 A / dm &lt; 2 &gt;, and the amount of Clemm is 20 As / dm &lt; 2 &gt;.

In addition, although the current density and the amount of Clemm forming the primary particles are in two stages, two-stage electroplating is usually required when primary particles are formed. That is, plating conditions for formation of the nuclear particles in the first stage and electroplating for growth of the nuclear particles in the second stage.

The first plating condition is an electroplating condition for forming the nucleation particles in the first step, and the following plating conditions are the electroplating conditions for growing the nuclear particles in the second step. The same is applied to the following embodiments and comparative examples, and a description thereof will be omitted.

As a result, the average particle diameter of the primary particles was 0.45 mu m, the average particle diameter of the secondary particles was 0.30 mu m, and the average height of the unevenness of the roughened surface by the laser microscope was 2689, satisfying the conditions of the present invention.

As a result, it was found that when the state peel strength was as high as 1.16 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) As shown in Fig.

The heat-resistant deterioration rate was determined by the following formula.

(%) = (State Peel Strength (kg / cm) - Peel Strength (kg / cm) after Heating at 180 ° C for 48 hours) / State Peel Strength (kg / cm) × 100

Example 2 is a case where the current density for forming the primary particles is 65 A / dm 2 and 2 A / dm 2, the amount of Clemm is 80 As / dm 2 and 4 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 15 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.40 mu m, the average particle size of the secondary particles was 0.15 mu m, and the average height of the unevenness of the roughened surface by the laser microscope was 1556, satisfying the conditions of the present invention.

As a result, the state peel strength was as high as 1.08 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured to determine the difference as the deterioration rate) was 30% or less As shown in Fig.

Example 3 is a case where the current density for forming primary particles is 60 A / dm 2 and 10 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

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

There was no drop of powder. The state peel strength was as high as 0.92 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was 30% or less .

Example 4 is a case where the current density for forming primary particles is 55 A / dm 2 and 1 A / dm 2, the amount of Clemm is 75 As / dm 2 and 5 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.35 mu m, the average particle size of the secondary particles was 0.25 mu m, and the average height of the roughed surface was 1862 by the laser microscope.

The state peel strength was as high as 0.94 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 5 is a case where the current density for forming the primary particles is 50 A / dm 2 and 5 A / dm 2, the amount of Clemm is 70 As / dm 2 and 10 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.30 mu m, the average particle size of the secondary particles was 0.25 mu m, and the average height of the roughened surface by the laser microscope was 1857, satisfying the conditions of the present invention. The state peel strength was as high as 0.94 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 6 is a case where the current density for forming primary particles is 60 A / dm 2 and 15 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, (Normal plating) with a current density of 20 A / dm 2 and a Coulomb amount of 60 As / dm 2 to form a secondary particle layer (secondary particle layer), the current density was set to 20 A / dm 2 again , And a coke amount of 20 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.35 mu m, the secondary particles had a two-step structure of a coating (normal) plating state (particle diameter of less than 0.1 mu m) and an average particle diameter of 0.15 mu m, The average value of the height of the concave and the convex was 1752, which satisfied the condition of the present invention. The state peel strength was as high as 0.83 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 7 is a case where the current density for forming primary particles is 65 A / dm 2 and 2 A / dm 2, the amount of Clemm is 80 As / dm 2 and 4 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 15 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.41 mu m, the average particle diameter of the secondary particles was 0.16 mu m, and the average height of the unevenness of the roughened surface by the laser microscope was 1560, satisfying the conditions of the present invention.

As a result, it was found that there was no powder falling, the state peel strength was as high as 1.09 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured, As shown in Fig.

Example 8 is a case in which the current density for forming primary particles is 60 A / dm 2 and 10 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.31 mu m, the average particle diameter of the secondary particles was 0.25 mu m, and the average value of the unevenness height of the roughened surface by the laser microscope was 1814, satisfying the conditions of the present invention.

There was no drop of powder. The state peel strength was as high as 0.93 kg / cm, and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measurement of the state peel was measured to determine the difference as the deterioration rate) was as small as 30% or less .

Example 9 is a case where the current density for forming primary particles is 55 A / dm 2 and 1 A / dm 2, the amount of Clemm is 75 As / dm 2 and 5 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.35 mu m, the average particle diameter of the secondary particles was 0.26 mu m, and the average height of the roughed surface was 1866 by the laser microscope.

