TW201524280A - Surface-treated copper foil, lamination board, printed circuit board, electronic machine, copper foil with carrier, and manufacturing method of printed circuit board - Google Patents

Abstract

The present invention provides a surface-treated copper foil to suppress the transmission loss well even if it is applied in a high-frequency circuit board. The surface-treated copper foil has a surface-treated layer on at least a surface. The total adhesion quantity of Co, Ni, Fe is less than 1000 [mu]g/dm 2. The surface-treated layer has a Zn metal layer or the alloy-treated layer containing Zn. The ratio of three-dimensional surface area to the two-dimensional surface area of the surface of surface-treated layer measured by a laser microscope is 1.0~1.9, and the surface roughness Rz JIS of at least a surface is less than 2.2 [mu]m.

Description

Surface treatment copper foil, laminated board, printed wiring board, electronic device, copper foil with carrier, and printed wiring board manufacturing method

The present invention relates to a surface-treated copper foil, a laminated board, a printed wiring board, an electronic device, a copper foil with a carrier, and a method of manufacturing a printed wiring board, and more particularly to a surface-treated copper foil and a laminate suitable for use in a high-frequency circuit substrate. A method of manufacturing a board, a printed wiring board, an electronic device, a copper foil with a carrier, and a printed wiring board.

With regard to printed wiring boards, great progress has been made in this half century, and today it has been used in almost all electronic machines. In recent years, the demand for miniaturization and high performance of electronic devices has increased, and high-density mounting of components and high-frequency signals have been developed, and high-frequency correspondence is required for printed wiring boards.

For the high-frequency substrate, in order to ensure the quality of the output signal, it is required to reduce the transmission loss. The transmission loss is mainly caused by the dielectric loss of the resin (substrate side) and the conductor loss due to the conductor (copper foil side). Regarding the dielectric loss, the dielectric constant and dielectric loss tangent of the resin become smaller, and the dielectric loss is reduced. In high-frequency signals, the main cause of conductor loss is that the higher the frequency becomes, the higher the cross-sectional area of the current flowing through the skin effect due to the current flowing only on the surface of the conductor, the higher the resistance becomes.

As a technique for reducing the transmission loss of a high-frequency copper foil, for example, Patent Document 1 A metal foil for high-frequency circuit is disclosed, which is coated with silver or a silver alloy on one or both sides of a surface of a metal foil, and a silver or silver alloy coating layer is provided on the silver or silver alloy coating layer to have a thickness smaller than that of the silver or silver alloy coating layer. A coating layer other than a silver alloy. Further, it is described that it is possible to provide a metal foil which can reduce the loss due to the skin effect even in an ultra-high frequency region used for satellite communication.

Further, Patent Document 2 discloses a rolled copper foil for roughening a high-frequency circuit, which is characterized in that it is a material for a printed circuit board, and a rolling surface after recrystallization annealing of the rolled copper foil is surrounded by X-rays. The integrated intensity (I(200)) of the (200) plane obtained by the shot is the integrated intensity (I ₀ (200)) of the (200) plane obtained by X-ray diffraction of the fine powder copper, which is I (200). /I ₀ (200)>40, the arithmetic mean roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment by the plating on the rolled surface is 0.02 μm to 0.2 μm, and the ten-point average roughness The degree (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm. Further, it is described that a printed circuit board which can be used at a high frequency exceeding 1 GHz can be provided.

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

[Patent Document 1] Japanese Patent No. 4161304

[Patent Document 2] Japanese Patent No. 4704025

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

The conductor loss due to the conductor (copper foil side), as described above, is due to the skin effect In the resistance, it is known that not only the influence of the electric resistance of the copper foil itself but also the surface treatment layer formed on the surface of the copper foil by the roughening treatment for ensuring adhesion to the resin substrate is known. The influence, in particular, the roughness of the surface of the copper foil is the main cause of the conductor loss, and the smaller the roughness, the smaller the transmission loss.

Further, when the roughening treatment is performed as the surface treatment of the copper foil, it is usually When a Cu-Ni alloy treatment or a Cu-Co-Ni alloy treatment is used, and in the case of heat treatment and rust prevention treatment, Ni-Zn alloy treatment or Co-Ni alloy treatment is usually used.

However, it is usually used in the above roughening treatment, heat treatment, and rust prevention treatment. Co, Ni, and Fe are metals which exhibit strong magnetism at normal temperature, and when they are contained as a component in the surface treatment layer, there are problems in that the current distribution and the magnetic field distribution in the conductor are affected by the influence of magnetism. The transmission characteristics of the copper foil deteriorate.

It is an object of the present invention to provide a transmission loss even when used in a high frequency circuit substrate. A surface-treated copper foil, a laminated board, a printed wiring board, an electronic device, a copper foil with a carrier, and a method of manufacturing a printed wiring board which are also excellently consumed.

The inventors have found that in order to suppress the influence of the ferromagnetic metal on the transmission characteristics, By controlling the total amount of adhesion of Co, Ni, and Fe in the surface treatment layer of the copper foil to be equal to or less than the predetermined amount, and containing Zn which does not exhibit ferromagnetism at normal temperature as a substitute component, the high-frequency transmission loss is further reduced. Further, it was found that, besides the surface roughness Rz of the tube controlled by the high-frequency copper foil significantly affecting the transmission loss, the ratio of the three-dimensional surface area to the two-dimensional surface area of the contact area with the resin (dielectric) is more accurately expressed. It also has a significant impact on transmission loss.

The present invention, which is completed based on the above findings, is a surface-treated copper foil having a surface treatment layer formed on at least one surface thereof, and a total adhesion amount of Co, Ni, and Fe in the surface treatment layer is 1000 μg/dm. ² , the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the surface of the surface treatment layer has a ratio of a three-dimensional surface area to a two-dimensional surface area measured by a laser microscope of 1.0 to 1.9, at least one surface The surface roughness Rz JIS is 2.2 μm or less.

In one embodiment, the surface-treated copper foil of the present invention has a total adhesion amount of Co, Ni, and Fe in the surface-treated layer of 500 μg/dm ² or less.

In another embodiment, the surface-treated copper foil of the present invention has a total adhesion amount of Co, Ni, and Fe in the surface-treated layer of 300 μg/dm ² or less.

In still another embodiment of the surface-treated copper foil of the present invention, the total amount of adhesion of Co, Ni, and Fe in the surface-treated layer is 0 μg/dm ² .

In still another embodiment of the surface-treated copper foil of the present invention, the surface roughness Rz JIS of both surfaces is 2.2 μm or less.

In still another embodiment of the surface treated copper foil of the present invention, the surface treated layer comprises a roughened layer.

In still another embodiment of the surface-treated copper foil of the present invention, the amount of Cu deposited in the roughened layer is 0.10 g/dm ² or less.

In still another embodiment of the surface-treated copper foil of the present invention, in the surface-treated layer, the Zn metal layer or the alloy-containing layer containing Zn is provided on the roughened layer.

