WO2015087942A1

WO2015087942A1 - Treated surface copper foil, copper-clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method

Info

Publication number: WO2015087942A1
Application number: PCT/JP2014/082766
Authority: WO
Inventors: 新井　英太; 敦史三木; 康修新井; 嘉一郎中室
Original assignee: Jx日鉱日石金属株式会社
Priority date: 2013-12-10
Filing date: 2014-12-10
Publication date: 2015-06-18
Also published as: PH12016501130A1; KR20160086378A; JPWO2015087942A1; CN105980609B; KR101944166B1; MY183375A; JP5819571B1; CN105980609A; TW201532485A; TWI573500B

Abstract

The present invention provides a treated surface copper foil, which adheres favorably to resin and achieves excellent visibility when observed through the resin. Provided is a treated surface copper foil in which respective surface treatments have been performed on the two surfaces, wherein the color difference (∆E*ab) based on JIS Z8730 of the through-polyimide surface of a copper-clad laminate, configured by laminating treated surface copper foil on a polyimide with a ∆B(PI) before bonding to the copper foil of 50 to 65, is at least 50. When the copper foil is photographed with a CCD camera through the polyimide, which has been laminated from the surface on which surface treatment has been performed, ∆B (∆B = Bt - Bb) in the observation point-brightness graph is at least 40. The ten-point mean roughness (Rz) of TD of the other surface of the treated surface copper foil measured with a laser microscope in which the wavelength of the laser light is 405 nm is at least 0.35 µm.

Description

Surface-treated copper foil, copper-clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method

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

For small electronic devices such as smartphones and tablet PCs, flexible printed wiring boards (hereinafter referred to as FPCs) are employed because of their ease of wiring and light weight. In recent years, with the enhancement of functions of these electronic devices, the signal transmission speed has been increased, and impedance matching has become an important factor in FPC. As a measure for impedance matching with respect to an increase in signal capacity, a resin insulation layer (for example, polyimide) serving as a base of an FPC has been increased in thickness. In addition, the demand for higher wiring density has further increased the number of FPC layers. On the other hand, processing such as bonding to a liquid crystal substrate and mounting of an IC chip is performed on the FPC, but the alignment at this time is the resin insulation remaining after etching the copper foil in the laminate of the copper foil and the resin insulating layer The visibility of the resin insulation layer is important because it is performed through a positioning pattern that is visible through the layer.

Also, a copper clad laminate that is a laminate of a copper foil and a resin insulating layer can be manufactured using a rolled copper foil having a roughened plating surface. This rolled copper foil usually uses tough pitch copper (oxygen content of 100 to 500 ppm by weight) or oxygen free copper (oxygen content of 10 ppm by weight or less) as a raw material, and after hot rolling these ingots, It is manufactured by repeating cold rolling and annealing to a thickness.

As such a technique, for example, in Patent Document 1, a polyimide film and a low-roughness copper foil are laminated, and a light transmittance at a wavelength of 600 nm of the film after copper foil etching is 40% or more, a haze value. An invention relating to a copper clad laminate having (HAZE) of 30% or less and an adhesive strength of 500 N / m or more is disclosed.
Further, Patent Document 2 has an insulating layer in which a conductive layer made of electrolytic copper foil is laminated, and the light transmittance of the insulating layer in the etching region when the circuit is formed by etching the conductive layer is 50% or more. In a flexible printed wiring board for chip-on-flex (COF), the electrolytic copper foil includes a rust-proofing layer made of a nickel-zinc alloy on an adhesive surface bonded to an insulating layer, and the surface roughness (Rz) of the adhesive surface ) Is 0.05 to 1.5 μm, and the specular gloss at an incident angle of 60 ° is 250 or more. An invention relating to a flexible printed wiring board for COF is disclosed.
Patent Document 3 discloses a method for treating a copper foil for a printed circuit, in which a cobalt-nickel alloy plating layer is formed on the surface of the copper foil after a roughening treatment by copper-cobalt-nickel alloy plating, and further zinc-nickel. An invention relating to a method for treating a copper foil for printed circuit, characterized by forming an alloy plating layer is disclosed.

JP 2004-98659 A WO2003 / 096776 Japanese Patent No. 2849059

In Patent Document 1, a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency.
Moreover, in patent document 2, the roughening process is not made and the adhesive strength of copper foil and resin is low and inadequate in uses other than the flexible printed wiring board for COF.
Furthermore, although the processing method described in Patent Document 3 allows fine processing of Cu-Co-Ni on a copper foil, excellent visibility can be realized when the copper foil is observed through a resin. Not.
The present invention provides a surface-treated copper foil that adheres well to a resin and realizes excellent visibility when observed through the resin.

As a result of intensive studies, the inventors of the present invention have obtained a copper foil whose surface color difference is controlled to a predetermined range by surface treatment and photographed with a CCD camera through a polyimide substrate laminated from the treated surface side. Paying attention to the slope of the brightness curve near the end of the copper foil drawn in the observation point-brightness graph obtained from the image, controlling the slope of the brightness curve can determine the type of substrate resin film and the thickness of the substrate resin film. It was found that the resin transparency was good without being affected.

The present invention completed on the basis of the above knowledge is, in one aspect, a surface-treated copper foil in which surface treatment is performed on one surface and the other surface, and the surface-treated copper foil is formed from the one surface side. In a copper clad laminate that is laminated with a polyimide having the following ΔB (PI) of 50 or more and 65 or less before being laminated to the copper foil, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more. When the CCD film is photographed with a CCD camera through the polyimide layered from one surface side, the image obtained by the photographing is observed along a direction perpendicular to the direction in which the observed copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each point, the top of the lightness curve generated from the end of the copper foil to the part without the copper foil The TD measured by a laser microscope in which the difference ΔB (ΔB = Bt−Bb) between the average value Bt and the bottom average value Bb is 40 or more and the wavelength of the laser light on the surface of the other copper foil is 405 nm. This is a surface-treated copper foil having a ten-point average roughness Rz of 0.35 μm or more.

Another aspect of the present invention is a surface-treated copper foil in which surface treatment is performed on one surface and the other surface, respectively, and the surface-treated copper foil is bonded to the copper foil from the one surface side. In a copper-clad laminate constructed by laminating with a polyimide having the following ΔB (PI) of 50 or more and 65 or less, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more, When photographed with a CCD camera through the polyimide laminated from the surface side of the surface, the brightness of each observation point was measured along the direction perpendicular to the direction in which the observed copper foil stretched for the image obtained by the photographing In the observation point-brightness graph prepared as described above, the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper foil to the portion without the copper foil. ΔB (ΔB = Bt−Bb), and in the observation point-lightness graph, the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and Bt is t1, and the lightness curve In the depth range from the intersection with Bt to 0.1 ΔB with respect to Bt, the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and 0.1 ΔB is t2. Sv defined by the following formula (1) becomes 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil has a TD ten-point average roughness Rz of 0.35 μm or more as measured by a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment.

In another embodiment of the surface-treated copper foil of the present invention, the average roughness Rz of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.00. It is 35 μm or more.

In another embodiment of the surface-treated copper foil of the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope whose wavelength of the laser beam on the surface of the copper foil subjected to the other surface treatment is 405 nm, 0.05 μm or more.

In another aspect of the present invention, the surface-treated copper foil is subjected to surface treatment on one surface and the other surface, and the surface-treated copper foil is bonded to the copper foil from the one surface side. In a copper-clad laminate composed by laminating with a polyimide having the following ΔB (PI) of 50 or more and 65 or less, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more, When photographed with a CCD camera through the polyimide laminated from the surface side of the surface, the brightness of each observation point was measured along the direction perpendicular to the direction in which the observed copper foil stretched for the image obtained by the photographing In the observation point-brightness graph prepared as above, the top average value Bt and the bottom average value of the brightness curve generated from the end of the copper foil to the portion without the copper foil The difference ΔB (ΔB = Bt−Bb) from b is 40 or more, and the arithmetic mean roughness Ra of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil treated with the other surface is 405 nm. The surface-treated copper foil is 0.05 μm or more.

In another aspect of the present invention, the surface-treated copper foil is subjected to surface treatment on one surface and the other surface, and the surface-treated copper foil is bonded to the copper foil from the one surface side. In a copper-clad laminate constituted by laminating with a polyimide having the following ΔB (PI) of 50 or more and 65 or less, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more, When photographing with a CCD camera through the polyimide laminated from one surface side, for the image obtained by the photographing, the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends is shown. In the observation point-brightness graph produced by measurement, the top average value Bt and the bottom average value of the brightness curve generated from the end of the copper foil to the portion without the copper foil The difference from b is ΔB (ΔB = Bt−Bb), and the value indicating the position of the intersection closest to the copper foil among the intersections of the brightness curve and Bt is t1 in the observation point-brightness graph. In the depth range from the intersection of the curve and Bt to 0.1 ΔB with reference to Bt, the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and 0.1 ΔB is t2. Sv defined by the following formula (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil has an arithmetic average roughness Ra of TD of 0.05 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment.

In yet another embodiment of the surface-treated copper foil of the present invention, the root mean square height Rq of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.08 μm or more.

In another aspect of the present invention, the surface-treated copper foil is subjected to surface treatment on one surface and the other surface, and the surface-treated copper foil is bonded to the copper foil from the one surface side. In a copper-clad laminate composed by laminating with a polyimide having the following ΔB (PI) of 50 or more and 65 or less, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more, When photographed with a CCD camera through the polyimide laminated from the surface side of the surface, the brightness of each observation point was measured along the direction perpendicular to the direction in which the observed copper foil stretched for the image obtained by the photographing In the observation point-brightness graph prepared as above, the top average value Bt and the bottom average value of the brightness curve generated from the end of the copper foil to the portion without the copper foil The root mean square height Rq of TD measured with a laser microscope in which the difference ΔB from Δb (ΔB = Bt−Bb) is 40 or more and the wavelength of the laser beam on the other surface treated copper foil surface is 405 nm Is a surface-treated copper foil of 0.08 μm or more.