The state peel strength was as high as 0.95 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 10 is a case where the current density for forming the primary particles is 50 A / dm 2 and 5 A / dm 2, the amount of Clemm is 70 As / dm 2 and 10 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.30 mu m, the average particle size of the secondary particles was 0.25 mu m, and the average height of the roughed surface was 1858 by the laser microscope. The state peel strength was as high as 0.94 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 11 is a case where the current density for forming primary particles is 60 A / dm 2 and 10 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.30 mu m, the average particle diameter of the secondary particles was 0.25 mu m, and the average value of the unevenness height of the roughened surface by the laser microscope was 1808, satisfying the conditions of the present invention.

There was no drop of powder. The state peel strength was as high as 0.93 kg / cm, and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measurement of the state peel was measured to determine the difference as the deterioration rate) was as small as 30% or less .

Example 12 is a case where the current density for forming primary particles is 55 A / dm 2 and 1 A / dm 2, the amount of Clemm is 75 As / dm 2 and 5 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.35 mu m, the average particle size of the secondary particles was 0.25 mu m, and the average height of the roughened surface by the laser microscope was 1861, satisfying the conditions of the present invention.

The state peel strength was as high as 0.94 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 13 is a case where the current density for forming primary particles is 50 A / dm 2 and 5 A / dm 2, the amount of Clemm is 70 As / dm 2 and 10 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.30 mu m, the average particle size of the secondary particles was 0.25 mu m, and the average height of the roughed surface was 1858 by the laser microscope. The state peel strength was as high as 0.94 kg / cm, the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 14 is a case where the current density for forming primary particles is 60 A / dm 2 and 15 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, (Normal plating) with a current density of 20 A / dm 2 and a Coulomb amount of 60 As / dm 2 to form a secondary particle layer (secondary particle layer), the current density was set to 20 A / dm 2 again , And a coke amount of 20 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.35 mu m, the secondary particles had a two-step structure of a coating (normal) plating state (particle diameter of less than 0.1 mu m) and an average particle diameter of 0.15 mu m, The average value of the height of the concave and the convex was 1751, which satisfied the condition of the present invention. The state peel strength was as high as 0.84 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 ° C for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was as small as 30% or less .

Example 15 is a case where the current density for forming the primary particles is 60 A / dm 2 and 10 A / dm 2, the amount of Clemm is 80 As / dm 2 and 20 As / dm 2, Is 25 A / dm &lt; 2 &gt;, and the amount of Clemm is 30 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.30 mu m, the average particle diameter of the secondary particles was 0.25 mu m, and the average value of the unevenness height of the roughened surface by the laser microscope was 1805, satisfying the conditions of the present invention.

There was no drop of powder. The state peel strength was as high as 0.93 kg / cm, and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after measurement of the state peel was measured to determine the difference as the deterioration rate) was as small as 30% or less .

On the other hand, the comparative example has the following results.

In Comparative Example 1, the current density for forming the primary particles was 63 A / dm 2 and 10 A / dm 2, the amount of Clemm was 80 As / dm 2 and 30 As / dm 2, Is not formed. As a result, the average particle size of the primary particles became 0.50 mu m, and the average value of the height of concavities and convexities by the laser microscope on the roughened surface was 2001, satisfying the conditions of the present invention. There was no flaking and the state peel strength was as high as 1.38 kg / cm, which was the embodiment level. However, the heat resistance deterioration rate (peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured, and the difference was regarded as the deterioration rate) was remarkably bad at 60%. The evaluation as a whole copper foil for a high-frequency circuit was defective.

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

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

A large amount of flaking of coarse particles occurred. The state peel strength was as high as 1.25 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 deg. C for 48 hours after measuring the state peel was measured and the difference was regarded as the deterioration rate) was 30% or less. As described above, since there is a problem that a large amount of flaking occurs, the overall evaluation as a whole copper foil for a high-frequency circuit is defective.