In still another embodiment of the surface treated copper foil of the present invention, the above-mentioned Zn is contained The alloy treatment layer is a Cu-Zn alloy layer.

In still another embodiment of the surface-treated copper foil of the present invention, the amount of Zn deposited in the surface-treated layer is 5 mg/dm ² or less.

In still another embodiment, the surface treated copper foil of the present invention is at the surface In the layer, a chromate treatment layer is provided on the Zn metal layer or the Zn-containing alloy treatment layer.

In still another embodiment, the surface treated copper foil of the present invention is at the above chromic acid A decane coupling treatment layer is disposed on the layer.

In still another embodiment, the surface-treated copper foil of the present invention has a total adhesion amount of Cu, Zn, Co, Ni, and Fe in the surface-treated layer of 0.10 g/dm ² or less.

In still another embodiment, the surface treated copper foil of the present invention is used for soft printing Brush the wiring board.

In still another embodiment, the surface-treated copper foil of the present invention is used for 5 GHz. The above high frequency circuit substrate.

In another aspect, the present invention is a surface treated copper foil and tree of the present invention A laminated board obtained by laminating a grease substrate.

In still another aspect of the present invention, a laminate of the present invention is used as a material Printed wiring board.

In still another aspect, the present invention is a printed wiring board using the present invention. Electronic machine.

In still another aspect of the present invention, a copper foil with a carrier is provided on one side of the carrier Or two sides sequentially have an intermediate layer, an extremely thin copper layer, and the above ultra-thin copper layer is the surface-treated copper of the present invention Foil.

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

In still another aspect of the invention, there is provided a laminate obtained by laminating a copper foil with a carrier of the invention and a resin substrate.

In still another aspect, the invention provides a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the carrier and the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, a metal-clad laminate is formed by peeling off the carrier of the carrier-attached copper foil, and then subjected to a semi-additive process or a subtractive method ( A step of forming a circuit by any one of a subtractive process, a partially additive process, or a modified semi-additive process.

In still another aspect of the invention, a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention or the side surface of the carrier; a step of forming a resin layer on the surface of the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier; a step of forming a circuit on the resin layer; and forming a circuit on the resin layer, Stepping off the above carrier or the above ultra-thin copper layer And after removing the carrier or the ultra-thin copper layer, removing the ultra-thin copper layer or the carrier, thereby forming a circuit formed on the side surface of the ultra-thin copper layer or the carrier-side surface by the resin layer The steps that are exposed.

According to the present invention, it is possible to provide a method for producing a surface-treated copper foil, a laminate, a printed wiring board, an electronic device, a copper foil with a carrier, and a printed wiring board which are excellent in transmission loss even when used for a high-frequency circuit substrate.

Fig. 1 is a graph showing the relationship between the total amount of adhesion of Co, Ni, and Fe and the surface roughness Rz in the examples and comparative examples.

Fig. 2 is a graph showing the relationship between the total amount of adhesion of Co, Ni, and Fe and the ratio of the three-dimensional surface area to the two-dimensional surface area in the examples and the comparative examples.

3 is a graph showing the relationship between the total adhesion amount of Co, Ni, Fe, Cu, and Zn and the transmission loss in the examples and comparative examples.

(copper foil substrate)

The form of the copper foil substrate which can be used in the present invention is not particularly limited, and is typically used in the form of a rolled copper foil or an electrolytic copper foil. In general, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeatedly performing plastic working and heat treatment by a calender roll. In applications requiring flexibility, rolled copper foil is often used.

As a material of the copper foil substrate, in addition to high-purity copper such as refined copper or oxygen-free copper which is generally used as a conductor pattern of a printed wiring board, for example, Sn-doped copper, Ag-doped copper, Cr added, or the like may be used. A copper alloy such as Zr or Mg, or a copper alloy such as a corson-based copper alloy such as Ni or Si. In addition, when the term "copper foil" is used alone in this specification, a copper alloy foil is also included. When a copper alloy foil is used as the copper foil for a high-frequency circuit substrate, the resistivity may not be significantly increased as compared with copper.

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

(surface treatment layer)

On the surface of the copper foil substrate, a surface treatment layer based on one or more layers selected from the group consisting of a roughening treatment layer, a rustproof layer, a heat resistant layer, and a decane coupling treatment layer is preferably formed. The surface treatment layer of the present invention may be formed on the surface (M surface) opposite to the resin as described above, or may be formed on the surface (S surface) opposite to the surface (M surface), or may be formed on both surfaces.

The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process can be fine. Further, after the roughening treatment, a cover plating treatment may be performed. The surface treatment layer formed by the roughening treatment, the rustproof treatment, the heat treatment, the decane treatment, the immersion treatment in the treatment liquid, or the plating treatment may also contain a material selected from the group consisting of Cu, Ni, Fe, Co, and Zn. Any one of a group consisting of Cr, Mo, W, P, As, Ag, Sn, and Ge, or an alloy of any one or more, or an organic substance.

In order to suppress the influence of the ferromagnetic metal on the transmission characteristics, the surface of the copper foil is The total amount of adhesion of Co, Ni, and Fe in the layer is controlled to be less than or equal to the following, and contains Zn which does not exhibit ferromagnetism at normal temperature as a substitute component, whereby the high-frequency transmission loss can be further reduced. Therefore, the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn. Further, the alloy-treated layer containing Zn may be a Cu-Zn alloy layer. By setting it as a Cu-Zn alloy layer, heat resistance and chemical resistance can be improved compared with the metal layer which is Zn alone.

When the surface treatment layer is a roughened layer, a rustproof layer, a heat-resistant layer, a decane couple In the case where any one of the layers is formed, the order of the layers is not particularly limited. For example, a roughened layer may be formed on the surface of the copper foil, and a Zn metal layer or Zn may be provided on the roughened layer. The alloy treatment layer serves as a rust-proof and heat-resistant layer. Further, a chromic acid treatment layer may be provided on the Zn metal layer or the alloy treatment layer containing Zn. Further, a decane coupling treatment layer may be provided on the chromic acid treatment layer.

(metal adhesion)

In the surface-treated copper foil of the present invention, the total adhesion amount of Co, Ni, and Fe in the surface treatment layer is controlled to be 1000 μg/dm ² or less. As described above, the surface-treated copper foil of the present invention controls the adhesion amount of Co, Ni, and Fe which is relatively high in magnetic permeability due to transmission loss and relatively low in electrical conductivity, so that high-frequency transmission loss can be reduced. The total adhesion amount of Co, Ni, and Fe in the surface treatment layer is preferably 500 μg/dm ² or less, more preferably 300 μg/dm ² or less, still more preferably 0 μg/dm ² (indicating the quantitative lower limit value of the analysis or less).

