CN108449868B

CN108449868B - Surface-treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device

Info

Publication number: CN108449868B
Application number: CN201810123868.9A
Authority: CN
Inventors: 森山晃正
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2017-02-07
Filing date: 2018-02-07
Publication date: 2022-08-16
Anticipated expiration: 2038-02-07
Also published as: CN108419363A; CN108449868A

Abstract

The present invention relates to a surface-treated copper foil, a copper foil with a carrier, a laminate, a method for manufacturing a printed wiring board, and a method for manufacturing an electronic device. Specifically disclosed is a surface-treated copper foil which can be used for a high-frequency circuit board, and which has excellent acid resistance while reducing transmission loss. A surface-treated copper foil comprising a copper foil and a surface-treated layer comprising a roughened layer on one or both surfaces of the copper foil, wherein the surface-treated layer comprises Ni, the Ni content in the surface-treated layer is 8 mass% or less (excluding 0 mass%), and the ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.4 [ mu ] m or less.

Description

Surface-treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device

Technical Field

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

Background

Over the half century, printed wiring boards have made great progress, and are now reaching the level of use in almost all electronic machines. With the recent increase in the demand for smaller and higher performance electronic devices, high-density mounting of mounted components and high-frequency signals have been advanced, and excellent high-frequency response has been required for printed wiring boards.

In order to ensure the quality of an output signal, a high-frequency substrate is required to have a low transmission loss. The transmission loss mainly includes a dielectric loss caused by a resin (substrate side) and a conductor loss caused by a conductor (copper foil side). The smaller the dielectric constant and the dielectric loss tangent of the resin are, the lower the dielectric loss is. In high frequency signals, the main causes of conductor loss are: as the frequency increases, the current has a skin effect of flowing only on the surface of the conductor, and the cross-sectional area through which the current flows decreases, thereby increasing the resistance.

As a technique for reducing the transmission loss of a copper foil for high frequency use, for example, patent document 1 discloses a metal foil for high frequency circuits in which one surface or both surfaces of the metal foil are coated with silver or a silver alloy, and a coating layer other than silver or a silver alloy is applied to the silver or silver alloy coating layer in a thickness smaller than the thickness of the silver or silver alloy coating layer. It is also described that a metal foil which reduces loss due to the skin effect even in an ultra-high frequency region used in satellite communication can be provided.

Patent document 2 discloses a roughened rolled copper foil for high-frequency circuits, which is characterized in that: the integrated intensity (I (200)) of the (200) surface obtained by X-ray diffraction on the rolled surface of the rolled copper foil after recrystallization annealing is I (200)/I0(200) > 40 relative to the integrated intensity (I0(200)) of the (200) surface obtained by X-ray diffraction of the fine powder copper, the arithmetic average roughness (Ra, hereinafter) of the roughened surface after roughening treatment by electroplating on the rolled surface is 0.02 to 0.2 [ mu ] m, the ten-point average roughness (Rz, hereinafter) is 0.1 to 1.5 [ mu ] m, and the roughened rolled copper foil for high-frequency circuits is a material for printed circuit boards. It is also described that a printed wiring board usable at a high frequency exceeding 1GHz can be provided.

Further, patent document 3 discloses an electrolytic copper foil characterized in that: the surface of the copper foil is partially uneven with a surface roughness of 2 to 4 [ mu ] m, which is composed of nodular protrusions. It is also described that an electrolytic copper foil having excellent high-frequency transmission characteristics can be provided.

Further, patent document 4 discloses a surface-treated copper foil having a surface-treated layer formed on at least one surface thereof, wherein the surface-treated layer includes a roughened layer, and the total adhesion amount of Co, Ni, and Fe in the surface-treated layer is 300 μ g/dm ² The surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, the surface treatment layer has a ratio of a three-dimensional surface area to a two-dimensional surface area of 1.0 to 1.9 as measured by a laser microscope, at least one surface has a surface roughness Rz JIS of 2.2 [ mu ] m or less, the surface treatment layer is formed on both surfaces, and the surface roughness Rz JIS of both surfaces is 2.2 [ mu ] m or less. It is also described that a surface-treated copper foil which can satisfactorily suppress transmission loss even when used for a high-frequency circuit board can be provided.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent No. 4161304 publication

[ patent document 2] Japanese patent No. 4704025

[ patent document 3] Japanese patent application laid-open No. 2004-244656

[ patent document 4] Japanese patent No. 5710737.

Disclosure of Invention

[ problems to be solved by the invention ]

As described above, various studies have been made on the control of the transmission loss of a copper foil when used in a high-frequency circuit board, but there is still a large room for development. In addition, in the manufacture of high-frequency circuit boards, circuits (copper wirings) may be subjected to soft etching with acid or the like, and therefore improvement in acid resistance of copper foils is still expected.

[ means for solving the problems ]

The present inventors have found that, in a surface-treated copper foil having a copper foil and a surface-treated layer including a roughened layer on one or both surfaces of the copper foil, by controlling the content ratio of Ni in the surface-treated layer and the ten-point average roughness Rz of the outermost surface of the surface-treated layer, transmission loss can be reduced favorably and acid resistance can be improved even when the surface-treated copper foil is used for a high-frequency circuit board.

The present invention has been made in view of the above-described circumstances, and one aspect of the present invention is a surface-treated copper foil comprising a copper foil and a surface-treated layer comprising a roughened layer on one or both surfaces of the copper foil, wherein the surface-treated layer comprises Ni, the content of Ni in the surface-treated layer is 8 mass% or less (excluding 0 mass%), and the ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.4 μm or less.

In one embodiment of the surface-treated copper foil of the present invention, the total amount of the surface-treated layers is 1.0 to 5.0g/m ² 。

In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Co, and the content ratio of Co in the surface-treated layer is 15 mass% or less (excluding 0 mass%).

In still another embodiment of the surface-treated copper foil of the present invention, the amount of Co adhered to the surface-treated layer is 30 to 2000. mu.g/dm ² 。

In still another aspect of the surface-treated copper foil of the present invention, the surface-treated layer contains Ni, and the amount of Ni adhered to the surface-treated layer is 10 to 1000. mu.g/dm ² 。

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer further includes 1 or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer.

In still another embodiment, the surface-treated copper foil of the present invention is used for a copper-clad laminate or a printed wiring board for a high-frequency circuit board.

In another aspect of the present invention, there is provided a resin-layer-equipped surface-treated copper foil comprising the surface-treated copper foil of the present invention and a resin layer.

In still another aspect of the present invention, there is provided a copper foil with a carrier, which has an intermediate layer and an extra thin copper layer on one or both surfaces of the carrier, and the extra thin copper layer is the surface-treated copper foil of the present invention or the surface-treated copper foil with a resin layer of the present invention.

In still another aspect, the present invention is a laminate comprising the surface-treated copper foil of the present invention, the surface-treated copper foil with a resin layer of the present invention, or the copper foil with a carrier of the present invention.

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

In yet another aspect, the invention is a laminate having two inventive copper foils with a carrier.

In still another aspect, the present invention is a method for producing a printed wiring board using the surface-treated copper foil of the present invention, the surface-treated copper foil with a resin layer of the present invention, or the copper foil with a carrier of the present invention.

In still another aspect of the present invention, a method for manufacturing a printed wiring board includes: a step of laminating the surface-treated copper foil of the present invention or the surface-treated copper foil with a resin layer of the present invention with an insulating substrate to form a copper-clad laminate, or a step of laminating the copper foil with a carrier of the present invention with an insulating substrate and then peeling off the carrier of the copper foil with a carrier to form a copper-clad laminate; and forming a circuit by any one of a half-addition method (セミアディティブ method), a subtraction method (サブトラクティブ method), a partial addition method (パートリーアディティブ method), and a modified half-addition method (モディファイドセミアディティブ method).

In still another aspect of the present invention, a method for manufacturing a printed wiring board includes: a step of forming a circuit on the surface of the surface-treated layer side of the surface-treated copper foil of the present invention, or a step of forming a circuit on the surface of the extra thin copper layer side or the surface of the carrier side of the copper foil with a carrier of the present invention; forming a resin layer on the surface of the surface-treated copper foil on the surface-treated layer side, or on the surface of the extra thin copper layer side or the surface of the carrier side of the carrier-attached copper foil so as to bury the circuit; and a step of exposing the circuit buried in the resin layer by removing the surface-treated copper foil after the resin layer is formed, or by removing the extra thin copper layer or the carrier after the carrier or the extra thin copper layer is peeled.

In still another aspect of the present invention, a method for manufacturing a printed wiring board includes: laminating a resin substrate on the surface of the carrier side or the surface of the extra thin copper layer of the carrier-attached copper foil of the present invention; providing a resin layer and a circuit on the surface of the copper foil with a carrier opposite to the side on which the resin substrate is laminated, at least 1 time; and a step of peeling the carrier or the extra thin copper layer from the carrier-attached copper foil after the resin layer and the circuit are formed.

In still another aspect of the present invention, a method for manufacturing a printed wiring board includes: a step of providing a resin layer and a circuit on one or both surfaces of a laminate having the carrier-attached copper foil of the present invention or the laminate of the present invention at least 1 time; and a step of peeling the carrier or the extra thin copper layer from the copper foil with carrier constituting the laminate after the resin layer and the circuit are formed.

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

[ Effect of the invention ]

According to the present invention, a surface-treated copper foil which can reduce transmission loss satisfactorily even when used for a high-frequency circuit board and has satisfactory acid resistance can be provided.

Drawings

Fig. 1 a to C are schematic diagrams of the cross section of the wiring board in the steps up to the removal of the circuit plating resist (レジスト) according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention.

Fig. 2D to F are schematic diagrams of the cross-section of the wiring board in the step from the lamination of the resin and the second layer carrier-attached copper foil to the laser drilling in the specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

G to I in fig. 3 are schematic diagrams of the cross section of the wiring board in the steps from the formation of the via-hole filling (ビアフィル) to the peeling of the carrier of the 1 st layer in the specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention.

J to K in fig. 4 are schematic diagrams of the cross section of the wiring board in the steps from the flash etching (フラッシュエッチング) to the formation of the bumps and the copper pillars, according to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 5 is a schematic diagram illustrating a cross section in the width direction of a circuit pattern and a calculation method of an etching factor (エッチングファクター).

Fig. 6 is a schematic cross-sectional view of a polyimide resin substrate and a copper circuit in the acid resistance evaluation test of the example.

Fig. 7 is a schematic surface view of a polyimide resin substrate and a copper circuit in the acid resistance evaluation test of the example.

Detailed Description

< surface-treated copper foil >

The surface-treated copper foil of the present invention has a copper foil and a surface-treated layer on at least one side of the copper foil, that is, 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 desired conductor pattern, and finally a printed wiring board can be produced. 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 in which the frequency of a signal transmitted by using a circuit of the circuit board is 1GHz or more. The frequency of the signal is preferably 3GHz or more, more preferably 5GHz or more, more preferably 8GHz or more, more preferably 10GHz or more, more preferably 15GHz or more, more preferably 18GHz or more, more preferably 20GHz or more, more preferably 30GHz or more, more preferably 38GHz or more, more preferably 40GHz or more, more preferably 45GHz or more, more preferably 48GHz or more, more preferably 50GHz or more, more preferably 55GHz or more, and more preferably 58GHz or more.

< copper foil >

The form of the copper foil usable in the present invention is not particularly limited, and typically, the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Generally, electrolytic copper foil is produced by electrodepositing copper from a copper sulfate plating bath onto a titanium or stainless steel can, and rolled copper foil is produced by repeating plastic working with a roll and heat treatment. Rolled copper foil is often used for applications requiring bendability.

As the copper foil material, in addition to high-purity copper such as tough pitch copper (JIS H3100 alloy No. C1100), oxygen-free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011), phosphorus deoxidized copper (JIS H3100 alloy No. C1201, C1220 or C1221) or electrolytic copper, which is generally used as a conductor pattern of a printed wiring board, for example, there can be used: copper with Sn, copper with Ag, copper alloys with Sn, Ag, In, Au, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, P, and/or Mg, and copper alloys such as Kesen (コルソン) type copper alloys with Ni and Si added. In addition, copper foil and copper alloy foil having a known composition can also be used. In addition, when the term "copper foil" is used alone in the present specification, a copper alloy foil is also included.

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

In another aspect of the present invention, the carrier-attached copper foil includes an intermediate layer and an extra thin copper layer on at least one side of the carrier, that is, one or both sides of the carrier, and the extra thin copper layer is the surface-treated copper foil of the present invention. In the present invention, when the copper foil with a carrier is used, the surface treatment layer such as the following roughening treatment layer is provided on the surface of the extra thin copper layer. In addition, another embodiment of the copper foil with carrier will be described below.