In Comparative Example 3, the current density for forming the primary particles was 63 A / dm 2 and 1 A / dm 2, the amount of Clemm was 80 As / dm 2 and 2 As / dm 2, Is 28 A / dm &lt; 2 &gt;, and the amount of Clemm is 73 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.35 mu m, the average particle diameter of the secondary particles was 0.60 mu m, and the average height of the unevenness of the roughened surface by the laser microscope was 1298, . There was a large amount of powder dropping. The state peel strength was as high as 1.42 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after the state peel measurement was regarded as the deterioration rate) was 30% or less. There was a large amount of powder dropping. The evaluation as a whole copper foil for a high-frequency circuit was defective.

In Comparative Example 4, the current density for forming the primary particles was 63 A / dm 2 and 1 A / dm 2, the amount of Clemm was 80 As / dm 2 and 2 As / dm 2, Is 31 A / dm &lt; 2 &gt;, and the amount of Clemm is 40 As / dm &lt; 2 &gt;.

As a result, the average particle size of the primary particles was 0.35 mu m, the average particle size of the secondary particles was 0.40 mu m, and the average height of the roughened surface by the laser microscope was 1227,

The state peel strength was as high as 1.37 kg / cm and the heat resistance deterioration rate (the peel strength after heating at 180 캜 for 48 hours after the state peel measurement was regarded as the deterioration rate) was 30% or less. There was a large amount of powder dropping. The evaluation as a whole copper foil for a high-frequency circuit was defective.

In Comparative Example 5, the current density for forming primary particles was 40 A / dm 2 and 1 A / dm 2, the amount of Clemm was 40 As / dm 2 and 2 As / dm 2, Is 20 A / dm &lt; 2 &gt;, and the amount of Clemm is 20 As / dm &lt; 2 &gt;.

As a result, the average particle diameter of the primary particles was 0.15 mu m, the average particle diameter of the secondary particles was 0.15 mu m, and the average height of the unevenness of the roughened surface by the laser microscope was 1367, . No flaking occurred. The state peel strength was 0.71 kg / cm, and the heat resistance deterioration rate (peel strength after heating at 180 캜 for 48 hours after measuring the state peel was measured, and the difference was regarded as the deterioration rate) was 35%.

As is clear from the comparison between the examples and the comparative examples, after the primary particle layer of copper was formed on the surface of the copper foil (original foil), a layer composed of a ternary alloy of copper, cobalt and nickel It is possible to stably suppress the phenomenon of dropping of the powder by setting the average value of the concavo-convex height of the roughened surface to 1,500 or more in the measurement analysis by the laser microscope in a certain region of the roughened surface And further, the peel strength can be increased and the high-frequency characteristics can be improved.

It is preferable that the mean particle diameter of the primary particle layer is 0.25 to 0.45 mu m and the average particle diameter of the secondary particle layer made of the ternary alloy made of copper, cobalt and nickel is 0.35 mu m or less in achieving the above effect Do.

In addition, when Co is included in the heat-resistant treated layer, the transmission loss tends to increase.

Fig. 9 shows an image of a computer screen showing the result of analysis by the analyzing software KVH1A9 of the average value (concavity and convexity height) of the height histogram of the first embodiment. The average value (irregularity height) of the height histogram is obtained by reading the item &quot; average &quot; (indicated here as 2688.98) of the table (concentration measurement) on the upper right side in Fig.

Claims (32)

