TW201822597A - Surface Treated Copper Foil, Copper Foil With Carrier, Laminate, Method for Manufacturing Printed Wiring Board, and Method for Manufacturing Electronic Device - Google Patents

Abstract

Also disclosed is a surface treated copper foil, comprising a copper foil, and a surface treatment layer on one or both sides of the copper foil, wherein the surface treatment layer has a primary particle layer, or has a primary particle layer and s secondary particle layer in this order from the side of the copper foil; the surface treatment layer contains Zn, a deposition amount of Zn in the surface treatment layer is 150 [mu]g/dm2 or more; the surface treatment layer does not contain Ni, or in the case where the surface treatment layer contains Ni, a deposition amount of Ni in the surface treatment layer is 800 [mu]g/dm2 or less; the surface treatment layer does not contain Co, or in the case where the surface treatment layer contains Co, a deposition amount of Co in the surface treatment layer is 3000 [mu]g/dm2 or less; and a ten point average roughness Rz of an outermost surface of the surface treatment layer is 1.5 [mu]m or less.

Description

   Method for manufacturing surface-treated copper foil, copper foil with carrier, laminated body, printed wiring board, and method for manufacturing electronic equipment   

The invention relates to a method for manufacturing a surface-treated copper foil, a copper foil with a carrier, a laminate, a printed wiring board, and a method for manufacturing an electronic device.

Great progress has been made in printed wiring boards in the last half century, and it is now used in almost all electronic machines. With the increasing demand for miniaturization and high performance of electronic devices in recent years, high-density mounting of components and high-frequency signals have been developed, and printed wiring boards are required to respond well to high frequencies.

In order to ensure the quality of the output signal, it is required to reduce the transmission loss of the high-frequency substrate. Transmission loss mainly includes dielectric loss caused by resin (substrate side) and conductor loss caused by conductor (copper foil side). The smaller the dielectric constant and the dielectric loss factor of the resin, the smaller the dielectric loss. In high-frequency signals, the main reason for conductor loss is that the higher the frequency, the smaller the cross-sectional area of the current flowing due to the skin effect of the current flowing only on the surface of the conductor, thereby increasing the resistance.

As a technique for reducing the transmission loss of high-frequency copper foil, for example, Patent Document 1 discloses a metal foil for high-frequency circuits, which is covered with silver or silver metal on one or both sides of the surface of the metal foil. A coating layer other than silver or a silver alloy, which is thinner than the thickness of the silver or silver alloy coating layer, is applied to the silver or silver alloy coating layer. Furthermore, it is described that it is possible to provide a metal foil which can reduce the loss due to the skin effect even in the ultra-high frequency region used for satellite communication.

In addition, Patent Document 2 discloses a roughened rolled copper foil for a high-frequency circuit, which is characterized in that the rolled surface of the rolled copper foil after recrystallization and annealing is obtained by X-ray diffraction. The integrated intensity (I (200)) is relative to the integrated intensity (I0 (200)) of the (200) plane obtained by X-ray diffraction of fine powder copper, and I (200) / I0 (200)> 40. After the rolled surface is roughened by electroplating, the arithmetic average roughness (hereinafter referred to as Ra) of the roughened surface is 0.02 μm to 0.2 μm, and the ten-point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm. The rolled copper foil is a material for a printed circuit board. Furthermore, it is described that it is possible to provide a printed circuit board that can be used at a high frequency exceeding 1 GHz.

Furthermore, Patent Document 3 discloses an electrolytic copper foil, which is characterized in that a part of the surface of the copper foil is a concave-convex surface composed of nodules and having a surface roughness of 2 μm to 4 μm. Furthermore, it is described that it is possible to provide an electrolytic copper foil excellent in high-frequency transmission characteristics.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 4161304

[Patent Document 2] Japanese Patent No. 4704025

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

Although various studies have been made on controlling the transmission loss of copper foil when used in high-frequency circuit substrates as described above, many areas remain to be developed. In addition, after the surface-treated copper foil is laminated with the resin from the surface-treated layer side and heated at a specified temperature and time (10 days at 180 ° C.), the peel strength of the surface-treated copper foil and the resin must be good.

The present inventors have found that the amount and surface treatment of a specified metal in a surface treatment layer obtained by forming a primary particle layer on a copper foil or a surface treatment layer obtained by forming a primary particle layer and a secondary particle layer are controlled. The ten-point average roughness Rz of the outermost layer of the layer can reduce transmission loss well even for high-frequency circuit substrates. After lamination with resin and heating at a specified temperature and time (10 days at 180 ° C), The peel strength of the surface-treated copper foil and the resin is good.

The present invention is based on the above-mentioned findings. In one aspect, it is a surface-treated copper foil having a copper foil and a surface-treated layer on one or both sides of the copper foil, the surface-treated layer having a primary particle layer, or It has a primary particle layer and a secondary particle layer in order from the copper foil side, the surface treatment layer contains Zn, and the amount of Zn in the surface treatment layer is 150 μg / dm ² or more; the surface treatment layer does not contain Ni, or When the surface treatment layer contains Ni, the adhesion amount of Ni in the surface treatment layer is 800 μg / dm ² or less; the surface treatment layer does not contain Co, or when the surface treatment layer contains Co, the surface treatment layer The adhesion amount of Co in the alloy is 3000 μg / dm ² or less; and the ten-point average roughness Rz of the outermost surface of the surface treatment layer is 1.5 μm or less.

In another aspect, the present invention is a surface-treated copper foil having a copper foil and a surface-treated layer on one or both sides of the copper foil, the surface-treated layer having a primary particle layer or from the copper foil side. It has a primary particle layer and a secondary particle layer in sequence; the surface treatment layer contains Zn and Mo, and the total adhesion amount of Zn and Mo in the surface treatment layer is 200 μg / dm ² or more; the surface treatment layer does not contain Ni, or When the surface treatment layer contains Ni, the adhesion amount of Ni in the surface treatment layer is 800 μg / dm ² or less; the surface treatment layer does not contain Co, or when the surface treatment layer contains Co, the surface treatment layer contains Co. The adhesion amount of Co is 3000 μg / dm ² or less; and the ten-point average roughness Rz of the outermost surface of the surface treatment layer is 1.5 μm or less.

In another embodiment of the surface-treated copper foil of this invention, the said surface-treatment layer contains Co.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Ni.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Co and Ni, and the total adhesion amount of Co and Ni in the surface-treated layer is 3500 μg / dm ² or less.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated copper foil and resin are prepared, and the surface-treated copper foil is laminated with the resin from the surface-treated layer side, and then the surface is peeled from the resin. When processing copper foil, peeling strength is 0.5 kg / cm or more.

In still another embodiment of the surface-treated copper foil of this invention, the said peeling strength is 0.7 kg / cm or more.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has, on the primary particle layer or the secondary particle layer, from the copper foil side in order: (A) selected from Ni and selected from Fe Alloy layer consisting of one or more elements in the group consisting of Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti, and (B) chromate treatment layer

Either or both of them.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has, on the primary particle layer or the secondary particle layer, from the copper foil side in this order: (A) selected from Ni and selected from Fe Alloy layer consisting of one or more elements in the group consisting of Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti, and (B) chromate treatment layer

Either one or two layers, and a silane coupling treatment layer.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has the Ni-Zn alloy layer and the chromate in this order from the copper foil side on the primary particle layer or the secondary particle layer. Either or both of the processing layers.

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has the Ni-Zn alloy layer and the chromate in this order from the copper foil side on the primary particle layer or the secondary particle layer. Either or both of the treatment layers, and a silane coupling treatment layer.

In still another embodiment of the surface-treated copper foil of this invention, the surface of the said surface-treated layer is equipped with the resin layer.

In another embodiment, the surface-treated copper foil of this invention is used for a high frequency circuit board.

In yet another aspect, the present invention is a copper foil with a carrier, which has an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier in sequence, and the ultra-thin copper layer is the surface-treated copper foil of the present invention.

In another aspect, this invention is a laminated body which has the surface-treated copper foil of this invention, or the copper foil with a carrier of this invention.

In still another aspect of the present invention, the present invention is a laminate including the copper foil with a carrier and the resin of the present invention, and a part or all of the end surface of the copper foil with a carrier is covered with the resin.

In still another aspect, the present invention is a laminated body in which one copper foil with a carrier of the present invention is laminated from the carrier side or the ultra-thin copper layer side to another carrier of the copper foil with a carrier of the present invention. Side or the ultra-thin copper layer side.

In another aspect, this invention is a manufacturing method of a printed wiring board using the surface-treated copper foil of this invention, or the copper foil with a carrier of this invention.

In yet another aspect, the present invention is a method for manufacturing a printed wiring board, including the steps of preparing the surface-treated copper foil of the present invention or the copper foil with a carrier of the present invention, and an insulating substrate; A step of laminating a foil with the insulating substrate to form a copper-clad laminated board, or a step of laminating the copper foil with a carrier and the insulating substrate after laminating the carrier with the copper foil with a carrier to form a copper-clad laminated board; Either the addition method, the subtraction method, the partial addition method, or the modified semi-addition method forms a circuit.

In still another aspect of the present invention, a method for manufacturing a printed wiring board includes the steps of forming a circuit on the surface of the surface-treated layer side of the surface-treated copper foil of the present invention, or forming the copper foil with a carrier of the present invention. Forming a circuit on the side surface of the ultra-thin copper layer or the side surface of the carrier; to bury the circuit, on the surface-treated layer side surface of the surface-treated copper foil, or on the side of the ultra-thin copper layer of the copper foil with a carrier Forming a resin layer on the surface or the carrier side surface; and by removing the surface-treated copper foil after forming the resin layer, or by removing the ultra-thin copper layer or the carrier after peeling the carrier or the ultra-thin copper layer, The circuit buried in the resin layer is exposed.

In yet another aspect, the present invention is a method for manufacturing a printed wiring board, comprising the steps of: laminating the carrier side surface or the ultra-thin copper layer side surface of the copper foil with a carrier of the present invention with a resin substrate; The surface of the copper foil with a carrier on the side opposite to the laminated side of the resin substrate is provided with two layers of a resin layer and a circuit at least once; and after the two layers of the resin layer and the circuit are formed, the above is peeled from the copper foil with a carrier Carrier or very thin copper layer as described above.

In yet another aspect, the present invention is a method for manufacturing a printed wiring board, comprising the steps of: providing at least one layer of a resin layer and a circuit on either or both sides of the laminated body of the present invention; and After the two layers of the resin layer and the circuit, the carrier or the ultra-thin copper layer is peeled from the copper foil with a carrier constituting the laminated body.

In still another aspect, the present invention is a method for manufacturing an electronic device using a printed wiring board, and the printed wiring board is manufactured by the method of the present invention.

According to the present invention, it is possible to provide a surface-treated copper foil that can reduce transmission loss well even when used in a high-frequency circuit board, and after being laminated with a resin and heated at a specified temperature and time (10 days at 180 ° C), The peel strength of the surface-treated copper foil and the resin is good.

FIGS. 1A to 1C are schematic cross-sectional views of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, in steps from plating a circuit to removing a resist.

2D to F are schematic cross-sectional views of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, in steps from a laminated resin and a second layer of copper foil with a carrier to laser openings.

3G to I are schematic cross-sectional views of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, from a step of forming a through-hole filler to a step of peeling a first-layer carrier.

4J ~ K are schematic cross-sectional views of a wiring board in a specific example of a method for manufacturing a printed wiring board using the copper foil with a carrier according to the present invention, in steps from rapid etching to formation of bumps and copper pillars.

