JP6537278B2 - Surface-treated copper foil, laminate using the same, printed wiring board, electronic device, and method of manufacturing printed wiring board - Google Patents

Description

  The present invention relates to a surface-treated copper foil, a laminate using the same, a printed wiring board, an electronic device, and a method for producing a printed wiring board, and in particular, the transparency of the remaining resin after etching the copper foil is required. The present invention relates to a surface-treated copper foil suitable for the field to be treated, a laminate using the same, a printed wiring board, an electronic device, and a method of manufacturing the printed wiring board.

  For small electronic devices such as smartphones and tablet PCs, flexible printed wiring boards (hereinafter referred to as FPCs) are adopted because of ease of wiring and lightness. In recent years, with the advancement of the functions of these electronic devices, the signal transmission speed has been increased, and impedance matching has become an important factor also in FPCs. As a measure of impedance matching with respect to the increase of signal capacity, thickening of a resin insulation layer (for example, polyimide) to be a base of FPC is in progress. In addition, with the demand for higher density of wiring, multi-layering of FPCs is further advanced. On the other hand, FPC is subjected to processing such as bonding to a liquid crystal substrate and mounting of an IC chip, but the alignment in this case is resin insulation remaining after etching the copper foil in the laminate of copper foil and resin insulation layer The visibility of the resin insulating layer is important because it is performed via a positioning pattern that is visible through the layer.

  Moreover, the copper clad laminated board which is a laminated board of copper foil and a resin insulation layer can be manufactured also using the rolled copper foil in which the roughening plating was given to the surface. The rolled copper foil is usually made of tough pitch copper (oxygen content 100 to 500 ppm by weight) or oxygen free copper (oxygen content 10 ppm by weight or less) as a raw material, and these ingots are hot-rolled. It is manufactured by repeating cold rolling and annealing to a thickness.

As such technology, for example, in Patent Document 1, a polyimide film and a low roughness copper foil are laminated, and the light transmittance of the film after copper foil etching at a wavelength of 600 nm is 40% or more, and the haze value is The invention which concerns on the copper clad laminated board whose (HAZE) is 30% or less and whose adhesive strength is 500 N / m or more is disclosed.
Further, Patent Document 2 has an insulating layer in which a conductor layer made of electrolytic copper foil is laminated, and the light transmittance of the insulating layer in the etching region at the time of forming the circuit by etching the conductor layer is 50% or more. In a flexible printed wiring board for a chip on flexible (COF), the electrodeposited copper foil is provided with a rustproofing layer of a nickel-zinc alloy on the bonding surface bonded to the insulating layer, and the surface roughness (Rz) of the bonding surface. The invention relating to a flexible printed wiring board for COF characterized in that is 0.05 to 1.5 μm and a specular gloss at an incident angle of 60 ° is 250 or more.
Further, in Patent Document 3, in a method of treating a copper foil for printed circuit, a cobalt-nickel alloy plated layer is formed on the surface of the copper foil after roughening treatment by copper-cobalt-nickel alloy plating, and further zinc-nickel The invention which concerns on the processing method of the copper foil for printed circuits characterized by forming an alloy plating layer is disclosed.

  In addition, when the signal transmission speed has been increased due to the high functionality of the electronic device, the high frequency substrate is required to reduce the transmission loss in order to ensure the quality of the output signal. The transmission loss mainly consists of dielectric loss due to the resin (substrate side) and conductor loss due to the conductor (copper foil side). The dielectric loss decreases as the dielectric constant and dielectric loss tangent of the resin decrease. In high frequency signals, conductor loss is mainly caused by a reduction in the cross section through which current flows due to the skin effect that the current flows only at the surface of the conductor as the frequency increases, and the resistance increases.

  Patent Document 4 discloses an electrodeposited copper foil characterized in that a part of the surface of the copper foil is an uneven surface having a surface roughness of 2 to 4 μm, which is a bump-like protrusion. And according to this, it is described that the electrolytic copper foil excellent in the high frequency transmission characteristic can be provided.