When the surface treatment layer contains a roughened layer, the amount of Cu deposited in the roughened layer is preferably 0.10 g/dm ² or less. According to this configuration, the high frequency transmission loss can be further reduced. The amount of Cu deposited in the roughened layer is more preferably 0.09 g/dm ² or less, still more preferably 0.08 g/dm ² or less, and typically 0.04 to 0.08 g/dm ² .

The amount of Zn deposited in the surface treated layer is preferably 5 mg/dm ² or less. According to this configuration, the chemical resistance is improved and the heat resistance is improved. The amount of Zn deposited in the surface treatment layer is more preferably 4.5 mg/dm ² or less, still more preferably 4 mg/dm ² or less, and typically 0.1 to 4.5 mg/dm ² .

The total adhesion amount of Cu, Zn, Co, Ni, and Fe in the surface treatment layer is preferably 0.10 g/dm ² or less. According to this configuration, the high frequency transmission loss can be further reduced. The total adhesion amount of Cu, Zn, Co, Ni, and Fe in the surface treatment layer is more preferably 0.09 g/dm ² or less, still more preferably 0.08 g/dm ² or less, and typically 0.04 to 0.08 g/dm ² .

(surface roughness Rz)

The roughness of the surface of the copper foil is the main cause of the loss of the conductor, and the smaller the roughness, the smaller the transmission loss. From this point of view, the surface-treated copper foil of the present invention can control the surface roughness Rz JIS of at least one surface to 2.2 μm or less, and the transmission loss can be favorably reduced. Further, it is preferable that the surface roughness Rz JIS of both surfaces is 2.2 μm or less. According to this configuration, the high frequency transmission loss can be further reduced.

The surface roughness Rz JIS is more preferably 1.5 μm or less, still more preferably 1.2 μm or less, and typically 0.5 to 2.2 μm.

(surface area ratio)

In addition to the surface roughness Rz of the previously controlled tube for high-frequency copper foil, it is necessary to more accurately represent the three-dimensional surface area of the contact area with the resin (dielectric) which affects the high-frequency transmission loss with respect to the two-dimensional surface area. The ratio is controlled in the appropriate range. From this point of view, in the surface-treated copper foil of the present invention, the ratio of the three-dimensional surface area to the two-dimensional surface area measured by the laser microscope on the surface of the surface treatment layer is controlled to 1.0 to 1.9, so that even for a high-frequency circuit substrate The transmission loss can also be suppressed more satisfactorily. This surface area ratio cannot be a value of less than 1.0 by definition, and if it exceeds 1.9, there arises a problem that a high frequency transmission loss becomes large. The surface area is preferably 1.0 to 1.9. More preferably, it is 1.0 to 1.6, and even more preferably 1.3 to 1.6.

(Manufacturing method of surface-treated copper foil)

In the present invention, it is preferred to carry out roughening treatment of the surface of the copper foil substrate (rolled copper foil or electrolytic copper foil) on the surface or both surfaces of the copper foil after pickling. The adhesion to the resin (dielectric) (peeling strength) is obtained by the roughening treatment. In the present invention, the roughening treatment can be performed, for example, by any one selected from the group consisting of Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, and Ge. Plating of one or more alloys or by surface treatment of an organic substance or the like. In the case of ordinary copper plating or the like, pretreatment before roughening may be performed, and after roughening, in order to impart heat resistance and chemical resistance, the metal may be coated with a surface as a surface treatment. Further, any one of a group selected from the group consisting of Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, and Ge may be used without any roughening treatment. Plating of the above alloys. Then, in order to impart heat resistance and chemical resistance, the metal may be coated with a surface as a surface treatment. When the roughening treatment is carried out, there is an advantage that the adhesion strength to the resin becomes high. Further, in the case where the roughening treatment is not performed, there is an advantage that the manufacturing steps of the surface-treated copper foil are simplified, the productivity is improved, the cost can be reduced, and the roughness can be made small. For the rolled copper foil and the electrolytic copper foil, the processing contents are sometimes slightly different. By adjusting the liquid composition, plating time, and current density of the plating treatment on the surface of the copper foil, the total amount of Co, Ni, and Fe in the surface treatment layer of the present invention can be controlled, and Zn metal is formed in the surface treatment layer. A layer or an alloy treatment layer containing Zn controls the surface of the surface treatment layer by a laser microscope to measure the ratio of the three-dimensional surface area to the two-dimensional surface area, thereby controlling the surface roughness Rz JIS.

Further, the electrolytic copper foil having the surface roughness Rz in the above range can be used as follows Method of making.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

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

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

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are those 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).

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

The surface-treated copper foil of the present invention can be attached to the resin base from the surface treatment layer side The laminate is made of a board. Moreover, if necessary, the surface-treated copper foil can be further processed to form a circuit, thereby producing a printed wiring board or the like. The resin substrate is not particularly limited as long as it has characteristics suitable for use in a printed wiring board or a printed circuit board. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber base can be used for the rigid PWB. Epoxy resin, fluororesin impregnated cloth, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, flexible printed circuit board (FPC) A polyester film or a polyimide film, a liquid crystal polymer (LCP) film, a fluororesin, and a fluororesin-polyimine composite material can be used. Further, since the dielectric loss of the liquid crystal polymer (LCP) is small, a liquid crystal polymer (LCP) film is preferably used for the printed wiring board or the printed circuit board for high-frequency circuit use. Furthermore, in the present invention, the "printed wiring board" also includes a printed wiring board on which components are mounted, a printed circuit board, and a printed circuit board. Further, two or more printed wiring boards of the present invention may be connected to each other to manufacture a printed wiring board in which two or more printed wiring boards are connected, and at least one printed wiring board of the present invention may be combined with another one. The printed wiring board of the invention or the printed wiring board which does not correspond to the printed wiring board of the present invention is connected, and an electronic device is manufactured using the printed wiring board. Furthermore, in the present invention, the "copper circuit" also includes copper wiring.

Regarding the method of fitting, in the case of rigid PWB, it is prepared to make glass cloth. The substrate is impregnated with a resin to harden the resin to a semi-hardened prepreg. This can be carried out by overlapping the copper foil with the prepreg and heating and pressurizing. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film is bonded to a copper foil at a high temperature and a high pressure via a bonding agent or a bonding agent, or a polyimide precursor is coated. Drying, hardening, etc., whereby a laminate can be produced.

The laminated board of the present invention can be used for various printed wiring boards (PWB) or printed electricity There are no special restrictions on the road board. As a printed wiring board, for example, from the viewpoint of the number of layers of the conductor pattern In other words, it can be applied to a single-sided PWB, a double-sided PWB, or a multi-layered PWB (three or more layers), and can be applied to a rigid PWB, a soft PWB (FPC), or a rigid-elastic PWB from the viewpoint of the type of the insulating substrate material.