<Surface-treated copper foil>

The surface-treated copper foil of the present invention includes a copper foil and a surface-treated layer on one or both sides of the copper foil. After the surface-treated copper foil of the present invention is bonded to an insulating substrate, the surface-treated copper foil can be etched into a target conductor pattern, and a printed wiring board can be finally manufactured. The surface-treated copper foil of the present invention can also be used as a surface-treated copper foil for a high-frequency circuit board. Here, the high-frequency circuit board refers to a circuit board having a frequency of a signal transmitted by a circuit using the circuit board of 1 GHz or higher. In addition, the frequency of the above signal is preferably 3 GHz or more, more preferably 5 GHz or more, more preferably 8 GHz or more, more preferably 10 GHz or more, more preferably 15 GHz or more, more preferably 18 GHz or more, more preferably 20 GHz or more, It is preferably at least 30 GHz, more preferably at least 38 GHz, and even more preferably at least 40 GHz.

<Copper foil>

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

As the copper foil material, in addition to fine copper (JIS H3100 alloy number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) or phosphorous deoxidized copper (JIS H3100 alloy), which are generally used as conductor patterns of printed wiring boards In addition to high-purity copper such as C1201, C1220, or C1221) or electrolytic copper, for example, Sn-added copper, Ag-added copper, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, and Ni can be used. , Copper alloys such as Si, Zr, and / or Mg, and copper alloys such as corson-based copper alloys to which Ni and Si are added. In addition, a copper foil and a copper alloy foil having a known composition can also be used. In this specification, when the term "copper foil" is used alone, copper alloy foil is also included.

In addition, the thickness of the copper foil need not be particularly limited, for example, 1 to 1000 μm, or 1 to 500 μm, or 1 to 300 μm, or 3 to 100 μm, or 5 to 70 μm, or 6 to 35 μm, or 9 ~ 18μm.

In addition, in another aspect, the present invention is a copper foil with a carrier. One or both sides of the carrier have an intermediate layer and an ultra-thin copper layer in this order, and the ultra-thin copper layer is the surface-treated copper foil of the present invention. 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 provided on the surface of the ultra-thin copper layer. In addition, another embodiment of the copper foil with a carrier will be described below.

<Surface treatment layer>

The surface treatment layer has a primary particle layer, or a primary particle layer and a secondary particle layer in this order from the copper foil side. The primary particle layer and the secondary particle layer are formed of a plating layer. The secondary particle is characterized in that it is one or a plurality of particles growing on the primary particle. Or the secondary particle layer is a normal plating layer grown on the primary particles. The secondary particles may have a dendritic shape. That is, in this specification, when the term "secondary particle layer" is used, a normal plating layer such as a coating plating layer is also included. In addition, the secondary particle layer may have one or more layers made of roughened particles, one or more normal plating layers, or one or more layers made of roughened particles and normal plating layers, respectively. The surface treatment layer may have one or more layers other than the primary particle layer or the secondary particle layer.

In addition, the primary particle layer is a layer containing roughened particles as described below: roughened particles directly formed on a copper foil; and roughened particles superimposed on the roughened particles, which are composed and formed directly on the copper foil. The roughened particles are the same or have the same elements as the roughened particles formed directly on the copper foil. The secondary particle layer is a layer containing roughened particles that are formed on the roughened particles included in the primary particle layer and have a composition different from that of the roughened particles that form the primary particle layer, or contain primary particles that form the primary particles. Element not contained in the coarsened particles of the layer.

When it is not possible to measure the presence or absence of an element constituting the primary particle and / or the secondary particle, and / or the concentration or adhesion amount of the element, the primary particle and the secondary particle are, for example, a scanning electron microscope. When observing a photograph, particles that appear to overlap and exist on the copper foil side (below) and non-overlapping particles can be regarded as primary particles, and particles that appear to overlap and exist on other particles can be determined as secondary particles. .

In one aspect of the surface-treated copper foil of the present invention, the surface-treated layer contains Zn, and the adhesion amount of Zn in the surface-treated layer is 150 μg / dm ² or more. If the adhesion amount of Zn is less than 150 μg / dm ² , there is a concern that heat resistance is poor when used as a surface-treated copper foil for a high-frequency circuit substrate. The deposition amount of Zn is preferably 155μg / dm ² or more, preferably 165μg / dm ² or more, preferably 180μg / dm ² or more, preferably 200μg / dm ² or more, preferably 250μg / dm ² or more, preferably 270μg / dm ² or more, preferably 280μg / dm ² or more, and further more preferably 290μg / dm ² or more. The upper limit of adhesion amount of Zn is no special setting, typically for example, 50000μg / ² or less dm, for example, 30000μg / ² or less dm, for example, 10000μg / ² or less dm, for example 5000μg / dm ² or less, for example 3000μg / dm ² Hereinafter, it is, for example, 2000 μg / dm ² or less, and for example, 1000 μg / dm ² or less.

In addition, in the present invention, although the adhesion amount of elements such as Zn, Ni, Co, and Mo in the surface treatment layer is specified, these are surface treatment layers for one surface when the surface treatment layer is present on both sides of the copper foil. The stipulation of 并非 is not the total value of the elements (such as Zn) contained in the surface-treated layer formed on both sides.

In another aspect of the surface-treated copper foil of the present invention, the surface-treated layer contains Zn and Mo, and the total adhesion amount of Zn and Mo in the surface-treated layer is 200 μg / dm ² or more. If the total adhesion amount of Zn and Mo is less than 200 μg / dm ² , there is a concern that the heat resistance is poor when used as a surface-treated copper foil for a high-frequency circuit substrate. The total deposition amount of Zn and Mo is preferably from 250μg / dm ² or more, more preferably 300μg / dm ² or more, more preferably 340μg / dm ² or more, more preferably 360μg / dm ² or more, more preferably 400μg / dm ² or more, more preferably 420 μg / dm ² or more, more preferably 450 μg / dm ² or more, more preferably 460 μg / dm ² or more, and even more preferably 500 μg / dm ² or more. The Zn and Mo, the total upper limit of adhesion amount is no special setting, typically for example 100000μg / ² or less dm, for example, 50000μg / ² or less dm, for example, 30000μg / ² or less dm, for example, 10000μg / ² or less dm, for example, 8000μg A / dm ^2, for example 5000μg / ² or less dm, for example 3000μg / ² or less dm, e.g. ² or less of 1000μg / dm.

The surface-treated layer of the surface-treated copper foil of the present invention does not contain Co, or when the surface-treated layer contains Co, the adhesion amount of Co in the surface-treated layer is 3000 μg / dm ² or less. If the adhesion amount of Co exceeds 3000 μg / dm ² , there is a concern that a problem of deterioration in high-frequency transmission characteristics may occur. The deposition amount of Co is more preferably 2900μg / dm ² or less, more preferably 2800μg / dm ² or less, more preferably 2790μg / dm ² or less, more preferably 2700μg / dm ² or less, more preferably 2500μg / dm ² or less, Further more preferably 1500μg / dm ² or less, and further more preferably 1000μg / dm ² or less. In addition, when the surface treatment layer contains Co, the lower limit of the adhesion amount of Co in the surface treatment layer does not need to be particularly limited, and the adhesion amount of Co is typically, for example, greater than 0 μg / dm ² , for example, 0.10 μg / dm ² or more, for example, 1 μg. A / dm ^2, for example, [mu] g A / dm ^2, for example 3 ug A / dm ^2, for example, 4 ug A / dm ^2, for example 5 ug A / dm ^2, for example, 10 g A / dm ^2, for example, 15μg / dm ² or more, for example, 20 μg / dm ² or more. In addition, when the surface-treated layer contains Co, the effect of improving the weather resistance of the surface-treated copper foil may be produced compared with the case where Co is not contained.

The surface-treated layer of the surface-treated copper foil of the present invention does not contain Ni, or when the surface-treated layer contains Ni, the adhesion amount of Ni in the surface-treated layer is 800 μg / dm ² or less. If the adhesion amount of Ni exceeds 800 μg / dm ² , there is a concern that a problem of deterioration in high-frequency transmission characteristics may occur. The amount of deposition of Ni is more preferably 750μg / dm ² or less, and further more preferably 600μg / dm ² or less, and further more preferably 400μg / dm ² or less, and more preferably ² or less 250μm / dm. In addition, when the surface treatment layer contains Ni, the lower limit of the adhesion amount of Ni in the surface treatment layer does not need to be particularly limited. The adhesion amount of Ni is typically, for example, greater than 0 μg / dm ² , for example, 0.10 μg / dm ² or more, for example, 1 μg. A / dm ^2, for example, [mu] g A / dm ^2, for example 3 ug A / dm ^2, for example, 4 ug A / dm ^2, for example 5 ug A / dm ^2, for example, 10 g A / dm ^2, for example, 15μg / dm ² or more, for example, 20 μg / dm ² or more. In addition, when the surface-treated layer contains Ni, the effect of improving the chemical resistance of the surface-treated copper foil may be produced compared with the case where Ni is not contained.

The surface-treated layer of the surface-treated copper foil of the present invention further contains Co and Ni, and the total adhesion amount of Co and Ni in the surface-treated layer is preferably 3500 μg / dm ² or less. If the total adhesion amount of Co and Ni exceeds 3500 μg / dm ² , there is a concern that a problem of deterioration in high-frequency transmission characteristics may occur. The total adhesion amount of Co and Ni is more preferably 3100 μg / dm ² or less, even more preferably 1900 μg / dm ² or less, and even more preferably 1400 μg / dm ² or less. In addition, when the surface treatment layer contains Co and Ni, the lower limit of the total adhesion amount of Co and Ni in the surface treatment layer need not be particularly limited, and the total adhesion amount of Co and Ni is typically, for example, greater than 0 μg / dm ² , for example, 0.10 μg A / dm ^2, for example, [mu] g A / dm ^2, for example, [mu] g A / dm ^2, for example 3 ug A / dm ^2, for example, 4 ug A / dm ^2, for example 5 ug A / dm ^2, for example, 10μg / dm ² or more, for example, 15 μg / dm ² or more, for example, 20 μg / dm ² or more, for example, 30 μg / dm ² or more, for example, 40 μg / dm ² or more, for example, 50 μg / dm ² or more, for example, 60 μg / dm ² or more It is, for example, 70 μg / dm ² or more. In addition, when the surface treatment layer contains Co and Ni, the effect of improving the chemical resistance and weather resistance of the surface-treated copper foil may be produced compared with the case where Co and Ni are not included.

In addition, by increasing the concentration of the element in the surface treatment liquid used when forming the surface treatment layer, and / or increasing the current density when the surface treatment is plating, and / or extending the surface treatment time (plating Time, etc.), the amount of adhesion of the elements contained in the surface treatment layer can be increased. In addition, by reducing the concentration of the element in the surface treatment liquid used when forming the surface treatment layer, and / or reducing the current density when the surface treatment is plating, and / or shortening the surface treatment time (plating is performed) Time, etc.), it is possible to reduce the amount of adhesion of elements contained in the surface treatment layer.