< surface treatment layer >

The surface-treated layer of the surface-treated copper foil of the present invention contains Ni. When the surface-treated layer of the surface-treated copper foil contains Ni, the acid resistance is improved. Further, when the content ratio of Ni in the surface-treated layer is 8 mass% or less (excluding 0 mass%), the high-frequency transmission characteristics can be further improved. If the Ni content exceeds 8 mass%, the problem of deterioration of the high-frequency transmission characteristics of the surface-treated copper foil may occur. The content ratio of Ni in the surface treatment layer is preferably 7.5% by mass or less, more preferably 7% by mass or less, more preferably 6.5% by mass or less, more preferably 6% by mass or less, more preferably 5.5% by mass or less, more preferably 5% by mass or less, more preferably 4.8% by mass or less, more preferably 4.5% by mass or less, more preferably 4.2% by mass or less, more preferably 4.0% by mass or less, more preferably 3.8% by mass or less, more preferably 3.5% by mass or less, more preferably 3.0% by mass or less, more preferably 2.5% by mass or less, more preferably 2.0% by mass or less, more preferably 1.9% by mass or less, and even more preferably 1.8% by mass or less. In addition, from the viewpoint of acid resistance, the content ratio of Ni in the surface treatment layer is preferably 0% by mass or more, preferably more than 0% by mass, preferably 0.01% by mass or more, preferably 0.02% by mass or more, preferably 0.03% by mass or more, preferably 0.04% by mass or more, preferably 0.05% by mass or more, preferably 0.06% by mass or more, preferably 0.07% by mass or more, preferably 0.08% by mass or more, preferably 0.09% by mass or more, preferably 0.10% by mass or more, preferably 0.11% by mass or more, preferably 0.15% by mass or more, preferably 0.18% by mass or more, preferably 0.20% by mass or more, preferably 0.25% by mass or more, preferably 0.50% by mass or more, preferably 0.80% by mass or more, preferably 0.90% by mass or more, preferably 1.0% by mass or more, preferably 1.2% by mass or more, preferably 1.3% by mass or more, preferably 1.4% by mass or more, and preferably 1.5% by mass or more.

The amount of Ni deposited in the surface-treated layer is preferably 10. mu.g/dm ² The above. The amount of Ni deposited was set to 10. mu.g/dm ² As described above, the acid resistance of the surface-treated copper foil may be further improved. Further, the amount of Ni deposited in the surface-treated layer is preferably 1000. mu.g/dm ² The following. The amount of Ni deposited was 1000. mu.g/dm ² Hereinafter, the high-frequency transmission characteristics may be further improved. The amount of Ni deposited is preferably 20. mu.g/dm from the viewpoint of acid resistance of the surface-treated copper foil ² Above, preferably 30. mu.g/dm ² Above, it is preferably 40. mu.g/dm ² Above, it is preferably 50. mu.g/dm ² Above, it is preferably 55. mu.g/dm ² Above, 60. mu.g/dm is preferable ² Above, it is preferably 70. mu.g/dm ² Above, it is preferably 75. mu.g/dm ² Above, it is preferably 100. mu.g/dm ² Above, it is preferably 110. mu.g/dm ² Above, it is preferably 120. mu.g/dm ² Above, preferably 130. mu.g/dm ² Above, it is preferably 140. mu.g/dm ² Above, it is preferably 160. mu.g/dm ² Above, it is preferably 180. mu.g/dm ² Above, it is preferably 200. mu.g/dm ² Above, it is preferably 220. mu.g/dm ² Above, it is preferably 240. mu.g/dm ² Above, it is preferably 260. mu.g/dm ² Above, it is preferably 280. mu.g/dm ² Above, it is preferably 530. mu.g/dm ² The above. In addition, the amount of Ni deposited is preferably 950. mu.g/dm from the viewpoint of the high-frequency transmission characteristics of the surface-treated copper foil ² Hereinafter, it is preferably 900. mu.g/dm ² Hereinafter, it is preferably 850. mu.g/dm ² Hereinafter, it is preferably 800. mu.g/dm ² Below, preferably 750. mu.g/dm ² Hereinafter, it is preferably 700. mu.g/dm ² Hereinafter, it is preferably 650. mu.g/dm ² Hereinafter, it is preferably 600. mu.g/dm ² Hereinafter, 550. mu.g/dm is preferable ² Hereinafter, it is preferably 500. mu.g/dm ² Hereinafter, it is preferably 450. mu.g/dm ² Hereinafter, it is preferably 400. mu.g/dm ² Hereinafter, it is preferably 350. mu.g/dm ² Hereinafter, it is preferably 300. mu.g/dm ² Hereinafter, it is preferably 250. mu.g/dm ² Hereinafter, it is preferably 200. mu.g/dm ² Hereinafter, it is preferably 180μg/dm ² Hereinafter, it is preferably 160. mu.g/dm ² Hereinafter, it is preferably 150. mu.g/dm ² Hereinafter, it is preferably 140. mu.g/dm ² Hereinafter, it is preferably 130. mu.g/dm ² Hereinafter, it is preferably 125. mu.g/dm ² Hereinafter, it is preferably 120. mu.g/dm ² Hereinafter, it is preferably 115. mu.g/dm ² Hereinafter, it is preferably 110. mu.g/dm ² Hereinafter, it is preferably 105. mu.g/dm ² Hereinafter, it is preferably 100. mu.g/dm ² Hereinafter, it is preferably 95. mu.g/dm ² Hereinafter, it is preferably 90. mu.g/dm ² Hereinafter, it is preferably 85. mu.g/dm ² Hereinafter, it is preferably 80. mu.g/dm ² The following.

The surface-treated layer of the surface-treated copper foil of the present invention preferably contains Co, and the content ratio of Co in the surface-treated layer is 15 mass% or less (excluding 0 mass%). When the content ratio of Co is 15 mass% or less, the high-frequency transmission characteristics may be further improved. The content ratio of Co is more preferably 14% by mass or less, more preferably 13% by mass or less, more preferably 12% by mass or less, more preferably 11% by mass or less, more preferably 10% by mass or less, more preferably 9% by mass or less, more preferably 8% by mass or less, more preferably 7.5% by mass or less, more preferably 7% by mass or less, even more preferably 6.5% by mass or less, even more preferably 6.0% by mass or less, and even more preferably 5.5% by mass or less. Further, the surface-treated layer of the surface-treated copper foil may contain Co, thereby improving the fine circuit formability. The content ratio of Co in the surface treatment layer is preferably 0% by mass or more, preferably more than 0% by mass, preferably 0.01% by mass or more, preferably 0.02% by mass or more, preferably 0.03% by mass or more, preferably 0.05% by mass or more, preferably 0.09% by mass or more, preferably 0.1% by mass or more, preferably 0.11% by mass or more, preferably 0.15% by mass or more, preferably 0.18% by mass or more, preferably 0.2% by mass or more, preferably 0.3% by mass or more, preferably 0.5% by mass or more, preferably 0.8% by mass or more, preferably 0.9% by mass or more, preferably 1.0% by mass or more, preferably 1.5% by mass or more, preferably 2.0% by mass or more, preferably 2.5% by mass or more, preferably 3.0% by mass or more, preferably 3.5% by mass or more, preferably 4.0% by mass or more, preferably 4.5% by mass or more.

The amount of Co adhesion in the surface-treated layer is preferably 30. mu.g/dm ² The above. The amount of Co adhesion was set to 30. mu.g/dm ² As described above, the solubility in the etching solution during circuit fabrication may be improved, and the fine wiring formability may be improved. Further, the amount of Co adhering to the surface-treated layer is preferably 2000. mu.g/dm ² The following. The amount of Co adhesion was 2000. mu.g/dm ² Hereinafter, the high-frequency transmission characteristics may be further improved. From the viewpoint of fine wiring formability of the surface-treated copper foil, the amount of Co adhering to the surface-treated layer is preferably 35. mu.g/dm ² Above, it is preferably 40. mu.g/dm ² Above, it is preferably 45. mu.g/dm ² Above, it is preferably 50. mu.g/dm ² Above, it is preferably 55. mu.g/dm ² Above, 60. mu.g/dm is preferable ² Above, it is preferably 70. mu.g/dm ² Above, it is preferably 80. mu.g/dm ² Above, it is preferably 90. mu.g/dm ² Above, it is preferably 100. mu.g/dm ² Above, it is preferably 150. mu.g/dm ² Above, it is preferably 200. mu.g/dm ² Above, it is preferably 250. mu.g/dm ² Above, it is preferably 300. mu.g/dm ² Above, it is preferably 350. mu.g/dm ² Above, it is preferably 400. mu.g/dm ² Above, it is preferably 450. mu.g/dm ² Above, it is preferably 500. mu.g/dm ² Above, 550. mu.g/dm is preferable ² Above, it is preferably 600. mu.g/dm ² Above, it is preferably 650. mu.g/dm ² Above, it is preferably 700. mu.g/dm ² Above, it is preferably 940. mu.g/dm ² As described above. In addition, the amount of Co adhering to the surface-treated layer is preferably 1950. mu.g/dm from the viewpoint of the high-frequency transmission characteristics of the surface-treated copper foil ² Below, 1900. mu.g/dm is preferable ² Below, it is preferably 1850. mu.g/dm ² Hereinafter, it is preferably 1800. mu.g/dm ² Below, 1750. mu.g/dm is preferable ² Hereinafter, 1700. mu.g/dm is preferable ² Below, it is preferably 1650. mu.g/dm ² Hereinafter, it is preferably 1600. mu.g/dm ² Hereinafter, 1550. mu.g/dm is preferable ² Below, 1500. mu.g/dm is preferred ² Hereinafter, 1450. mu.g/dm is preferable ² Hereinafter, 1400. mu.g/dm is preferable ² Hereinafter, it is preferably 1350. mu.g/dm ² Hereinafter, 1300. mu.g/dm is preferred ² Hereinafter, 1250. mu.g/dm is preferable ² Hereinafter, 1200. mu.g/dm is preferred ² Hereinafter, it is preferably 1150. mu.g/dm ² Below, 1100. mu.g/dm is preferable ² Hereinafter, 1050. mu.g/dm is preferable ² Hereinafter, it is preferably 1000. mu.g/dm ² Hereinafter, preferably 950. mu.g/dm ² Hereinafter, it is preferably 900. mu.g/dm ² Hereinafter, preferably 730. mu.g/dm ² Hereinafter, it is preferably 700. mu.g/dm ² Hereinafter, it is preferably 600. mu.g/dm ² Hereinafter, it is preferably 570. mu.g/dm ² Hereinafter, 550. mu.g/dm is preferable ² Hereinafter, it is preferably 500. mu.g/dm ² Hereinafter, 475. mu.g/dm is preferable ² The following.

The surface-treated copper foil of the present invention preferably has a total adhesion amount of the surface-treated layers of 1.0g/m ² The above. The total amount of the surface-treated layer is the total amount of the elements constituting the surface-treated layer. Examples of the elements constituting the surface treatment layer include: cu, Ni, Co, Cr, Zn, W, As, Mo, P, Fe, etc. The total amount of the surface-treated layer was 1.0g/m ² As described above, the adhesiveness between the surface-treated copper foil and the resin may be improved. The total adhesion amount of the surface treatment layer is preferably 5.0g/m ² The following. The total amount of the deposit formed by the surface treatment layer was set to 5.0g/m ² Hereinafter, the high-frequency transmission characteristics may be further improved. From the viewpoint of adhesion between the surface-treated copper foil and the resin, the total adhesion amount of the surface-treated layer is preferably 1.05g/m ² Above, preferably 1.1g/m ² Above, preferably 1.15g/m ² Above, preferably 1.2g/m ² Above, preferably 1.25g/m ² Above, preferably 1.3g/m ² Above, preferably 1.35g/m ² Above, preferably 1.4g/m ² Above, preferably 1.5g/m ² The above. In addition, from the viewpoint of the high-frequency transmission characteristics of the surface-treated copper foil, the total adhesion amount of the surface-treated layers is preferably 4.8g/m ² The followingPreferably 4.6g/m ² Hereinafter, it is preferably 4.5g/m ² Hereinafter, it is preferably 4.4g/m ² Hereinafter, it is preferably 4.3g/m ² Hereinafter, it is preferably 4.0g/m ² Hereinafter, it is preferably 3.5g/m ² Hereinafter, it is preferably 3.0g/m ² Hereinafter, it is preferably 2.5g/m ² Hereinafter, it is preferably 2.0g/m ² Hereinafter, it is preferably 1.9g/m ² Hereinafter, it is preferably 1.8g/m ² The amount of the surfactant is preferably 1.7g/m or less ² Below, it is preferably 1.65g/m ² Hereinafter, it is preferably 1.60g/m ² Hereinafter, it is preferably 1.55g/m ² Hereinafter, it is preferably 1.50g/m ² Hereinafter, it is preferably 1.45g/m ² More preferably 1.43. mu.g/dm ² The amount of the surfactant is more preferably 1.4g/m or less ² The following.