Further, in another embodiment, the present invention may be a surface-treated copper foil having a surface-treated layer formed on at least one surface thereof, the surface-treated layer comprising a roughened layer, and Co in the surface-treated layer The total adhesion amount of Ni and Fe is 300 μg/dm ² or less, and the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the surface of the surface treatment layer is measured by a laser microscope to have a three-dimensional surface area with respect to a two-dimensional surface area. The surface roughness Rz JIS of at least one surface is 2.2 μm or less, and the surface treatment layer is formed on both surfaces, and the surface roughness Rz JIS of the both surfaces is 2.2 μm or less.

Further, in another embodiment, the present invention may be a surface-treated copper foil having a surface-treated layer formed on at least one surface thereof, the surface-treated layer comprising a roughened layer, and Co in the surface-treated layer The total adhesion amount of Ni and Fe is 300 μg/dm ² or less, and the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the surface of the surface treatment layer is measured by a laser microscope to have a three-dimensional surface area with respect to a two-dimensional surface area. The ratio is 1.0 to 1.9, and the surface roughness Rz JIS of at least one surface is 2.2 μm or less, and the alloy-treated layer containing Zn is a Cu-Zn alloy layer.

Further, in another embodiment, the present invention may be a surface-treated copper foil having a surface-treated layer formed on at least one surface thereof, the surface-treated layer comprising a roughened layer, and Co in the surface-treated layer The total adhesion amount of Ni and Fe is 300 μg/dm ² or less, and the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the surface of the surface treatment layer is measured by a laser microscope to have a three-dimensional surface area with respect to a two-dimensional surface area. The ratio of the surface roughness Rz JIS of at least one surface is 2.2 μm or less, and the total adhesion amount of Cu, Zn, Co, Ni, and Fe in the surface treatment layer is 0.10 g/dm ² or less.

Further, in another embodiment, the present invention may be a surface-treated copper foil having a surface-treated layer formed on at least one surface thereof, and a total adhesion amount of Co, Ni, and Fe in the surface-treated layer is 986 μg/dm. ^{In the} following, the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the surface of the surface treatment layer has a ratio of a three-dimensional surface area to a two-dimensional surface area measured by a laser microscope of 1.0 to 1.9, which is formed on both surfaces. In the surface treatment layer, the surface roughness Rz JIS of the both surfaces is 0.6 μm or less.

(with carrier copper foil)

A copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an extremely thin copper layer on one surface or both sides of the carrier. Further, the ultra-thin copper layer is a surface-treated copper foil according to an embodiment of the present invention.

<carrier>

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

As the carrier which can be used in the present invention, a copper foil is preferably used. The reason for this is that since the copper foil has a high electrical conductivity, it is easy to form an intermediate layer and an extremely thin copper layer thereafter. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeatedly performing plastic working and heat treatment by a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, copper doped with Sn, copper doped with Ag, copper alloy to which Cr, Zr or Mg is added, or the like may be added. And a copper alloy such as a Cason copper alloy such as Si.

Regarding the thickness of the carrier usable in the present invention, there is no particular limitation as long as appropriate It may be adjusted to a suitable thickness as a carrier, and for example, it may be 5 μm or more. However, if the production cost is increased if it is too thick, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

Further, the carrier used in the present invention can be controlled to form an intermediate layer by the following The surface roughness Rz and the surface area ratio of the side are controlled, and the surface roughness Rz and the surface area ratio of the surface of the extremely thin copper layer (i.e., the surface of the surface treatment layer) after the surface treatment are controlled.

Regarding the carrier used in the present invention, the shape of the carrier before the formation of the intermediate layer is controlled in advance The roughness (Rz) and surface area ratio of the TD on the side of the intermediate layer are also important. Specifically, the surface roughness (Rz) of the TD of the carrier before the formation of the intermediate layer is 0.20 to 1.50 μm, preferably 0.20 to 1.00 μm, and the surface area ratio is 1.0 to 1.9, preferably 1.0 to 1.5. Such a copper foil can be produced by adjusting the oil film equivalent of the rolling oil for calendering, chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution, and adding a predetermined additive to produce an electrolytic copper foil. . By using the surface roughness (Rz) of the TD of the copper foil before the treatment in the above manner The surface area ratio is set to the above range, and the surface roughness (Rz) to surface area ratio of the treated copper foil can be easily controlled.

Further, the rolling can be carried out by setting the oil film equivalent of the following formula to 13,000 to 35,000 or less.

Oil film equivalent = {(calender oil viscosity [cSt]) × (over-plate speed [mPm] + roll peripheral speed [mpm])} / {(roller bite angle [rad]) × (material fall stress [kg/mm] ² ])}

Calendered oil viscosity [cSt] is a dynamic viscosity of 40 °C.

In order to make the oil film equivalent lower in the range of 13,000 to 35,000, a well-known method of using a low-viscosity rolling oil or slowing the plate speed can be used. Further, in order to make the oil film equivalent higher in the range of 13,000 to 35,000, a known method of using a high-viscosity rolling oil or increasing the speed of the plate can be used.

Further, an electrolytic copper foil having a surface roughness Rz and a surface area ratio within the above range can be produced by the following method. The electrolytic copper foil can be used as a carrier.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

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

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

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are those 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).

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

Further, a roughened layer may be provided on the surface on the side opposite to the side on which the carrier is provided with the ultra-thin copper layer. The roughening treatment layer may be provided by a known method, and the roughening treatment layer may be provided by the above-described roughening treatment. The case where the surface on the side where the carrier is provided with the ultra-thin copper layer is provided with the roughened layer on the surface on the opposite side has the advantage that when the carrier is laminated on the surface of the resin substrate or the like from the surface side having the roughened layer, the carrier It becomes difficult to peel off from the resin substrate.

<intermediate layer>

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

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

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

Further, as the intermediate layer, a known organic substance can be used as the organic substance, and at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid is preferably used. For example, as a specific nitrogen-containing organic compound, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzotriazole) which is a triazole compound having a substituent is preferably used. Azylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like are preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid, and the like are preferably used.

Further, for example, the intermediate layer may be formed by sequentially laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer on the carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, peeling occurs at the interface between the ultra-thin copper layer and the chromium-containing layer. Further, for the nickel of the intermediate layer, a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer is expected. The amount of deposition of nickel intermediate layer is preferably from 100μg / dm ² or more 40000μg / dm ² or less, more preferably 100μg / dm ² or more 4000μg / dm ² or less, more preferably 100μg / dm ² or more 2500μg / dm ² or less, More preferably, it is 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a Ni plating layer on the opposite side of the carrier. The chromium layer of the above intermediate layer can be provided by chrome plating or chromic acid treatment.