In another aspect of the present invention, the surface-treated copper foil is subjected to surface treatment on one surface and the other surface, and the surface-treated copper foil is bonded to the copper foil from the one surface side. In a copper-clad laminate constituted by laminating with a polyimide having the following ΔB (PI) of 50 or more and 65 or less, the color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide is 50 or more, When photographing with a CCD camera through the polyimide laminated from one surface side, for the image obtained by the photographing, the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends is shown. In the observation point-brightness graph produced by measurement, the top average value Bt and the bottom average value of the brightness curve generated from the end of the copper foil to the portion without the copper foil The difference from b is ΔB (ΔB = Bt−Bb), and the value indicating the position of the intersection closest to the copper foil among the intersections of the brightness curve and Bt is t1 in the observation point-brightness graph. In the depth range from the intersection of the curve and Bt to 0.1 ΔB with reference to Bt, the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and 0.1 ΔB is t2. Sv defined by the following formula (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The other surface-treated copper foil is a surface-treated copper foil having a root mean square height Rq of TD of 0.08 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm.

In another embodiment of the surface-treated copper foil of the present invention, the surface treatment of the other surface is a roughening treatment.

In another embodiment of the surface-treated copper foil according to the present invention, in the observation point-lightness graph, a value indicating a position of an intersection closest to the copper foil among intersections of the lightness curve and Bt is defined as t1. In the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt, a value indicating the position of the intersection closest to the copper foil among the intersections of the brightness curve and 0.1 ΔB was defined as t2. Sometimes, Sv defined by the following formula (1) is 3.0 or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In still another embodiment of the surface-treated copper foil according to the present invention, the following ΔB (PI) before pasting the surface-treated copper foil from the one surface side to the copper foil is 50 or more and 65 or less; The color difference ΔE * ab based on JIS Z8730 of the surface over the polyimide in the copper clad laminate formed by laminating is 53 or more.

In yet another embodiment of the surface-treated copper foil according to the present invention, Sv defined by the formula (1) in the brightness curve is 3.5 or more.

In yet another embodiment of the surface-treated copper foil according to the present invention, Sv defined by the formula (1) in the brightness curve is 3.9 or more.

In yet another embodiment of the surface-treated copper foil according to the present invention, Sv defined by the formula (1) in the brightness curve is 5.0 or more.

In still another embodiment of the surface-treated copper foil according to the present invention, the ten-point average roughness Rz of TD measured with the contact-type roughness meter on the one surface is 0.20 to 0.64 μm, The ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B on the copper foil surface is 1.0 to 1.7.

In yet another embodiment of the surface-treated copper foil according to the present invention, the TD ten-point average roughness Rz measured by the contact-type roughness meter on the one surface is 0.26 to 0.62 μm.

In still another embodiment of the surface-treated copper foil according to the present invention, the A / B is 1.0 to 1.6.

In yet another aspect, the present invention is a copper clad laminate configured by laminating the surface-treated copper foil of the present invention and a resin substrate.

In yet another aspect, the present invention is a printed wiring board using the surface-treated copper foil of the present invention.

In yet another aspect, the present invention is an electronic device using at least one printed wiring board of the present invention.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, and the copper circuit includes one surface on the insulating resin substrate side, A color difference ΔE * ab based on JIS Z8730 on the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit passes through the insulating resin substrate. In an observation point-brightness graph prepared by measuring the lightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper circuit to the portion where there is no copper circuit is 40 or more, Square ten-point average roughness Rz of the TD to the wavelength of the laser light is measured by a laser microscope is 405nm of surface treatment copper circuit surface of a printed wiring board is 0.35μm or more.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, and the copper circuit includes one surface on the insulating resin substrate side, A color difference ΔE * ab based on JIS Z8730 on the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit passes through the insulating resin substrate. In an observation point-brightness graph prepared by measuring the lightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb), and the observation point−lightness In the graph, the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and Bt is t1, and in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt. When the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The printed circuit board has a TD ten-point average roughness Rz of 0.35 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment.

In another embodiment of the printed wiring board of the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment is 0.00. It is 05 μm or more.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, the copper circuit including one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit through the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate. An observation point-brightness graph produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. , The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion where the copper circuit is not present is 40 or more. Arithmetic average roughness Ra of the TD to the wavelength of the laser light is measured by a laser microscope is 405nm of other surface treatment copper circuit surface is a printed circuit board is 0.05μm or more.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, the copper circuit including one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate. An observation point-brightness graph produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. , The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb), and the observation point−light In the degree graph, the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and Bt is t1, and the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt , When the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The printed circuit board has an arithmetic average roughness Ra of TD of 0.05 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment.

In still another embodiment of the printed wiring board of the present invention, the root mean square height Rq of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper circuit subjected to the other surface treatment is 0.08 μm or more.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, the copper circuit including one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit through the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate. An observation point-brightness graph produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. , The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion where the copper circuit is not present is 40 or more. Root-mean-square height Rq of TD that the wavelength of the laser beam of the other surface treatment copper circuit surface is measured by a laser microscope is 405nm is a printed circuit board is at least 0.08 .mu.m.

In yet another aspect of the present invention, the printed circuit board includes an insulating resin substrate and a copper circuit provided on the insulating resin substrate, the copper circuit including one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate. An observation point-brightness graph produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. , The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb), and the observation point−light In the degree graph, the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and Bt is t1, and the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt , When the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The printed circuit board having a root mean square height Rq of TD of 0.08 μm or more measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper circuit subjected to the other surface treatment.

In another embodiment of the printed wiring board of the present invention, the surface treatment of the other surface is a roughening treatment.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards of the present invention.

In yet another aspect, the present invention includes at least a step of connecting at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention. This is a method of manufacturing a printed wiring board in which two or more printed wiring boards are connected.

In yet another aspect, the present invention is an electronic device using one or more printed wiring boards to which at least one printed wiring board of the present invention is connected.

In yet another aspect, the present invention is a surface-treated copper foil used for the printed wiring board of the present invention.

In still another aspect, the present invention provides a copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, the copper foil having one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper foil through the insulating resin substrate is 50 or more, and the copper foil of the copper-clad laminate Is etched into a line-shaped copper foil and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along the direction, the top average value of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil B The difference ΔB between t and the bottom average value Bb (ΔB = Bt−Bb) is 40 or more, and the TD measured by a laser microscope whose wavelength of the laser light on the surface of the other copper foil is 405 nm is 10%. This is a copper clad laminate having a point average roughness Rz of 0.35 μm or more.

In still another aspect, the present invention provides a copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, the copper foil having one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the copper foil of the copper-clad laminate Is etched into a line-shaped copper foil and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along the direction, the top average value of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil Bt A difference ΔB (ΔB = Bt−Bb) with respect to the bottom average value Bb, and a value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the brightness curve and Bt in the observation point-brightness graph Is the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and 0.1 ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt Sv defined by the following formula (1) is 3.0 or more when the value indicating is t2,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The copper-clad laminate having a TD ten-point average roughness Rz of 0.35 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment.

In one embodiment, the copper clad laminate of the present invention has an average roughness Rz of TD measured by a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment of 0.35 μm or more. is there.

In another embodiment of the copper clad laminate of the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0. .05 μm or more.

Still another aspect of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, wherein the copper foil is one surface on the insulating resin substrate side. A color difference ΔE * ab based on JIS ８７ Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the copper of the copper-clad laminate When the foil is formed into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along a certain direction, the top average of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil value Arithmetic of TD measured with a laser microscope in which the difference ΔB (ΔB = Bt−Bb) between Bt and the bottom average value Bb is 40 or more and the wavelength of the laser light on the surface of the other copper foil is 405 nm It is a copper clad laminate having an average roughness Ra of 0.05 μm or more.

Still another aspect of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, wherein the copper foil is one surface on the insulating resin substrate side. A color difference ΔE * ab based on JIS Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the copper of the copper-clad laminate When the foil is formed into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along a certain direction, the top average of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil Value B The difference ΔB (ΔB = Bt−Bb) between the average value and the bottom average value Bb indicates the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and Bt in the observation point-lightness graph. With the value t1, in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt, the intersection of the lightness curve and 0.1ΔB closest to the line-shaped copper foil When the value indicating the position is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The copper-clad laminate having a TD arithmetic average roughness Ra of 0.05 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the other surface-treated copper foil surface.

In yet another embodiment of the copper clad laminate of the present invention, the root mean square height Rq of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.08 μm or more.

Still another aspect of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, wherein the copper foil is one surface on the insulating resin substrate side. A color difference ΔE * ab based on JIS ８７ Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the copper of the copper-clad laminate When the foil is formed into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along a certain direction, the top average of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil value The difference ΔB between Bt and the bottom average value Bb (ΔB = Bt−Bb) is 40 or more, and the square of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the other surface treated copper foil surface This is a copper clad laminate having an average square root height Rq of 0.08 μm or more.

Still another aspect of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, wherein the copper foil is one surface on the insulating resin substrate side. A color difference ΔE * ab based on JIS Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the copper of the copper-clad laminate When the foil is formed into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate, the image obtained by the photographing is perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point along a certain direction, the top average of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil Value B The difference ΔB (ΔB = Bt−Bb) between the average value and the bottom average value Bb indicates the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and Bt in the observation point-lightness graph. With the value t1, in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt, the intersection of the lightness curve and 0.1ΔB closest to the line-shaped copper foil When the value indicating the position is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The copper-clad laminate having a root mean square height Rq of TD of 0.08 μm or more measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the other surface treatment.

In another embodiment of the copper clad laminate of the present invention, the surface treatment of the other surface is a roughening treatment.

In yet another aspect, the present invention is a surface-treated copper foil used for the copper-clad laminate of the present invention.

In yet another aspect, the present invention is a printed wiring board manufactured using the copper clad laminate of the present invention.

According to the present invention, it is possible to provide a surface-treated copper foil that adheres well to a resin and realizes excellent visibility when observed through the resin.