In the present invention, when the surface-treated layers are present on both sides of the copper foil, the total amount of the surface-treated layers, the Co content, the Ni content, and the amount of the elements such as Co and Ni deposited are equivalent amounts in the surface-treated layer on one side, and are not the total amount of the elements (for example, Co) contained in the surface-treated layers formed on both sides.

Further, the total amount of the surface treatment layer deposited, the amount of the elements (Co and/or Ni) contained in the surface treatment layer deposited, the Co content in the surface treatment layer, and the Ni content in the surface treatment layer can be increased or increased by: the concentration of the element in the surface treatment solution used for forming the surface treatment layer is increased, and/or when the surface treatment is plating, the current density is increased, and/or the surface treatment time (energization time when plating is performed) is prolonged. In addition, the total amount of adhesion of the surface treatment layers, the amount of adhesion of the elements (Co and/or Ni) contained in the surface treatment layers, the content of Co in the surface treatment layers, and the content of Ni in the surface treatment layers can be reduced and/or decreased by: the concentration of the element in the surface treatment solution used for forming the surface treatment layer is reduced, and/or, in the case where the surface treatment is plating, the current density is reduced, and/or the surface treatment time (the energization time when plating is performed) is shortened.

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 1.4 μm or less. If the ten-point average roughness Rz of the outermost surface of the surface-treated layer exceeds 1.4 μm, there is a concern that the high-frequency transmission characteristics may deteriorate. The ten-point average roughness Rz of the outermost surface of the surface-treated layer is more preferably 1.3 μm or less, more preferably 1.2 μm or less, still more preferably 1.1 μm or less, yet more preferably 1.0 μm or less, yet more preferably 0.9 μm or less, and yet more preferably 0.8 μm or less. The "outermost surface of the surface-treated layer" refers to a surface of an outermost (outermost) layer of the plurality of layers when the surface-treated layer is formed of the plurality of layers formed by the surface treatment. Then, the ten-point average roughness Rz was measured for the surface of the outermost (outermost) layer of the plurality of layers. The lower limit of the ten-point average roughness Rz of the outermost surface of the surface-treated 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.

Further, in the case where the surface treatment is plating, the ten-point average roughness Rz of the outermost surface of the surface treatment layer may be increased by: increase in current density, and/or increase in surface treatment time (energization time when plating is performed). In addition, in the case where the surface treatment is plating, the ten-point average roughness Rz of the outermost surface of the surface treatment layer can be reduced by: a reduction in current density, and/or a reduction in surface treatment time (energization time when plating is performed).

The surface treatment layer of the surface-treated copper foil of the present invention has a roughening treatment layer. The roughened layer is usually formed by "nodular" electrodeposition on the surface of the degreased copper foil, with the aim of improving the peel strength of the laminated copper foil, on the roughened surface, which is the surface of the copper foil to be bonded to the resin substrate. In some cases, ordinary copper plating or the like is performed as a pretreatment before roughening, and in some cases, ordinary copper plating or the like is also performed as a finishing treatment after roughening in order to prevent removal of an electrodeposition. In the present invention, the pretreatment and the finishing treatment are also included, and are referred to as "roughening treatment".

The surface treatment layer may further include 1 or more layers selected from the group consisting of a heat-resistant layer, an anti-rust layer, a chromate treatment layer, and a silane coupling treatment layer. The heat-resistant layer, the rust-preventive layer, the chromate treatment layer, and the silane coupling treatment layer may be formed of a plurality of layers (for example, 2 or more layers, 3 or more layers, etc.). In addition, the surface treatment layer may have: 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/or a chromate treatment layer, and/or a silane coupling treatment layer, and/or a Ni-Zn alloy layer.

The heat-resistant layer and the rust-proof layer may be known ones. For example, the heat-resistant layer and/or the rust-preventive layer may be a layer composed of 1 or more elements 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, and tantalum, or may be a metal layer or an alloy layer composed of 1 or more elements 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, and tantalum. In addition, the heat-resistant layer and/or the rust-preventive layer may also contain an oxide, a nitride, a silicide containing the element. In addition, the heat-resistant layer and/or the rust preventive layer may also be a layer containing a nickel-zinc alloy. In addition, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 to 99 wt% of nickel and 50 to 1 wt% of zinc, in addition to unavoidable impurities. The total amount of zinc and nickel deposited on the nickel-zinc alloy layer may be 5 to 1000mg/m ² Preferably 10 to 500mg/m ² Preferably 20 to 100mg/m ² . The ratio of the amount of nickel deposited to the amount of zinc deposited (nickel deposited/zinc deposited) in the layer comprising the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 1.5 to 10. In addition, the amount of nickel deposited on the layer containing a nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5mg/m ² ～500mg/m ² More preferably 1mg/m ² ～50mg/m ² . In the case where the heat-resistant layer and/or the rust preventive layer is a layer comprising a nickel-zinc alloyWhen the inner wall of the via hole (スルーホール), the through hole (ビアホール), or the like comes into contact with the desmear (デスミア) liquid, the interface between the copper foil and the resin substrate is less likely to be eroded by the desmear liquid, and the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust preventive layer may be formed so as to be attached in an amount of 1mg/m ² ～100mg/m ² Preferably 5mg/m ² ～ 50mg/m ² With an adhesion amount of 1mg/m ² ～80mg/m ² Preferably 5mg/m ² ～40mg/m ² The nickel alloy layer may be made of any one of a nickel-molybdenum alloy, a nickel-zinc alloy, a nickel-molybdenum-cobalt alloy, and a nickel-tin alloy.

In the present specification, the chromate treatment layer refers to a layer treated with a solution containing anhydrous chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer may contain elements (in any form of metal, alloy, oxide, nitride, sulfide, etc.) such As Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti. Specific examples of the chromate treatment layer include: a chromate treatment layer treated with an aqueous solution of anhydrous chromic acid or potassium dichromate, a chromate treatment layer treated with a treatment liquid containing anhydrous chromic acid or potassium dichromate and zinc, or the like.

The silane coupling treatment layer may be formed using a known silane coupling agent, or may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, or triazine silane. Further, 2 or more silane coupling agents may be mixed and used. Among these, a layer formed using an amino silane coupling agent or an epoxy silane coupling agent is preferable.

In addition, the surface of the copper foil, the extra thin copper layer, the roughening treatment layer, the heat resistant layer, the rust preventive layer, the silane coupling treatment layer, or the chromate treatment layer may be subjected to a known surface treatment.

Further, the surface of the copper foil, the extremely thin copper layer, the roughening-treated layer, the heat-resistant layer, the rust-preventive layer, the silane-coupling-treated layer or the chromate-treated layer may be subjected to surface treatment as described in International publication No. WO2008/053878, Japanese patent laid-open No. 2008-111169, Japanese patent laid-open No. 5024930, International publication No. WO2006/028207, Japanese patent laid-open No. 4828427, International publication No. WO2006/134868, Japanese patent No. 5046927, International publication No. WO2007/105635, Japanese patent laid-open No. 5180815, Japanese patent laid-open No. 2013-19056.

< Transmission loss >

When the transmission loss is small, since attenuation of a signal is suppressed when a signal is transmitted at a high frequency, stable signal transmission can be performed in a circuit that transmits a signal at a high frequency. Therefore, a smaller value of the transmission loss is preferable because it is suitable for circuit applications in which signals are transmitted at high frequencies. When a microstrip line is formed by etching after a surface-treated copper foil is bonded to a commercially available liquid crystal polymer resin (a resin of a copolymer of Vecstar CTZ-50 μm thick, hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester) manufactured by Coli (クラレ) Ltd.) so that the characteristic impedance becomes 50. omega. and the transmission loss at a frequency of 40GHz is determined by measuring the transmission coefficient using a network analyzer HP8720C manufactured by HP, the transmission loss at a frequency of 40GHz is preferably less than 7.5 dB/10cm, more preferably less than 7.3dB/10cm, more preferably less than 7.1dB/10cm, more preferably less than 7.0 dB/10cm, more preferably less than 6.9dB/10cm, more preferably less than 6.8dB/10cm, more preferably less than 6.7 dB/10cm, more preferably less than 6.6dB/10cm, and even more preferably less than 6.5dB/10 cm.

< copper foil with Carrier >

In another embodiment of the present invention, a copper foil with a carrier has an intermediate layer and an extremely thin copper layer in this order on at least one side of the carrier, that is, on one side or both sides of the carrier. The extra thin copper layer is the surface-treated copper foil according to the embodiment of the present invention.

< vector >

The carrier usable in the present invention is typically a metal foil or a resin film, and is provided in the form of, for example, a copper foil, a copper alloy foil, a nickel alloy foil, an iron alloy foil, a stainless steel foil, an aluminum alloy foil, an insulating resin film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin film, a PET (polyethylene terephthalate) film, a PP (polypropylene) film, a polyamide film, or a polyamideimide film.

The carrier usable in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, electrolytic copper foil is produced by electroplating copper from a copper sulfate plating bath into a titanium or stainless steel can, and rolled copper foil is produced by repeating plastic working with a roll and heat treatment. As the material of the copper foil, in addition to high-purity copper such as tough pitch copper (JIS H3100 alloy No. C1100), oxygen-free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011), phosphorus deoxidized copper, electrolytic copper, and the like, for example: copper with Sn added, copper with Ag added, copper alloys with Cr, Zr, Mg added, and the like, copper alloys such as corson-based copper alloys with Ni, Si, and the like added. In addition, a known copper alloy may be used. In addition, when the term "copper foil" is used alone in the present specification, a copper alloy foil is also included.

The thickness of the carrier usable in the present invention is also not particularly limited as long as it is appropriately adjusted to a thickness suitable for the function as a carrier, and for example, it may be set to 5 μm or more. However, since the production cost increases when the thickness is too large, it is generally preferable 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 still more typically 18 to 35 μm. In addition, the thickness of the support is preferably small from the viewpoint of reducing the cost of raw materials. Therefore, the thickness of the carrier is typically 5 μm to 35 μm, preferably 5 μm to 18 μm, preferably 5 μm to 12 μm, preferably 5 μm to 11 μm, preferably 5 μm to 10 μm. In addition, when the thickness of the carrier is small, wrinkles are likely to occur at the time of foil passing of the carrier. In order to prevent the occurrence of wrinkles, it is effective to smooth a conveying roller of a copper foil manufacturing apparatus with a carrier, or to shorten the distance between the conveying roller and the next conveying roller, for example. In addition, when a copper foil with a carrier is used in an embedding Process (エンベッティド method) which is one of the methods for manufacturing a printed wiring board, the carrier must have high rigidity. Therefore, when used in an embedding process, the thickness of the carrier is preferably 18 μm to 300 μm, preferably 25 μm to 150 μm, preferably 35 μm to 100 μm, and more preferably 35 μm to 70 μm.

Further, the primary particle layer and the secondary particle layer may be provided on the surface of the carrier opposite to the surface on which the extremely thin copper layer is provided. The primary particle layer and the secondary particle layer are provided on the surface of the carrier opposite to the surface on which the extremely thin copper layer is provided, which has the following advantages: when the carrier is laminated on a support such as a resin substrate from the surface side having the primary particle layer and the secondary particle layer, the carrier and the resin substrate are difficult to be peeled.

An example of manufacturing conditions in the case of using an electrolytic copper foil as a carrier is shown below.

< composition of electrolyte >

Copper: 90-110 g/L

Sulfuric acid: 90-110 g/L

Chlorine: 50 to 100ppm

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

Leveling agent 2 (amine compound): 10 to 30ppm of

As the amine compound, an amine compound represented by the following chemical formula can be used.

Unless otherwise specified, the remaining part of the treatment solution used in the electrolysis, surface treatment, plating, or the like used in the present invention is water.

[ solution 1]

(in the above chemical formula, R ₁ And R ₂ Is selected from the group consisting of hydroxyalkyl, ether, aryl, aromatic substituted alkyl, unsaturated hydrocarbon, alkyl groups

< manufacturing Condition >

Current density: 70 to 100A/dm ²

Temperature of the electrolyte: 50-60 DEG C

Linear speed of electrolyte: 3 to 5m/sec

And (3) electrolysis time: 0.5 to 10 minutes

< intermediate layer >

An intermediate layer is disposed on the support. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it has the following structure: the extra thin copper layer is difficult to be peeled from the carrier before the step of laminating the copper foil with the carrier on the insulating substrate, and the extra thin copper layer can be peeled from the carrier after the step of laminating the copper foil with the carrier on the insulating substrate. For example, the intermediate layer of the copper foil with carrier of the present invention may contain one or more selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, and organic substances thereof. In addition, the intermediate layer may be a plurality of layers.

In addition, for example, the intermediate layer may be constituted by: a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, and a layer composed of a hydrate or an oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, or an organic material, or a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, or a single metal layer composed of one element selected from the group consisting of Cr, Ni, Mo, Ti, W, P, Cu, Al and Zn, or a single metal layer composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, or a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, An alloy layer composed of one or more elements selected from the group consisting of Zn.