The ten-point average roughness Rz of the outermost surface of the surface-treated layer of the surface-treated copper foil of the present invention is 1.5 μm or less. If the ten-point average roughness Rz of the outermost surface of the surface treatment layer exceeds 1.5 μm, there is a concern that a problem of deterioration in high-frequency transmission characteristics may occur. The ten-point average roughness Rz of the outermost surface of the surface treatment layer is more preferably 1.3 μm or less, still more preferably 1.1 μm or less, even more preferably 1.0 μm or less, and still more preferably 0.9 μm or less. When a surface treatment layer is formed by a plurality of layers formed by surface treatment, the "surface treatment layer outermost surface" refers to the surface of the outermost (most surface) layer of the plurality of layers. The ten-point average roughness Rz was measured on the surface of the outermost (topmost) layer of the plurality of layers. The lower limit of the ten-point average roughness Rz of the outermost surface of the surface treatment layer is not particularly limited, and is typically, for example, 0.01 μm or more, for example, 0.05 μm or more, for example, 0.1 μm or more.

The surface-treated layer of the surface-treated copper foil of the present invention may be provided on the primary particle layer or the secondary particle layer in order from the copper foil side: (A) from Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta Alloy layer composed of one or more elements in the group consisting of Cu, Al, P, W, Mn, Sn, As, and Ti, and (B) a chromate-treated layer

Either or both of them.

In addition, the surface-treated layer of the surface-treated copper foil of the present invention may have, on the primary particle layer or the secondary particle layer, from the copper foil side in order: (A) from Ni and selected from Fe, Cr, Mo, Zn, An alloy layer composed of one or more elements in a group consisting of Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and (B) a chromate-treated layer

Either one or two layers, and a silane coupling treatment layer.

In addition, the surface-treated layer of the surface-treated copper foil of the present invention may have any one or both of a Ni-Zn alloy layer and a chromate-treated layer in order from the copper foil side on the primary particle layer or the secondary particle layer. Floor.

In addition, the surface-treated layer of the surface-treated copper foil of the present invention may have any one or both of a Ni-Zn alloy layer and a chromate-treated layer in order from the copper foil side on the primary particle layer or the secondary particle layer. Layer, and a silane coupling treatment layer.

The Ni-Zn alloy layer is an alloy layer containing Ni and Zn. The Ni-Zn alloy layer may be a layer in which the total concentration of Ni and Zn is 80 atomic% or more. The total concentration of Ni and Zn can be measured by performing atomic concentration analysis of Ni and Zn in the depth direction using XPS or the like, and totalizing the obtained Ni atom concentration and Zn atom concentration. The Ni-Zn alloy layer may be a layer composed of only Ni and Zn.

In the surface-treated copper foil of the present invention, the surface-treated copper foil and the resin are prepared, the surface-treated copper foil is laminated with the resin from the surface-treated layer side, and the surface-treated copper foil is etched to produce a 10 mm wide circuit. When the resin peels the circuit in the 90 ° direction, the peel strength can reach 0.5 kg / cm or more, and the peel strength can further reach 0.7 kg / cm or more.

In addition, in the surface-treated copper foil of the present invention, the surface-treated copper foil and the resin are prepared, the surface-treated copper foil is laminated with the resin from the surface-treated layer side, and the surface-treated copper foil is etched to produce a 10 mm wide circuit, and After the circuit was heated at 180 ° C. for 10 days in the atmosphere, when the circuit was peeled from the resin in a 90 ° direction, the peel strength could reach 0.4 kg / cm or more, and the peel strength could further reach 0.5 kg / cm or more.

The conditions for the resin and the laminate are any one, two, or three of the following (1) to (3). That is, it is preferable that the peeling strength obtained based on any one of the conditions (1) to (3) be within the above range.

(1) Resin: a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, that is, a liquid crystal polymer resin, with a thickness of 50 μm

Conditions of lamination: pressure 3.5MPa, heating temperature 300 ℃, heating time 10 minutes

(2) Resin: low-dielectric polyfluorene imide resin, thickness 50 μm

Layering conditions: pressure 4MPa, heating temperature 300 ℃, heating time 10 minutes

(3) Resin: polytetrafluoroethylene, thickness 50μm

<Transmission loss>

When the transmission loss is small, the signal attenuation is suppressed when the signal is transmitted at a high frequency. Therefore, in a circuit where the signal is transmitted at a high frequency, stable signal transmission can be performed. Therefore, a small transmission loss value is suitable for a circuit application in which a signal is transmitted at a high frequency, so it is preferable. The surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ manufactured by Kuraray Co., Ltd.-a resin having a thickness of 50 μm and a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)). The microstrip circuit is formed by etching so that the characteristic impedance becomes 50Ω. The transmission coefficient is measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20GHz and 40GHz is obtained. At this time, the transmission loss at a frequency of 20GHz is better. It is less than 5.0dB / 10cm, more preferably less than 4.1dB / 10cm, and even more preferably less than 3.7dB / 10cm.

<Copper foil with carrier>

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

<Carrier>

The carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin film, Polyimide film, LCP (liquid crystal polymer) film, fluororesin film, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyimide film, polyimide film Provided by the form.

The carrier that can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and rolled copper foil is produced by repeatedly performing plastic processing and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), phosphorus deoxidized copper, or electrolytic copper, for example, Copper alloys such as Sn-added copper, Ag-added copper, copper alloys such as Cr, Zr, or Mg, and Carson-based copper alloys such as Ni and Si may also be used. Alternatively, a known copper alloy may be used. In addition, in this specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is not particularly limited as long as it functions as a carrier and is appropriately adjusted to a suitable thickness, for example, it can be 5 m or more. However, if it is too thick, the production cost will increase, so it is generally preferred to be 35 μm or less. Therefore, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. From the viewpoint of reducing the cost of raw materials, the thickness of the carrier is preferably small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, and preferably 5 μm or more and 10 μm or less. In addition, when the thickness of the carrier is small, folding wrinkles are easily generated when the carrier sends the foil. In order to prevent the occurrence of folding wrinkles, for example, it is effective to smooth the conveyance roller of the copper foil manufacturing apparatus with a carrier or shorten the distance between the conveyance roller and the next conveyance roller. In addition, when the copper foil with a carrier is used for the embedding method (Enbedded Process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, in the case of the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and further preferably 35 μm or more and 70 μm or less. the following.

In addition, a primary particle layer and a secondary particle layer may be provided on the surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided. Providing the primary particle layer and the secondary particle layer on the surface of the carrier opposite to the surface on which the ultra-thin copper layer is provided has the advantage that when the carrier is laminated from the surface side having the primary particle layer and the secondary particle layer on When a support such as a resin substrate is used, the carrier and the resin substrate are not easily separated.

Hereinafter, an example of the manufacturing conditions when an electrolytic copper foil is used as a carrier is shown.

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

The rest of the treatment liquid used in the electrolysis, surface treatment, plating, or the like of the present invention is water unless otherwise specified.

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

<Manufacturing conditions>

Current density: 70 ~ 100A / dm ²

Electrolyte temperature: 50 ~ 60 ℃

Linear speed of electrolyte: 3 ~ 5m / sec

Electrolysis time: 0.5 ~ 10 minutes

<Middle layer>

An intermediate layer is provided on the carrier. Other layers may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it has a structure that "the extremely thin copper layer is not easily peeled from the carrier before the step of laminating the copper foil with the carrier onto the insulating substrate, and on the other hand, After the step of laminating, the ultra-thin copper layer can be peeled from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may contain a material selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloys, these hydrates, these One or two or more of the group consisting of oxides and organic substances. The intermediate layer may be a plurality of layers.

In addition, for example, the intermediate layer can be formed by forming a single metal layer from the carrier side, which is composed of an element group selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. Or an alloy layer consisting of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn ; And a layer is formed thereon, which is a hydrate of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or Consisting of an oxide or an organic substance; or a single metal layer consisting of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn; or The alloy layer is composed of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn.

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

In addition, for example, the intermediate layer may be formed by sequentially stacking nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, and chromium on a carrier. Because the adhesion between nickel and copper is higher than the adhesion between chromium and copper, peeling occurs at the interface between the ultra-thin copper layer and chromium when the ultra-thin copper layer is peeled. In addition, for the nickel in the intermediate layer, a barrier effect to prevent the diffusion of the copper component from the carrier to the ultra-thin copper layer is expected. The intermediate layer adhering amount of nickel is preferably 100μg / dm ² or more and 40000μg / dm ² or less, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² Hereinafter, it is 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>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating with electrolytic baths of copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., because copper sulfate bath is used for general electrolytic copper foil and can be formed with high current density Copper foil is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, and is, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, even more typically 1.5 to 5 μm, and even more typically 2 to 5 μm. In addition, an extremely thin copper layer may be provided on both sides of the carrier.

<Formation Conditions of Primary Particle Layer and Secondary Particle Layer>

In the case of surface-treated copper foil, a primary particle layer is formed on the copper foil, or a primary particle layer and a secondary particle layer are sequentially formed. In the case of a copper foil with a carrier, primary particles are formed on an extremely thin copper layer. Layer, or a primary particle layer and a secondary particle layer are sequentially formed. The formation conditions of the primary particle layer and the secondary particle layer are shown below, but this is only an appropriate example. As long as the adhesive strength with the resin used is sufficient, for example, the initial peeling is in the range of 0.5 kg / cm or more, the following Any plating conditions other than those shown may be used. The invention includes these conditions.

‧Primary particle layer

After the treatment with the primary particle plating solution (I) and the treatment with the primary particle plating solution (II), a primary particle layer can be formed under the following conditions.

(Treatment with primary particle plating solution (I))

<Electrolyte composition>

Copper: 5 ~ 10g / L

Sulfuric acid: 70 ~ 80g / L

<Manufacturing conditions>

Current density: 50 ~ 55A / dm ²

Electrolyte temperature: 35 ° C

Electrolysis time: 0.5 ~ 1.6 seconds

(Treatment with primary particle plating solution (II))

<Electrolyte composition>

Copper: 20 ~ 50g / L

Sulfuric acid: 60 ~ 100g / L

<Manufacturing conditions>

Current density: 4 ~ 10A / dm ²

Electrolyte temperature: 35 ~ 45 ℃

Electrolysis time: 1.4 ~ 2.5 seconds

In the case where the primary particle layer is formed only by processing with the primary particle plating solution (I), the following treatments using the primary particle plating solution (I) 1 or the primary particle plating solution (I) It is implemented under the conditions described in Process 2.

(Treatment with primary particle plating solution (I) 1)

<Electrolyte composition>

Copper: 10 ~ 45g / L

Cobalt: 5 ~ 30g / L

Nickel: 5 ~ 30g / L

pH value: 2.8 ~ 3.2

<Manufacturing conditions>

Current density: 30 ~ 45A / dm ²

Electrolyte temperature: 30 ~ 40 ℃

Electrolysis time: 0.3 ~ 0.8 seconds

(Treatment with primary particle plating solution (I) 2)

<Electrolyte composition>

Copper: 5 ~ 15g / L

Nickel: 3 ~ 30g / L

pH value: 2.6 ~ 3.0

<Manufacturing conditions>

Current density: 50 ~ 70A / dm ²

Electrolyte temperature: 30 ~ 40 ℃

Electrolysis time: 0.3 ~ 0.9 seconds

‧Secondary particle layer

When forming a secondary particle layer, it can implement by the following process using a secondary particle plating liquid (I) or a secondary particle plating liquid (II).