Unexamined-Japanese-Patent No. 2004-98659 WO2003 / 096776 Patent No. 2849059 Japanese Patent Application Publication No. 2004-244656

In Patent Document 1, the low-roughness copper foil obtained by improving the adhesion with the organic treatment agent after the blackening treatment or plating treatment is broken due to fatigue in applications where the copper-clad laminate is required to have flexibility. And may be inferior to resin transparency.
Further, in Patent Document 2, roughening treatment is not performed, and in applications other than the flexible printed wiring board for COF, the adhesion strength between the copper foil and the resin is low and insufficient.
Furthermore, although the fine processing to Cu-Co-Ni to copper foil was possible by the processing method of patent document 3, it is excellent about the resin after making the said copper foil adhere to resin and removing by etching Transparency has not been achieved.
Moreover, in patent documents 1-3, it has not realized about reduction of a transmission loss.
In Patent Document 4, excellent transparency can not be realized for a resin after the copper foil is adhered to a resin and removed by etching.
The present invention provides a surface-treated copper foil which adheres well to a resin, is excellent in transparency of the resin after removing the copper foil by etching, and has a small signal transmission loss, and a laminate using the same.

As a result of intensive researches, the present inventors put a printed matter with a mark down on a polyimide substrate removed by bonding copper foils, and the mark portion obtained by photographing the printed matter with a CCD camera through the polyimide substrate. The point of observation obtained from the image of the image-Focusing on the slope of the lightness curve in the vicinity of the end of the mark drawn in the brightness graph, and controlling the slope of the lightness curve It has been found that, without being affected, it affects resin transparency and signal transmission loss after etching away the copper foil.
In addition, the inventors of the present invention have found that the surface-treated metal species of the copper foil and the amount of adhesion thereof are factors affecting the signal transmission loss, and these factors together with the number density and the glossiness of the roughened particles on the copper foil surface By controlling, it discovered that the surface treatment copper foil with a small transmission loss of a signal was obtained, even if it used for a high frequency circuit board.

In the present invention completed based on the above findings, in one aspect, one copper foil surface is a roughened surface S on which roughened particles are formed by roughening treatment, and the other copper foil surface The ten-point average roughness Rz of TD measured by a laser microscope in which the wavelength of the laser light of the surface of the copper foil which is not the roughened surface S is 405 nm is 0. The polyimide substrate is 35 μm or more, and the roughened surface S is attached to both sides of the polyimide resin substrate, and then the copper foils on the both surfaces are removed by etching to expose printed matter on which line marks are printed. When the printed matter is photographed with a CCD camera through the polyimide substrate, the image obtained by the photographing is perpendicular to the direction in which the observed linear marks extend In the observation point-lightness graph produced by measuring the lightness at each observation point along the line, let Bt be the top average value of the lightness curve generated from the end of the mark to the part without the mark, and Bb be the bottom average value. And, as the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb, in the observation point-lightness graph, of the intersections of the lightness curve and Bt, it is closest to the line mark Assuming that the value indicating the position of the intersection point is t1, in the depth range from the intersection point of the lightness curve and Bt to 0.1 ΔB on the basis of Bt, of the intersection points of the lightness curve and 0.1 ΔB, the line mark When the value indicating the position of the closest intersection point is t2, Sv defined by the following equation (1) is 3.5 or more, and the roughened surface S is selected from the group consisting of Ni and Co. Or 1 Include more elements, deposition of Ni in the case where the roughening treated surface S comprises Ni is less 1400μg / dm ^2, the adhesion amount of Co in the case where the roughening treated surface S contains Co is It is a surface-treated copper foil which is 2400 μg / dm ² or less.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In another aspect of the present invention, one copper foil surface is a roughened surface S having roughened particles formed by roughening treatment, and the other copper foil surface is surface-treated. Arithmetic mean roughness Ra of TD measured with a laser microscope which is a treated copper foil and the wavelength of the laser light of the copper foil surface which is not the roughening treated surface S is 405 nm is 0.05 μm or more, and the roughening After bonding the treated surface S to both sides of the polyimide resin substrate, the copper foils on the both sides are removed by etching, and the printed matter on which the linear marks are printed is laid under the exposed polyimide substrate, the printed matter When the image obtained by the photographing is photographed with the CCD camera through the polyimide substrate, the brightness of each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends In the observation point-lightness graph prepared and measured, the top average value of the lightness curve generated from the end of the mark to the portion without the mark is Bt, the bottom average value is Bb, and the top average value Bt and the bottom As a difference ΔB (ΔB = Bt−Bb) from the average value Bb, in the observation point-lightness graph, a value indicating the position of the intersection closest to the linear mark among the intersections of the lightness curve and Bt is t1. A value indicating the position of the closest intersection point to the line-shaped mark among the intersection points 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 When t2 is set, Sv defined by the following formula (1) is 3.5 or more, and the roughened surface S contains one or more elements selected from the group consisting of Ni and Co, Said roughening Adhesion amount of Ni in the case of physical surface S comprises Ni is less 1400μg / dm ^2, the surface treatment coating weight of Co is less than 2400μg / dm ² in the case where the roughening treated surface S contains Co It is a copper foil.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In another aspect of the present invention, one copper foil surface is a roughened surface S on which roughened particles are formed by roughening treatment, and the other copper foil surface is surface-treated. The root mean square height Rq of TD measured with a laser microscope of which the wavelength of the laser light of the surface of the copper foil which is a surface-treated copper foil and which is not the roughened surface S is 405 nm is 0.08 μm or more After bonding the roughened surface S to both sides of the polyimide resin substrate, the copper foils on the both sides are removed by etching, and a printed material on which line marks are printed is laid under the exposed polyimide substrate, When the printed matter is photographed by the CCD camera through the polyimide substrate, the observation point of the image obtained by the photographing, along the direction perpendicular to the extending direction of the observed linear mark In the observation point-lightness graph produced by measuring the lightness of, the top average value of the lightness curve generated from the end of the mark to the portion without the mark is Bt, the bottom average value is Bb, and the top average value As the difference ΔB (ΔB = Bt−Bb) between the value Bt and the bottom average value Bb, the position of the intersection closest to the linear mark among the intersections of the lightness curve and Bt is shown in the observation point-lightness graph Assuming that the value is t1, in the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB on the basis of Bt, the position of the intersection closest to the linear mark among the intersections of the lightness curve and 0.1 ΔB When the value indicating t is t2, Sv defined by the following equation (1) is 3.5 or more, and the roughened surface S is at least one selected from the group consisting of Ni and Co. Contains elements Adhesion amount of Ni in the case where the roughening treated surface S comprises Ni is less 1400μg / dm ^2, the adhesion amount of Co in the case where the roughening treated surface S comprises a Co is 2400μg / dm ² or less It is a surface-treated copper foil.
Sv = (ΔB × 0.1) / (t1-t2) (1)