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

Further, for example, the intermediate layer may be formed by laminating nickel, a nickel-phosphorus alloy, or a nickel-cobalt alloy with chromium in this order on the support. Since the adhesion between nickel and copper is higher than that between chromium and copper, when the extremely thin copper layer is peeled, the extremely thin copper layer is peeled at the interface between chromium and the extremely thin copper layer. Further, nickel in the intermediate layer is expected to have a barrier effect, i.e., to prevent diffusion of copper components from the support to the extremely thin copper layer. The adhesion amount of nickel in the intermediate layer is preferably 100. mu.g/dm ² 40000 mu g/dm above ² Hereinafter, more preferably 100. mu.g/dm ² Above 4000 mug/dm ² Hereinafter, more preferably 100. mu.g/dm ² Above 2500 μ g/dm ² Hereinafter, more preferably 100. mu.g/dm ² Above and below 1000 mu g/dm ² The amount of chromium adhered to the intermediate layer is preferably 5. mu.g/dm ² Above 100 mu g/dm ² The following.

< ultra thin copper layer >

An extremely thin copper layer is provided on the intermediate layer. Other layers may also be provided between the intermediate layer and the extremely thin copper layer. The extra thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, or copper cyanide, and is preferably a copper sulfate bath in view of being applicable to a general electrolytic copper foil and being capable of forming a copper foil at a high current density. The thickness of the extremely thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically 0.5 to 12 μm, more typically 1 to 5 μm, further typically 1.5 to 4 μm, further typically 2 to 3.5 μm. In addition, very thin copper layers may be provided on both sides of the carrier.

The surface-treated copper foil of the present invention, and/or the copper foil with a carrier of the present invention itself, is used in a method well known to those skilled in the art, for example, a surface-treated copper foil and/or an extra thin copper layer is bonded to an insulating substrate such as a paper-based phenol resin, a paper-based epoxy resin, a synthetic fiber cloth-based epoxy resin, a glass cloth-paper composite-based epoxy resin, a glass cloth-glass nonwoven fabric composite-based epoxy resin, a glass cloth-based epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer, a fluororesin, a polyamide resin, or a low dielectric polyimide film, and a copper-clad laminate is formed (in the case of a copper foil with a carrier, the carrier is peeled off after thermocompression bonding) and the surface-treated copper foil and/or the extra thin copper layer bonded to the insulating substrate is etched into a desired conductor pattern to finally produce a printed wiring board.

< resin layer >

The surface-treated copper foil of the present invention may be a resin-layer-provided surface-treated copper foil provided with a resin layer on the surface or the outermost surface of the surface-treated layer. Further, the surface of the 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, or the chromate layer, the silane coupling layer, or the Ni — Zn alloy layer may be provided with a resin 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, and on the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer.

The resin layer may be an adhesive or an insulating resin layer in a semi-cured state (B stage) for bonding. The semi-cured state (B stage) includes the following states: the insulating resin layers can be stored in a stacked state without giving a sticky feeling when the surface is touched with a finger, and a curing reaction occurs when the insulating resin layers are further subjected to a heat treatment.

The resin layer may contain a thermosetting resin or may be a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. The kind thereof is not particularly limited, and examples thereof include a resin containing one or more selected from the following group as a preferable one: epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide-based resin, aromatic maleimide resin, polyvinyl acetal resin, polyurethane resin, polyethersulfone resin, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl-modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide-triazine resin, thermosetting polyphenylene ether resin, cyanate ester-based resin, anhydride of carboxylic acid, anhydride of polycarboxylic acid, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2-bis (4-cyanatophenyl) propane, phosphorus-containing phenol compound, epoxy resin, polyether sulfone resin, polyether resin polymer, polyether polyamine, polyamide-imide resin, polyether-modified epoxy resin, polyether-based on a polyfunctional isocyanate compound, a polyisocyanate-based resin, a polymer-based resin, a polymer-based polymer-, Manganese naphthenate, 2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate ester resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy group, high molecular epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerization polyimide resin, and cyanoester resin.

The epoxy resin may be a resin having 2 or more epoxy groups in the molecule, and is usable without particular problem in the case of being a resin usable for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized by using a compound having 2 or more glycidyl groups in the molecule. In addition, 1 or 2 or more selected from the following group may be used in combination: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AD-type epoxy resin, novolac-type epoxy resin, cresol novolac-type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac-type epoxy resin, naphthalene-type epoxy resin, brominated bisphenol a-type epoxy resin, o-cresol novolac-type epoxy resin, rubber-modified bisphenol a-type epoxy resin, glycidyl amine compounds such as triglycidyl isocyanurate and N, N-diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resin, biphenyl-type epoxy resin, biphenol-aldehyde varnish-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin; alternatively, a hydrogenated or halogenated epoxy resin may be used.

The phosphorus-containing epoxy resin may be a known phosphorus-containing epoxy resin. In addition, the phosphorus-containing epoxy resin is preferably: for example, an epoxy resin obtained as a derivative from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having 2 or more epoxy groups in the molecule.

The resin layer may include: known resins, resin curing agents, compounds, curing accelerators, dielectrics (any dielectric such as a dielectric containing an inorganic compound and/or an organic compound or a dielectric containing a metal oxide can be used), reaction catalysts, crosslinking agents, polymers, prepregs, and skeleton materials. The resin layer can be formed by using a method and an apparatus for forming a resin layer and/or a substance (resin, resin curing agent, compound, curing accelerator, dielectric substance, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) described in the following patent documents, for example: international publication No. WO2008/004399, International publication No. WO2008/053878, International publication No. WO2009/084533, Japanese patent laid-open No. 11-5828, Japanese patent laid-open No. 11-140281, Japanese patent No. 3184485, International publication No. WO97/02728, Japanese patent No. 3676375, Japanese patent laid-open No. 2000-4 43188, Japanese patent No. 3612594, Japanese patent laid-open No. 2002-179772, Japanese patent laid-open No. 2002-359444, Japanese patent laid-open No. 2003-304068, Japanese patent No. 3992225, Japanese patent laid-open No. 2003-249739, Japanese patent No. 4136509, Japanese patent laid-open No. 2004-82687, Japanese patent No. 4025177, Japanese patent laid-open No. 2004-349654, Japanese patent No. 4286060, Japanese patent laid-open No. 2005-262506, Japanese patent No. 4570070, Japanese patent laid-open No. 2005-53218, Japanese patent No. 36 3949676, Japanese patent No. 4178415, Japanese patent publication No. WO2004/005588, Japanese laid-open patent publication No. 2006-257153, Japanese laid-open patent publication No. 2007-326923, Japanese laid-open patent publication No. 2008-111169, Japanese patent publication No. 5024930, International publication No. WO2006/028207, Japanese patent publication No. 4828427, Japanese laid-open patent publication No. 2009-67029, International publication No. WO2006/134868, Japanese patent publication No. 5046927, Japanese laid-open patent publication No. 2009-173017, International publication No. WO2007/105635, Japanese patent publication No. 5180815, International publication No. WO2008/114858, International publication No. WO2009/008471, Japanese laid-open patent publication No. 2011-14727, International publication No. WO2009/001850, International publication No. WO2009/145179, International publication No. WO2011/068157, Japanese laid-open patent publication No. 2013-19056.

These resins are dissolved in a solvent such as Methyl Ethyl Ketone (MEK) or toluene to prepare a resin solution, and the resin solution is applied to the surface-treated copper foil and/or the extra thin copper layer or the surface-treated layer including the heat-resistant layer, the rust-preventive layer, the chromate coating layer, or the silane coupling agent layer by, for example, a roll coater method, and then dried by heating as necessary to remove the solvent, thereby forming a B-stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature is preferably 100 to 250 ℃, more preferably 130 to 200 ℃.

The surface-treated copper foil and/or the copper foil with a carrier (resin-coated copper foil with a carrier) provided with the resin layer are used in the following embodiments: after the resin layer is laminated on the substrate, the whole is thermally pressed to thermally cure the resin layer, and then, in the case of a copper foil with a carrier, the carrier is peeled to expose the extra thin copper layer (of course, the surface of the extra thin copper layer on the intermediate layer side is exposed), and a predetermined wiring pattern is formed on the surface-treated copper foil or the extra thin copper layer.

When the resin-coated surface-treated copper foil and/or the copper foil with a carrier is used, the number of prepreg materials used in the production of a multilayer printed wiring board can be reduced. Further, the resin layer is formed to have a thickness that ensures interlayer insulation, and a copper-clad laminate can be produced without using any prepreg. In this case, the surface of the substrate may be coated with an insulating resin to further improve the surface smoothness.

Further, in the case where the prepreg material is not used, the material cost of the prepreg material is saved, and in addition, the laminating step becomes simple, so that it becomes advantageous in terms of economy, and there are advantages in that: the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is reduced, and an extremely thin multilayer printed wiring board having a thickness of 100 μm or less can be manufactured by 1 layer.

The thickness of the resin layer is preferably 0.1 to 80 μm. If the thickness of the resin layer is less than 0.1 μm, the adhesive strength is lowered, and when the copper foil with the resin-attached carrier is laminated on a base material provided with an inner layer material without interposing a prepreg material, it may be difficult to secure interlayer insulation with a circuit of the inner layer material.

On the other hand, if the thickness of the resin layer is made thicker than 80 μm, it is difficult to form a resin layer having a desired thickness by 1 coating step, and it takes extra material cost and man-hours, which is disadvantageous in terms of economy. Further, the formed resin layer is deteriorated in flexibility, and therefore, there are cases where: cracks and the like are easily generated during handling, and excessive resin flow is generated during thermocompression bonding with the inner layer material, so that smooth lamination is difficult.

Further, as another product form of the resin-coated copper foil with carrier, it is also possible to manufacture the resin-coated copper foil without carrier by coating the surface treatment layer of the extremely thin copper layer, or the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer with a resin layer to form a semi-cured state, and then peeling off the carrier.

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

Further, an electronic device can be produced using the printed wiring board on which electronic components are mounted, or an electronic device can be produced using the printed circuit board on which electronic components are mounted. Several examples of the steps for manufacturing a printed wiring board using the copper foil with a carrier of the present invention are shown below. Further, a printed wiring board can be similarly produced by using the surface-treated copper foil of the present invention as an extremely thin copper layer of a copper foil with a carrier.

In one embodiment of the method for manufacturing a printed wiring board of the present invention, the method includes: a step of preparing the copper foil with carrier of the present invention (hereinafter, the "copper foil with carrier" and the "extra thin copper layer" may be referred to as "surface-treated copper foil" and the "extra thin copper layer side" may be referred to as "surface-treated layer side" to manufacture a printed wiring board; in the case of the above-mentioned substitution, the printed wiring board may be manufactured as a carrier-free one); laminating the copper foil with the carrier and an insulating substrate; and a step of forming a circuit by any one of a semi-additive method, an improved semi-additive method, a partial additive method, and a subtractive method after the copper foil with carrier and the insulating substrate are laminated so that the ultra-thin copper layer side faces the insulating substrate, and the carrier-attached copper foil is peeled off to form a copper-clad laminate. The insulating substrate may be a substrate with an inner layer circuit incorporated therein.

In the present invention, the semi-additive method is a method of forming a conductor pattern by performing thin electroless plating on an insulating substrate or a copper foil seed (シード) layer to form a pattern, and then using electroplating and etching.

Therefore, an embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

a step of peeling off the carrier of the copper foil with the carrier after laminating the copper foil with the carrier and an insulating substrate;

removing the entire extremely thin copper layer exposed by peeling off the carrier by etching using an etching solution such as an acid or by a plasma method;

a step of providing a via hole and/or a blind hole in the resin exposed by removing the extremely thin copper layer by etching;

a step of performing decontamination treatment on the area containing the through hole or/and the blind hole;

providing an electroless plating layer on the resin and a region including the via hole and/or the blind hole;

a step of providing an anti-plating layer (めっきレジスト) on the electroless plating layer;

exposing the plating resist layer, and then removing the plating resist layer in the region where the circuit is formed;

providing an electrolytic plating layer on the circuit-forming region from which the plating resist layer has been removed;

removing the plating resist layer; and

and a step of removing the electroless plating layer located in a region other than the region where the circuit is formed by flash etching or the like.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method, the method includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

a step of providing a via hole and/or a blind hole in the extremely thin copper layer exposed by peeling off the carrier and the insulating resin substrate;

a step of performing decontamination treatment on the area containing the via hole or/and the blind hole;

a step of providing an electroless plating layer on the resin exposed by removing the extremely thin copper layer by etching or the like and on a region including the via hole and/or the blind hole;

a step of providing an anti-plating layer on the electroless plating layer;

removing the plating resist layer; and

laminating the copper foil with the carrier and an insulating substrate;

a step of providing a via hole and/or a blind hole in the ultra-thin copper layer exposed by peeling the carrier and the insulating resin substrate;

a step of providing an anti-plating layer on the electroless plating layer;

removing the plating resist layer; and

a step of laminating the copper foil with carrier and an insulating substrate,

a step of providing an electroless plating layer on the surface of the resin exposed by removing the extremely thin copper layer by etching;

a step of providing an anti-plating layer on the electroless plating layer;

removing the plating resist layer; and

and a step of removing the electroless plating layer and the extremely thin copper layer located in the region other than the region where the circuit is formed by flash etching or the like.