If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer may affect the surface roughness Rz and the glossiness of the surface of the extremely thin copper layer after the surface treatment, so that the surface of the surface of the extremely thin copper layer is in the middle of the surface layer. The layer thickness is preferably from 1 to 1000 nm, preferably from 1 to 500 nm, preferably from 2 to 200 nm, more preferably from 2 to 100 nm, still more preferably from 3 to 60 nm. Furthermore, the intermediate layer may also be disposed on both sides of the carrier.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. An extremely thin copper layer having the carrier is a surface treatment metal according to an embodiment of the present invention material. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1.5 to 5 μm. Further, before the ultra-thin copper layer is provided on the intermediate layer, strike plating using a copper-phosphorus alloy may be performed in order to reduce pinholes of the ultra-thin copper layer. The base plating may be, for example, a copper pyrophosphate plating solution. Furthermore, an extremely thin copper layer may be provided on both sides of the carrier. The ultra-thin copper layer may be a layer containing a copper alloy or a layer composed of a copper alloy, and the ultra-thin copper layer may also contain an organic or inorganic substance. Further, as the ultra-thin copper layer, an extremely thin copper layer having a Cu concentration of 75 mass% or more is preferably used. The reason for this is that an extremely thin copper layer having a Cu concentration of 75 mass% or more has high conductivity and is suitable for use in circuits and the like.

Further, the ultra-thin copper layer of the present invention may be an extremely thin copper layer formed under the following conditions. The reason for this is that the surface roughness Rz and the surface area ratio of the surface-treated layer of the copper foil with a carrier are controlled by forming a smooth ultra-thin copper layer.

̇ electrolyte composition

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

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

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

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are those 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).

̇ manufacturing conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

Hereinafter, examples of manufacturing steps of a printed wiring board using the copper foil with a carrier of the present invention will be disclosed.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and the carrier After the copper foil and the insulating substrate are laminated such that the ultra-thin copper layer side faces the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then the semi-additive method is modified by semi-addition. The steps of forming a circuit by any of the methods of forming, partially adding, and subtracting. The insulating substrate may also be an insulating substrate having an inner layer circuit.

In the present invention, the so-called semi-additive method refers to the following method: on an insulating substrate or copper. A thin electroless plating is applied to the foil seed layer, and after forming a pattern, a conductor pattern is formed by plating and etching.

Therefore, one of the manufacturing methods of the printed wiring board of the present invention using the semi-additive method The embodiment includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate; a step of peeling off the carrier of the copper foil; a step of removing all of the ultra-thin copper layer exposed by peeling off the carrier by etching or plasma etching using an etching solution such as acid; and etching the ultra-thin copper layer by etching a step of removing the exposed resin, providing a through hole or/and a blind via; and performing a desmear treatment on the region containing the perforation or/and the blind hole; a step of providing an electroless plating layer in the region of the resin and the perforated or/and blind via; a step of providing a plating resist on the electroless plating layer; exposing the plating resist and then plating the region forming the circuit a step of removing the resist; a step of providing a plating layer in a region where the plating resist is removed to form the circuit; and removing the plating resist; and performing rapid etching (f Leash etching) or the like, the step of removing the electroless plating layer existing in a region other than the region where the above-described circuit is formed.

Another method for manufacturing a printed wiring board of the present invention using a semi-additive method The method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the insulating substrate and the insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate; a step of peeling off the carrier of the copper foil; a step of removing all of the extremely thin copper layer exposed by peeling off the carrier by etching or plasma etching using an etching solution such as acid; and etching the ultra-thin copper layer by etching a step of removing the exposed surface of the resin, providing an electroless plating layer; and providing a plating resist on the electroless plating layer; and exposing the plating resist a step of removing the plating resist in the region where the circuit is formed; a step of providing a plating layer in a region where the plating resist is removed to form the circuit; and a step of removing the plating resist; Etching or the like, the step of removing the electroless plating layer and the ultra-thin copper layer existing in a region other than the region where the above-described circuit is formed.

In the present invention, the so-called modified semi-additive method refers to the following method: on the insulating layer The laminated metal foil protects the non-circuit forming portion by a plating resist, increases the copper thickness of the circuit forming portion by plating, removes the resist, and removes the metal foil other than the circuit forming portion by (rapid) etching. A circuit is formed on the insulating layer.

Therefore, the printed wiring board manufacturing method of the present invention using the improved semi-additive method In one embodiment, the method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and laminating the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil; a step of providing a perforated or/and blind via hole for peeling off the carrier and exposing the ultra-thin copper layer and the insulating substrate; and removing the adhesive containing the perforated or/and blind vias a step of treating the slag; a step of providing an electroless plating layer on the region containing the perforation or/and the blind hole; a step of providing a plating resist on the surface of the extremely thin copper layer exposed by peeling the carrier; and setting the plating resistance After the agent, the step of forming a circuit by electroplating; the step of removing the plating resist; and the step of removing the extremely thin copper layer exposed by removing the plating resist by rapid etching.

Further, the step of forming the circuit on the resin layer may be to attach another The carrier copper foil is bonded to the resin layer from the side of the ultra-thin copper layer, and the circuit is formed by using a copper foil with a carrier adhered to the resin layer. Further, the additional copper foil with a carrier adhered to the above resin layer may be the copper foil with a carrier of the present invention. Further, a step of forming a circuit on the above resin layer, It can also be carried out by any one of a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Further, the copper foil with a carrier on which the circuit is formed on the surface may have a substrate or a resin layer on the surface of the carrier of the copper foil with the carrier.

Another method for manufacturing a printed wiring board of the present invention using a modified semi-additive method In one embodiment, the method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; a step of peeling off the carrier of the carrier copper foil; a step of providing a plating resist on the extremely thin copper layer exposed by peeling the carrier; exposing the plating resist, and then plating resisting the region forming the circuit a step of removing; a step of providing a plating layer in a region where the plating resist is removed to form the circuit; and a step of removing the plating resist; and being formed outside the region where the circuit is formed by rapid etching or the like The step of removing the electroless plating layer and the extremely thin copper layer in the region.

In the present invention, the partial addition method refers to a method in which a conductor layer is provided. The substrate is formed, and a catalyst core is provided on a substrate on which a hole for a via hole or a via hole is opened, and etching is performed to form a conductor circuit. If a solder resist or a plating resist is provided as needed, the conductor is formed. On the circuit, a perforation, a via hole, or the like is thickened by an electroless plating treatment to thereby manufacture a printed wiring board.

Therefore, in the method of manufacturing a printed wiring board of the present invention using a partial addition method In one embodiment, the method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; a step of peeling off the carrier of the carrier copper foil; a step of providing perforations or/and blind vias for stripping the ultra-thin copper layer and the insulating substrate exposed by the carrier; And a step of desmear treatment in the region of the blind hole; a step of imparting a catalyst core to the region containing the perforation or/and the blind hole; and providing a resist on the surface of the extremely thin copper layer exposed by peeling off the carrier a step of exposing the resist to form a circuit pattern; and removing the ultra-thin copper layer and the catalyst core by using etching or plasma etching of an acid or the like to form a circuit; The step of removing the resist; removing the surface of the insulating substrate by exposing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an etching solution such as an acid, and providing a solder resist or plating a step of a resist; a step of providing an electroless plating layer in a region where the above-mentioned solder resist or plating resist is not provided.