(Treatment with secondary particle plating solution (I))

<Electrolyte composition>

Copper: 10 ~ 15g / L

Cobalt: 5 ~ 15g / L

Nickel: 5 ~ 15g / L

pH value: 2.8 ~ 3.2

<Manufacturing conditions>

Current density: 30 ~ 35A / dm ²

Electrolyte temperature: 33 ~ 37 ℃

Electrolysis time: 0.5 ~ 1.0 seconds

(Treatment with secondary particle plating solution (II))

<Electrolyte composition>

Copper: 5 ~ 12g / L

Nickel: 2 ~ 11g / L

pH value: 2.8

<Manufacturing conditions>

Current density: 55 ~ 65A / dm ²

Electrolyte temperature: 35 ~ 40 ℃

Electrolysis time: 0.3 ~ 0.9 seconds

<Coated plating>

Coating is performed on the primary particle layer or, when forming the secondary particle layer, on the secondary particle layer. Examples of the layer formed by the coating plating include a Zn-Cr alloy layer, a Ni-Mo alloy layer, a Zn layer, a Co-Mo alloy layer, a Co-Ni alloy layer, a Ni-W alloy layer, and a Ni-P alloy. Layer, Ni-Fe alloy layer, Ni-Al alloy layer, Co-Zn alloy layer, Co-P alloy layer, Zn-Co alloy layer, Ni layer, Co layer, Cr layer, Al layer, Sn layer, Sn-Ni Layers, Ni-Sn layers, Zn-Ni alloy layers, etc. are selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, and Co. A metal layer composed of one element in the group or a group selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, and Co Two or three or more alloy layers, or an alloy layer composed of two or more elements selected from the above-mentioned element group.

The coating plating can be performed by using the following coating plating liquids or the like, or by combining these processes. In addition, a metal layer and / or an alloy layer that cannot be provided by wet plating can be provided by a dry plating method such as sputtering, physical vapor deposition (PVD), or chemical vapor deposition (CVD).

‧Treatment with coating solution (1) Zn-Cr

Liquid composition: potassium dichromate 1 ~ 1g / L, Zn0.1 ~ 5g / L

Liquid temperature: 40 ~ 60 ℃

pH value: 0.5 ~ 10

Current density: 0.01 ~ 2.6A / dm ²

Power-on time: 0.05 ~ 30 seconds

‧Treatment by coating liquid (2) Ni-Mo

Liquid composition: nickel sulfate 270 ~ 280g / L, nickel chloride 35 ~ 45g / L, nickel acetate 10 ~ 20g / L, sodium molybdate 1 ~ 60g / L, trisodium citrate 10 ~ 50g / L, dodecane Sodium sulfate 50 ~ 90ppm

Liquid temperature: 20 ~ 65 ℃

pH value: 4 ~ 12

Current density: 0.5 ~ 5A / dm ²

Power-on time: 0.1 ~ 5 seconds

‧Treatment by coating liquid (3) Zn

Liquid composition: Zn1 ~ 15g / L

Liquid temperature: 25 ~ 50 ℃

pH value: 2 ~ 6

Current density: 0.5 ~ 5A / dm ²

Power-on time: 0.01 ~ 0.3 seconds

‧Treatment by coating liquid (4) Co-Mo

Liquid composition: Co1 ~ 20g / L, sodium molybdate 1 ~ 60g / L, sodium citrate 10 ~ 110g / L

Liquid temperature: 25 ~ 50 ℃

pH value: 5 ~ 7

Current density: 1 ~ 4A / dm ²

Power-on time: 0.1 ~ 5 seconds

‧Treatment with coating bath (5) Co-Ni

Liquid composition: Co1 ~ 20g / L, N1 ~ 20g / L

Liquid temperature: 30 ~ 80 ℃

pH value: 1.5 ~ 3.5

Current density: 1 ~ 20A / dm ²

Power-on time: 0.1 ~ 4 seconds

‧Treatment with coating solution (6) Zn-Ni

Liquid composition: Zn1 ~ 30g / L, N1 ~ 30g / L

Liquid temperature: 40 ~ 50 ℃

pH value: 2 ~ 5

Current density: 0.5 ~ 5A / dm ²

Power-on time: 0.01 ~ 0.3 seconds

‧Treatment by coating liquid (7) Ni-W

Liquid composition: Ni1 ~ 30g / L, W1 ~ 300mg / L

Liquid temperature: 30 ~ 50 ℃

pH value: 2 ~ 5

Current density: 0.1 ~ 5A / dm ²

Power-on time: 0.01 ~ 0.3 seconds

‧Treatment with coating plating solution (8) Ni-P

Liquid composition: Ni1 ~ 30g / L, P1 ~ 10g / L

Liquid temperature: 30 ~ 50 ℃

pH value: 2 ~ 5

Current density: 0.1 ~ 5A / dm ²

Power-on time: 0.01 ~ 0.3 seconds

<Other surface treatments>

After the coating is plated, treatments such as chromate treatment and silane coupling treatment may be performed on the surface. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface of the primary particle layer or the secondary particle layer. In addition, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

In the present specification, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate-treated layer may also contain elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti (can be metals, alloys, oxides, nitrides, sulfides And so on). Specific examples of the chromate treatment layer include a chromate treatment layer treated with a chromic anhydride or an aqueous potassium dichromate solution or a chromate treated with a treatment solution containing chromic anhydride, potassium dichromate, and zinc. Processing layer, etc.

As a heat-resistant layer and a rust-proof layer, a well-known heat-resistant layer and a rust-proof layer can be used. For example, the heat-resistant layer and / or the rust-proof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron A layer of one or more elements in the group of tantalum may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. A metal layer or an alloy layer composed of one or more elements of the group of elements, iron, and tantalum. The heat-resistant layer and / or the rust-preventive layer may have oxides, nitrides, and silicides containing the above elements. The heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The above nickel-zinc alloy layer may contain, in addition to unavoidable impurities, 50% to 99% by weight of nickel and 50% to 1% by weight of zinc. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , and preferably 20 to 100 mg / m ² . The ratio of the amount of nickel deposited to the amount of nickel deposited on the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer (= nickel deposited / zinc deposited) is preferably 1.5 to 10. The nickel-zinc alloy-containing layer or the nickel-zinc alloy layer preferably has an adhesion amount of nickel of 0.5 mg / m ² to 500 mg / m ² , and more preferably 1 mg / m ² to 50 mg / m ² . In the case where the heat-resistant layer and / or the rust-proof layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is not easily removed when the inner wall portion of the through hole or the via hole is in contact with the desizing solution. The slag liquid is eroded, and the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and / or the rust-proof layer are sequentially laminated with a nickel or nickel alloy layer with an adhesion amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and an adhesion amount of 1 mg / m ² m ² to 80 mg / m ² , preferably 5 mg / m ² to 40 mg / m ² , the above-mentioned nickel alloy layer may also be made of nickel-molybdenum alloy, nickel-zinc alloy, nickel-molybdenum-cobalt alloy, It is composed of any of nickel-tin alloys.

The silane coupling treatment layer may be formed using a known silane coupling agent, or epoxy silane, amine silane, methacryloxy silane, mercapto silane, ethylene silane, imidazole silane, trisilane It is formed by a silane coupling agent such as silane. The silane coupling agent may be used in combination of two or more. Among them, it is preferably formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent.

In addition, the surface of a copper foil, an ultra-thin copper layer, a roughened layer, a heat-resistant layer, a rust-proof layer, a silane coupling-treated layer, or a chromate-treated layer can be subjected to a known surface treatment.

The surface-treated layer of the present invention may contain a layer formed by the surface treatment. For example, the surface treatment layer of the present invention may contain one or more of the above-mentioned coated plating layers, and / or metal layers, and / or alloy layers, and / or heat-resistant layers, and / or rust-proof layers, and / or chromates. The treatment layer and / or the silane coupling treatment layer and / or the roughening treatment layer.

As described above, a surface-treated copper foil and / or a copper foil with a carrier including a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer are produced. The use of the surface-treated copper foil and / or the copper foil with a carrier itself is well known to the industry. For example, the surface of the surface-treated copper foil and / or the ultra-thin copper layer can be bonded to a paper base phenol resin, Paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin, glass cloth substrate epoxy resin, polyester film , Polyimide film, liquid crystal polymer, fluororesin, polyimide resin, low dielectric polyimide film and other insulating substrates (in the case of copper foil with a carrier, the carrier is peeled off after thermocompression bonding) A copper-clad laminated board is formed, and then a copper foil and / or an ultra-thin copper layer on the surface of the insulating substrate is etched into a target conductor pattern, and a printed wiring board is finally manufactured.

<Resin layer>

The surface-treated copper foil of the present invention may include a resin layer on the surface of the surface-treated layer. In addition, an alloy layer composed of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and chromium may also be used. A resin layer is provided on the surface of the acid-treated layer, the silane coupling-treated layer, or the Ni-Zn alloy layer. The resin layer is more preferably formed on the outermost surface of the surface-treated copper foil.

The copper foil with a carrier of the present invention may be provided with a resin layer on the primary particle layer or the secondary particle layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer.

The resin layer may be an adhesive or a semi-hardened (B-stage) insulating resin layer. The semi-hardened state (stage B) includes a state in which the surface of the insulating resin layer is not overlapped when touched with a finger, and the insulating resin layer can be stored in an overlapping manner, and a hardening reaction occurs when subjected to heat treatment.

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The type is not particularly limited, and examples of preferred resins include those selected from epoxy resins, polyimide resins, polyfunctional cyanate compounds, maleimide compounds, and polymaleimide compounds. , Maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, amine ester resin, polyether resin (also known as polyethersulphone), polyether resin (polyethersulphone) resin, aromatic polymer Fluorene resin, aromatic polyamine resin polymer, rubber resin, polyamine, aromatic polyamine, polyamidamine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile- Butadiene resin, polyphenylene ether, bismaleimide Resin, thermosetting polyphenylene ether resin, cyanate resin, anhydride of carboxylic acid, anhydride of polycarboxylic acid, linear polymer having functional group capable of crosslinking, polyphenylene ether resin, 2,2-bis ( 4-cyanophenyl) propane, phosphorus-containing phenol compounds, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, silicone Modified polyamidoimide resin, cyanoester resin, phosphazene-based resin, rubber modified polyamidoimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, One or more resins in the group of phenoxy resin, polymer epoxy, aromatic polyamido, fluororesin, bisphenol, block copolymer polyamidoimide resin, and cyanoester resin.

In addition, as long as the epoxy resin has two or more epoxy groups in the molecule and can be used for electrical and electronic material applications, it can be used without particular problems. The epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in a molecule. In addition, it can be selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, and cresol novolac type. Epoxy resin, alicyclic epoxy resin, brominated (stinky) epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac Type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, glycidylamine compounds such as N, N-diglycidylaniline, etc. Glycidyl ester compounds such as diglycidyl hydrophthalate, epoxy resin containing phosphorus, biphenyl epoxy resin, biphenol novolac epoxy resin, trihydroxyphenylmethane epoxy resin, tetrabenzene One or two or more of the ethane type epoxy resins are used, or a hydride or halide of the epoxy resin can be used.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. The above-mentioned phosphorus-containing epoxy resin is preferably in the form of a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule, for example. Obtained epoxy resin.

The resin layer may contain any dielectric such as a known resin, a resin hardener, a compound, a hardening accelerator, and a dielectric (a dielectric containing an inorganic compound and / or an organic compound, a dielectric containing a metal oxide, or the like may be used) Body), reaction catalyst, cross-linking agent, polymer, prepreg, framework material, etc. The resin layer may be formed using a known formation method or formation device.