In the present invention, the improved semi-addition method is a method comprising: a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, thick copper plating is performed on the circuit forming portion by electrolytic plating, a resist is removed, and the metal foil other than the circuit forming portion is removed by flash etching (フラッシュ), thereby forming a circuit on the insulating layer.

Therefore, an embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

a step of providing a via hole and/or a blind hole in the ultra-thin copper layer and the insulation substrate exposed by peeling off the carrier;

providing an electroless plating layer on a region including the via hole and/or the blind hole;

a step of providing an anti-plating layer on the surface of the ultra-thin copper layer exposed by peeling the carrier;

forming a circuit by electrolytic plating after providing the plating resist layer;

removing the plating resist layer; and

and a step of removing the extremely thin copper layer exposed by the removal of the plating resist layer by flash etching.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method, the method includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

a step of providing an anti-plating layer on the extremely thin copper layer exposed by peeling off the carrier;

removing the plating resist layer; and

In the present invention, the partial addition method means the following method: a printed wiring board is manufactured by providing a substrate having a conductor layer provided thereon, or a substrate having a via hole or a hole for a through hole as needed, with a catalyst core, etching the substrate to form a conductor circuit, providing a solder resist layer (ソルダレジスト) or a plating resist layer as needed, and then performing electroless plating treatment to thickly plate the via hole or the through hole on the conductor circuit.

Therefore, an embodiment of the method for manufacturing a printed wiring board of the present invention using a partial addition method includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

a step of providing a via hole or/and a blind hole in the ultra-thin copper layer and the insulation substrate exposed by peeling the carrier;

a step of providing a catalyst core to a region including the via hole and/or the blind hole;

a step of providing an etching resist layer (エッチングレジスト) on the surface of the extremely thin copper layer exposed by peeling the carrier;

exposing the etching resist layer to form a circuit pattern;

a step of forming a circuit by removing the extremely thin copper layer and the catalyst nuclei by etching using an etching solution such as an acid or by a plasma method;

removing the etching-resistant layer;

a step of providing a solder resist layer or a plating resist layer on the surface of the insulating substrate exposed by removing the extra thin copper layer and the catalyst nuclei by etching using an etching solution such as an acid or by a plasma method; and

and a step of providing an electroless plating layer on a region where the solder resist layer or the plating resist layer is not provided.

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

Therefore, an embodiment of the method for manufacturing a printed wiring board of the present invention using a subtractive process includes: preparing the copper foil with carrier and the insulating substrate of the present invention;

a step of laminating the copper foil with carrier and an insulating substrate,

providing an electroless plating layer in a region including the via hole and/or the blind hole;

a step of providing an electrolytic plating layer on the surface of the electroless plating layer;

providing an etching resist layer on the surface of the electrolytic plating layer and/or the surface of the extremely thin copper layer;

exposing the etching resist layer to form a circuit pattern;

a step of forming a circuit by removing the extra thin copper layer, the electroless plating layer, and the electrolytic plating layer by etching using an etching solution such as an acid or by a plasma method; and

and removing the etching-resistant layer.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive process, the method comprises: preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with the carrier and an insulating substrate;

forming a mask on the surface of the electroless plating layer;

providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed;

exposing the etching resist layer to form a circuit pattern;

a step of forming a circuit by removing the extra thin copper layer and the electroless plating layer by etching using an etching solution such as an acid or by a plasma method; and

and removing the etching-resistant layer.

The step of providing the via holes and/or the blind holes and the subsequent desmear step may not be performed.

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

First, as shown in fig. 1 a, a copper foil with a carrier (layer 1) having an extremely thin copper layer with a roughened layer formed on the surface thereof is prepared.

Next, as shown in fig. 1B, a resist is applied to the roughened layer of the extremely thin copper layer, and exposure and development are performed to etch the resist into a predetermined shape.

Next, as shown in fig. 1C, after a plating layer for a circuit is formed, the resist is removed, thereby forming a circuit plating layer having a predetermined shape.

Next, as shown in fig. 2D, a resin layer is laminated by providing an embedding resin on the extra thin copper layer so as to cover the circuit plating layer (so as to bury the circuit plating layer), and then another copper foil with a carrier (second layer) is bonded from the extra thin copper layer side.

Next, as shown in fig. 2E, the carrier is peeled off from the carrier-attached copper foil of the second layer.

Next, as shown in fig. 2F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating layer, thereby forming a blind via.

Next, as shown in G of fig. 3, copper is embedded in the blind via to form a via-fill.

Next, as shown in fig. 3H, a circuit plating layer is formed on the via filling as described above in fig. 1B and 1C.

Next, as shown in fig. 3I, the carrier is peeled off from the carrier-attached copper foil of the 1 st layer.

Next, as shown in J of fig. 4, the extremely thin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating layer in the resin layer is exposed.

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

In the above-described method for manufacturing a printed wiring board, the "extra thin copper layer" may be referred to as a carrier, the "carrier" may be referred to as an extra thin copper layer, a circuit may be formed on the surface of the carrier side of the copper foil with a carrier, and the circuit may be embedded with a resin to manufacture a printed wiring board. In the above method for manufacturing a printed wiring board, a "copper foil with a carrier having an extremely thin copper layer with a roughened layer formed on the surface thereof" may be referred to as a surface-treated copper foil, a circuit may be formed on the surface of the surface-treated copper foil on the side of the surface-treated layer or on the surface of the surface-treated copper foil on the opposite side of the surface-treated layer, the circuit may be embedded with a resin, and then the surface-treated copper foil may be removed to manufacture a printed wiring board. In the present specification, the term "surface-treated layer side surface of the surface-treated copper foil" refers to a surface of the surface-treated copper foil on the side having the surface-treated layer, or, when a part or all of the surface-treated layer is removed, refers to a surface of the surface-treated copper foil on the side having the surface-treated layer after a part or all of the surface-treated layer is removed. That is, the "surface-treated-layer-side surface of the surface-treated copper foil" is a concept including "the outermost surface of the surface-treated layer" and the surface of the surface-treated copper foil from which a part or all of the surface-treated layer has been removed.

The other copper foil with carrier (second layer) may be the copper foil with carrier of the present invention, the conventional copper foil with carrier, or a general copper foil. Further, a circuit having 1 or more layers may be formed over the circuit of the second layer shown in H of fig. 3, and these circuits may be formed by any of a semi-additive method, a subtractive method, a partial additive method, or an improved semi-additive method.

In the method for manufacturing a printed wiring board as described above, since the circuit plating layer is embedded in the resin layer, when the extremely thin copper layer is removed by flash etching as shown in, for example, J of fig. 4, the circuit plating layer is protected by the resin layer and retains its shape, thereby facilitating the formation of a fine circuit. Further, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit is favorably suppressed. Therefore, a fine circuit is easily formed. Further, when the extremely thin copper layer is removed by flash etching as shown in J of fig. 4 and K of fig. 4, the exposed surface of the circuit plating layer is recessed from the resin layer, so that bumps are easily formed on the circuit plating layer, and further, copper pillars are easily formed thereon, thereby improving the manufacturing efficiency.

The embedding resin may be a known resin or a prepreg. For example, the following may be used: BT (スマレイミドトリアジン, bismaleimide triazine) resin or as a prepreg containing a glass cloth impregnated with BT resin, ABF film or ABF manufactured by ajinomoto fine chemical corporation. The resin layer and/or the resin and/or the prepreg described in the present specification can be used as the embedding resin.

The carrier-attached copper foil used for the first layer may have a substrate or a resin layer on the surface of the carrier-attached copper foil. The use of the substrate or the resin layer has an advantage that the copper foil with a carrier used in the first layer is supported and wrinkles are less likely to occur, thereby improving productivity. In addition, any substrate or resin layer may be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the substrate or the resin layer may be a carrier, a prepreg, a resin layer, or a known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, or organic compound foil described in the specification of the present application.

In addition, the method for manufacturing a printed wiring board of the present invention may be a method for manufacturing a printed wiring board (coreless (コアレス) process) including the steps of: laminating the surface of the carrier-attached copper foil on the side of the extra thin copper layer or the surface on the side of the carrier with a resin substrate; a step of providing a resin layer and a circuit on the surface of the copper foil with a carrier on the side opposite to the side of the extremely thin copper layer laminated on the resin substrate or the side of the carrier at least 1 time; and a step of peeling the carrier or the extra thin copper layer from the carrier-attached copper foil after 2 layers of the resin layer and the circuit are formed. Specific examples of the coreless process are: first, a laminate (also referred to as a copper-clad laminate or a copper-clad laminate) is produced by laminating the surface of the carrier-attached copper foil on the surface of the extra thin copper layer or the surface of the carrier with a resin substrate. Then, a resin layer is formed on the surface of the copper foil with a carrier on the side opposite to the surface on which the extremely thin copper layer is laminated with the resin substrate or the surface on the side of the carrier. Further, another copper foil with a carrier may be laminated on the resin layer formed on the surface of the carrier or the surface of the extra thin copper layer from the carrier side or the extra thin copper layer side. In addition, the following laminate may also be used in the above-described method for manufacturing a printed wiring board (coreless process): a laminate having a copper foil structure in which a tape carrier is laminated in the order of carrier/intermediate layer/extra thin copper layer or the order of extra thin copper layer/intermediate layer/carrier on both surface sides of a resin substrate, resin or prepreg; or a laminate having a constitution in which "carrier/intermediate layer/extremely thin copper layer/resin substrate or resin or prepreg/carrier/intermediate layer/extremely thin copper layer" is laminated in this order; or a laminate having a constitution of "carrier/intermediate layer/extremely thin copper layer/resin substrate/carrier/intermediate layer/extremely thin copper layer" laminated in this order; or a laminate having a constitution of "extremely thin copper layer/intermediate layer/carrier/resin substrate/carrier/intermediate layer/extremely thin copper layer" laminated in this order. Further, the circuit may be formed by providing another resin layer, and further providing a copper layer or a metal layer on the exposed surface of the extremely thin copper layer or the carrier at both ends of the laminate, and then processing the copper layer or the metal layer. Further, another resin layer may be provided on the circuit so as to be embedded in the circuit. The formation of the circuit and the resin layer as described above may be performed 1 or more times (layer-increasing (ビルドアップ) process). In the laminate (hereinafter, also referred to as laminate B) formed as described above, the extra thin copper layer of each carrier-attached copper foil or the carrier can be peeled from the carrier or the extra thin copper layer to produce a coreless substrate. In the above-described coreless substrate production, a laminate having a configuration of extra thin copper layer/intermediate layer/carrier/intermediate layer/extra thin copper layer, a laminate having a configuration of carrier/intermediate layer/extra thin copper layer/intermediate layer/carrier, or a laminate having a configuration of carrier/intermediate layer/extra thin copper layer/carrier/intermediate layer/extra thin copper layer, which will be described later, may be produced using 2 copper foils with carriers, and the laminate may be used as a core. The coreless substrate can be produced by providing the resin layer and the circuit 1 or more times on the surface of the extra thin copper layer or the carrier on both sides of the laminate (hereinafter, also referred to as a laminate a), and then peeling the extra thin copper layer or the carrier of each copper foil with a carrier from the carrier or the extra thin copper layer after providing the resin layer and the circuit 1 or more times. The laminate may also have other layers on the surface of the extremely thin copper layer, on the surface of the carrier, between the carrier and the carrier, between the extremely thin copper layer and the extremely thin copper layer, and between the extremely thin copper layer and the carrier. The other layer may be a resin substrate or a resin layer. In the present specification, when the extra thin copper layer, the carrier, or the laminate has another layer on the surface of the extra thin copper layer, the surface of the carrier, or the surface of the laminate, "the surface of the extra thin copper layer", "the surface of the carrier", "the surface of the laminate", or "the surface of the laminate" is a concept including the surface (outermost surface) of the other layer. In addition, the laminate preferably has a structure of extremely thin copper layer/intermediate layer/carrier/intermediate layer/extremely thin copper layer. This is because, when a coreless substrate is manufactured using this laminate, since an extremely thin copper layer is disposed on the coreless substrate side, it is easy to form a circuit on the coreless substrate using an improved semi-additive method. The other reason is that the extremely thin copper layer is easily removed because of its small thickness, and a circuit is easily formed on the coreless substrate by using a semi-additive method after the extremely thin copper layer is removed.