It is a schematic diagram which defines Bt and Bb. It is a schematic diagram which defines t1, t2, and Sv. It is a schematic diagram showing the structure of an imaging device and the measuring method of the inclination of a lightness curve in the case of evaluation of the lightness curve inclination. It is a SEM observation photograph of the copper foil surface of the comparative example 1 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 1 in the case of Rz evaluation. It is an external appearance photograph of the foreign material used in the Example. It is an external appearance photograph of the foreign material used in the Example.

[Form and manufacturing method of surface-treated copper foil]
The copper foil used in the present invention is useful for a copper foil or the like used by laminating a resin substrate to produce a laminate and forming a circuit by etching.
The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Usually, after degreasing, the surface of the copper foil to be bonded to the resin substrate (in the present invention, this surface is also referred to as “one surface”) for the purpose of improving the peel strength of the copper foil after lamination. The surface of the copper foil may be subjected to a roughening treatment for performing fist-like electrodeposition. Although the electrolytic copper foil has irregularities at the time of manufacture, the irregularities can be further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. In the present invention, this roughening treatment can be performed by alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating, preferably copper alloy plating. Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off.
The copper foil used in the present invention may be applied with a heat-resistant plating layer or a rust-proof plating layer on one surface after roughening treatment on one surface or by omitting the roughening treatment. As a treatment for omitting the roughening treatment and applying a heat-resistant plating layer or a rust-proof plating layer to the surface, a plating treatment using a Ni—W plating bath under the following conditions can be used. The balance of the treatment liquid used in the present invention for electrolysis, surface treatment or plating is water unless otherwise specified.

Plating bath composition: Ni: 20-30 g / L, W: 15-40 mg / L
pH: 3.0-4.0
Temperature: 35-45 ° C
Current density D _k : 1.7 to 2.3 A / dm ²
Plating time: 18 to 25 seconds The thickness of the copper foil used in the present invention is not particularly limited, but is, for example, 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, for example, 3000 μm or less, 1500 μm or less, 800 μm. Below, it is 300 micrometers or less, 150 micrometers or less, 100 micrometers or less, 70 micrometers or less, 50 micrometers or less, and 40 micrometers or less.

The copper foil according to the present invention includes a copper alloy containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B, and Co. Foil is also included. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The rolled copper foil includes copper foil produced using tough pitch copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020).

Moreover, the manufacturing conditions of the electrolytic copper foil used for this invention are shown below.
<Electrolyte composition>
Copper: 90-110g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

<Production conditions>
Current density: 70-100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5m / sec
Electrolysis time: 0.5 to 10 minutes

The copper-cobalt-nickel alloy plating as the roughening treatment is, as a result of electrolytic plating, an amount of adhesion of 15 to 40 mg / dm ² of copper—100 to 3000 μg / dm ² of cobalt—100 to 1500 μg / dm ² of nickel. It can be carried out so as to form a ternary alloy layer. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

The plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating are as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1 to 4
Temperature: 30-50 ° C
Current density D _k : 20 to 30 A / dm ²
Plating time: 1-5 seconds

The copper-nickel-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 10-50 g / L, Ni 3-20 g / L, P1-10 g / L
pH: 1 to 4
Temperature: 30-40 ° C
Current density D _k : 20 to 50 A / dm ²
Plating time: 0.5-3 seconds

The copper-nickel-cobalt-tungsten alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 5-20 g / L, Ni 5-20 g / L, Co 5-20 g / L, W 1-10 g / L
pH: 1-5
Temperature: 30-50 ° C
Current density D _k : 20 to 50 A / dm ²
Plating time: 0.5-5 seconds

The copper-nickel-molybdenum-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 5-20 g / L, Ni 5-20 g / L, Mo 1-10 g / L, P 1-10 g / L
pH: 1-5
Temperature: 20-50 ° C
Current density D _k : 20 to 50 A / dm ²
Plating time: 0.5-5 seconds

After the roughening treatment, one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer and a weather-resistant layer may be provided on the roughened surface. In addition, each layer may be a plurality of layers such as two layers, three layers, and the order of stacking the layers may be any order, and the layers may be stacked alternately.

Here, a known heat-resistant layer can be used as the heat-resistant layer. Further, for example, the following surface treatment can be used.
As the heat-resistant layer and rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, 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 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . The ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the amount of nickel deposited on the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg / m ² to 500 mg / m ² , and 1 mg / m ² to 50 mg / m ² . More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall of a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate. The rust prevention layer may be a chromate treatment layer. A known chromate treatment layer can be used for the chromate treatment layer. For example, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

For example, the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer with an adhesion amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and an adhesion amount of 1 mg / m ^2. A tin layer of ˜80 mg / m ² , preferably 5 mg / m ² ˜40 mg / m ² may be sequentially laminated. The nickel alloy layer may be nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. You may be comprised by any one of these. The heat-resistant layer and / or rust-preventing layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m ² to 150 mg / m ² and 10 mg / m ² to 70 mg / m ² . It is more preferable. In addition, the heat-resistant layer and / or the rust-preventing layer preferably has [amount of nickel deposited in nickel or nickel alloy] / [amount of tin deposited] = 0.25 to 10, preferably 0.33 to 3. More preferred.

Further, as the heat-resistant layer and / or anticorrosive layer, coating weight of cobalt 200 ~ 2000μg / dm ² of cobalt -50 ~ 700 [mu] g / dm ² of nickel - can form a nickel alloy plating layer. This treatment can be regarded as a kind of rust prevention treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered. If the amount of cobalt adhesion is less than 200 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. As another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable.

After roughening treatment, cobalt nickel cobalt -100 ~ 700μg / dm ² weight deposited on the roughened surface is 200 ~ 3000μg / dm ² - can form a nickel alloy plating layer. This treatment can be regarded as a kind of rust prevention treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered. If the amount of cobalt adhesion is less than 200 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. As another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable. When the amount of cobalt deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, and etching spots may occur, and acid resistance and chemical resistance may deteriorate. A preferable cobalt adhesion amount is 500 to 2500 μg / dm ² . On the other hand, if the nickel adhesion amount is less than 100 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. When nickel exceeds 1300 microgram / dm < ² >, alkali etching property will worsen. A preferable nickel adhesion amount is 200 to 1200 μg / dm ² .

The conditions for cobalt-nickel alloy plating are as follows:
Plating bath composition: Co 1-20 g / L, Ni 1-20 g / L
pH: 1.5 to 3.5
Temperature: 30-80 ° C
Current density D _k : 1.0 to 20.0 A / dm ²
Plating time: 0.5-4 seconds

According to the present invention, a zinc plating layer having an adhesion amount of 30 to 250 μg / dm ² is further formed on the cobalt-nickel alloy plating. If the zinc adhesion amount is less than 30 μg / dm ² , the heat deterioration rate improving effect may be lost. On the other hand, when the zinc adhesion amount exceeds 250 μg / dm ² , the hydrochloric acid deterioration rate may be extremely deteriorated. Preferably, the zinc coating weight is 30 ~ 240μg / dm ^2, more preferably 80 ~ 220μg / dm ^2.

The galvanizing conditions are as follows:
Plating bath composition: Zn 100 to 300 g / L
pH: 3-4
Temperature: 50-60 ° C
Current density Dk: 0.1 to 0.5 A / dm ²
Plating time: 1 to 3 seconds

A zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer may be formed on the outermost surface by chromate treatment or application of a silane coupling agent. Good.

A known weathering layer can be used as the weathering layer. Moreover, as a weather resistance layer, a well-known silane coupling process layer can be used, for example, The silane coupling process layer formed using the following silanes can be used.
As the silane coupling agent used for the silane coupling treatment, a known silane coupling agent may be used. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

The silane coupling treatment layer may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, -(2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3 -Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- ( 2-N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N -Dimethyl-3-aminopropyl) Trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

The silane coupling treatment layer is 0.05 mg / m ² to 200 mg / m ² , preferably 0.15 mg / m ² to 20 mg / m ² , preferably 0.3 mg / m ² to 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

Usually, when roughening treatment is applied to the surface of copper foil, burnt plating in an aqueous copper sulfate solution is a conventional technique. However, copper-cobalt-nickel alloy plating or copper-containing a metal other than copper in the plating bath. A copper clad laminate in which the copper foil is laminated with a polyimide having a ΔB (PI) of 50 or more and 65 or less before being bonded to the copper foil from one surface side by alloy plating such as nickel-phosphorus alloy plating The surface treatment through which the color difference ΔE * ab based on JIS Z8730 on the surface over polyimide can be 50 or more can be performed.

[Surface color difference ΔE * ab]
The surface-treated copper foil of the present invention is a copper clad laminate in which the following ΔB (PI) before being laminated to the copper foil is laminated with a polyimide having a thickness of 50 or more and 65 or less, over the polyimide. The color difference ΔE * ab based on JIS Z8730 on the surface is controlled to 50 or more. With such a configuration, the contrast with the back surface becomes clear and the visibility when the copper foil is observed through the polyimide substrate is enhanced. As a result, when the copper foil is used for circuit formation, alignment or the like when mounting an IC chip through a positioning pattern that is visible through the polyimide substrate is facilitated. If the color difference ΔE * ab is less than 50, the contrast with the back surface may become unclear. The color difference ΔE * ab is more preferably 53 or more, 55 or more, and more preferably 60 or more. The upper limit of the color difference ΔE * ab is not particularly limited, but is, for example, 90 or less, 88 or less, or 87 or less, or 85 or less, or 75 or less, or 70 or less.
Here, the color difference ΔE * ab is measured by a color difference meter, and is a comprehensive index shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. Yes, ΔL: black and white, Δa: red-green, Δb: yellow-blue, represented by the following formula;

[10-point average roughness Rz of copper foil surface]
The surface-treated copper foil of the present invention may be a non-roughened copper foil or a roughened copper foil in which roughened particles are formed on one surface of the copper foil. The TD ten-point average roughness Rz measured in (1) is preferably 0.20 to 0.64 μm. With such a configuration, the peel strength is increased and the resin is satisfactorily bonded to the resin, and the transparency of the resin after the copper foil is removed by etching is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin are facilitated. If the ten-point average roughness Rz of TD measured with a contact-type roughness meter is less than 0.20 μm on one surface of the copper foil, the copper foil surface may be insufficiently roughened, and the resin There is a possibility that a problem of insufficient adhesion may occur. On the other hand, if the ten-point average roughness Rz of TD measured with a contact roughness meter is greater than 0.64 μm on one surface of the copper foil, the unevenness of the resin surface after removing the copper foil by etching is large. As a result, there may be a problem that the transparency of the resin becomes poor. The ten-point average roughness Rz of TD measured with a contact-type roughness meter on one surface of the copper foil is more preferably 0.26 to 0.62 μm, still more preferably 0.40 to 0.55 μm.