These resins are dissolved in a solvent such as methyl ethyl ketone (MEK), toluene and the like to prepare a resin solution, and the resin is applied to the surface-treated copper foil by a roll coater method, and / or the above. On the ultra-thin copper layer, or on the surface treatment layer containing the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane coupling agent layer, etc., next, it is heated and dried as necessary to remove the solvent. It is a B-phase state. For the 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 surface-treated copper foil provided with the said resin layer and / or the copper foil with a carrier (copper foil with a resin with a carrier) are used in the form which superimposed this resin layer on a base material, and thermocompression-bonded the whole, The resin layer is thermally cured. Next, in the case of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed). A very thin copper layer forms a specified wiring pattern.

By using the surface-treated copper foil with a resin and / or a copper foil with a carrier, it is possible to reduce the number of sheets of prepreg used in manufacturing a multilayer printed wiring board. In addition, the thickness of the resin layer can be set to a thickness capable of ensuring interlayer insulation, or a copper-clad laminated board can be manufactured without using a prepreg at all. In addition, at this time, the surface of the substrate may be under-coated with an insulating resin to further improve the surface smoothness.

In addition, when a prepreg material is not used, there are advantages in that the material cost of the prepreg material is saved, and the lamination step is also simplified, so it is economically advantageous, and the multilayer printed wiring board is manufactured. The reduced thickness reduces the thickness of the prepreg material, and it is possible to manufacture an extremely thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of this resin layer is preferably 0.1 to 80 μm. If the thickness of the resin layer is less than 0.1 μm, the adhesion force will be reduced. When the resin-coated copper foil with a carrier is laminated on a substrate having an inner layer material without interposing a prepreg, it may be difficult to secure the inner layer. Insulation between layers of metal circuits.

On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer of a target thickness in a single coating step, and excessive material costs and man-hours are consumed, which is economically disadvantageous. Furthermore, since the formed resin layer has poor flexibility, cracks and the like are likely to occur during processing. In addition, excessive resin flow may occur during thermal compression bonding with the inner layer material, and it may be difficult to perform lamination smoothly.

Furthermore, as another product form of the copper foil with a carrier and a resin, the surface treatment layer of the ultra-thin copper layer, the heat-resistant layer, the rust-proof layer, or the chromate-treated layer, or The silane coupling treatment layer is coated with a resin layer to form a semi-hardened state, and then the carrier is peeled off to produce the resin-coated copper foil without the carrier.

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

In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using the printed circuit board on which electronic components are mounted, or an electronic device may be manufactured using the printed circuit board on which electronic components are mounted. Hereinafter, several examples of the manufacturing process of the printed wiring board using the copper foil with a carrier of this invention are shown. In addition, a printed wiring board can be produced in the same manner by using the surface-treated copper foil of the present invention as an ultra-thin copper layer of a copper foil with a carrier.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, the method includes the steps of preparing the copper foil with a carrier of the present invention (hereinafter, "copper foil with a carrier" and "ultra-thin copper layer" may be replaced with " Surface-treated copper foil, and the "ultra-thin copper layer side" is replaced with "surface-treated layer side" to manufacture a printed wiring board; when the description is replaced like this, the printed wiring board may be manufactured without a carrier) and Insulating substrate; laminating the copper foil with carrier and the insulating substrate; laminating the copper foil with carrier and the insulating substrate such that the ultra-thin copper layer side faces the insulating substrate, and then peeling the carrier of the copper foil with the carrier Steps to form a copper clad laminate, and then use any of the semi-additive method, the modified semi-additive method, the partial additive method, and the subtractive method to form a circuit. The insulating substrate may be an insulating substrate provided with an inner layer circuit.

In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer to form a pattern, and then a conductor pattern is formed using electroplating and etching.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; and laminating the copper foil with a carrier and the insulating substrate ; After laminating the copper foil with a carrier and an insulating substrate, peel the carrier of the copper foil with a carrier; and remove all the ultra-thin copper layers exposed by peeling the carrier by using an etching solution such as an acid or an etching solution or plasma. ; Through holes or blind holes are provided on the resin exposed by removing the ultra-thin copper layer by etching; slag removal treatment is performed on the area containing the through holes or / and blind holes; An electroless plating layer is provided in the area of the through hole or / and the blind hole; a plating resist is provided on the electroless plating layer; the plating resist is exposed, and thereafter, the plating in the area where the circuit is to be formed is removed. A resist; an electrolytic plating layer is provided in the above-mentioned region where the circuit to be formed has been removed; the above-mentioned plating resist is removed; and the above-mentioned region where the circuit is to be formed is removed by rapid etching or the like Electroless plating is present in the outer area.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method, the method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the copper foil with a carrier and an insulating substrate, the carrier with the copper foil with a carrier is peeled off; a through hole or / and a blind hole is provided in the ultra-thin copper layer and the insulating resin substrate exposed by peeling the carrier; Holes and / or blind holes are subjected to slag removal treatment; the ultra-thin copper layer exposed by peeling the carrier is completely removed by etching using an etching solution such as an acid or a plasma; the removal by etching or the like An electroless plating layer is provided on the resin exposed by the ultra-thin copper layer and an area including the through hole or / and a blind hole; a plating resist is provided on the electroless plating layer; and the plating resist is performed. After the exposure, the plating resist in the region where the circuit is to be formed is removed; an electrolytic plating layer is provided in the above-mentioned region where the circuit is to be formed in which the plating resist has been removed; the plating resist is removed; and Quick etching or the like removes the electroless plating layer existing in the area other than the above-mentioned area where the circuit is to be formed.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method, the method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the copper foil with a carrier and an insulating substrate, the carrier with the copper foil with a carrier is peeled off; a through-hole or / and a blind hole is provided in the ultra-thin copper layer and the insulating resin substrate exposed by peeling the carrier; by using an acid Etching method such as etching solution or plasma, etc., all the ultra-thin copper layer exposed by peeling the carrier is removed; the area containing the above-mentioned through hole and / or blind hole is subjected to slag removal treatment; An electroless plating layer is provided on the resin exposed by the ultra-thin copper layer and an area including the through hole or / and a blind hole; a plating resist is provided on the electroless plating layer; and the plating resist is performed. After the exposure, the plating resist in the region where the circuit is to be formed is removed; an electrolytic plating layer is provided in the above-mentioned region where the circuit is to be formed in which the plating resist has been removed; the plating resist is removed; and Quick etching or the like removes the electroless plating layer existing in the area other than the above-mentioned area where the circuit is to be formed.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method, the method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the copper foil with a carrier and the insulating substrate are laminated, the carrier with the copper foil with the carrier is peeled off; all the ultra-thin copper layers exposed by peeling the carrier are removed by etching using an etching solution such as an acid or a plasma; An electroless plating layer is provided on the surface of the resin exposed by removing the ultra-thin copper layer by etching; a plating resist is provided on the electroless plating layer; the plating resist is exposed, and thereafter Removing the plating resist in the region where the circuit is to be formed; providing an electrolytic plating layer in the above-mentioned region where the circuit is to be formed where the plating resist has been removed; removing the aforementioned plating resist; and removing the aforementioned resist by rapid etching or the like An electroless plating layer and an extremely thin copper layer are present in a region other than a region where a circuit is formed.

In the present invention, the modified semi-additive method refers to a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and copper is added to the circuit forming portion by electrolytic plating, and then removed. The resist is used to form a circuit on the insulating layer by (fast) etching removing the metal foil other than the circuit forming portion.

Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using an improved semi-additive method, the method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; Lamination; after laminating the copper foil with a carrier and an insulating substrate, peeling the carrier with the copper foil from the carrier; providing a through hole or / and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; Holes and / or blind holes are subjected to slag removal treatment; an electroless plating layer is provided on the area containing the above-mentioned through holes and / or blind holes; a plating resist is provided on the surface of the ultra-thin copper layer exposed by peeling the carrier ; After the above-mentioned plating resist is provided, a circuit is formed by electrolytic plating; the above-mentioned plating resist is removed; and the ultra-thin copper layer exposed by removing the above-mentioned plating resist is removed by rapid etching.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using an improved semi-additive method, the method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and laminating the copper foil with a carrier and the insulating substrate. ; After laminating the copper foil with a carrier and an insulating substrate, peeling the carrier with the copper foil from the carrier; setting a plating resist on the ultra-thin copper layer exposed by peeling the carrier; exposing the plating resist, After that, the plating resist in the region where the circuit is to be formed is removed; an electrolytic plating layer is provided in the above-mentioned region where the circuit is to be formed where the plating resist has been removed; the plating resist is removed; and the above is removed by rapid etching or the like An electroless plating layer and an extremely thin copper layer are present in a region other than a region where a circuit is to be formed.

In the present invention, the partial addition method refers to a method in which a substrate provided with a conductor layer and a substrate provided with through holes or via holes as required are provided with a catalytic core, and are etched to form a conductor circuit. It is necessary to provide a solder resist or a plating resist, and then thicken the above-mentioned conductor circuit, a through hole or a via hole by an electroless plating process, thereby manufacturing a printed wiring board.

Therefore, an embodiment of the method for manufacturing a printed wiring board of the present invention using a partial addition method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and laminating the copper foil with a carrier and the insulating substrate. ; After laminating the copper foil with a carrier and an insulating substrate, peeling the carrier with the copper foil with a carrier; providing a through hole or / and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; and including the through hole Or / and the blind hole area to carry out the slag removal treatment; to give a catalytic core to the area containing the through hole or / and the blind hole; to provide an etching resist on the surface of the ultra-thin copper layer exposed by peeling the carrier; Exposure with an agent to form a circuit pattern; removal of the ultra-thin copper layer and the catalytic nucleus by means of etching using an etching solution such as an acid or plasma to form a circuit; removal of the above-mentioned etching resist; use of an etching solution such as an acid Using a method such as etching or plasma to remove the ultra-thin copper layer and the catalytic core and expose the surface of the insulating substrate, a solder resist or a plating resist is provided; and the resist is not provided The area of the solder or plating resist is provided with an electroless plating layer.

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

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and laminating the copper foil with a carrier and the insulating substrate; After the copper foil with a carrier and the insulating substrate are laminated, the carrier with the copper foil with a carrier is peeled off; through holes or / and blind holes are provided in the ultra-thin copper layer and the insulating substrate that are exposed after the carrier is peeled off; / And the area of the blind hole is subjected to slag removal treatment; the area containing the above-mentioned through hole or / and the blind hole is provided with an electroless plating layer; an electrolytic plating layer is provided on the surface of the above electroless plating layer; An etching resist is provided on the surface of the cladding layer or / and the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; the ultra-thin copper layer is removed by etching using an etching solution such as an acid or a plasma, and Forming the circuit by the electroless plating layer and the electrolytic plating layer; and removing the etching resist.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the copper foil with a carrier and the insulating substrate are laminated, the carrier with the copper foil with a carrier is peeled off; through holes or / and blind holes are provided in the ultra-thin copper layer and the insulating substrate that are exposed after the carrier is peeled off; Deslagging treatment is performed in the area of the blind hole and the blind hole; an electroless plating layer is provided in the area containing the above-mentioned through hole or / and the blind hole; a mask is formed on the surface of the electroless plating layer; The surface of the electroless plating layer of the film is provided with an electrolytic plating layer; an etching resist is provided on the surface of the electrolytic plating layer or / and the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching using an etching solution such as acid or plasma to form a circuit; and removing the etching resist.

The step of setting the through hole and / or the blind hole and the subsequent step of removing the slag may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, the case where a primary particle layer and a secondary particle layer are provided as a roughening process layer is demonstrated here.

First, as shown in FIG. 1-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened layer formed on the surface is prepared.

Next, as shown in FIG. 1-B, a resist is coated on the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a predetermined shape.

Next, as shown in FIG. 1-C, after forming a plating layer for a circuit, the resist is removed to form a circuit plating layer of a predetermined shape.