In the present specification, the "laminate" not particularly described as "laminate a" or "laminate B" means a laminate including at least laminate a and laminate B.

In the above method for producing a coreless substrate, a part or all of the end face of the copper foil with carrier or the laminate (including the laminate a) is covered with a resin, whereby, when a printed wiring board is produced by a build-up process, a chemical solution is prevented from penetrating between the copper foil with carrier and the copper foil with carrier of the intermediate layer or the copper foil with carrier of the laminate 1, separation of the extra thin copper layer from the carrier or corrosion of the copper foil with carrier due to penetration of the chemical solution is prevented, and the productivity can be improved. As the "resin covering part or all of the end face of the copper foil with carrier" or "resin covering part or all of the end face of the laminate" used herein, a resin usable for the resin layer or a known resin can be used. In the above method for producing a coreless substrate, at least a part of the outer periphery of the laminated portion of the copper foil with carrier or the laminated body (the laminated portion of the carrier and the extra thin copper layer, or the laminated portion of 1 copper foil with carrier and another 1 copper foil with carrier) may be covered with a resin or a prepreg in a plan view of the copper foil with carrier or the laminated body. In addition, the laminate (laminate a) formed by the above method for manufacturing a coreless substrate may be configured such that a pair of copper foils with carriers are in contact with each other so as to be separable. In addition, in the copper foil with carrier, when viewed from above, the entire outer periphery of the copper foil with carrier or the entire laminated portion of the laminated portion (the laminated portion of the carrier and the extra thin copper layer, or the laminated portion of 1 copper foil with carrier and another 1 copper foil with carrier) or the entire laminated portion may be covered with a resin or a prepreg. In addition, in a plan view, the resin or prepreg is preferably larger than the copper foil with carrier or the laminate or the laminated portion of the laminate, and the resin or prepreg is preferably laminated on both sides of the copper foil with carrier or the laminate to form a laminate having a structure in which the copper foil with carrier or the laminate is bagged (wrapped) with the resin or prepreg. With the above-described configuration, when the copper foil with carrier or the laminate is viewed from above, the laminated portion of the copper foil with carrier or the laminate is covered with the resin or the prepreg, and the other member can be prevented from colliding with the side of the portion, that is, the direction transverse to the laminating direction, and as a result, peeling between the carrier and the extra thin copper layer or the copper foil with carrier during handling can be reduced. Further, by covering the copper foil with a carrier or the outer periphery of the laminated portion of the laminate with a resin or a prepreg so as not to expose the outer periphery, the chemical liquid in the chemical liquid treatment step described above can be prevented from entering the interface of the laminated portion, and the copper foil with a carrier can be prevented from corrosion or erosion. Further, when the copper foil with carrier is separated from the pair of copper foils with carrier of the laminate or when the carrier of the copper foil with carrier is separated from the copper foil (extra thin copper layer), in the case where the copper foil with carrier or the laminated portion of the laminate (the laminated portion of the carrier and the extra thin copper layer, or the laminated portion of 1 copper foil with carrier and the copper foil with carrier of the other 1) covered with the resin or the prepreg is strongly adhered with the resin or the prepreg or the like, the laminated portion or the like may have to be removed by cutting or the like.

The copper foil with carrier of the present invention may be laminated on the carrier side or the extra thin copper layer side of another copper foil with carrier of the present invention from the carrier side or the extra thin copper layer side to form a laminate. The carrier-side surface or the extra thin copper layer-side surface of the copper foil with one carrier and the carrier-side surface or the extra thin copper layer-side surface of the copper foil with the other carrier may be laminated directly with an adhesive as needed. The carrier or the extra thin copper layer of the copper foil with one carrier may be bonded to the carrier or the extra thin copper layer of the copper foil with another carrier. Here, in the case where the carrier or the extremely thin copper layer has a surface-treated layer, the "bonding" also includes an embodiment in which the carriers or the extremely thin copper layer are bonded to each other via the surface-treated layer. In addition, a part or all of the end faces of the laminate may be covered with a resin.

The lamination of the carriers, the extra thin copper layers, the carriers and the extra thin copper layers, and the copper foils with the carriers can be performed by, for example, the following method, except for simple overlapping.

(a) The metallurgical bonding method comprises the following steps: welding (arc welding, TIG (タングステン, イナート, ガス, tungsten, inert gas) welding, MIG (メタル, イナート, ガス, metal, inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, friction stir welding), brazing;

(b) mechanical joining method: caulking, joining with rivets (joining by self-piercing riveting, joining by riveting), quilting machines;

(c) the physical bonding method comprises the following steps: adhesive, double-sided tape.

By using the above-described joining method, a laminate in which carriers are brought into separable contact with each other or with an extremely thin copper layer can be produced by joining a part or all of one carrier with a part or all of another carrier or a part or all of an extremely thin copper layer and laminating the one carrier with the other carrier or the extremely thin copper layer. In the case where one carrier is gently joined to another carrier or an extremely thin copper layer and one carrier is laminated to another carrier or an extremely thin copper layer, even if the joint portion of one carrier to another carrier or an extremely thin copper layer is not removed, one carrier can be separated from another carrier or an extremely thin copper layer. In addition, when one carrier is strongly bonded to another carrier or an extremely thin copper layer, a portion where one carrier is bonded to another carrier or an extremely thin copper layer is removed by cutting, chemical polishing (etching or the like), mechanical polishing or the like, whereby one carrier can be separated from another carrier or an extremely thin copper layer.

Further, a printed wiring board without a core can be produced by carrying out the following steps: a step of providing a resin layer and a circuit on the laminate constituted as described above at least 1 time; and a step of peeling the extra thin copper layer or the carrier from the carrier-attached copper foil of the laminate after the resin layer and the circuit are formed at least 1 time. Further, a resin layer and a circuit may be provided on at least one surface of the laminate, that is, one or both surfaces of the laminate.

The resin substrate, the resin layer, the resin, and the prepreg used in the laminate may be the resin layer described in the present specification, or may include the resin, the resin curing agent, the compound, the curing accelerator, the dielectric substance, the reaction catalyst, the crosslinking agent, the polymer, the prepreg, the skeleton material, and the like used in the resin layer described in the present specification. Further, the carrier-attached copper foil or laminate may be smaller than the resin or prepreg or resin substrate or resin layer in a plan view.

The resin substrate is not particularly limited as long as it has properties applicable to printed wiring boards and the like, and for example, for rigid PWB applications: paper-based phenol resins, paper-based epoxy resins, synthetic fiber cloth-based epoxy resins, glass cloth-paper composite-based epoxy resins, glass cloth-glass nonwoven fabric-based epoxy resins, and the like, and polyester films, polyimide films, LCP (liquid crystal polymer) films, fluorine resins, and the like can be used for FPC applications. In addition, when an LCP film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when an LCP film or a fluororesin film is used, if the copper circuit is covered with a cover layer after the copper circuit is formed, the film and the copper circuit are less likely to peel off, and peeling between the film and the copper circuit due to a decrease in peel strength can be prevented.

[ examples ]

The following description will be made based on examples and comparative examples. The present embodiment is an example, and is not limited to this example. That is, the present invention includes other embodiments and modifications included in the present invention.

The raw foil of example 6 and comparative example 4 was a rolled copper foil TPC (tough pitch defined in JIS H3100C 1100, manufactured by JX metal, with a ten-point average roughness Rz of the surface of 0.7 μm) having a thickness of 12 μm. The base foils of example 7 and comparative example 5 were electrolytic copper foils (HLP foils made of JX metal, ten-point average roughness Rz of the surface of the deposition surface (M surface) was 0.7 μ M) with a thickness of 12 μ M, and a surface treatment layer was provided on the deposition surface (M surface).

The base foils of examples 1 to 5, 8 to 15 and comparative examples 1 to 3 were copper foils with a carrier prepared by the following method.

Examples 1 to 5, 8, 10 to 15 and comparative examples 1 to 3 were prepared by using electrolytic copper foil (JTC foil made of JX metal) having a thickness of 18 μm as a carrier, and example 9 was prepared by using standard rolled copper foil TPC having a thickness of 18 μm as a carrier. Then, an intermediate layer was formed on the surface of the carrier under the following conditions, and an extremely thin copper layer having a thickness (1 μm or 3 μm) shown in Table 1 was formed on the surface of the intermediate layer. When the carrier is an electrolytic copper foil, an intermediate layer is formed on the glossy surface (S surface).

● examples 1 to 5, 8 to 15 and comparative examples 1 to 3

< intermediate layer >

(1) Ni layer (Ni plating)

The carrier was electroplated on a roll-to-roll type continuous plating line under the following conditions to form a plating layer of 3000. mu.g/dm ² The deposited amount of Ni layer. Specific plating conditions are described below.

Nickel sulfate: 270 to 280g/L

Nickel chloride: 35-45 g/L

Nickel acetate: 10 to 20g/L

Boric acid: 30 to 40g/L

A brightener: saccharin, butynediol, and the like

Sodium lauryl sulfate: 55 to 75ppm of

pH：4～6

Liquid temperature: 55-65 DEG C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) was washed with water and acid, and then, on a roll-to-roll continuous plating line, an electrolytic chromate treatment was performed under the following conditions to adhere 11. mu.g/dm to the Ni layer ² The amount of Cr layer deposited.

1-10 g/L potassium dichromate and 0g/L zinc

pH：7～10

Liquid temperature: 40-60 DEG C

Current density: 2A/dm ²

< ultra thin copper layer >

Next, the surface of the Cr layer formed in (2) was washed with water and acid, and then, an extra thin copper layer having a thickness (1 μm or 3 μm) described in table 1 was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line under the following conditions, thereby producing a copper foil with a carrier.

Copper concentration: 90-110 g/L

Concentration of sulfuric acid: 90-110 g/L

Chloride ion concentration: 50 to 90ppm

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

Leveling agent 2 (amine compound): 10 to 30ppm of

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

[ solution 2]

Temperature of the electrolyte: 50-80 DEG C

Current density: 100A/dm ²

Linear speed of electrolyte: 1.5 to 5m/sec

< roughening treatment 1, roughening treatment 2 >

Then, roughening treatment 1 was performed as shown in table 1 using the plating bath shown in table 3. In examples 3, 12 to 14 and comparative examples 1, 4 and 5, roughening treatment 2 was performed as shown in table 1 using the plating bath shown in table 3 after roughening treatment 1.

< Heat resistance treatment, Rust prevention treatment >

Then, in examples 2, 3, and 9 to 14, heat resistance treatment was performed as described in table 1 using the plating bath described in table 4. Further, in examples 9 and 11, rust prevention treatment was performed as described in table 1 using the plating bath described in table 4.

< chromate treatment, silane coupling treatment >

Then, the following electrolytic chromate treatment was performed on examples 1 to 5, 8 to 15, and comparative examples 1 to 5.

● electrolytic chromating

The liquid composition is as follows: potassium dichromate 1g/L

Liquid temperature: 40-60 DEG C

pH：0.5～10

Current density: 0.01 to 2.6A/dm ²

Energization time: 0.05 to 30 seconds

Then, the silane coupling treatment using the diaminosilane was performed as described below for examples 1 to 5, 7, 9 to 15, and comparative examples 1 to 5.

● silane coupling treatment

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

Concentration of silane coupling agent: 0.5 to 1.5 vol%

Treatment temperature: 20-70 DEG C

Treatment time: 0.5 to 5 seconds

(Total adhesion amount of surface treatment layer)

● determination of the number of roughening particles before etching

Photographs were taken of the surface side having the surface treatment layer of examples and comparative examples at 10000 times by a Scanning Electron Microscope (SEM). The number of the grained particles was counted in 3 arbitrary fields of 5 μm × 5 μm in size of the obtained photograph. The arithmetic average of the number of the grained particles in 3 visual fields was defined as the number of the grained particles per 1 visual field. The number of the roughened particles including a part of the roughened particles in the visual field is counted as the roughened particles.

● implementation of the etch

Etching was performed for 0.5 seconds under the following conditions.

(etching conditions)

● etch form: spray etching

● spray nozzle: solid cone (フルコーン) type

● spray pressure: 0.10MPa

● etchant temperature: 30 deg.C

● etching solution composition:

H ₂ O ₂ 18g/L

H ₂ SO ₄ 92g/L

Cu 8g/L

an appropriate amount of FE-830IIW3C manufactured by JCU Ltd

The rest part of water

In order to prevent the etching by the etching solution, the surface on the side not to be etched is masked with an acid-resistant tape, prepreg, or the like.

● measurement of the number of roughened particles on the surface of the sample after etching and determination of the etching end time

The number of the grained particles on the surface of the sample after etching was measured in the same manner as described above.

When the number of the coarse particles is 5% to 20% of the number of the coarse particles before etching, the etching is terminated.