In the present invention, the subtractive method refers to a method of selecting by etching or the like. The unnecessary portions of the copper foil on the copper clad laminate are removed to form a conductor pattern.

Therefore, one of the manufacturing methods of the printed wiring board of the present invention using the subtractive method is The method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the insulating substrate and the insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate; a step of peeling off the carrier of the copper foil; a step of providing a perforated or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling the carrier; and performing desmear treatment on the region containing the perforation and/or the blind hole a step of providing an electroless plating layer on the region containing the perforation or/and the blind via; a step of providing a plating layer on the surface of the electroless plating layer; and providing a resist on the surface of the plating layer or/and the ultra-thin copper layer a step of exposing the resist to form a circuit pattern; removing the ultra-thin copper layer and the electroless plating layer and the plating layer by etching or plasma etching using an acid or the like, a step of forming a circuit; a step of removing the above resist.

Another implementation of the method of manufacturing a printed wiring board of the present invention using a subtractive method The method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and stacking the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate a step of peeling off the carrier of the foil; a step of providing a perforated or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling the carrier; and performing desmear treatment on the region containing the perforation or/and the blind hole a step of providing an electroless plating layer on a region containing the perforated or/and blind via holes; a step of forming a mask on a surface of the electroless plating layer; and a step of providing a plating layer on a surface of the electroless plating layer not having a mask a step of providing a resist on the surface of the plating layer or/and the ultra-thin copper layer; a step of exposing the resist to form a circuit pattern; etching or plasma etching using an acid or the like a step of removing the ultra-thin copper layer and the electroless plating layer to form a circuit; and removing the resist.

The steps of setting the perforation or/and the blind hole and the subsequent desmear step may not Row.

Here, the manufacture of a printed wiring board using the copper foil with a carrier of the present invention will be described in detail. Specific examples of the method. Here, the copper foil with a carrier having the ultra-thin copper layer in which the roughening layer is formed is described as an example, but the invention is not limited thereto, and an ultrathin copper layer having no roughened layer is used. The carrier copper foil can also be similarly produced by the following method of manufacturing a printed wiring board.

First, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed on its surface was prepared.

Next, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a predetermined shape.

Next, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a predetermined shape.

Next, a resin layer is laminated on the ultra-thin copper layer by covering the circuit plating (buried circuit plating), and then another carrier copper foil (the second layer) is attached to the side of the ultra-thin copper layer. then.

Next, the carrier was peeled off from the carrier copper foil attached to the second layer.

Secondly, the laser opening is performed at a predetermined position of the resin layer, so that the circuit plating is exposed to form a blind hole.

Next, copper is buried in the blind hole to form a via fill.

Next, on the hole filling, circuit plating is formed in the above manner.

Next, the carrier was peeled off from the first layer of the carrier-attached copper foil.

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

Next, a bump is formed on the circuit plating in the resin layer, and a pillar is formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in this manner.

The above additional carrier copper foil (second layer) can be used with the carrier of the present invention As the copper foil, a conventional copper foil with a carrier can be used, and a usual copper foil can be used. Further, a circuit of one layer or a plurality of layers may be further formed on the circuit of the second layer, or may be formed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method. Perform such circuit formation.

The copper foil with carrier of the present invention is preferably controlled to be extremely thin in the manner of (1) below. The color difference of the surface of the copper layer. In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer, or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably satisfies the following (1) to control the chromatic aberration of the roughened surface of the ultra-thin copper layer. Furthermore, the surface treatment gold of the present invention In the case of the material, the surface of the roughening treatment refers to the surface treatment after the surface treatment such as the heat-resistant layer, the rust-preventing layer, and the weather-resistant layer is performed after the roughening treatment. The surface of a metal material (very thin copper layer). In the case where the surface-treated metal material is an extremely thin copper layer with a carrier copper foil, the term "roughening treatment surface" refers to a heat-resistant layer, a rust-proof layer, and weather resistance after the roughening treatment. In the case of surface treatment of a layer or the like, the surface of the ultra-thin copper layer after the surface treatment is performed.

(1) Regarding the chromatic aberration of the surface of the ultra-thin copper layer, the color difference ΔE*ab based on JIS Z8730 is 45 or more.

Here, the color difference ΔL, Δa, Δb are measured by a color difference meter, respectively, plus black /white/red/green/yellow/blue, using the L*a*b color system based on JIS Z8730 for comprehensive indicators, in the form of △L: white black, △a: red green, △b: yellow blue Said. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

The above chromatic aberration can be adjusted by increasing the current density at the time of forming an extremely thin copper layer, lowering the concentration of copper in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the chromatic aberration described above may be adjusted by providing a roughening treatment on the surface of the ultra-thin copper layer to provide a roughened layer. In the case where the roughening treatment layer is provided, an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum can be used, and the current density is higher than the conventional current density ( For example, 40~60A/dm ² ), the processing time is shorter than the previous processing time (for example, 0.1 to 1.3 seconds), and the adjustment is performed. When the roughened layer is not provided on the surface of the ultra-thin copper layer, it can be achieved by using a plating bath having a Ni concentration of twice or more of other elements, and using a current density lower than the conventional one ( 0.1~1.3A/dm ² ), and the treatment time (20 seconds to 40 seconds) is set longer, and the surface of the ultra-thin copper layer or the heat-resistant layer or the rust-proof layer or the chromic acid treatment layer or the decane coupling treatment layer Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, and Ni-Zn alloy plating) treatment is performed.

Regarding the chromatic aberration of the surface of the extremely thin copper layer, if the color difference ΔE* based on JIS Z8730 When the ab is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil, the contrast between the ultra-thin copper layer and the circuit becomes clear, and as a result, the visibility is improved, and the position of the circuit can be accurately performed. alignment. The surface of the ultra-thin copper layer based on JIS Z8730 has a color difference ΔE*ab of preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the chromatic aberration of the surface of the ultra-thin copper layer is controlled in the above manner, The contrast of the dress becomes clear and the visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, circuit plating can be formed accurately at a predetermined position. Further, according to the method for manufacturing a printed wiring board as described above, since the resin layer is embedded in the circuit plating, for example, when the ultra-thin copper layer is removed by rapid etching, the circuit plating is protected by the resin layer, and the shape thereof is protected. It is maintained, whereby it becomes easy to form a fine circuit. Moreover, 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 satisfactorily suppressed. Therefore, it becomes easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching, the exposed surface of the circuit plating becomes a shape recessed from the resin layer, so that it becomes easy to form a bump on the circuit plating, and it becomes easy to form thereon. Copper column, manufacturing efficiency is improved.

Further, as the embedded resin (RESIN), a known resin or a prepreg can be used. For example, BT (bis-s-butylene diimide III) can be used. The resin is a prepreg of a glass cloth impregnated with a BT resin, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd., or ABF. Moreover, the resin layer and/or the resin and/or the prepreg described in this specification can be used for the said insert resin (resin).