Next, as shown in Fig. 2-D, the resin layer is laminated on the ultra-thin copper layer by covering the circuit plating layer (by burying the circuit plating layer). Next, the resin layer is laminated from the ultra-thin copper layer side. One copper foil with carrier (second layer).

Next, as shown in Figure 2-E, the carrier is peeled from the second layer of copper foil with a carrier.

Next, as shown in Figure 2-F, laser drilling is performed at a specified position of the resin layer to expose the circuit plating layer and form blind holes.

Secondly, as shown in Figure 3-G, copper is buried in the blind holes to form through-hole fillers.

Next, as shown in Fig. 3-H, a circuit plating layer is formed on the via filler as shown in Figs. 1-B and 1-C.

Next, as shown in Fig. 3-I, the carrier is peeled from the first layer of copper foil with a carrier.

Secondly, as shown in FIG. 4-J, the ultra-thin copper layers on both surfaces are removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Next, as shown in FIG. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. In this manner, a printed wiring board using the copper foil with a carrier of the present invention was produced.

In addition, in the manufacturing method of the printed wiring board described above, the "ultra-thin copper layer" may be replaced with a carrier, the "carrier" may be replaced with an ultra-thin copper layer, and a circuit may be formed on a surface of a carrier side with a copper foil with a carrier. , The circuit is embedded with resin to manufacture a printed wiring board.

As the other copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, or the existing copper foil with a carrier may be used, and a general copper foil may also be used. In addition, it is also possible to form one or more layers of circuits on the second layer of the circuit shown in Fig. 3-H. It is also possible to use a semi-additive method, a subtractive method, a partial addition method, or an improved semi-additive method. Either method is used to form these circuits.

According to the manufacturing method of the printed wiring board as described above, the circuit plating layer is embedded in the resin layer. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 4-J, the circuit plating layer is covered by the resin layer. It is easy to form a fine circuit by protecting its shape. In addition, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the conduction of the circuit wiring is well suppressed. Therefore, it becomes easy to form a fine circuit. In addition, as shown in FIGS. 4-J and 4-K, when the ultra-thin copper layer is removed by rapid etching, the exposed surface of the circuit plating layer becomes a shape recessed from the resin layer, so it is easy to form bumps on the circuit plating layer. It is easy to form copper pillars thereon, thereby improving manufacturing efficiency.

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

Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate or a resin layer on the surface of this copper foil with a carrier. By having the substrate or the resin layer to support the copper foil with a carrier for the first layer, wrinkles are less likely to occur, and therefore there is an advantage that productivity is improved. In addition, as long as the substrate or the resin layer has the effect of supporting the copper foil with a carrier used in the first layer, all the substrates or the resin layer can be used. For example, as the substrate or the resin layer, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, or an inorganic material described in the present specification can be used. Compound foil, plate of organic compound, foil of organic compound.

In addition, the manufacturing method (coreless construction method) of the printed wiring board of the present invention may include the steps of: laminating the ultra-thin copper layer side surface of the copper foil with a carrier or the carrier side surface of the present invention with a resin substrate; The resin substrate laminated surface of the ultra-thin copper layer or the surface of the copper foil with a carrier on the opposite side to the carrier side surface should be provided with a resin layer and a circuit at least once; and when the resin layer and the circuit are formed After these two layers, the carrier or the ultra-thin copper layer is peeled from the copper foil with a carrier. Regarding this coreless construction method, as a specific example, first, the ultra-thin copper layer side surface or carrier side surface of the copper foil with a carrier of the present invention is laminated with a resin substrate to produce a laminated body (also referred to as a copper-clad laminated board, copper-clad Laminated body). Thereafter, a resin layer is formed on the surface of the ultra-thin copper layer laminated with the resin substrate, or on the surface of the copper foil with a carrier on the side opposite to the carrier-side surface. A copper foil with a carrier may be laminated on the resin layer formed on the carrier-side surface or the ultra-thin copper layer side surface from the carrier side or the ultra-thin copper layer side. In addition, a laminated body may be used in the method for manufacturing the printed wiring board (coreless construction method). The laminated body has a resin substrate or a resin or a prepreg as a center. Both sides of the surface, in the order of carrier / intermediate layer / ultra-thin copper layer or super-thin copper layer / intermediate layer / carrier in the order of lamination with carrier copper foil; Resin substrate or resin or prepreg / carrier / intermediate layer / extremely thin copper layer "; or having a" carrier / intermediate layer / extremely thin copper layer / resin substrate / carrier / intermediate layer / extremely thin copper layer " Layer ", or a structure in which the layers are laminated in the order of" ultra-thin copper layer / intermediate layer / carrier / resin substrate / carrier / intermediate layer / ultra-thin copper layer ". In addition, another resin layer may be provided on the ultra-thin copper layer or the exposed surface of the carrier at both ends of the laminated body, and further, a copper layer or a metal layer may be provided, and then the copper layer or the metal layer may be processed to form a circuit. Furthermore, another resin layer may be provided on the circuit so as to be buried in the circuit. In addition, the formation of the circuit and the resin layer (stacking method) may be performed more than once. Then, with respect to the multilayer body (hereinafter also referred to as multilayer body B) thus formed, the ultra-thin copper layer or carrier of each copper foil with a carrier can be peeled from the carrier or the ultra-thin copper layer to produce a coreless substrate. In addition, in the production of the above-mentioned coreless substrate, two copper foils with a carrier may be used to produce a laminated body having the following structure having an ultra-thin copper layer / intermediate layer / carrier / carrier / intermediate layer / extremely thin copper layer or a carrier Laminated body consisting of / intermediate layer / ultra-thin copper layer / ultra-thin copper layer / intermediate layer / carrier, or a laminate having a carrier / intermediate layer / ultra-thin copper layer / carrier / intermediate layer / ultra-thin copper layer Use this laminate for the center. The resin layer and the circuit layer can be provided more than once on the surface of the ultra-thin copper layer or the carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the resin layer and the circuit layer can be provided more than once. After that, the ultra-thin copper layer or carrier of each copper foil with a carrier is peeled from the carrier or the ultra-thin copper layer to produce a coreless substrate. The laminated body may have other layers on the surface of the ultra-thin copper layer, the surface of the carrier, between the carrier and the carrier, between the ultra-thin copper layer and the ultra-thin copper layer, and between the ultra-thin copper layer and the carrier. The other layer may be a resin substrate or a resin layer. In addition, in this specification, “the surface of the ultra-thin copper layer”, “the surface of the ultra-thin copper layer”, “the surface of the ultra-thin copper layer”, “the surface of the carrier”, “the surface of the carrier side”, “the surface of the carrier”, When the "layer surface" and "layer surface" have other layers on the surface of the ultra-thin copper layer, the carrier, and the surface of the layer, the surface of the layer, and the surface of the multilayer body include other layers ( The most superficial) concept. Moreover, it is preferable that a laminated body has a structure which has an ultra-thin copper layer, an intermediate layer, a carrier, a carrier, an intermediate layer, and an ultra-thin copper layer. The reason is that when using this laminated body to make a coreless substrate, an ultra-thin copper layer is arranged on the coreless substrate side, so it is easy to form a circuit on the coreless substrate using an improved semi-additive method. In addition, the reason is that the thickness of the ultra-thin copper layer is thin, so it is easy to remove the ultra-thin copper layer, and it is easy to form a circuit on the coreless substrate by using a semi-additive method after removing the ultra-thin copper layer.

In addition, in this specification, a "laminated body" not specifically described as "laminated body A" or "laminated body B" means a laminated body including at least laminated body A and laminated body B.

In addition, in the method for manufacturing a coreless substrate described above, when a part or all of the end face of the copper foil with a carrier or the laminated body (including the laminated body A) is covered with a resin, a printed wiring board can be prevented from being deposited by a stacking method. The medicinal solution penetrates into the middle layer or between one copper foil with a carrier and another copper foil with a carrier, so as to prevent the ultra-thin copper layer from being separated from the carrier due to the penetration of the medicinal solution or the corrosion of the copper foil with the carrier, which can improve the production. rate. As the "resin covering part or all of the end surface of the copper foil with a carrier" or "resin covering part or all of the end surface of the laminated body" used herein, a resin usable in a resin layer or a known resin can be used. In addition, in the method for manufacturing a coreless substrate described above, when the copper foil with a carrier or a laminated body is viewed from above, the laminated portion of the copper foil with a carrier or a laminated body (a laminated portion of a carrier and an extremely thin copper layer, or a copper foil with a carrier) At least a part of the outer periphery of the laminated layer with another copper foil with a carrier) may be covered with a resin or a prepreg. Moreover, the laminated body (laminated body A) formed by the manufacturing method of the said coreless board | substrate can also be comprised so that a pair of copper foil with a carrier may be contacted separately from each other. In addition, when the copper foil with a carrier is viewed from the top, it can also be spread over the copper foil with a carrier or a laminate (a laminate of a carrier and an ultra-thin copper layer, or a laminate of one copper foil with a carrier and another copper foil with a carrier). The entire periphery of the part) or the entire surface of the laminated part is covered with resin or prepreg. In addition, it is preferable that the resin or the prepreg is larger than the copper foil or the laminated body or the laminated part of the laminated body when viewed from the top, and is preferably set as a laminated body having a two-area layer on the copper foil or the laminated body with the carrier. Resin or prepreg, and the resin or prepreg is used to wrap (enclose) the copper foil with carrier or laminate. With such a configuration, when the copper foil with a carrier or a laminated body is viewed from above, the laminated portion of the copper foil with a carrier or a laminated body is covered with a resin or a prepreg, which can prevent other parts from hitting the part from a direction from the side. The lateral direction, that is, the lamination direction, can reduce the peeling between the carrier and the ultra-thin copper layer or the copper foil with the carrier during the process. In addition, by covering with a resin or a prepreg so that the outer periphery of the laminated portion of the copper foil with the carrier or the laminated body is not exposed, it is possible to prevent the chemical solution from penetrating into the laminated portion in the chemical solution processing step as described above. Interface to prevent corrosion or erosion of copper foil with carrier. In addition, when one copper foil with a carrier is separated from a pair of copper foils with a carrier of the laminated body, or when a copper foil with a carrier is separated from a copper foil (a very thin copper layer), The laminated part of the copper foil with the carrier or the laminated body (the laminated part of the carrier and the ultra-thin copper layer, or the laminated part of the copper foil with the carrier and the other copper foil with the carrier) is firmly adhered by resin, prepreg, etc. In some cases, it is necessary to remove the laminated portion by cutting or the like.

The copper foil with a carrier of the present invention may be laminated on the carrier side or the ultra-thin copper layer side of another copper foil with a carrier from the carrier side or the ultra-thin copper layer side to form a laminated body. In addition, the carrier-side surface or the ultra-thin copper layer side surface of the one copper foil with a carrier and the carrier-side surface or the ultra-thin copper layer side surface of the other copper foil with a carrier may be passed through an adhesive as necessary. Laminated directly to obtain a laminated body. In addition, the carrier or the ultra-thin copper layer of the one copper foil with a carrier may be bonded to the carrier or the ultra-thin copper layer of the other copper foil with a carrier. Here, in the case where the carrier or the ultra-thin copper layer has a surface-treated layer, the “bonding” also includes a form in which they are bonded to each other via the surface-treated layer. In addition, a part or all of the end face of the laminated body may be covered with a resin.

The lamination of the carriers, the ultra-thin copper layer, the carrier and the ultra-thin copper layer, and the copper foil with the carrier can be performed by the following method, for example, in addition to simply overlapping them.