The determination as to whether or not the number of the above-mentioned coarse particles is 5% to 20% of the number of the coarse particles before etching is made based on whether or not the value A of the following expression is 5% to 20%.

A (%). As the number of grained particles after etching (one/25 μm) ² ) Roughening particles before etchingNumber (number/25 μm) ² )×100％

The reason why the above-mentioned etching is completed is that the copper foil or the extra thin copper layer under the surface treatment layer may be etched at a portion of the sample surface where the roughened particles are not present. When the number of the coarse particles exceeded 20% of the number of the coarse particles before etching, etching was performed again for 0.5 seconds. Then, the measurement of the number of the above-mentioned coarse particles and the above-mentioned etching for 0.5 second were repeated until the number of the coarse particles became 20% or less of the number of the coarse particles before the etching. In addition, when the first 0.5 seconds of etching was performed, the number of the coarse particles on the surface of the sample after the etching was measured by setting the etching time to any time (for example, 0.05 seconds, 0.1 seconds, 0.15 seconds, 0.2 seconds, 0.25 seconds, 0.3 seconds, 0.35 seconds, or 0.4 seconds) within a range of 0.05 seconds to 0.4 seconds when the number of the coarse particles was less than 5% of the number of the coarse particles before the etching. The total etching time, in which the number of the primary particles is 5% to 20% of the number of the primary particles before etching, is defined as the etching end time.

● gravimetric determination of pre-etch samples

Size of the sample: 10cm square sheet (10 cm square sheet punched by a press)

Collecting a sample: 3 arbitrary parts

In addition, a precision balance capable of measuring up to the fourth decimal place was used for the weight measurement of the sample. The measured value of the weight thus obtained was used as it is for the above calculation.

The precision balance was IBA-200 from Suawax (アズワン) GmbH. The press was HAP-12 manufactured by Okinawa Press (Okinawa プレス, Inc.).

The weight measurement may be performed by including a masking member such as an acid-resistant tape or a prepreg used in the following etching. In this case, the weight measurement is performed by including a mask member in the measurement of the weight of the sample after etching, which will be described later. In addition, when the sample is a copper foil with a carrier, the above-mentioned weight measurement may be performed with the carrier included. In this case, the weight of the sample after etching described later is measured with the carrier included.

● gravimetric determination of etched samples

After masking the surface of the sample opposite to the surface having the surface-treated layer, the surface-treated surface of the sample was etched between the etching end times. The weight of the sample was then determined. In addition, when the specimen is observed by a scanning electron microscope, the specimen weight is larger than the actual specimen weight because the specimen observed by the scanning electron microscope is deposited with a noble metal such as platinum. Therefore, the weight of the sample after etching was measured using a sample which was not observed by a scanning electron microscope. The roughening treatment layer is formed substantially uniformly on the copper foil or the extremely thin copper layer. Therefore, it is determined that a sample which is not observed with a scanning electron microscope is preferably used.

● calculation of the Total adhering amount of surface treatment layer

The total amount (g/m) of the surface-treated layer ² ) Weight of sample of 10cm square sheet before etching (g/100 cm) ² ) Weight (g/100 cm) of a sample of a 10cm square sheet after etching ² ))}×100(m ² /100 cm ² )

The arithmetic average of the total adhesion amounts of the surface-treated layers at the 3 sites was defined as the value of the total adhesion amount of the surface-treated layers.

(measurement of Co content, Ni content, Co and Ni deposit amount in surface-treated layer)

The amounts of Co and Ni deposited were measured by ICP emission spectrometry using an ICP emission spectrometer (model: SPS3100) manufactured by SII corporation, in which samples having a size of 10cm × 10cm in examples and comparative examples were dissolved in a nitric acid aqueous solution having a concentration of 20 mass% and a thickness of 1 μm from the surface. The arithmetic mean of the amounts of Co and Ni deposited on the 3 samples was defined as the value of the amount of Co and Ni deposited.

In the examples and comparative examples in which surface-treated layers were provided on both sides of the copper foil, the adhesion amounts of Co, Ni, and other elements were measured by applying an acid-resistant tape or a prepreg such as thermocompression bonding FR4 to one surface of the copper foil to cover the copper foil, and dissolving the surface-treated layer on one surface. Then, the mask was removed, and the amount of Co, Ni, and other elements attached to the other surface was measured, or another sample was used to measure the amount of Co, Ni, and other elements attached to the other surface. The values shown in table 2 are values on one side. In the copper foil having surface-treated layers on both surfaces, the amounts of Co, Ni, and other elements deposited on both surfaces are the same. In the case where Co, Ni and other elements are not dissolved in the nitric acid aqueous solution having a concentration of 20 mass%, the measurement can be performed by the ICP emission analysis after dissolving them in a liquid capable of dissolving Co, Ni and other elements (for example, a mixed aqueous solution of nitric acid and hydrochloric acid having a nitric acid concentration of 20 mass% and a hydrochloric acid concentration of 12 mass%). The liquid capable of dissolving Co and Ni may be a known liquid, a known acidic liquid, or a known alkaline liquid.

When the copper foil or the extra thin copper layer has a large unevenness and the thickness of the copper foil or the extra thin copper layer is 1.5 μm or less, the surface treatment component on the surface opposite to the surface treatment layer or the component of the intermediate layer of the copper foil with a carrier is dissolved when only the thickness of 1 μm from the surface on the surface treatment layer side is dissolved. Therefore, in this case, 30% of the thickness of the copper foil or the extra thin copper layer is dissolved from the surface of the copper foil or the extra thin copper layer on the surface treatment layer side.

The "amount of the element" attached to the surface of the sample "means the amount per unit area (1 dm) ² Or 1m ² ) The amount (mass) of the element attached.

The Co content and the Ni content in the surface-treated layer were calculated by the following formulas.

The Co content (%) in the surface-treated layer was equal to the amount of Co deposited (μ g/dm) ² ) (total amount of surface-treated layers adhered (g/m)) ² )×10 ^-4 (g/m ² )/(μg/dm ² )×100

The Ni content (%) in the surface-treated layer was Ni adhesion (μ g/dm) ² ) (total amount of surface-treated layers adhered (g/m)) ² )×10 ^-4 (g/m ² )/(μg/dm ² )×100

(measurement of Ten-Point average roughness Rz)

The surface roughness Rz (ten-point average roughness) of the surface on the side of the roughened layer was measured according to JIS B0601-1982 using a contact roughness meter Surfcorder SE-3C stylus roughness meter manufactured by Osaka research corporation. Rz at 10 sites was arbitrarily measured, and the average value of 10 sites of Rz was defined as the value of Rz.

(measurement of Transmission loss)

For each sample, a liquid crystal polymer resin substrate (a resin having a thickness of 50 μm, which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester), manufactured by gory gmbh) was bonded thereto, and then a microstrip line was formed by etching so that the characteristic impedance became 50 Ω, and the transmission loss at a frequency of 40GHz was determined by measuring the transmission coefficient using a network analyzer N5247A manufactured by HP. Further, after the sample was laminated with a liquid crystal polymer resin substrate, the total thickness of the copper foil and the copper plating layer was set to 3 μm by copper plating for a sample having a copper foil thickness of less than 3 μm. After the sample was laminated with a liquid crystal polymer resin substrate, the copper foil was etched to a thickness of 3 μm when the thickness of the copper foil was more than 3 μm.

(measurement of peeling Strength)

Each sample was bonded to a liquid crystal polymer resin substrate (a resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester) and has a thickness of 50 μm Vecstar CTZ manufactured by Coli Ltd.) from the surface-treated layer side. Then, in the case where the sample was a copper foil with a carrier, the carrier was peeled off. When the thickness of the copper foil or the extra thin copper layer of the sample is less than 18 μm, the surface of the copper foil or the extra thin copper layer is copper-plated, and the total thickness of the copper foil or the extra thin copper layer and the copper-plated layer is set to 18 μm. When the thickness of the copper foil or the extra thin copper layer of the sample is larger than 18 μm, the copper foil or the extra thin copper layer is etched to have a thickness of 18 μm. The peel strength was measured by a 90 ° peel method (JIS C64718.1) by stretching the liquid crystal polymer resin substrate side with a load cell (ロードセル). In addition, the peel strength was measured for 3 samples in each example and each comparative example. The arithmetic mean of the peel strengths of the 3 samples of each example and each comparative example was defined as the value of the peel strength of each example and each comparative example. Further, the peel strength is preferably 0.5kN/m or more.

(Fine Wiring Forming Property)

Each of the samples of examples and comparative examples was bonded to a liquid crystal polymer resin substrate (a resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester) and has a thickness of 50 μm of Vecstar CTZ manufactured by Colorado corporation). Then, in the case where the sample was a copper foil with a carrier, the extremely thin copper layer was peeled off from the carrier. Then, for the sample in which the copper foil or the extra thin copper layer of the sample is thinner than 3 μm, the total thickness of the copper foil or the extra thin copper layer and the copper plating layer is set to 3 μm by copper plating. When the thickness of the copper foil or the extra thin copper layer is more than 3 μm, the copper foil is etched to have a thickness of 3 μm. Then, after applying a photosensitive resist to the surface of the copper foil or the extra thin copper layer or the copper plated layer on the liquid crystal polymer resin substrate, 50 circuits each having an L/S of 5 μm/5 μm width were printed in an exposure step, and etching treatment for removing unnecessary portions of the surface of the copper foil or the extra thin copper layer or the copper plated layer was performed under the following spray etching conditions.

(spray etching conditions)

Etching solution: ferric chloride aqueous solution (Baume degree (ボーメ degree): 40 degree)

Liquid temperature: 60 deg.C

Spraying pressure: 2.0MPa

The etching was continued, and the width of the bottom of the circuit (the length of the bottom side X) and the etching factor were evaluated when the width of the top of the circuit became 4 μm. The etching factor is a ratio of a to a thickness b of the copper foil, where a is a distance of a recess length from an intersection of a perpendicular line from an upper surface of the copper foil and the resin substrate when the circuit is assumed to be etched vertically, in a case where the recess (ダレ) is generated in a stepwise expanding form (end Wide "" り): the larger the value of b/a, the larger the tilt angle, the less etching residue remains and the smaller the dishing. Fig. 5 is a schematic diagram showing a cross section in the width direction of a circuit pattern, and an outline of a method of calculating an etching factor using the schematic diagram. The X is measured by SEM observation from above the circuit, and the etching factor (EF ═ b/a) is calculated. Further, a ═ X (μm) -4 (μm))/2 was calculated. By using the etching factor, the quality of the etching performance can be easily determined. In the present invention, an etching factor of 6 or more is evaluated as etching property: very excellent, 5 or more and less than 6 was evaluated as etching property: x, 4 or more and less than 5 were evaluated as etching properties: o, 3 or more and less than 4 were evaluated as etchability: o, less than 3 or not calculated as etching property: x. In the table, "connected" in "the length of the base X" means that the circuit is connected to an adjacent circuit at least in the base portion and cannot be formed.

(acid resistance)

A polyamic acid (U-varnish-a manufactured by yushu co., ltd., BPDA (biphenyltetracarboxylic dianhydride) series) was applied to each of the samples of examples and comparative examples, dried at 100 ℃, and cured at 315 ℃ to form a copper clad laminate having a polyimide resin substrate (BPDA (biphenyltetracarboxylic dianhydride) series polyimide) and a copper foil. Then, in the case where the sample was a copper foil with a carrier, the extremely thin copper layer was peeled off from the carrier. Then, for the sample in which the copper foil or the extra thin copper layer of the sample is thinner than 3 μm, the total thickness of the copper foil or the extra thin copper layer and the copper plating layer is set to 3 μm by copper plating. When the thickness of the copper foil or the extra thin copper layer is more than 3 μm, the copper foil is etched to have a thickness of 3 μm. Then, after applying a photosensitive resist to the surface of the copper foil or the extra thin copper layer or the copper plated layer on the polyimide resin substrate, 50 circuits (wirings) having an L/S of 5 μm/5 μm width were printed by an exposure step, and etching treatment for removing unnecessary portions of the surface of the copper foil or the extra thin copper layer or the copper plated layer was performed under the following spray etching conditions.

(spray etching conditions)

Etching solution: ferric chloride aqueous solution (Baume degree: 40 degree)

Liquid temperature: 60 deg.C

Spraying pressure: 2.0MPa

Etching was continued until the top width of the circuit became 4 μm. Then, the polyimide resin substrate having the copper circuit was immersed in an aqueous solution containing 10 wt% of sulfuric acid and 2 wt% of hydrogen peroxide for 1 minute, and then the interface between the polyimide resin substrate and the copper circuit was observed with an optical microscope. The width of the circuit corroded by the aqueous solution of sulfuric acid and hydrogen peroxide was observed (see fig. 6 and 7), and the acid resistance was evaluated as follows. The width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is defined as the length of the eroded portion of the circuit in the width direction of the circuit. The maximum value of the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide in the circuit of the sample to be observed was defined as the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide of the sample.