In order to achieve the effect of visibility, the roughness (Rz) and glossiness of TD measured with a contact-type roughness meter on one surface of the copper foil before the surface treatment are controlled. Specifically, the surface roughness (Rz) of TD measured with a contact-type roughness meter on one surface of the copper foil before the surface treatment is 0.20 to 0.55 μm, preferably 0.20 to 0.00. 42 μm. Such a copper foil is produced by adjusting the oil film equivalent of the rolling oil (high gloss rolling), or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, the surface roughness (Rz) on the one surface of the copper foil after a process is carried out by making the surface roughness (Rz) and glossiness of TD in the one surface of the copper foil before a process into the said range. In addition, the surface area can be easily controlled.

The copper foil before the surface treatment has a TD 60-degree glossiness of 300 to 910% on one surface, more preferably 500 to 810%, and more preferably 500 to 710%. If the 60 degree glossiness of MD on one surface of the copper foil before the surface treatment is less than 300%, the transparency of the resin may be poorer than the case of 300% or more, and if it exceeds 910% This may cause a problem that it is difficult to manufacture.
The high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000 or less.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 13000 to 24000, a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used.
Chemical polishing is performed with an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a lower concentration than usual and for a long time.

[Brightness curve]
The surface-treated copper foil of the present invention is obtained by laminating a polyimide having the following ΔB (PI) of 50 or more and 65 or less before being laminated to the copper foil from one surface side, and then photographing the copper foil with a CCD camera through the polyimide In the observation point-brightness graph, the edge of the copper foil was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil stretched. The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the portion where no copper foil is present is 40 or more.
In the observation point-lightness graph, a value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and Bt is defined as t1, and 0.1 ΔB based on Bt from the intersection of the lightness curve and Bt. Sv defined by the following equation (1) is 3 when the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and 0.1 ΔB in the depth range up to 0.0 or more is preferable.
Sv = (ΔB × 0.1) / (t1-t2) (1)

Here, “top average value Bt of the lightness curve”, “bottom average value Bb of the lightness curve”, and “t1”, “t2”, and “Sv” described later will be described with reference to the drawings.
FIG. 1A and FIG. 1B are schematic views that define Bt and Bb when the width of the copper foil is about 0.3 mm. When the width of the copper foil is about 0.3 mm, a V-shaped brightness curve as shown in FIG. 1A and a brightness curve having a bottom as shown in FIG. 1B are obtained. is there. In any case, the “top average value Bt of the lightness curve” is the average value of lightness when measured at 5 locations (total 10 locations on both sides) at 30 μm intervals from the positions 50 μm away from the end positions on both sides of the copper foil. Show. On the other hand, the “bottom average value Bb of the lightness curve” indicates the minimum value of lightness at the tip of the V-shaped valley when the lightness curve is V-shaped as shown in FIG. When it has the bottom of (b), the value of the center part of about 0.3 mm is shown. The mark width may be about 0.2 mm, 0.16 mm, or 0.1 mm. Furthermore, the “top average value Bt of the lightness curve” is 5 points at 30 μm intervals from a position 100 μm apart, a position 300 μm apart, or a position 500 μm apart from the end positions on both sides of the mark (total 10 on both sides). Location) It may be the average value of brightness when measured.

FIG. 2 shows a schematic diagram defining t1, t2, and Sv. “T1 (pixel × 0.1)” indicates an intersection closest to the copper foil among the intersections of the lightness curve and Bt. “T2 (pixel × 0.1)” is a distance between the intersection of the lightness curve and Bt and the depth of 0.1ΔB from the intersection of Bt to 0.1ΔB. Indicates the closest intersection. At this time, regarding the slope of the brightness curve indicated by the line connecting t1 and t2, Sv (gradation / pixel × 0.1) calculated by 0.1ΔB in the y-axis direction and (t1−t2) in the x-axis direction. ). One pixel on the horizontal axis corresponds to a length of 10 μm. Moreover, Sv measures the both sides of copper foil, and employ | adopts a small value. Further, when the shape of the lightness curve is unstable and there are a plurality of the “intersections between the lightness curve and Bt”, the intersection closest to the copper foil is adopted.

In the above image taken with a CCD camera, the brightness is high where there is no copper foil, but the brightness decreases as soon as the end of the copper foil is reached. If the visibility when viewed through the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the visibility when viewed through the polyimide substrate is poor, the brightness does not suddenly drop from “high” to “low” at the end of the copper foil, but the state of decline is moderate and the brightness is low. The state of decline becomes unclear.

The present invention is based on such knowledge, and the surface-treated copper foil of the present invention is a polyimide having a ΔB (PI) of 50 or more and 65 or less before being bonded to the copper foil from the surface side where the surface treatment is performed. After laminating, when the copper foil was photographed with a CCD camera over polyimide, the brightness of each observation point was measured along the direction perpendicular to the direction in which the observed copper foil stretched for the image obtained by photographing. In the observed observation point-brightness graph, the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the copper foil to the portion without the copper foil is 40 or more. It is controlled. Alternatively, in the surface-treated copper foil of the present invention, the Sv value is controlled to 3.0 or more.

According to such a configuration, the discriminating power of the copper foil through the polyimide by the CCD camera is improved without being affected by the type and thickness of the substrate resin. For this reason, good visibility when observing from a polyimide substrate is obtained, and positioning accuracy such as marking with a copper foil is improved when a predetermined treatment is performed on a polyimide substrate in an electronic substrate manufacturing process, thereby yield. The effect of improving is obtained.

In the present invention, Sv is preferably 3.5 or more, more preferably 3.9 or more, more preferably 4.5 or more, more preferably 5.0 or more, and more preferably 5.5 or more. The upper limit of Sv is not particularly limited, but is, for example, 15 or less and 10 or less. According to such a configuration, the boundary between the copper foil and the non-copper foil becomes clearer, the positioning accuracy is improved, the error due to the copper foil image recognition is reduced, and the alignment can be performed more accurately. become.
In addition, after laminating the surface-treated copper foil on both surfaces of the polyimide, the copper foil on both surfaces is removed by etching, and only the copper foil on one surface is formed into a circuit shape. If the visibility obtained by observation is good, such a surface-treated copper foil has good visibility obtained by laminating it on polyimide and then observing through polyimide.

[Surface area ratio]
The ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B on one surface of the copper foil greatly affects the transparency of the resin. That is, if the surface roughness Rz is the same, the smaller the ratio A / B, the better the transparency of the resin. For this reason, in the surface-treated copper foil of the present invention, the ratio A / B is preferably 1.0 to 1.7, and more preferably 1.0 to 1.6. Here, the ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the roughened particles on the surface treated surface is, for example, when the surface is roughened, and the surface area A of the roughened particles, It can also be referred to as the ratio A / B with the area B obtained when the copper foil is viewed in plan from the copper foil surface side.

By controlling the current density and plating time during surface treatment such as particle formation, the surface state such as particle morphology, formation density, and surface roughness is determined, and the surface roughness Rz, glossiness and copper foil are determined. The surface area ratio A / B of the surface can be controlled.

The surface-treated copper foil of the present invention is also subjected to a surface treatment on the surface of the copper foil opposite to the surface to be bonded to the resin substrate (in the present invention, this surface is also referred to as “the other surface”). When the surface-treated copper foil is bonded to the resin substrate from one surface side, generally, the resin substrate / surface-treated copper foil / protective film is laminated in this order, and heat and pressure are applied from the protective film side by a laminating roll. to paste together. At this time, there arises a problem that the protective film adheres to the surface (the other surface) opposite to the resin substrate side of the surface-treated copper foil (it does not slip between the surface-treated copper foil and the protective film). There is. When such a problem occurs, wrinkles and streaks occur on the other surface of the copper foil. On the other hand, the other surface of the surface-treated copper foil of the present invention is surface-treated, and by increasing the contact area between the copper foil and the protective film, the copper foil during the lamination process with the resin substrate is used. The problem that a protective film sticks can be suppressed favorably.

The surface-treated copper foil of the present invention has, on one side, a TD ten-point average roughness Rz measured by a laser microscope having a laser beam wavelength of 405 nm on the other surface-treated copper foil surface of 0.35 μm. That's it. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention has a TD ten-point average roughness Rz of 0.40 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment. Is more preferably 0.50 μm or more, still more preferably 0.60 μm or more, still more preferably 0.8 μm or more, typically 0.40 to 4. 0 μm, more typically 0.50 to 3.0 μm. The upper limit of the TD ten-point average roughness Rz of the surface-treated copper foil of the present invention measured with a laser microscope having a laser beam wavelength of 405 nm on the other surface-treated copper foil surface must be specifically limited. Is typically 4.0 μm or less, more typically 3.0 μm or less, more typically 2.5 μm or less, and more typically 2.0 μm or less. .

In another aspect of the surface-treated copper foil of the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.05 μm. That's it. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. In the surface-treated copper foil of the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.08 μm or more. More preferably, it is still more preferably 0.10 μm or more, still more preferably 0.20 μm or more, and still more preferably 0.30 μm or more. In addition, the upper limit of the arithmetic average roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the surface-treated copper foil of the present invention on the other surface-treated copper foil is 405 nm needs to be specifically limited. None, but typically 0.80 μm or less, more typically 0.65 μm or less, more typically 0.50 μm or less, and more typically 0.40 μm or less.