(a) Metallurgical joining methods: fusion welding (arc welding, TIG (Tungsten Inert Gas) welding, MIG (Metal inert gas) welding, resistance welding, seam welding, spot welding), pressure Welding (ultrasonic welding, friction stir welding), soft welding and brazing; (b) mechanical joining methods: caulking, joining by rivets (joining by Self-piercing Rivet, joining by rivets), Nail box machine; (c) Physical bonding method: adhesive, (double-sided) tape

A carrier can be laminated with another carrier or an ultra-thin copper layer by joining a part or all of one carrier with a part or all of another carrier or a part or all of an ultra-thin copper layer by using the above-mentioned bonding method, thereby enabling manufacture A laminated body formed by detachably contacting the carriers or the carrier with the ultra-thin copper layer. In the case of laminating a carrier with another carrier or an ultra-thin copper layer with a weak junction between one carrier and another carrier or an ultra-thin copper layer, even if the joint between one carrier and another carrier or the ultra-thin copper layer is not removed It is also possible to separate one carrier from another carrier or an extremely thin copper layer. In addition, in the case where one carrier is firmly bonded to another carrier or an ultra-thin copper layer, the one carrier is bonded to another carrier or an ultra-thin copper layer by removing by cutting or chemical polishing (etching, etc.), mechanical polishing, or the like. Can separate one carrier from another carrier or a very thin copper layer.

In addition, a coreless printed wiring board can be produced by performing the following steps: the step of providing the resin layer and the circuit with the two layers of the laminated body configured in this manner at least once, and at least once A step of peeling the ultra-thin copper layer or the carrier from the copper foil with a carrier of the laminated body after forming the two layers of the resin layer and the circuit at a time is performed. In addition, two layers of a resin layer and a circuit may be provided on one surface or both surfaces of the laminated body.

The resin substrate, resin layer, resin, and prepreg used in the laminated body may be the resin layer described in this specification, or may contain the resin, resin hardener, compound, and hardening accelerator used in the resin layer described in this specification. Agents, dielectrics, reaction catalysts, crosslinkers, polymers, prepregs, framework materials, etc. In addition, the copper foil or laminate with a carrier may be smaller than a resin or a prepreg, a resin substrate, or a resin layer in a plan view.

In addition, the resin substrate is not particularly limited as long as it has characteristics that can be applied to printed wiring boards. For example, when it is used for rigid PWB, paper substrate phenol resin, paper substrate epoxy resin, and synthetic fiber cloth substrate can be used. Epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin, and glass cloth substrate epoxy resin, etc. When used in FPC, polyester film or polymer can be used.醯 imine film, LCP (liquid crystal polymer) film, fluororesin, etc. In addition, when a LCP (liquid crystal polymer) film or a fluororesin film is used, the peeling strength of the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when an LCP (liquid crystal polymer) film or a fluororesin film is used, the copper circuit is covered with a cover layer after the copper circuit is formed, so that the film and the copper circuit cannot be easily peeled off, and a reduction in peel strength can be prevented This caused the film to peel from the copper circuit.

[Example]

Hereinafter, it demonstrates based on an Example and a comparative example. In addition, this embodiment is only an example, and is not limited to this example. That is, other aspects and changes included in the present invention are also included.

The original foils of Examples 1 ~ 2, 4 ~ 6, 9 ~ 16 and Comparative Examples 1 ~ 2, 4, 6 ~ 7 are made of standard rolled copper foil TPC (thick copper specified by JIS H3100 C1100, JX metal) with a thickness of 12 μm. , The ten-point average roughness of the surface Rz = 0.7 μm). The original foils of Examples 3 and 8 and Comparative Examples 3 and 5 were electrolytic copper foils (HLP foils made of JX Metal, the ten-point average roughness Rz = 0.7 μm of the surface of the precipitation surface (M surface)) of 12 μm. The surface (M surface) is provided with a surface treatment layer.

In addition, as the original foil of Example 7 and Comparative Example 8, a copper foil with a carrier manufactured by the following method was used.

In Example 7, an electrolytic copper foil (JTC foil manufactured by JX Metal) having a thickness of 18 μm was prepared as a carrier, and Comparative Example 8 was preparing a standard rolled copper foil TPC having a thickness of 18 μm as a carrier. Then, under the following conditions, an intermediate layer was formed on the surface of the carrier, and an extremely thin copper layer was formed on the surface of the intermediate layer. When the carrier is an electrolytic copper foil, an intermediate layer is formed on a glossy surface (S surface).

‧Example 7, Comparative Example 8

<Middle layer>

(1) Ni layer (Ni plating)

An Ni layer having an adhesion amount of 1000 μg / dm ^{2 was} formed on the carrier by electroplating using a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are as follows.

Nickel sulfate: 270 ~ 280g / L

Nickel chloride: 35 ~ 45g / L

Nickel acetate: 10 ~ 20g / L

Boric acid: 30 ~ 40g / L

Luster: Saccharin, butynediol, etc.

Sodium lauryl sulfate: 55 ~ 75ppm

pH value: 4 ~ 6

Liquid temperature: 55 ~ 65 ℃

Current density: 10A / dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, after the surface of the Ni layer formed by (1) was washed with water and pickled, an electrolytic chromate treatment was performed on the roll-to-roll continuous plating line under the following conditions so that the adhesion amount was 11 μg / The Cr layer of dm ² is attached to the Ni layer.

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

pH value: 7 ~ 10

Liquid temperature: 40 ~ 60 ℃

Current density: 2A / dm ²

<Ultra-thin copper layer>

Next, after the surface of the Cr layer formed in (2) was washed with water and pickled, a 1.5 μm-thick electrode was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line under the following conditions. Thin copper layer to make 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

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

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

Electrolyte temperature: 50 ~ 80 ℃

Current density: 100A / dm ²

Linear speed of electrolyte: 1.5 ~ 5m / sec

Next, a primary particle layer, a primary particle layer, and a secondary particle layer were formed on the surface of the ultra-thin copper layer of the rolled copper foil, electrolytic copper foil, or copper foil with a carrier under the conditions shown in Tables 1-3. Examples of the two current conditions and the coulomb amount are listed in the column of the primary particle current conditions in Table 1. It means that after plating under the conditions described on the left, plating is performed under the conditions described on the right. For example, "(50A / dm ² , 65As / dm ² ) + (8A / dm ² , 16As / dm ² )" is described in the column of the primary particle current conditions in Example 1, which indicates the current density at which primary particles will be formed. After plating was performed at 50 A / dm ² and the coulomb amount was 65 As / dm ² , the current density for forming primary particles was 8 A / dm ² , and the coulomb amount was 16 As / dm ² for plating.

Next, a coating layer is formed on the primary particle layer or on the secondary particle layer under the conditions shown in Tables 1 and 4 when the secondary particle layer is formed. It should be noted that when a plurality of processes are performed in the column for coating, it means that the processes from the left side are sequentially performed. For example, in Example 2, "(2) Ni-Mo + (1) Zn-Cr" is described in the column of "Coating plating conditions (Coating plating liquid of Table 4)" in Table 1, and "Coating "(2) 0.17, (1) 1.0" is described in the column of "Plating current (second)". This means that in Example 2, the coating plating was performed in the order of (2) Ni-Mo plating and (1) Zn-Cr plating in Table 4, and the conduction times were set to (2) Ni- Mo plating was 0.17 seconds, and (1) Zn-Cr plating was 1.0 seconds.

<Surface treatment layer other than primary particle layer, secondary particle layer, and coating plating layer>

After the coating plating layer was formed, Examples 3, 5 and Comparative Example 6 were subjected to the following electrolytic chromate treatment. The following Examples and Comparative Examples were not subjected to the following electrolytic chromate treatment.

‧Electrolytic chromate treatment

Liquid composition: potassium dichromate 1 ~ 1g / L

Liquid temperature: 40 ~ 60 ℃

pH value: 0.5 ~ 10

Current density: 0.01 ~ 2.6A / dm ²

Power-on time: 0.05 ~ 30 seconds

Thereafter, Examples 3 to 5 and 10 were subjected to the following silane coupling treatment using diaminosilane.

‧Silane coupling treatment

Silane coupling agent: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane

Silane coupling agent concentration: 0.5 ~ 1.5vol%

Processing temperature: 20 ~ 70 ℃

Processing time: 0.5 ~ 5 seconds

(Measurement of ten-point average roughness Rz)

In accordance with JIS B0601-1982, a surface roughness Rz (ten-point average roughness) of the surface of the roughened layer was measured using a Surfcorder SE-3C stylus type roughness meter manufactured by Kosaka Research Co., Ltd. The Rz was measured at any 10 points, and the average value of the 10 Rz values was set as the Rz value.

(Measurement of transmission loss)

Each sample was bonded to a liquid crystal polymer resin substrate (Vecstar CTZ manufactured by Kuraray Co., Ltd., a thickness of 50 μm, and a resin that is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), followed by etching. A microstrip circuit was formed so that the characteristic impedance became 50 Ω. The transmission coefficient was measured using a network analyzer N5247A manufactured by HP, and the transmission loss at a frequency of 20 GHz was obtained. As the evaluation of the transmission loss at a frequency of 20 GHz, 4.0 dB / 10 cm or less was ○, and 4.1 dB / 10 cm or more was X.

(Measurement of peeling strength)

A copper-clad laminated board was prepared by bonding the surface of the copper foil to the resin substrate described in Table 2 by hot pressing, and a common copper chloride circuit etching solution was used to produce a 10 mm wide circuit. The copper foil was peeled from the substrate. The initial peel strength was measured while being stretched in the 90 ° direction. In addition, the produced circuit was put into an oven under an atmosphere of 180 ° C., and was taken out after 10 days, and the peel strength after heating was measured while being stretched in the direction of 90 ° in the same manner as normal peeling. The evaluation of the peeling strength was performed when the initial peeling strength was 0.5 kg / cm or more and the peeling strength after heating was 0.3 kg / cm or more. The initial peeling strength was less than 0.5 kg / cm or the peeling strength after heating was less than 0.3 kg. In the case of / cm, it is set to x.

In addition, regarding the laminated resin described in Table 2, "LCP" is a liquid crystal polymer, "low dielectric PI" is a low dielectric polyfluorene, and "PTFE" is polytetrafluoroethylene.

A liquid crystal polymer resin, vecstor CT-Z manufactured by Kuraray, was used for the liquid crystal polymer, and the liquid crystal polymer resin was a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester).

As the low-dielectric polyimide, a polyimide having a dielectric loss factor of 0.002 is used. In this specification, a polyimide having a dielectric loss factor value of 0.01 or less is referred to as a low-dielectric polyimide. The dielectric loss factor can be obtained by the three-plate resonator method described in "Specific permittivity and dielectric loss factor of copper clad laminated board test methods for printed wiring boards" by the Japan Electronic Circuits Association, JPCA-TM001-2007. Determination.

The hot-pressing conditions of the copper foil and the resin substrate are as follows.

When the liquid crystal polymer is a resin substrate: a pressure of 3.5 MPa, a heating temperature of 300 ° C, and a heating time of 10 minutes

When using a low-dielectric polyfluorene imide as the resin substrate: pressure 4 MPa, heating temperature 360 ° C, heating time 5 minutes

When using polytetrafluoroethylene as the resin substrate: pressure 5MPa, heating temperature 350 ° C, heating time 30 minutes

The thickness of the resin substrate was 50 μm.