The acid resistance was evaluated as follows. Very good ": the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is less than 0.6 μm; "verygood": the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is more than 0.6 μm and less than 0.8 μm; ". o": the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is more than 0.8 μm and less than 1.0 μm; ". o": the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is more than 1.0 μm and less than 1.2 μm; "×": the width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is 1.2 μm or more.

The production conditions and the evaluation results are shown in tables 1 to 4.

[ Table 3]

[ Table 4]

(evaluation results)

Examples 1 to 15 all suppressed the transmission loss well, and had good acid resistance.

The surface-treated layers of comparative examples 1, 4 and 5 had a Ni content of 0 mass%, and the ten-point average roughness Rz of the outermost surface of the surface-treated layers exceeded 1.4 μm, and were high in transmission loss and poor in acid resistance.

The content ratio of Ni in the surface-treated layer of comparative example 2 exceeds 8 mass%, and the transmission loss is large.

The content of Ni in the surface-treated layer of comparative example 3 was 0 mass%, and the acid resistance was poor.

Further, the present application claims priority based on japanese patent application No. 2017-020508 filed on 7.2.2017, the entire contents of which are incorporated herein by reference.

Claims

1. A surface-treated copper foil comprising:

copper foil and

a surface treatment layer is arranged on one or two surfaces of the copper foil;

the surface treatment layer comprises a roughening treatment layer and a layer containing 1 or more elements 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, and tantalum,

the surface treatment layer contains Ni, the content of Ni in the surface treatment layer is more than 0 mass% and not more than 8 mass%,

the amount of Co adhered to the surface-treated layer was 0. mu.g/dm ² Or 30 to 90 mu g/dm ² ，

The ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.4 [ mu ] m or less,

wherein the Ni content in the surface-treated layer is calculated by the following formula:

the Ni content (%) in the surface-treated layer was Ni adhesion (μ g/dm) ² ) (total amount of surface-treated layers adhered (g/m)) ² )×10 ^-4 (g/m ² )/(μg/dm ² )×100。

2. The surface-treated copper foil according to claim 1, wherein the surface-treated layers are deposited in a total amount of 1.0 to 5.0g/m ² 。

3. The surface-treated copper foil according to claim 1, wherein the surface-treated layer contains Co, and the content ratio of Co in the surface-treated layer is more than 0 mass% and 15 mass% or less.

4. The surface-treated copper foil according to claim 2, wherein the surface-treated layer contains Co, and the content ratio of Co in the surface-treated layer is more than 0 mass% and 15 mass% or less.

5. The surface-treated copper foil according to any one of claims 1 to 4, wherein the amount of Co adhered to the surface-treated layer is 30 to 90 μ g/dm ² 。

6. The surface-treated copper foil according to any one of claims 1 to 4, wherein the surface-treated layer contains Ni, and the amount of Ni adhered to the surface-treated layer is 10 to 1000. mu.g/dm ² 。

7. The surface-treated copper foil according to any one of claims 1 to 4, which satisfies any one or two or three or four or five or six of the following (7-1) to (7-6),

(7-1) the Ni content in the surface-treated layer satisfies either or both of the following (7-1-1) and (7-1-2),

(7-1-1) the content ratio of Ni in the surface treatment layer satisfies any one of the following conditions:

more than 0 mass%,

At least 0.01 mass%,

0.02 mass% or more,

0.03 mass% or more,

At least 0.04 mass%,

0.05% by mass or more,

0.06% by mass or more,

0.07% by mass or more,

0.08% by mass or more,

0.09% by mass or more,

0.10% by mass or more,

0.11% by mass or more,

0.15% by mass or more,

0.20% by mass or more,

0.25% by mass or more of,

(7-1-2) the content ratio of Ni in the surface treatment layer satisfies any one of the following conditions:

7.5% by mass or less,

7% by mass or less,

6.5% by mass or less,

6 mass% or less,

5.5% by mass or less,

5% by mass or less of,

4.8% by mass or less,

4.5% by mass or less,

4.0% by mass or less,

3.5% by mass or less,

3.0% by mass or less of,

2.5% by mass or less,

2.0% by mass or less,

1.9% by mass or less,

1.8% by mass or less;

(7-2) the ten-point average roughness Rz of the outermost surface of the surface-treated layer satisfies either or both of the following (7-2-1) and (7-2-2),

(7-2-1) the ten-point average roughness Rz of the outermost surface of the surface treatment layer satisfies any one of the following:

1.3 μm or less,

1.2 μm or less,

1.1 μm or less,

1.0 μm or less,

0.9 μm or less,

0.8 μm or less,

(7-2-2) the ten-point average roughness Rz of the outermost surface of the surface treatment layer satisfies any one of the following:

0.01 μm or more,

0.05 μm or more,

0.1 μm or more;

(7-3) the total amount of the surface-treated layers satisfies either one or both of the following (7-3-1) and (7-3-2),

(7-3-1) the total adhesion amount of the surface treatment layers satisfies any one of the following conditions:

·1.05g/m ² the above,

·1.1g/m ² The above,

·1.2g/m ² The above,

·1.3g/m ² The above,

·1.4g/m ² The above,

·1.5g/m ² In the above-mentioned manner,

(7-3-2) the total adhesion amount of the surface treatment layers satisfies any one of the following conditions:

·4.5g/m ² the following components,

·4.0g/m ² The following components,

·3.5g/m ² The following components,

·3.0g/m ² The following;

(7-4) the content ratio of Co in the surface treatment layer satisfies either or both of the following (7-4-1) and (7-4-2),

(7-4-1) the content ratio of Co in the surface treatment layer satisfies any one of the following conditions:

more than 0 mass%,

0.01% by mass or more,

0.02 mass% or more,

0.03 mass% or more,

0.05% by mass or more,

0.1% by mass or more,

0.11% by mass or more,

0.15% by mass or more,

0.2% by mass or more,

0.3% by mass or more,

At least 0.5 mass%,

1.0% by mass or more,

1.5% by mass or more,

2.0% by mass or more,

2.5% by mass or more,

3.0% by mass or more,

3.5% by mass or more,

4.0% by mass or more,

4.5% by mass or more of,

(7-4-2) the content ratio of Co in the surface treatment layer satisfies any one of the following conditions:

14% by mass or less,

13% by mass or less,

12% by mass or less,

11% by mass or less,

10% by mass or less of,

9% by mass or less,

8% by mass or less,

7% by mass or less,

7.5% by mass or less,

6.5% by mass or less,

6.0% by mass or less,

5.5% by mass or less;

(7-5) the amount of Co deposited in the surface-treated layer satisfies the following (7-5-1),

(7-5-1) the amount of Co deposited in the surface treatment layer satisfies the following (7-5-1-1),

(7-5-1-1) the amount of Co deposited in the surface treatment layer satisfies any one of the following conditions:

·40μg/dm ² the above,

·50μg/dm ² The above,

·60μg/dm ² The above,

·70μg/dm ² The above,

·80μg/dm ² The above,

(7-6) the amount of Ni deposited on the surface-treated layer satisfies any one of the following requirements (7-6-1) and (7-6-2),

(7-6-1) the amount of Ni deposited in the surface-treated layer satisfies either or both of the following (7-6-1-1) and (7-6-1-2),

(7-6-1-1) the amount of Ni deposited in the surface treatment layer satisfies any one of the following:

·20μg/dm ² the above,

·55μg/dm ² The above,

·60μg/dm ² The above,

·70μg/dm ² The above,

·75μg/dm ² The above,

·110μg/dm ² In the above-mentioned manner,

·120μg/dm ² the above,

·130μg/dm ² The above,

·530μg/dm ² In the above-mentioned manner,

(7-6-1-2) the amount of Ni deposited in the surface treatment layer satisfies any one of the following:

·800μg/dm ² the following components,

·700μg/dm ² The following components,

·650μg/dm ² The following components,

·600μg/dm ² The following components,

·550μg/dm ² In the following, the following description is given,

(7-6-2) the amount of Ni deposited in the surface-treated layer satisfies either or both of the following (7-6-2-1) and (7-6-2-2),

(7-6-2-1) the amount of Ni deposited in the surface treatment layer satisfies any one of the following:

·20μg/dm ² the above,

·55μg/dm ² The above,

·60μg/dm ² The above,

·70μg/dm ² The above,

·75μg/dm ² In the above-mentioned manner,

(7-6-2-2) the amount of Ni deposited in the surface treatment layer satisfies any one of the following:

·800μg/dm ² the following components,

·700μg/dm ² The following components,

·650μg/dm ² The following components,

·600μg/dm ² The following components,

·550μg/dm ² The following components,

·500μg/dm ² The following components,

·450μg/dm ² The following components,

·400μg/dm ² The following components,

·350μg/dm ² The following components,

·300μg/dm ² The following components,

·250μg/dm ² The following components,

·200μg/dm ² The following components,

·160μg/dm ² The following components,

·150μg/dm ² The following components,

·140μg/dm ² The following components,

·130μg/dm ² The following components,

·125μg/dm ² The following components,

·120μg/dm ² The following components,

·115μg/dm ² The following components,

·110μg/dm ² The following components,

·105μg/dm ² The following components,

·100μg/dm ² The following components,

·95μg/dm ² The following components,

·90μg/dm ² The following components,

·85μg/dm ² The following components,

·80μg/dm ² The following.

8. The surface-treated copper foil according to any one of claims 1 to 4, wherein the surface-treated layer further comprises 1 or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer and a silane coupling treatment layer.

9. The surface-treated copper foil according to any one of claims 1 to 4, which is used for a copper-clad laminate for a high-frequency circuit substrate or a printed wiring board.

10. A surface-treated copper foil with a resin layer, comprising:

the surface-treated copper foil according to any one of claims 1 to 9, and

and a resin layer.

11. A copper foil with a carrier, which has an intermediate layer and an extra thin copper layer on one surface or both surfaces of the carrier, wherein the extra thin copper layer is the surface-treated copper foil according to any one of claims 1 to 9 or the surface-treated copper foil with a resin layer according to claim 10.

12. A laminate having any one of the following (12-1) to (12-3):

(12-1) the surface-treated copper foil according to any one of claims 1 to 9,

(12-2) the resin layer-provided surface-treated copper foil according to claim 10, and

(12-3) the copper foil with carrier according to claim 11.

13. A laminate comprising the copper foil with a carrier according to claim 11 and a resin, wherein part or all of an end face of the copper foil with a carrier is covered with the resin.

14. A laminate having two copper foils with a carrier according to claim 11.

15. A method for manufacturing a printed wiring board, using any one of the following (15-1) to (15-3):

(15-1) the surface-treated copper foil according to any one of claims 1 to 9,

(15-2) the resin layer-provided surface-treated copper foil according to claim 10, and

(15-3) the copper foil with carrier according to claim 11.

16. A method of manufacturing a printed wiring board, comprising: the following step (16-1) or (16-2),

(16-1) a step of laminating the surface-treated copper foil according to any one of claims 1 to 9 or the resin-layer-provided surface-treated copper foil according to claim 10 with an insulating substrate to form a copper-clad laminate,

(16-2) a step of forming a copper-clad laminate by laminating the copper foil with a carrier according to claim 11 and an insulating substrate and then peeling off the carrier with the copper foil with a carrier; and

a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method.

17. A method of manufacturing a printed wiring board, comprising:

a step 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 9, or a step of forming a circuit on the surface of the extra thin copper layer side or the surface of the carrier side of the copper foil with a carrier according to claim 11;

forming a resin layer on the surface of the surface-treated copper foil on the surface-treated layer side, or on the surface of the extra thin copper layer side or the surface of the carrier side of the carrier-attached copper foil so as to bury the circuit; and

and a step of removing the surface-treated copper foil after the resin layer is formed, or removing the extra thin copper layer or the carrier after the carrier or the extra thin copper layer is peeled, thereby exposing the circuit buried in the resin layer.

18. A method of manufacturing a printed wiring board, comprising:

laminating the carrier-side surface or the extra thin copper layer-side surface of the copper foil with a carrier according to claim 11 with a resin substrate;

a step of providing a resin layer and a circuit on the surface of the copper foil with a carrier on the opposite side to the side laminated with the resin substrate at least 1 time; and

and a step of peeling the carrier or the extra thin copper layer from the carrier-attached copper foil after the resin layer and the circuit are formed.

19. A method of manufacturing a printed wiring board, comprising:

a step of providing a resin layer and a circuit on either or both surfaces of a laminate having the copper foil with a carrier according to claim 11 or either or both surfaces of a laminate according to claim 13 or 14 at least 1 time; and

and a step of peeling the carrier or the extra thin copper layer from the copper foil with carrier constituting the laminate after the resin layer and the circuit are formed.

20. A method of manufacturing an electronic machine using a printed wiring board manufactured by the method according to any one of claims 15 to 19.