Further, the aforementioned copper foil with a carrier used for the first layer, in the form of the copper foil with the carrier The face may also have a substrate or a resin layer. The copper foil with a carrier used for the first layer is supported by the substrate or the resin layer, and wrinkles are less likely to occur, so that productivity is improved. Further, if the substrate or the resin layer has an effect of supporting the copper foil with a carrier to be used for the first layer, all of the substrate or the resin layer can be used. For example, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, an organic compound plate, or an organic compound described in the present specification can be used. The foil serves as the aforementioned substrate or resin layer.

[Examples]

A rolled copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd.) or an electrolytic copper foil having a thickness of 18 μm having a thickness of 18 μm was prepared as the copper foil substrates of Examples 1 to 10 and Comparative Examples 1 to 6.

Next, plating was carried out under the conditions shown in Tables 1 and 2 as a surface treatment. In Examples 1 to 4, the surface of the deposited copper foil (Rz 0.6 μm) produced by the above method was subjected to surface treatment, and Examples 5 to 7 and Comparative Examples 1 and 4 to 6 were used for the electrolytic copper. The foil drum surface (Rz 1.5 μm) was surface treated. In Comparative Examples 2 and 3, the deposition surface (Rz 2.0 μm) of the produced electrolytic copper foil was subjected to surface treatment using an electrolytic solution containing no leveling agent. Further, in Examples 8 to 10, the rolled copper foil controlled to have a predetermined surface roughness was subjected to surface treatment. Table 1 shows the liquid composition, pH value, temperature, and current density of each of the plating solutions 1 to 10. Table 2 shows the plating treatments 1 to 3 in the order of the bath composition and time described. Further, after the plating, plating is performed by Zn, Ni or the alloys thereof. And chromic acid treatment to ensure heat resistance, and the peel strength is improved by coating a decane coupling agent.

The coating conditions of the decane coupling agent are as follows.

̇3-methylpropenyloxypropyltrimethoxydecane

Decane concentration: 0.6 vol% (remaining part: water)

̇Processing temperature: 30~40°C

̇ Processing time: 5 seconds

Drying after decane treatment: 100 ° C × 3 seconds

Further, the surface treatments of Examples 1 and 9 and the following Example 11 correspond to a smooth plating treatment (a surface treatment which is not a roughening treatment), and the surface treatments in the examples and comparative examples are equivalent to coarse Processing.

Further, the copper foil with a carrier described below was prepared as the basis of Examples 11 to 15. material.

In Examples 11 to 13, an electrolytic copper foil (HLP foil manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 18 μm was prepared as a carrier, and in Example 14, an electrolytic copper foil having a thickness of 18 μm was prepared (JX Nippon Mining & Metal Co., Ltd.) In the fifteenth embodiment, a rolled copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 18 μm was prepared as a carrier. Further, under the following conditions, in Examples 11 to 13, an intermediate layer was formed on the surface of the deposition surface side of the carrier, and in Example 14, an intermediate layer was formed on the surface of the rotor surface (gloss surface side) of the carrier. In Example 15, an intermediate layer was formed on the surface of the carrier. Then, in each of the examples, an extremely thin copper layer was formed on the surface of the intermediate layer. Further, when the carrier is required, the surface roughness Rz and the surface area ratio of the surface before the formation of the surface intermediate layer on the side where the intermediate layer is formed are controlled by the above method.

̇Example 11

<intermediate layer>

(1) Ni layer (Ni plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Ni layer having an adhesion amount of 1000 μg/dm ² . The specific plating conditions are described below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromic acid treatment)

Next, the surface of the Ni layer formed in (1) was washed with water and pickled, and then subjected to electrolytic chromic acid treatment on a continuous roll line of a roll-to-roll type under the following conditions to obtain 11 μg/dm ^{2 .} The adhesion amount of the Cr layer adheres to the Ni layer.

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

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

<very thin copper layer>

Next, after the surface of the Cr layer formed in (2) is washed with water and pickled, it is then plated on a continuous roll line of a roll-to-roll type under the following conditions to form a thickness of 1.5 μm on the Cr layer. Very thin copper layer, made of ultra-thin copper foil with carrier.

Copper concentration: 90~110g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

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

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

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

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

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

̇Example 12

<intermediate layer>

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

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

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

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 11 except that the thickness of the ultra-thin copper layer was changed to 2 μm.

̇Example 13

<intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 11.

(2) Organic layer (organic layer formation treatment)

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

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 11 except that the thickness of the ultra-thin copper layer was changed to 3 μm.

̇Examples 14, 15

<intermediate layer>

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

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

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

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed in (1). In Example 14, the thickness of the ultra-thin copper layer was set to 3 μm, and in the same manner as in Example 15, except that the thickness of the ultra-thin copper layer was set to 5 μm, ultrathin copper was formed under the same conditions as in Example 11. Floor.

Each of the samples of the examples and the comparative examples produced in the above manner was subjected to various evaluations as follows.

<Measurement of adhesion amount>

The measurement of the adhesion amount of various metals other than Cu in the surface treatment layer was such that a film of a surface of a copper foil of 50 mm × 50 mm was dissolved in a solution in which HNO ₃ (2% by weight) and HCl (5% by weight) were mixed, and ICP was used. The emission spectrum analyzer (manufactured by Seiko Instruments Inc., SFC-3100) quantifies the metal concentration in the solution, and derives the amount of metal per unit area (μg/dm ² ). At this time, the amount of metal adhesion on the surface opposite to the surface to be measured is not mixed, and is shielded as needed to be analyzed. Further, the measurement system is performed on a sample obtained by performing the above-described Zn, Co, Ni, Fe or alloy plating, chromic acid treatment, and further decane coupling treatment. The measurement of the amount of Cu adhesion of the surface treatment layer is based on the weight of the surface-treated copper foil of a size of 100 mm × 100 mm minus the amount of adhesion of various metals other than Cu and the surface treatment measured by the above method. The weight of the front copper foil per unit area was determined.

<Measurement of Surface Roughness Rz>

Ten-point average roughness (Rz) was measured on the surface-treated surface using a contact roughness meter SP-11 manufactured by Kosaka Research Institute Co., Ltd. in accordance with JIS B0601-1994. Under the conditions of a measurement reference length of 0.8 mm, an evaluation length of 4 mm, a cutoff value of 0.25 mm, and a conveying speed of 0.1 mm/sec, the measurement position was changed 10 times, and the average value of the measured values of 10 times was set as the value of the surface roughness Rz. . Further, the respective electrolytic copper foils and rolled copper foils used in the examples and the comparative examples were also measured in advance for the roughness Rz before the surface treatment. Further, the measurement of the ten-point average roughness is performed in the TD direction (the width direction of the copper foil (the direction perpendicular to the advancing direction of the copper foil in the copper foil manufacturing apparatus)).