  In one embodiment of the surface-treated copper foil according to the present invention, the one copper foil surface is a roughened surface S, and the other copper foil surface is surface-treated.

In another embodiment of the surface-treated copper foil according to the present invention, when the roughened surface S contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less.

In still another embodiment of the surface-treated copper foil according to the present invention, when the roughened surface S contains Ni, the adhesion amount of Ni is 100 μg / dm ² or more.

In still another embodiment of the surface-treated copper foil according to the present invention, when the roughened surface S contains Co, the adhesion amount of Co is 2000 μg / dm ² or less.

In still another embodiment of the surface-treated copper foil according to the present invention, when the roughened surface S contains Co, the adhesion amount of Co is 300 μg / dm ² or more.

  In still another embodiment of the surface-treated copper foil according to the present invention, the difference ΔB (ΔB = Bt) between the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the mark to the portion without the mark -Bb) is 40 or more.

  In still another embodiment of the surface-treated copper foil according to the present invention, in the observation point-brightness graph produced from the image obtained by the photographing, ΔB is 50 or more.

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

  In another embodiment of the surface-treated copper foil which concerns on this invention, Sv defined by (1) Formula in the said brightness curve becomes 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 by the contact-type roughness meter of the roughened surface S is 0.20 to 0.80 μm. 60 degree glossiness of MD of said roughening treated surface S is 76 to 350%, obtained when the surface area A of said roughening particles and said roughening particles are viewed in plan from said roughening treated surface S side The ratio A / B to the area B to be produced is 1.90 to 2.40.

  In still another embodiment of the surface-treated copper foil according to the present invention, the 60 ° glossiness of the MD is 90 to 250%.

  In still another embodiment of the surface-treated copper foil according to the present invention, the ten-point average roughness Rz of TD measured by the contact-type roughness meter is 0.30 to 0.60 μm.

  In still another embodiment of the surface-treated copper foil according to the present invention, the A / B is 2.00 to 2.20.

  In still another embodiment of the surface-treated copper foil according to the present invention, a ratio C (C = (60-degree gloss of MD) of 60-degree gloss of MD of the roughened surface S and 60-degree gloss of TD) Degree) / (60 degree gloss of TD)) is 0.80 to 1.40.

  In still another embodiment of the surface-treated copper foil according to the present invention, a ratio C (C = (60-degree gloss of MD) of 60-degree gloss of MD of the roughened surface S and 60-degree gloss of TD) Degree) / (TD 60 degree glossiness)) is 0.90 to 1.35.

  In still another embodiment of the surface-treated copper foil according to the present invention, the ten-point average roughness Rz of TD measured by a laser microscope in which the wavelength of the laser light of the roughened surface S is 405 nm is 0.35 μm It is above.