A copper foil in which a primary particle layer of copper is formed on the surface of a copper foil and then a secondary particle layer of a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer. When observed with a laser microscope, The average value of the height of the unevenness of the treated surface is 1500 or more,
The average value of the concavity and convexity of the roughened surface was set to 0.1 mu m on the basis of the description on page 4-3 of VK-8500 User's manual using Laser Microscope VK8500 manufactured by Keith Corporation, The image obtained by measuring the roughened surface was subjected to a measurement analysis at an effective area of 786432 μm ² (measurement area 100%) to obtain a histogram of the rugged height using the analysis software KVH1A9, . The method according to claim 1,
Wherein the primary particle layer of the copper has an average particle diameter of 0.25 to 0.45 占 퐉 and the secondary particle layer of a ternary alloy composed of copper, cobalt and nickel has an average particle diameter of 0.35 占 퐉 or less. The method according to claim 1,
Wherein the primary particle layer and the secondary particle layer are electroplating layers. The method according to claim 1,
Wherein the secondary particle is a normal plating layer grown on one or a plurality of branch-like particles grown on the primary particles or on the primary particles. The method according to claim 1,
Wherein the average height of the unevenness of the roughened surface when observed with a laser microscope is 1500 or more and 2000 or less. The method according to claim 1,
Wherein the primary particle layer and the secondary particle layer have a peak strength of 0.80 kg / cm or more. The method according to claim 1,
Wherein the primary particle layer and the secondary particle layer have a fill strength of 0.90 kg / cm or more. The method according to claim 1,
On the secondary particle layer,
(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn,
(B) a chromate layer
Wherein one or two copper foils are formed. The method according to claim 1,
On the secondary particle layer,
(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn,
(B) a chromate layer
1 &lt; / RTI &gt; or 2 &lt;
The silane coupling layer
The copper foil for a high frequency circuit formed in this order. The method according to claim 1,
On the secondary particle layer,
A Ni-Zn alloy layer, and a chromate layer. The method according to claim 1,
On the secondary particle layer,
One or two Ni-Zn alloy layers, and a chromate layer,
The silane coupling layer
The copper foil for a high frequency circuit formed in this order. The method according to claim 1,
And a resin layer on the surface of the secondary particle layer. 9. The method of claim 8,
An alloy layer comprising at least one element selected from the group consisting of Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti; And a resin layer formed on the resin layer. 10. The method of claim 9,
An alloy layer comprising at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti; And a resin layer on the surface of the silane coupling layer. A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one surface or both surfaces of the carrier, wherein the ultra-thin copper layer is a copper foil for a high- . 11. A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one surface or both surfaces of a carrier, wherein the ultra-thin copper layer is a high-frequency circuit according to any one of claims 2 to 11, Copper foil with a carrier which is a copper foil. 17. The method of claim 16,
Wherein the intermediate layer and the ultra thin copper layer are provided on one side of the carrier in this order and a carrier having a roughened treatment layer is attached to the other side of the carrier. A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of a carrier, wherein the ultra-thin copper layer is a copper foil for a high- . A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one surface or both surfaces of the carrier, wherein the ultra-thin copper layer is a copper foil for a high frequency circuit, . A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of the carrier, wherein the ultra-thin copper layer is a copper foil for a high frequency circuit, . 16. The method of claim 15,
Wherein the intermediate layer and the ultra thin copper layer are provided on one side of the carrier in this order and a carrier having a roughened treatment layer is attached to the other side of the carrier. 19. The method of claim 18,
Wherein the intermediate layer and the ultra thin copper layer are provided on one side of the carrier in this order and a carrier having a roughened treatment layer is attached to the other side of the carrier. 20. The method of claim 19,
Wherein the intermediate layer and the ultra thin copper layer are provided on one side of the carrier in this order and a carrier having a roughened treatment layer is attached to the other side of the carrier. 21. The method of claim 20,
Wherein the intermediate layer and the ultra thin copper layer are provided on one side of the carrier in this order and a carrier having a roughened treatment layer is attached to the other side of the carrier. A copper clad laminate for high frequency circuit using the copper foil according to any one of claims 1 to 15 and 18 to 21. A printed circuit board for a high frequency circuit using the copper foil according to any one of claims 1 to 15 and 18 to 21. 26. The method of claim 25,
A copper clad laminate for a high frequency circuit, wherein the copper foil and a polyimide, a liquid crystal polymer or a fluororesin are laminated. 27. The method of claim 26,
A printed circuit board for a high-frequency circuit using any one of polyimide, liquid crystal polymer and fluorine resin. An electronic device using the printed wiring board according to claim 26. 29. An electronic device using the printed wiring board according to claim 28. A step of preparing the copper foil and the insulating substrate with the carrier according to any one of claims 15 and 18 to 23,
A step of laminating the copper foil on which the carrier is adhered and the insulating substrate,
After the step of laminating the copper foil on which the carrier is adhered and the insulating substrate is peeled off from the carrier of the copper foil on which the carrier is adhered to form a copper clad laminate,
And then forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, and a modified semi-additive method. A step of forming a circuit on the surface of the ultra thin copper layer side of the copper foil having the carrier according to any one of claims 15 and 18 to 23,
Forming a resin layer on the ultra-thin copper layer side surface of the copper foil on which the carrier is adhered so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
Exposing a circuit buried in the resin layer formed on the extremely thin copper layer side surface by removing the extremely thin copper layer after peeling the carrier.

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