<Measurement of surface area ratio>

Regarding the three-dimensional surface area, a laser microscope LEXT OLS4000 (laser wavelength 405 nm, differential dry method) manufactured by Olympus Co., Ltd. was used to carry out a region having a two-dimensional surface area of 66455 μm ^{2 in} the deposition surface of the surface-treated copper foil. measuring. The value obtained by dividing the measured three-dimensional surface area by the two-dimensional surface area is taken as the surface area ratio.

<Measurement of transmission loss>

Each sample having a thickness of 18 μm and a commercially available liquid crystal polymer resin (Kuraray Co., Ltd. After the Vecstar CTZ-50μm manufactured by the company was bonded, the microstrip line was formed by etching with a characteristic impedance of 50 Ω, and the penetration coefficient was measured using a network analyzer HP8720C manufactured by HP, and the frequency was determined at 20 GHz. Transmission loss. The evaluation of the transmission loss at a frequency of 20 GHz is set to ◎ of less than 5.0 dB/10 cm, ○ of 5.0 dB/10 cm or more and less than 6.0 dB/10 cm, and × of 6.0 dB/10 cm or more. Since the magnitude of the transmission loss is affected by the relative dielectric constant, dielectric loss tangent, and thickness of the resin to be used, the copper foil used in the general printed wiring board (copper foil used in Comparative Example 2) will be used. The one having the significant transmission loss reduction effect is set as the above-described determination criterion.

The test results are shown in Table 3.

(Evaluation results)

In Examples 1 to 15, the total adhesion amount of Co, Ni, and Fe in the surface treatment layer was 1000 μg/dm ² or less, and the surface treatment layer had a Zn metal layer or an alloy treatment layer containing Zn, and the surface area ratio was 1.0~. 1.9, the surface roughness Rz JIS is 2.2 μm or less. Therefore, the transmission loss of Examples 1 to 15 was well suppressed.

In Comparative Example 1, since the surface area ratio exceeded 1.9, the transmission loss was large.

In Comparative Example 2, since the surface roughness Rz JIS exceeded 2.2 μm and the surface area ratio exceeded 1.9, the transmission loss was large.

In Comparative Example 3, since the surface roughness Rz JIS exceeded 2.2 μm, the transmission loss was large.

In Comparative Examples 4 to 6, since the plating treatment 3 of Example 7 was changed to contain Co, Ni, and Fe, and the total adhesion amount of Co, Ni, and Fe in the surface treated layer exceeded 1000 μg/dm ² , Comparative Example 4 was used. The transmission loss of 6 is greater than that of Embodiment 7.

Fig. 1 is a graph showing the relationship between the total amount of adhesion of Co, Ni, and Fe and the surface roughness Rz in the examples and comparative examples. 2 is a graph showing the relationship between the total adhesion amount of Co, Ni, and Fe and the ratio of the three-dimensional surface area to the two-dimensional surface area in the examples and the comparative examples. Fig. 3 is a graph showing the relationship between the total adhesion amount of Co, Ni, Fe, Cu, and Zn and the transmission loss in the examples and comparative examples.

Claims (25)

A surface-treated copper foil having a surface treatment layer formed on at least one surface thereof, wherein a total amount of Co, Ni, and Fe adhered to the surface treatment layer is 1000 μg/dm ² or less, and the surface treatment layer has a Zn metal layer or an alloy containing Zn In the treatment layer, the surface of the surface treatment layer has a ratio of a three-dimensional surface area measured by a laser microscope to a two-dimensional surface area of 1.0 to 1.9, and at least one surface has a surface roughness Rz JIS of 2.2 μm or less. The surface-treated copper foil according to the first aspect of the invention, wherein the total amount of Co, Ni, and Fe in the surface-treated layer is 500 μg/dm ² or less. The surface-treated copper foil according to the second aspect of the invention, wherein the total amount of Co, Ni, and Fe adhered to the surface treated layer is 300 μg/dm ² or less. The surface-treated copper foil according to claim 3, wherein a total amount of Co, Ni, and Fe adhered to the surface treated layer is 0 μg/dm ² . The surface-treated copper foil according to the first aspect of the invention, wherein the surface roughness Rz JIS of both surfaces is 2.2 μm or less. The surface treated copper foil of claim 1, wherein the surface treatment layer comprises a roughened layer. The surface-treated copper foil according to claim 6, wherein the amount of Cu deposited in the roughened layer is 0.10 g/dm ² or less. The surface-treated copper foil according to claim 6, wherein the Zn metal layer or the alloy-containing layer containing Zn is provided on the roughened layer in the surface-treated layer. The surface treated copper foil of claim 1, wherein the alloy containing Zn is treated The layer is a Cu-Zn alloy layer. The surface-treated copper foil according to the first aspect of the invention, wherein the surface-treated layer has a Zn adhesion amount of 5 mg/dm ² or less. The surface-treated copper foil according to claim 1, wherein a chromic treatment layer is provided on the Zn metal layer or the Zn-containing alloy treatment layer in the surface treatment layer. The surface-treated copper foil according to claim 11, wherein a decane coupling treatment layer is provided on the chromic acid treatment layer. The surface-treated copper foil according to the first aspect of the invention, wherein the total amount of Cu, Zn, Co, Ni, and Fe in the surface-treated layer is 0.10 g/dm ² or less. A surface-treated copper foil according to any one of claims 1 to 13, which is used for a flexible printed wiring board. The surface-treated copper foil according to any one of claims 1 to 13, which is used for a high frequency circuit substrate of 5 GHz or more. A laminated board produced by laminating a surface-treated copper foil according to any one of claims 1 to 13 and a resin substrate. A printed wiring board is made of a laminate of the 16th article of the patent application. An electronic machine using a printed wiring board of the 17th patent application. A copper foil with a carrier which has an intermediate layer or an extremely thin copper layer on one or both sides of the carrier. The ultra-thin copper layer is a surface-treated copper foil according to any one of claims 1 to 13. The copper foil with a carrier according to claim 19, wherein the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other side of the carrier. A laminated board produced by laminating a carrier copper foil of claim 19 or 20 with a resin substrate. A printed wiring board manufactured by using a laminate of the 21st patent application. An electronic machine using a printed wiring board of the 22nd patent application. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate of claim 19 or 20; and laminating the copper foil with the insulating substrate; After laminating the foil and the insulating substrate, the metal-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by a semi-additive process, a subtractive process, a portion A step of forming a circuit by any one of a partial additive process or a modified semi-additive process. A method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the carrier copper foil of claim 19 or 20 or the side surface of the carrier; and burying the circuit a step of forming a resin layer on the side surface of the ultra-thin copper layer of the carrier copper foil or the side surface of the carrier; a step of forming a circuit on the resin layer; after forming a circuit on the resin layer, the carrier or the a step of peeling off the ultra-thin copper layer; and after peeling off the carrier or the ultra-thin copper layer, removing the ultra-thin copper layer or the carrier, thereby forming the side surface of the ultra-thin copper layer or the side surface of the carrier The circuit layer buried circuit The steps that are exposed.