  In still another embodiment of the surface-treated copper foil according to the present invention, the arithmetic average roughness Ra of TD measured with a laser microscope in which the wavelength of the laser light of the roughened surface S is 405 nm is 0.05 μm or more It is.

  In still another embodiment of the surface-treated copper foil according to the present invention, the root mean square height Rq of TD measured with a laser microscope in which the wavelength of the laser light of the roughened surface S is 405 nm is 0.08 μm It is above.

  In still another embodiment of the surface-treated copper foil according to the present invention, the roughened surface S is selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. Or one or more.

  In another embodiment of the surface-treated copper foil according to the present invention, the roughened surface S is provided with a resin layer.

  In still another embodiment of the surface-treated copper foil according to the present invention, the resin layer contains a dielectric.

  The present invention provides, in still another aspect, a copper foil with a carrier comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the ultrathin copper layer is a surface-treated copper foil according to the present invention. It is a foil.

  In still another embodiment of the copper foil with carrier according to the present invention, the ultrathin copper layer is provided on both sides of the carrier.

  In still another embodiment of the copper foil with a carrier according to the present invention, a roughening treatment layer is provided on the surface of the carrier opposite to the very thin copper layer side.

  In still another aspect, the present invention is a laminate produced by laminating the surface-treated copper foil of the present invention or the copper foil with a carrier of the present invention and a resin substrate.

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

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

According to still another aspect of the present invention, there is provided a printed wiring board including an insulating resin substrate and a copper circuit provided on the insulating substrate, wherein the copper circuit is photographed by a CCD camera through the insulating resin substrate. 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 circuit extends in the image obtained by the photographing; Let Bt be the top average value of the lightness curve generated from the part to the part without the copper circuit and Bb be the bottom average value, and the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb In the observation point-lightness graph, among the intersection points of the lightness curve and Bt, a value indicating the position of the intersection point closest to the copper circuit is t1 and 0 from the intersection point of the lightness curve and Bt based on Bt Sv defined by the following equation (1), where t2 represents the position of the intersection closest to the copper circuit among the intersections of the lightness curve and 0.1ΔB in the depth range up to 1ΔB: Is 3.5 or more, and the surface on the insulating resin substrate side of the copper circuit contains at least one element selected from the group consisting of Ni and Co, and the surface on the insulating resin substrate side of the copper circuit is Ni In the case of including Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the surface on the insulating resin substrate side of the copper circuit contains Co, the adhesion amount of Co is 2400 μg / dm ² or less It is.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In one embodiment of the printed wiring board according to the present invention, when the surface on the insulating resin substrate side of the copper circuit contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less.

In one embodiment of the printed wiring board according to the present invention, when the surface on the insulating resin substrate side of the copper circuit contains Ni, the adhesion amount of Ni is 100 μg / dm ² or more.

In one embodiment of the printed wiring board according to the present invention, when the surface on the insulating resin substrate side of the copper circuit contains Co, the adhesion amount of Co is 2000 μg / dm ² or less.

In one embodiment of the printed wiring board according to the present invention, when the surface on the insulating resin substrate side of the copper circuit contains Co, the adhesion amount of Co is 300 μg / dm ² or more.

According to still another aspect of the present invention, there is provided a copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating substrate, wherein the copper foil of the copper-clad laminate is formed into a line by etching. When taken with a CCD camera through the insulating resin substrate after forming the copper foil, the observation point of the image obtained by the photographing along the direction perpendicular to the direction in which the observed linear copper foil extends In the observation point-lightness graph produced by measuring the lightness of each point, 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 is Bt, bottom average value Bb, and the difference ΔB between the top average Bt and the bottom average Bb (ΔB = Bt−Bb), in the observation point-lightness graph, of the intersections of the lightness curve and the Bt, the line-shaped table A value indicating the position of the intersection closest to the surface-treated copper foil is t1, and within the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB based on Bt, within the intersection of the brightness curve and 0.1 ΔB When the value indicating the position of the intersection closest to the linear surface-treated copper foil is t2, Sv defined by the following formula (1) is 3.5 or more, and the insulating resin substrate side of the copper foil The surface of the copper foil contains any one or more elements selected from the group consisting of Ni and Co, and when the surface on the insulating resin substrate side of the copper foil contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less In the case where the surface on the insulating resin substrate side of the copper foil contains Co, the adhesion amount of Co is a copper-clad laminate in which the coated amount is 2400 μg / dm ² or less.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In one embodiment of the copper clad laminate according to the present invention, when the surface of the copper foil on the insulating resin substrate side contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less.