In another aspect of the surface-treated copper foil of the present invention, the root mean square height Rq of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the other surface-treated copper foil is 0.00. It is 08 μm or more. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. In the surface-treated copper foil of the present invention, the root mean square height Rq of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the other copper foil is 0.10 μm or more. Is more preferably 0.15 μm or more, still more preferably 0.20 μm or more, still more preferably 0.30 μm or more, and typically 0.08 to 0.003. 60 μm, more typically 0.10 to 0.50 μm. In addition, the upper limit of the root mean square height Rq of TD measured with the laser microscope whose wavelength of the laser beam of the surface treated copper foil of the present invention is 405 nm is particularly limited. Although not required, it is typically 0.80 μm or less, more typically 0.60 μm or less, more typically 0.50 μm or less, and more typically 0.40 μm or less. is there.

The other surface treatment in the surface-treated copper foil of the present invention is not particularly limited and may be a roughening treatment, omitting the roughening treatment, and heat resistant by plating (plating that is not normal plating or roughening plating). The process which provides a layer or a rust prevention layer may be sufficient.
For example, the roughening treatment may be performed using a plating solution containing copper sulfate and an aqueous sulfuric acid solution, or the roughening treatment may be performed using a plating solution comprising copper sulfate and an aqueous sulfuric acid solution. Alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, nickel-zinc alloy plating may be used. Moreover, Preferably it can carry out by copper alloy plating. As the copper alloy plating bath, for example, a plating bath containing one or more elements other than copper and copper, more preferably any selected from the group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum It is preferable to use a plating bath containing at least one kind.

In addition, the other surface treatment in the surface-treated copper foil of the present invention may be a surface treatment other than the above roughening treatment and plating treatment.
As a surface treatment for forming irregularities on the other surface, a surface treatment by electropolishing may be performed. For example, unevenness can be formed on the other surface of the copper foil by electropolishing the other surface of the copper foil in a solution composed of copper sulfate and an aqueous sulfuric acid solution. In general, electropolishing aims at smoothing, but the other surface treatment of the present invention forms concavities and convexities by electropolishing. The method for forming the irregularities by electrolytic polishing may be performed by a known technique. Examples of known techniques of electropolishing for forming the unevenness include the methods described in JP-A-2005-240132, JP-A-2010-059547, and JP-A-2010-047842. As specific conditions for the treatment for forming irregularities by electrolytic polishing, for example,
Treatment solution: Cu: 20 g / L, H ₂ SO ₄ : 100 g / L, temperature: 50 ° C.
-Electropolishing current: 15 A / dm ²
-Electropolishing time: 15 seconds etc. are mentioned.

As the surface treatment for forming the unevenness on the other surface, for example, the unevenness may be formed by mechanically polishing the other surface. Mechanical polishing may be performed by a known technique.
In addition, you may provide a heat-resistant layer, a rust prevention layer, and a weather resistant layer after the other surface treatment in the surface-treated copper foil of this invention. The heat-resistant layer, the rust-proof layer, and the weather-resistant layer may be the method described in the above description or experimental example, or may be a known technique.

The laminate can be produced by bonding the surface-treated copper foil of the present invention to an insulating resin substrate from one surface side. The insulating resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, for a rigid PWB, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy Resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc., polyester film, polyimide film, liquid crystal polymer (LCP) film for FPC, Teflon (registered trademark) film or the like can be used.

In the case of the rigid PWB, a prepreg is prepared by impregnating a base material such as a glass cloth with a resin and curing the resin to a semi-cured state. It can be carried out by superposing a copper foil on the prepreg from the opposite surface of the coating layer and heating and pressing. In the case of FPC, it is laminated on a copper foil under high temperature and high pressure without using an adhesive on a substrate such as a polyimide film, or a polyimide precursor is applied, dried, cured, etc. A laminated board can be manufactured by performing.
The thickness of the polyimide base resin is not particularly limited, but generally 25 μm or 50 μm can be mentioned.

The laminate of the present invention can be used for various printed wiring boards (PWB) and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, the single-sided PWB, the double-sided PWB, and the multilayer PWB (3 It is applicable to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material. The electronic device of the present invention can be manufactured using such a printed wiring board.

Moreover, the printed wiring board of the present invention is a printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate, and the copper circuit is connected to one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate with a CCD camera. In the observation point-lightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by shooting, The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the portion to the portion where there is no copper circuit is 40 or more. When such a printed wiring board is used, the printed wiring board can be positioned more accurately.

Moreover, the printed wiring board of the present invention is a printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate, and the copper circuit is connected to one surface on the insulating resin substrate side. The color difference ΔE * ab based on JIS Z8730 of the surface of the copper circuit over the insulating resin substrate is 50 or more, and the copper circuit is passed through the insulating resin substrate. An observation point-brightness graph produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends for the image obtained by the CCD camera. , The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb), and the observation point−light In the degree graph, the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and Bt is t1, and the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt , When the value indicating the position of the intersection closest to the copper circuit is t2 among the intersections of the lightness curve and 0.1 ΔB, Sv defined by the following equation (1) is 3.0 or more . When such a printed wiring board is used, the printed wiring board can be positioned more accurately.
Sv = (ΔB × 0.1) / (t1-t2) (1)

Moreover, the copper clad laminate of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, the copper foil being one of the insulating resin substrates. The surface of the copper foil over the insulating resin substrate, the color difference ΔE * ab based on JIS Z8730 is 50 or more, and the copper foil of the copper-clad laminate is Then, after forming a line-shaped copper foil by etching and taking a picture with a CCD camera through an insulating resin substrate, the image obtained by the shooting is along a direction perpendicular to the direction in which the observed line-shaped copper foil extends. In the observation point-lightness graph prepared by measuring the lightness at each observation point, the top average value Bt and the bottom average value of the lightness curve that occurs from the end of the line-shaped copper foil to the portion without the line-shaped copper foil Difference from Bb ΔB (Δ B = Bt−Bb) is 40 or more.
The surface-treated copper foil of the present invention can be used for the copper foil of the copper clad laminate of the present invention.
When a printed wiring board is manufactured using such a copper-clad laminate, the printed wiring board can be positioned more accurately.

Moreover, the copper clad laminate of the present invention is a copper clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate, the copper foil being one of the insulating resin substrates. A color difference ΔE * ab based on JIS Z8730 of the surface of the copper foil over the insulating resin substrate is 50 or more, and the surface of the copper-clad laminate has the surface and the other surface subjected to surface treatment. After the copper foil is formed into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate, the observed direction of the line-shaped copper foil extends for the image obtained by the photographing. In the observation point-lightness graph prepared by measuring the lightness at each observation point along the vertical direction, the top of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil Average value Bt The difference ΔB (ΔB = Bt−Bb) from the Tom average value Bb is a value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the brightness curve and Bt in the observation point-lightness graph. Is the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and 0.1 ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt Sv defined by the following formula (1) is 3.0 or more when a value indicating the value is t2.
The surface-treated copper foil of the present invention can be used for the copper foil of the copper clad laminate of the present invention.
When a printed wiring board is manufactured using such a copper-clad laminate, the printed wiring board can be positioned more accurately.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In the above-described printed wiring board or copper clad laminate of the present invention, the surface of the copper circuit or copper foil opposite to the surface to be bonded to the resin substrate (the other surface) is also subjected to surface treatment. When passing a printed wiring board or copper-clad laminate through a roll-to-roll production line, between the transport roll in the production line and the surface opposite to the resin substrate side of the printed wiring board or copper-clad laminate The problem of sticking (cannot slip) may occur. When such a problem arises, wrinkles and streaks occur on the other surface of the copper circuit or copper foil. On the other hand, the other surface of the printed wiring board or the copper clad laminate of the present invention is surface-treated, and by increasing the contact area between the copper circuit or the copper foil and the protective film, it is conveyed in the production line. The problem of sticking to the roll (no longer slipping) can be satisfactorily suppressed. Furthermore, since the adhesion between the other surface, the dry film, and the coverlay is improved, the weather resistance of the printed wiring board or the copper clad laminate is improved.

(Laminated body and printed wiring board positioning method using the same)
A method for positioning the laminate of the metal and resin of the present invention will be described. First, a laminate of metal and resin is prepared. The form of the laminate of the metal and the resin is not particularly limited as long as it is configured by bonding the metal to the resin. As a specific example of the laminate of the metal and resin of the present invention, copper or the like is used on at least one surface of a resin such as polyimide, which is used to electrically connect the main body substrate and the attached circuit board, and the circuit board. In an electronic device composed of a flexible printed circuit board on which metal wiring is formed, there is a laminate produced by accurately positioning the flexible printed circuit board and crimping it to the wiring ends of the main circuit board and the attached circuit board. It is done. That is, in this case, the laminate is a laminate in which the wiring end portions of the flexible printed circuit board and the main body substrate are bonded together by pressure bonding, or the wiring edge portions of the flexible printed circuit board and the circuit board are bonded together by pressure bonding. It becomes a laminated body. The laminate has a mark formed of a part of the metal wiring and a separate material. The position of the mark is not particularly limited as long as it can be photographed by photographing means such as a CCD camera through the resin constituting the laminate.

In the laminated body thus prepared, the above-mentioned mark is photographed by the photographing means through the resin, and the image obtained by the photographing is observed for each observation point along the direction perpendicular to the direction in which the observed mark extends. Is measured to produce an observation point-lightness graph, and a difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a lightness curve generated from an end portion of the mark to a portion without the mark. ) Is used to detect the position of the mark, and the laminate of the metal and the resin is positioned based on the detected position of the mark.

At this time, the position of the mark may be detected using only the Sv value, and the laminate of the metal and the resin may be positioned based on the detected position of the mark. The position of the mark may be detected using both the value and the laminate of the metal and the resin may be positioned based on the detected position of the mark.