The manufacturing conditions and evaluation results are shown in Tables 1 to 4.

(Evaluation results)

In Examples 1 to 16, the transmission loss was well suppressed, and the peeling strength was also good.

The adhesion amount of Zn in the surface-treated layers of Comparative Examples 1 and 6 was less than 150 μg / dm ^2. Furthermore, the total adhesion amount of Zn and Mo in the surface-treated layer was less than 200 μg / dm ² , and the peeling strength was poor.

The adhesion amount of Co in the surface-treated layer of Comparative Example 2 exceeded 3000 μg / dm ² , and thus the transmission loss was poor.

The ten-point average roughness Rz of the outermost surface of the surface-treated layers of Comparative Examples 3 and 8 exceeded 1.5 μm, and therefore the transmission loss was poor.

In Comparative Example 4, the primary particle layer and the secondary particle layer were not formed, and the peeling strength was poor.

The adhesion amount of Zn in the surface treatment layer of Comparative Example 5 was less than 150 μg / dm ² , and the total adhesion amount of Zn and Mo was less than 200 μg / dm ^2. Furthermore, the ten-point average roughness Rz of the outermost surface of the surface treatment layer exceeded 1.5 μm, the transmission loss and peel strength are poor.

Comparative Example 7 contains Ni in the surface-treated layer, but the adhesion amount of Ni exceeds 800 μg / dm ² , so the transmission loss is poor.

Claims (36)

A surface-treated copper foil having a surface-treated layer on at least one side, the surface-treated layer having a primary particle layer, or a primary particle layer and a secondary particle layer, and an Zn adhesion amount in the surface-treated layer being 150 μg / dm ² or more The surface treatment layer does not contain Ni, or the adhesion amount of Ni is 800 μg / dm ² or less, the surface treatment layer does not contain Co, or the adhesion amount of Co is 3000 μg / dm ² or less, and the topmost surface of the surface treatment layer is ten The point average roughness Rz is 1.5 μm or less. A surface-treated copper foil having a surface-treated layer on at least one side, the surface-treated layer having a primary particle layer, or a primary particle layer and a secondary particle layer, the surface-treated layer containing Zn and Mo, and Zn in the surface-treated layer The total adhesion amount of Mo and Mo is 200 μg / dm ² or more, the surface treatment layer does not contain Ni, or the adhesion amount of Ni is 800 μg / dm ² or less, the surface treatment layer does not contain Co, or the adhesion amount of Co is 3000 μg / dm ² or less, and the ten-point average roughness Rz of the outermost surface of the surface treatment layer is 1.5 μm or less. For example, the surface-treated copper foil of the first or second scope of the patent application, wherein the adhesion amount of Zn in the surface-treated layer is 165 μg / dm ² or more. For example, the surface-treated copper foil of item 1 or 2 of the scope of patent application, wherein the Zn adhesion amount in the surface-treated layer is 180 μg / dm ² or more. For example, the surface-treated copper foil of the first or second scope of application for a patent, wherein the adhesion amount of Zn in the surface-treated layer is 200 μg / dm ² or more. For example, the surface-treated copper foil of the scope of application for the patent No. 1 or 2, wherein the adhesion amount of Zn in the surface-treated layer is 250 μg / dm ² or more. For example, for the surface-treated copper foil of the scope of application for the first or second patent, the amount of Ni in the surface-treated layer is 750 μg / dm ² or less. For example, for the surface-treated copper foil of the scope of application for patent No. 1 or 2, the amount of Co in the surface-treated layer is 2790 μg / dm ² or less.     For example, the surface-treated copper foil according to item 1 or 2 of the patent application scope, wherein the ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.0 μm or less.     For example, in the surface-treated copper foil according to item 2 of the application, the total adhesion amount of Zn and Mo in the surface-treated layer is 340 μg / dm ² or more.     For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated layer contains Co.         For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated layer contains Ni.     For example, the surface-treated copper foils of the scope of application for patents No. 1 or 2, wherein the surface-treated layer contains Co and Ni, and the total adhesion amount of Co and Ni in the surface-treated layer is 3500 μg / dm ² or less.     For example, the surface-treated copper foils of the scope of application for patents 1 or 2 have the above-mentioned surface-treated layers on both sides.     For example, if the surface-treated copper foil of item 1 or 2 of the patent application scope satisfies any one or both of the following (D) or (E): (D) The amount of Zn in the surface-treated layer meets any of the following: ‧270 μg / dm ² or more, ‧280 μg / dm ² or more, ‧290 μg / dm ² or more, (E) The total adhesion amount of Zn and Mo in the surface treatment layer satisfies any of the following: ‧ 360 μg / dm ² or more, ‧ 400μg / dm ² or more, ‧420μg / dm ² or more, ‧460μg / dm ² or more, ‧500μg / dm ² or more.     For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated copper foil is laminated with a resin from the surface-treated layer side, the surface-treated copper foil is etched to make a 10 mm wide circuit, and When the resin is peeled from the circuit in the 90 ° direction, the peel strength is 0.5 kg / cm or more. The conditions for the resin and the laminate are any one, two, or three of the following (1) to (3): (1 ) Resin: liquid crystal polymer resin with a thickness of 50 μm. The liquid crystal polymer resin is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid. The conditions for lamination: pressure 3.5MPa, heating temperature 300 ° C, heating time 10 minutes; : Low dielectric polyfluorene imide resin, thickness 50 μm, laminated conditions: pressure 4 MPa, heating temperature 360 ° C, heating time 5 minutes; (3) resin: polytetrafluoroethylene, thickness 50 μm, laminated conditions: pressure 5 MPa, The heating temperature is 350 ° C, and the heating time is 30 minutes.         For example, the surface-treated copper foil according to item 16 of the patent application scope, wherein the peeling strength is 0.7 kg / cm or more.         For example, the surface-treated copper foil according to item 1 or 2 of the patent application scope, wherein the surface-treated copper foil is laminated with a resin from the surface-treated layer side, and the surface-treated copper foil is etched to produce a 10 mm wide circuit in the atmosphere. After the circuit was heated at 180 ° C for 10 days, when the circuit was peeled from the resin in the direction of 90 °, the peel strength was 0.4 kg / cm or more. The conditions for the resin and the laminate were as follows (1) to (3) Any one, two or three: (1) Resin: liquid crystal polymer resin with a thickness of 50 μm, the liquid crystal polymer resin is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, and the conditions for lamination: pressure 3.5MPa, heating temperature 300 ° C, heating time 10 minutes; (2) resin: low-dielectric polyfluorene imine resin, thickness 50 μm, laminated conditions: pressure 4MPa, heating temperature 360 ° C, heating time 5 minutes; (3) resin: polytetrafluoro Ethylene, thickness 50 μm, conditions for lamination: pressure 5 MPa, heating temperature 350 ° C., heating time 30 minutes.         For example, the surface-treated copper foil according to item 18 of the patent application scope, wherein the surface-treated copper foil is laminated with a resin from the surface-treated layer side, and the surface-treated copper foil is etched to produce a 10-mm-wide circuit. After the circuit was heated at 180 ° C for 10 days, when the circuit was peeled from the resin in a 90 ° direction, the peeling strength was 0.5 kg / cm or more.         For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated layer has the primary particle layer or the secondary particle layer: (A) from Ni and selected from Fe, Cr, Mo, Zn Alloy layer consisting of one or more elements in the group consisting of Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and (B) any one or two of the chromate-treated layers.         For example, the surface-treated copper foil according to item 1 or 2 of the patent application scope, wherein the surface-treated layer has at least one or two of the following (A) and (B) on the primary particle layer or the secondary particle layer, And (C): (A) an alloy of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti Layer (B) chromate-treated layer (C) silane coupling-treated layer.         For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated layer has at least one or two of a Ni-Zn alloy layer and a chromate-treated layer on the primary particle layer or the secondary particle layer. Floor.         For example, the surface-treated copper foil of item 1 or 2 of the patent application scope, wherein the surface-treated layer has at least one or two of a Ni-Zn alloy layer and a chromate-treated layer on the primary particle layer or the secondary particle layer. Layer, and a silane coupling treatment layer.         For example, the surface-treated copper foil in the scope of patent application No. 1 or 2 is used for high-frequency circuit substrates.         A surface-treated copper foil with a resin layer is provided with a resin layer on the surface of the surface-treated copper foil of the surface-treated copper foil according to any one of claims 1 to 24.         A copper foil with a carrier has an intermediate layer and an ultra-thin copper layer on at least one side of the carrier, and the ultra-thin copper layer is a surface-treated copper foil according to any one of claims 1 to 24 or a scope of patent application 25 Surface-treated copper foil with resin layer.         A laminated body having a surface-treated copper foil according to any one of claims 1 to 24 or a surface-treated copper foil with a resin layer included in claim 25.         A laminated body having a copper foil with a carrier and the scope of application for patent No. 26.         A laminated body includes a copper foil with a carrier and a resin in accordance with item 26 of the application, and a part or all of the end surface of the copper foil with a carrier is covered with the resin.         A laminated body having two copper foils with a carrier and the scope of application for patent No. 26.         A method for manufacturing a printed wiring board, using a surface-treated copper foil according to any one of claims 1 to 24, a surface-treated copper foil with a resin layer included in claim 25, or a claim 26 Comes with carrier copper foil.         A method for manufacturing a printed wiring board includes the following steps: preparing a surface-treated copper foil according to any one of the scope of patent applications 1 to 24, applying a surface-treated copper foil with a resin layer within the scope of applying for patent scope 25, or applying for a patent A copper foil with a carrier and an insulating substrate within the scope of item 26; forming a copper-clad laminated board including any of the following steps (1) to (3): (1) laminating the surface-treated copper foil with the insulating substrate, (2) laminating the surface-treated copper foil with a resin layer and the insulating substrate, (3) laminating the copper foil with a carrier and the insulating substrate, and then peeling the carrier with the copper foil from the carrier; and using a semi-addition Any of the methods, the subtractive method, the partial additive method, or the improved semi-additive method, uses the copper-clad laminated board described above to form a circuit.         A method for manufacturing a printed wiring board includes the steps of forming a circuit on the surface of the surface-treated layer side of the surface-treated copper foil according to any one of claims 1 to 24, or forming a circuit on the side of claim 26 A circuit is formed on the side surface of the ultra-thin copper layer of the carrier copper foil or the side surface of the carrier; to bury the circuit, the surface of the surface-treated layer side of the surface-treated copper foil or the ultra-thin surface of the copper foil with a carrier Forming a resin layer on the copper layer side surface or the carrier side surface; and by removing the surface-treated copper foil after forming the resin layer, or by removing the ultra-thin copper layer after peeling off the carrier or the ultra-thin copper layer or The carrier exposes a circuit buried in the resin layer.         A method for manufacturing a printed wiring board includes the steps of: laminating the carrier side surface of the copper foil with a carrier or the side surface of the ultra-thin copper layer on a resin substrate with a resin substrate; A resin layer and a circuit are provided on the opposite surface of the resin substrate laminated side; and after the resin layer and the circuit are formed, the carrier or the ultra-thin copper layer is peeled from the copper foil with a carrier.         A method for manufacturing a printed wiring board includes the steps of: providing a resin layer and a circuit in a multilayer body according to any one of claims 28 to 30; and forming the resin layer and the circuit, and then The copper foil with a carrier peels the said carrier or the said ultra-thin copper layer.         An electronic device manufacturing method uses a printed wiring board. The printed wiring board is manufactured by a method according to any one of claims 31 to 35 of the scope of patent application.