According to such a positioning method, the boundary between the mark and the non-mark portion becomes clearer, the positioning accuracy is improved, the error due to the mark image recognition is reduced, and the alignment can be performed more accurately. For example, when the ΔB value, the Sv value, or the ΔB value and the Sv value are equal to or greater than a predetermined value, the apparatus for detecting the position can determine that the mark is present at the position. Specifically, for example, when the determination is made only with the ΔB value, when ΔB is 40 or more, when the determination is made with only the Sv value, when the Sv is 3.0 or more, or with the ΔB value and the Sv value, When the determination is performed, the device for detecting the position can determine that the mark is present at the position when ΔB is 40 or more and Sv is 3.0 or more. When such a positioning method is used, the printed wiring board can be positioned more accurately.

Therefore, it is considered that when one printed wiring board and another printed wiring board are connected, the connection failure is reduced and the yield is improved. At this time, the copper foil may have been subjected to a surface treatment. In addition, as a method for connecting one printed wiring board and another printed wiring board, soldering, connection through an anisotropic conductive film (Anisotropic Conductive Film, ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. Also, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring.

The positioning method according to the embodiment of the present invention may include a step of moving a laminated body (including a laminated body of copper and resin and a printed wiring board). In the moving process, for example, it may be moved by a conveyor such as a belt conveyor or a chain conveyor, may be moved by a moving device equipped with an arm mechanism, or may be moved by floating a laminate using gas. The moving device may be moved by a moving means, such as a moving device or moving means (including a roller or a bearing) that moves a laminated body by rotating an object such as a substantially cylindrical shape, a moving device or moving means that uses hydraulic pressure as a power source, Moving devices and moving means powered by air pressure, moving devices and moving means powered by motors, gantry moving linear guide stages, gantry moving air guide stages, stacked linear guide stages, linear motor drive stages, etc. It may be moved by a moving device or moving means having a stage. Moreover, you may perform the movement process by a well-known moving means.
The positioning method according to the embodiment of the present invention may be used for a surface mounter or a chip mounter.
Moreover, the printed wiring board which has the circuit provided on the resin board and the said resin board may be sufficient as the laminated body of the said metal and resin positioned in this invention. In that case, the mark may be the circuit.

In the present invention, “positioning” includes “detecting the position of a mark or an object”. In the present invention, “alignment” includes “after detecting the position of a mark or object, moving the mark or object to a predetermined position based on the detected position”.

As Examples 1 to 9 and Comparative Examples 1 to 6, each copper foil was prepared, and one surface was plated under the conditions described in Tables 2 and 3 as a roughening treatment.

Rolled copper foil was manufactured as follows. A predetermined copper ingot was manufactured and hot-rolled, and then annealing and cold rolling of a continuous annealing line at 300 to 800 ° C. were repeated to obtain a rolled sheet having a thickness of 1 to 2 mm. This rolled sheet was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thickness shown in Table 1 to obtain a copper foil. “Tough pitch copper” in Table 1 indicates tough pitch copper standardized in JIS H3100 C1100. “Oxygen-free copper” in Table 1 represents oxygen-free copper standardized in JIS H3100 C1020. “Ppm” of the additive element described in Table 1 indicates mass ppm. For example, “Tough pitch copper + Ag 180 ppm” in the type column of the metal foil (before surface treatment) in Table 1 means that 180 mass ppm of Ag is added to the tough pitch copper.

The electrolytic copper foil was produced under the following conditions.
Electrolyte composition (copper: 100 g / L, sulfuric acid: 100 g / L, chlorine: 50 ppm, leveling agent 1 (bis (3sulfopropyl) disulfide): 10-30 ppm, leveling agent 2 (amine compound): 10-30 ppm)
・ Electrolyte temperature: 50-60 ℃
・ Current density: 70 to 100 A / dm ²
Electrolysis time: 1 minute Electrolytic solution linear velocity: 4 m / sec The following amine compounds were used as amine compounds.

In Table 1, the point of the copper foil preparation process before surface treatment in one surface was described. “High gloss rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the value of the oil film equivalent.
Further, for Comparative Example 5, the same surface treatment as in Example 2 was performed, and for Comparative Example 6, the same surface treatment as in Example 6 was performed.

Moreover, about the Example, the following surface treatment was performed to the other surface of copper foil.
-Surface treatment conditions Example of plating bath Cu: 15 g / L, Co: 9 g / L, Ni: 9 g / L
pH: 3
Temperature: 38 ° C
Current density: 25 A / dm ²
Plating time: 1 second

Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
-Measurement of surface roughness (Rz);
For the copper foils after the surface treatment of each example and comparative example, one-point average roughness was measured according to JIS B0601-1994 using a contact type roughness meter Surfcoder SE-3C manufactured by Kosaka Laboratory Ltd. The surface was measured. On the condition of measurement standard length 0.8mm, evaluation length 4mm, cut-off value 0.25mm, feed rate 0.1mm / sec, the measurement position is in the direction perpendicular to the rolling direction (TD) for rolled copper foil. For the electrolytic copper foil, change the measurement position in the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the electrolytic copper foil manufacturing apparatus, and perform the measurement 10 times for each value. Asked.
In addition, the surface roughness (Rz) was calculated | required similarly about the copper foil before surface treatment.

Moreover, about the other surface after the surface treatment of each Example and a comparative example, it is preferable to measure the surface roughness using a non-contact type method. Specifically, the state of the other surface after the surface treatment of each example and comparative example is evaluated by the roughness value measured with a laser microscope. This is because the state of the surface can be evaluated in more detail.
About the other surface of the surface-treated copper foil, surface roughness (ten-point average roughness) Rz was measured based on JIS B0601 1994 with an Olympus laser microscope OLS4000. Using an objective lens 50 times, in the observation of the copper foil surface, the evaluation length is 258 μm, the cut-off value is zero, and the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction or electrolytic copper About foil, the value was calculated | required by the measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of electrolytic copper foil, respectively. The measurement environment temperature of the surface roughness Rz with a laser microscope was 23 to 25 ° C. Rz was arbitrarily measured at 10 locations, and the average value at 10 locations of Rz was defined as the value of surface roughness (10-point average roughness) Rz. Further, the wavelength of the laser beam of the laser microscope used for the measurement was 405 nm.

Measurement of the root mean square height Rq of the surface;
About the other surface of the copper foil of each Example and a comparative example, the root mean square height Rq of the copper foil surface was measured based on JIS B0601 2001 with the Olympus laser microscope OLS4000. Using an objective lens 50 times, in the observation of the copper foil surface, the evaluation length is 258 μm, the cut-off value is zero, and the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction or electrolytic copper About foil, the value was calculated | required by the measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of electrolytic copper foil, respectively. The measurement environment temperature of the root mean square height Rq of the surface with a laser microscope was 23 to 25 ° C. Rq was measured arbitrarily at 10 locations, and the average value at 10 locations of the Rq was taken as the value of the root mean square height Rq. Further, the wavelength of the laser beam of the laser microscope used for the measurement was 405 nm.

-Measurement of arithmetic mean roughness Ra of the surface;
The surface roughness Ra of the other surface of the copper foil after the surface treatment of each example and comparative example was measured with an Olympus laser microscope OLS4000 in accordance with JIS B0601-1994. Using an objective lens 50 times, in the observation of the copper foil surface, the evaluation length is 258 μm, the cut-off value is zero, and the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction. About foil, the value was calculated | required by the measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of electrolytic copper foil, respectively. Note that the measurement environment temperature of the arithmetic average roughness Ra of the surface with a laser microscope was set to 23 to 25 ° C. Ra was measured arbitrarily at 10 locations, and the average value of 10 locations of Ra was used as the value of arithmetic average roughness Ra. Further, the wavelength of the laser beam of the laser microscope used for the measurement was 405 nm.

・ Measurement of color difference ΔE * ab over polyimide;
Over the polyimide film in the copper clad laminate formed by laminating the surface-treated copper foil and a polyimide film (Kaneka thickness 25 μm or 50 μm) having a ΔB (PI) of 50 to 65 before bonding to the copper foil The color difference ΔE * ab based on JIS Z8730 on the surface was measured. The color difference ΔE * ab was measured according to JIS Z8730 using a color difference meter MiniScan XE Plus manufactured by HunterLab. In the above color difference meter, the measured value of the white plate is ΔE * ab = 0, and the measured value when measured in the dark with a black bag covered is ΔE * ab = 90, and the color difference is calibrated. ΔE * ab was measured based on the following formula using the L * a * b color system, ΔL: black and white, Δa: reddish green, Δb: yellow blue. Where the color difference ΔE * ab is defined as zero for white and 90 for black;

Note that the color difference ΔE * ab based on JIS Z8730 on the surface of a copper circuit is, for example, a small surface spectral colorimeter (model: VSS400, etc.) manufactured by Nippon Denshoku Industries Co., Ltd. or a small surface spectral colorimeter manufactured by Suga Test Instruments Co., Ltd. Measurement can be performed using a known measuring device such as (model: SC-50μ, etc.).

-Area ratio (A / B) of copper foil surface;
The surface area of one surface of the copper foil was measured by a laser microscope. About one surface of the copper foil after the surface treatment of each Example and Comparative Example, using an Olympus laser microscope OLS4000, an area B equivalent to 647 μm × 646 μm at a magnification of 20 times the treated surface (417,953 μm ^{2 in} actual data) The three-dimensional surface area A was measured, and setting was performed by a method of three-dimensional surface area A ÷ two-dimensional surface area B = area ratio (A / B). The measurement environment temperature of the three-dimensional surface area A with a laser microscope was 23 to 25 ° C.

・ Glossiness;
A gloss meter PG-1 made by Nippon Denshoku Industries Co., Ltd. compliant with JIS Z8741 is used, and the rolled copper foil is perpendicular to the rolling direction (the traveling direction of the copper foil during rolling, ie, the width direction). Measurement was performed on one surface before surface treatment at an incident angle of 60 degrees in the direction (TD). Moreover, about the electrolytic copper foil, it measured about the surface (mat surface) before surface treatment by the incident angle of 60 degree | times of the direction (namely, width direction) (TD) orthogonal to the copper foil conveyance direction at the time of electrolytic treatment.

-Inclination of brightness curve The produced copper foil was laminated | stacked on both surfaces of the polyimide film toward the polyimide film from the one surface side.
Here, about the said polyimide film, Kaneka-made polyimide film with a thickness of 25 μm or 50 μm [PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminate, PMDA (pyromellitic anhydride) -based polyimide film (PMDA-ODA (4,4′-diaminodiphenyl ether) based polyimide film)] was used.
In addition, in the evaluation of “visibility (resin transparency)”, “peel strength (adhesion strength)”, and “yield” described later, the polyimide film that bonds the surface of the surface-treated copper foil for each test example is It is the same as the polyimide film used in the evaluation of “lightness curve inclination”.
And all the copper foil of one side was removed by the etching. Further, the copper foil on the other surface was etched to form a line having a width of 0.3 mm. Thereafter, a white paper was laid on the back of the 0.3 mm wide line-shaped copper foil, and was photographed with a CCD camera (line CCD camera of 8192 pixels) through the polyimide film, and an image obtained by photographing was observed. In an observation point-brightness graph produced by measuring the lightness at each observation point along the direction perpendicular to the direction in which the copper foil extends, ΔB and t1, t2 from the lightness curve generated from the end of the mark to the portion without the mark. , Sv was measured. FIG. 3 is a schematic diagram showing the configuration of the photographing apparatus used at this time and the measurement method of the brightness curve. The polyimide having a thickness of 25 μm or 50 μm used for the evaluation of the slope of the lightness curve was a polyimide having a ΔB (PI) of 50 or more and 65 or less with respect to the polyimide before being bonded to the copper foil. In addition, when measuring ΔB (PI) for the polyimide before being bonded to the copper foil, instead of a 0.3 mm wide line-shaped copper foil, a 0.3 mm wide line-shaped black mark is used on a blank sheet. ΔB (PI) was measured using the printed material (printed material printed with a line-shaped black mark).

Further, ΔB, t1, t2, and Sv were measured with the following photographing apparatus. One pixel on the horizontal axis corresponds to a length of 10 μm.
In addition, white glossy paper having a gloss level of 43.0 ± 2 was used for the “white paper” laid on the “back surface of a 0.3 mm wide lined copper foil”.
The above-mentioned “printed matter printed with a line-shaped black mark” is printed on white glossy paper having a glossiness of 43.0 ± 2 according to JIS P8208 (1998) (a copy of the dust measurement chart of FIG. 1) and JIS P8145 (2011) ( Annex JA (normative) Visual foreign matter comparison chart Figure JA.1-Copy of visual foreign matter comparison chart) Dirt with various lines printed on the transparent film shown in Fig. 6 (Contamination) (Product name: Choyokai Co., Ltd., product name: “Measurement chart of dust-full size”, product number: JQA160-20151-1 (manufactured by the National Printing Bureau)) was used. .
The glossiness of the glossy paper was measured at an incident angle of 60 degrees using a gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741.

The photographing device is a CCD camera, a white paper on which a polyimide substrate laminated with a sample copper foil is placed (the polyimide substrate laminated with a copper foil is placed with the surface opposite to the surface having a line-shaped copper foil facing the CCD camera. ), An illumination power source for irradiating light to the imaging part of the polyimide substrate, a copper foil to be imaged, and a transporter (not shown) for transporting the polyimide substrate onto the stage. The main specifications of the camera are as follows:
・ Photographing device: Sheet inspection device Mujken manufactured by Nireco Corporation
Line CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits)
・ Power supply for lighting: High-frequency lighting power supply (power supply unit x 2)
・ Illumination: fluorescent lamp (30W, model name: FPL27EX-D, twin fluorescent lamp)

As a line for ΔB (PI) measurement, a line indicated by an arrow drawn on the contaminant of FIG. 5 of 0.7 mm ² was used. The width of the line is 0.3 mm. Further, the line CCD camera field of view is arranged in a dotted line in FIG.
When shooting with a line CCD camera, the signal is confirmed at 256 gradations on the full scale, and the place where the black mark of the printed matter does not exist (on the white glossy paper above) without placing the polyimide film (polyimide substrate) to be measured. The lens aperture was adjusted so that the peak gradation signal of 230 ± 5 falls within the range (when a portion outside the mark printed on the contaminants is measured with a CCD camera from the transparent film side). The camera scan time (the time when the camera shutter is open and the time when light is captured) is fixed at 250 μs, and the lens aperture is adjusted so that it falls within the above gradation.
For the lightness shown in FIG. 3, 0 means “black”, lightness 255 means “white”, and the gray level from “black” to “white” (black and white shading, gray scale) Is divided into 256 gradations for display.

・ Visibility (resin transparency);
The copper foil was bonded to both surfaces of the polyimide film from one surface side, and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A printed material (black circle with a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer. “◎” indicates that the outline of the black circle of the printed material is clear when the length is 90% or more of the circumference, and “Clear” indicates that the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. “O” (passed above), a black circle with a clear outline of 0 to less than 80% of the circumference and a broken outline were evaluated as “x” (failed).

・ Peel strength (adhesive strength);
In accordance with IPC-TM-650, the normal peel strength was measured with a tensile tester Autograph 100, and the normal peel strength of 0.7 N / mm or more could be used for laminated substrates. In addition, the sample which bonded together the polyimide film and the surface treatment surface which is one surface of the surface treatment copper foil which concerns on the experiment example of this invention was used for the measurement of this peel strength. The peel strength was measured with a copper foil thickness of 18 μm. About the copper foil whose thickness is less than 18 micrometers, copper plating was performed and copper foil thickness was 18 micrometers. Moreover, when thickness was larger than 18 micrometers, it etched and copper foil thickness was 18 micrometers.

・ Yield;
The copper foil was bonded to both sides of the polyimide film from one surface side of the copper foil, and the copper foil was etched (ferric chloride aqueous solution) to prepare an FPC having a circuit width of L / S of 30 μm / 30 μm. After that, an attempt was made to detect a 20 μm × 20 μm square mark with a CCD camera through polyimide. “◎” if 9 or more out of 10 times can be detected, “○” if 7 to 8 times can be detected, “△” if 6 times can be detected, or if 5 times or less can be detected. Is “×”.
In the printed wiring board or the copper-clad laminate, the above-mentioned (1) surface roughness (Rz) and (3) the area of the copper foil surface can be obtained by dissolving and removing the resin. The ratio (A / B) can be measured.

-Evaluation of copper foil wrinkles by laminating;
The surface-treated copper foils of Examples and Comparative Examples were laminated on both surfaces of a polyimide resin with a thickness of 25 μm from one surface side, respectively, and further the protection with a thickness of 125 μm was applied to the other surface side of each surface-treated copper foil. In a state where films (made of polyimide) are laminated, that is, in a state of five layers of protective film / surface-treated copper foil / polyimide resin / surface-treated copper foil / protective film, a laminate roll is used from the outside of both protective films. Bonding (laminating) was performed while applying heat and pressure, and surface-treated copper foil was bonded to both sides of the polyimide resin. Subsequently, after peeling off the protective films on both surfaces, visually observe the other surface of the surface-treated copper foil, confirm the presence or absence of wrinkles or lines, and when no wrinkles or lines occur at all, the length of the copper foil The case where only one wrinkle or streak was observed per 5 m was evaluated as “◯”, and the case where two or more wrinkles or streaks were observed per 5 m of the copper foil was evaluated as “x”.
Tables 1 to 4 show the conditions and evaluation of each test.

(Evaluation results)
In each of Examples 1 to 9, the color difference ΔE * ab over polyimide was 50 or more and ΔB was 40 or more, and the visibility was good. Moreover, since the surface treatment was formed in the other surface, generation | occurrence | production of a wrinkle and a stripe was suppressed favorably on the said other surface of the copper foil in the double-sided laminating method.
In Comparative Examples 1 to 4, the color difference ΔE * ab over polyimide was less than 50 or ΔB was less than 40, and the visibility was poor.
In Comparative Examples 1 to 4 and Comparative Examples 5 and 6, since the surface treatment is not formed on the other surface, the generation of wrinkles and lines on the other surface of the copper foil in the double-sided laminating method cannot be suppressed. It was.

In FIG. 4, the SEM observation photograph on the copper foil surface of (a) Comparative example 1 and (b) Example 1 in the case of said Rz evaluation is shown, respectively.
Further, in Examples 1 to 9, the width of the mark made of a copper foil formed into a line having a width of 0.3 mm and the mark of the contaminants were changed from 0.3 mm to 0.16 mm (the area of the contaminant sheet was 0.5 mm ^2). In the same manner, ΔB (PI), Sv value, and ΔB value were measured by changing to the third mark (mark indicated by the arrow in FIG. 6) from the side closest to the description of 0.5. The (PI), Sv value, and ΔB value were the same as when the mark width was 0.3 mm.
Further, in Examples 1 to 9, with respect to the “top average value Bt of the lightness curve”, a position 50 μm away from the end positions on both sides of the mark is defined as a position 100 μm apart, a position 300 μm apart, and a position 500 μm apart. From this position, the same ΔB (PI), Sv value and ΔB value were measured by changing to the average value of the brightness when measured at 5 locations (total 10 locations on both sides) at 30 μm intervals. ΔB (PI), Sv value, and ΔB value are average values of brightness when measured at 5 locations at a distance of 30 μm from a position 50 μm away from the end positions on both sides of the mark (total 10 locations on both sides). The value was the same as ΔB (PI), Sv value, and ΔB value in the case of “top average value Bt”.

In addition, as a result of performing the surface treatment on both surfaces of the copper foil under the same conditions as the surface treatment for one surface using the same copper foil as each of the above examples, and producing and evaluating the surface-treated copper foil, The same evaluation result as that of one surface of each example was obtained on both sides. When electrolytic polishing or chemical polishing was performed on the copper foil, surface treatment was performed after electrolytic polishing or chemical polishing was performed on both surfaces. In Example 8, the glossy surface of the copper foil (the surface on the side in contact with the drum during the production of the electrolytic copper foil) is subjected to electrolytic polishing and / or chemical polishing, whereby the TD roughness Rz and glossiness are obtained. After the same as the precipitation surface, a predetermined surface treatment or formation of an intermediate layer or the like was performed.
When surface treatment such as roughening treatment is performed on both surfaces of the copper foil, the surface treatment may be performed on both surfaces simultaneously, or the surface treatment may be separately performed on one surface and the other surface. In addition, when performing surface treatment on both surfaces simultaneously, it is good to perform surface treatment using the surface treatment apparatus (plating apparatus) which provided the anode on both surfaces side of copper foil. In this example, surface treatment was performed on both sides simultaneously.

Further, the ten-point average roughness Rz of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the roughening treatment in each example was 0.35 μm or more. Moreover, arithmetic mean roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the roughened copper foil surface of each Example was 405 nm was all 0.05 micrometer or more. Moreover, the root mean square height Rq of TD measured with the laser microscope whose wavelength of the laser beam of the roughened copper foil surface of each Example was 405 nm was 0.08 micrometer or more in all.

Claims

A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When photographed with a CCD camera over the polyimide laminated the copper foil from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is 40 or more,
The surface-treated copper foil whose 10-point average roughness Rz of TD measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.35 micrometer or more.
A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When the copper foil was photographed with a CCD camera through the polyimide laminated from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper foil among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB on the basis of Bt, Sv defined by the following equation (1) is 3.0 or more when the value indicating the position of the closest intersection to the copper foil is 0.12 among the intersections with 0.1 ΔB,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil whose 10-point average roughness Rz of TD measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.35 micrometer or more.
3. The surface treatment according to claim 1, wherein an arithmetic average roughness Ra of TD measured by a laser microscope having a laser light wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.05 μm or more. Copper foil.
A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When photographed with a CCD camera over the polyimide laminated the copper foil from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is 40 or more,
The surface-treated copper foil whose arithmetic mean roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.05 micrometer or more.
A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When the copper foil was photographed with a CCD camera through the polyimide laminated from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper foil among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB on the basis of Bt, Sv defined by the following equation (1) is 3.0 or more when the value indicating the position of the closest intersection to the copper foil is 0.12 among the intersections with 0.1 ΔB,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil whose arithmetic mean roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.05 micrometer or more.
6. The root mean square height Rq of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.08 μm or more. The surface-treated copper foil as described in the item.
A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When photographed with a CCD camera over the polyimide laminated the copper foil from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is 40 or more,
The surface-treated copper foil whose TD root mean square height Rq measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.08 micrometer or more.
A surface-treated copper foil in which surface treatment is performed on one surface and the other surface,
JIS of the surface over the said polyimide in the copper clad laminated board comprised by laminating | stacking the surface treatment copper foil from the said one surface side with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50-65. The color difference ΔE * ab based on Z8730 is 50 or more,
When the copper foil was photographed with a CCD camera through the polyimide laminated from one surface side,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper foil extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end portion of the copper foil to the portion without the copper foil is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper foil among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB on the basis of Bt, Sv defined by the following equation (1) is 3.0 or more when the value indicating the position of the closest intersection to the copper foil is 0.12 among the intersections with 0.1 ΔB,
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil whose TD root mean square height Rq measured with the laser microscope whose wavelength of the laser beam of the said other surface-treated copper foil surface is 405 nm is 0.08 micrometer or more.
The surface-treated copper foil according to any one of claims 1 to 8, wherein the surface treatment of the other surface is a roughening treatment.
In the observation point-lightness graph, the value indicating the position of the intersection closest to the copper foil among the intersections of the lightness curve and Bt is t1, and from the intersection of the lightness curve and Bt to 0.1 ΔB based on Bt Sv defined by the following equation (1) is 3. where the value indicating the position of the intersection closest to the copper foil in the intersection of the lightness curve and 0.1 ΔB in the depth range is t2. The surface-treated copper foil as described in any one of Claim 1, 3, 4, 6, 7, and 9 which becomes zero or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)
In the copper clad laminated board which laminated | stacked the said surface treatment copper foil from the said one surface side, and laminated | stacked with the polyimide whose following (DELTA) B (PI) before bonding to copper foil is 50 or more and 65 or less, The surface-treated copper foil according to any one of claims 1 to 10, wherein a color difference ΔE * ab based on JIS Z8730 is 53 or more.
The surface-treated copper foil according to any one of claims 2, 3, 5, 6, and 8 to 11, wherein Sv defined by the formula (1) in the brightness curve is 3.5 or more.
The surface-treated copper foil according to claim 12, wherein Sv defined by the formula (1) in the lightness curve is 3.9 or more.
The surface-treated copper foil according to claim 13, wherein Sv defined by the formula (1) in the brightness curve is 5.0 or more.
The ten-point average roughness Rz of TD measured with a contact roughness meter on one surface is 0.20 to 0.64 μm, and the ratio A between the three-dimensional surface area A and the two-dimensional surface area B of the copper foil surface The surface-treated copper foil according to any one of claims 1 to 14, wherein / B is 1.0 to 1.7.
The surface-treated copper foil according to claim 15, wherein the ten-point average roughness Rz of TD measured by a contact-type roughness meter on the one surface is 0.26 to 0.62 µm.
The surface-treated copper foil according to claim 15 or 16, wherein the A / B is 1.0 to 1.6.
A copper clad laminate comprising a laminate of the surface-treated copper foil according to any one of claims 1 to 17 and a resin substrate.
A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 17.
An electronic device using at least one printed wiring board according to claim 19.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is 40 or more, and the other surface treatment is performed. A printed wiring board having a TD ten-point average roughness Rz of 0.35 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper circuit among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt, When the value indicating the position of the intersection closest to the copper circuit among the intersections with 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A printed wiring board having a ten-point average roughness Rz of TD of 0.35 μm or more measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper circuit subjected to the other surface treatment.
23. The printed wiring according to claim 21, wherein an arithmetic average roughness Ra of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment is 0.05 μm or more. Board.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is 40 or more, and the other surface treatment is performed. A printed wiring board having an arithmetic average roughness Ra of TD of 0.05 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper circuit among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt, When the value indicating the position of the intersection closest to the copper circuit among the intersections with 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A printed wiring board having an arithmetic average roughness Ra of TD of 0.05 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment.
26. The root mean square height Rq of TD measured with a laser microscope having a laser light wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment is 0.08 μm or more. Printed wiring board according to item.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is 40 or more, and the other surface treatment is performed. A printed wiring board having a root mean square height Rq of TD of 0.08 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit.
A printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating resin substrate,
The copper circuit has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 of the copper circuit surface over the insulating resin substrate is 50 or more,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the copper circuit among the intersections of the curve and Bt is t1, and in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt, When the value indicating the position of the intersection closest to the copper circuit among the intersections with 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A printed wiring board having a root mean square height Rq of TD of 0.08 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper circuit subjected to the other surface treatment.
The printed wiring board according to any one of claims 21 to 28, wherein the surface treatment of the other surface is a roughening treatment.
A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to any one of claims 21 to 29.
30. At least one printed wiring board according to any one of claims 21 to 29 and another printed wiring board according to any one of claims 21 to 29 or any one of claims 21 to 29. A method for producing a printed wiring board in which two or more printed wiring boards are connected, comprising at least a step of connecting a printed wiring board not corresponding to the printed wiring board described in the section.
An electronic device using one or more printed wiring boards to which at least one printed wiring board according to any one of claims 21 to 29 is connected.
A surface-treated copper foil used for the printed wiring board according to any one of claims 21 to 29.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where there is no line-shaped copper foil is 40 or more, A copper clad laminate having a TD ten-point average roughness Rz of 0.35 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the other surface treated copper foil surface.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where the line-shaped copper foil is not present, and the observation point− In the lightness graph, a value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and Bt is t1, and from the intersection of the lightness curve and Bt to 0.1 ΔB based on Bt In the depth range, when the value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A copper-clad laminate having a TD ten-point average roughness Rz of 0.35 μm or more as measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment.
36. The copper-clad wire according to claim 34 or 35, wherein an arithmetic average roughness Ra of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.05 μm or more. Laminated board.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where there is no line-shaped copper foil is 40 or more, The copper clad laminated board whose arithmetic mean roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the other surface-treated copper foil surface is 405 nm is 0.05 micrometer or more.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where the line-shaped copper foil is not present, and the observation point− In the lightness graph, a value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and Bt is t1, and from the intersection of the lightness curve and Bt to 0.1 ΔB based on Bt In the depth range, when the value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A copper-clad laminate having an arithmetic average roughness Ra of TD of 0.05 μm or more measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment.
39. The root mean square height Rq of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the other surface treatment is 0.08 μm or more. The copper-clad laminate according to item.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where there is no line-shaped copper foil is 40 or more, A copper clad laminate having a root mean square height Rq of TD of 0.08 μm or more measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the other surface treatment.
A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating resin substrate,
The copper foil has one surface on the insulating resin substrate side and the other surface subjected to surface treatment,
The color difference ΔE * ab based on JIS Z8730 on the surface of the copper foil through the insulating resin substrate is 50 or more,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then taken with a CCD camera over the insulating resin substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness for each observation point along a direction perpendicular to the direction in which the observed line-shaped copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped copper foil to a portion where the line-shaped copper foil is not present, and the observation point− In the lightness graph, a value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and Bt is t1, and from the intersection of the lightness curve and Bt to 0.1 ΔB based on Bt In the depth range, when the value indicating the position of the intersection closest to the line-shaped copper foil among the intersections of the lightness curve and 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.0 or more,
Sv = (ΔB × 0.1) / (t1-t2) (1)
A copper-clad laminate having a root mean square height Rq of TD of 0.08 μm or more measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the other surface treatment.
The copper clad laminate according to any one of claims 34 to 41, wherein the surface treatment of the other surface is a roughening treatment.
A surface-treated copper foil used in the copper-clad laminate according to any one of claims 34 to 42.
A printed wiring board manufactured using the copper-clad laminate according to any one of claims 34 to 42.
An electronic device using the printed wiring board according to claim 44.