In one embodiment of the copper clad laminate according to the present invention, when the surface of the copper foil on the insulating resin substrate side contains Ni, the adhesion amount of Ni is 100 μg / dm ² or more.

In one embodiment of the copper clad laminate according to the present invention, when the surface of the copper foil on the insulating resin substrate side contains Co, the adhesion amount of Co is 2000 μg / dm ² or less.

In one embodiment of the copper clad laminate according to the present invention, when the surface on the insulating resin substrate side of the copper foil contains Co, the adhesion amount of Co is 300 μg / dm ² or more.

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

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

  According to still another aspect, the present invention is an electronic device using the copper clad laminate of the present invention.

  In still 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 according to the present invention.

  In yet another aspect, the present invention includes the step of connecting at least one printed wiring board of the present invention to a printed wiring board other than the printed wiring board of the present invention or 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 still another aspect, the present invention is an electronic device using a printed wiring board to which at least one printed wiring board of the present invention is connected.

  In still another aspect, the present invention is a method for producing a printed wiring board, comprising at least the step of connecting the printed wiring board of the present invention or the printed wiring board produced by the method of the present invention and components. .

In still another aspect, the present invention connects a printed wiring board according to the present invention to at least one printed wiring board according to the present invention and a printed wiring board not corresponding to the printed wiring board according to the present invention or the present invention. A process of producing A, and
It is a method of manufacturing the printed wiring board which two or more printed wiring boards connected including the process of connecting the said printed wiring board A and components at least.

In still another aspect of the present invention, a printed wiring board of the present invention,
A printed wiring board produced by the method of the present invention, and
A printed wiring board which does not correspond to either the printed wiring board of the present invention or the printed wiring board produced by the method of the present invention,
And at least one printed wiring board selected from the group consisting of
A printed wiring board manufactured by the method of the present invention,
Are connected to produce a printed wiring board in which two or more printed wiring boards are connected.

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

  The present invention, in still another aspect, is a surface-treated copper foil for use in the copper-clad laminate of the present invention.

In another aspect of the present invention, a process of preparing the copper foil with carrier of the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier.
Thereafter, the method is a method for producing a printed wiring board including the step of forming a circuit by any of a semi-additive method, a subtractive method, a partial additive method or a modified semi-additive method.

In another aspect of the present invention, a circuit is formed on the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is embedded;
Forming a circuit on the resin layer;
Separating the carrier or the ultrathin copper layer after forming a circuit on the resin layer;
After peeling off the carrier or the ultrathin copper layer, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. Method of manufacturing a printed wiring board including the step of exposing the circuit.

  In still another embodiment of the method for producing a printed wiring board of the present invention, the step of forming a circuit on the resin layer comprises laminating another copper foil with a carrier on the resin layer from the very thin copper layer side It is the process of forming the said circuit using the copper foil with a carrier bonded together to the said resin layer.

  In another aspect, the present invention is the method for producing a printed wiring board, wherein the other copper foil with a carrier to be bonded on the resin layer is the copper foil with a carrier of the present invention.

  In still another embodiment of the method for producing a printed wiring board of the present invention, the step of forming a circuit on the resin layer is any one of a semi-additive method, a subtractive method, a partory additive method or a modified semi-additive method. Done by the way.

  In still another embodiment of the method for producing a printed wiring board of the present invention, the copper foil with carrier forming a circuit on the surface is the surface on the carrier side of the copper foil with carrier or the surface on the ultrathin copper layer side And a substrate or resin layer.

  According to the present invention, a surface-treated copper foil which adheres well to the resin, is excellent in transparency of the resin after removing the copper foil by etching, and has a small signal transmission loss, and a laminate using the same Can be provided.

It is a schematic diagram which defines Bt and Bb. It is a schematic diagram which defines t1 and t2 and Sv. It is a schematic diagram showing the structure of an imaging device in the case of inclination evaluation of a lightness curve, and the measuring method of the inclination of a lightness curve. It is a SEM observation photograph of the copper foil surface of (a) comparative example 1 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (b) comparative example 3 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (c) comparative example 5 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of (d) comparative example 6 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of (e) Example 1 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (f) Example 2 in the case of Rz evaluation. A to C are schematic views of the cross section of the wiring board in the steps up to circuit plating and resist removal, according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention. D to F are schematic views of a cross section of a wiring board in a process from resin and second layer copper foil lamination with carrier to laser drilling according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention It is. G to I are schematic views of a cross section of a wiring board in steps from via fill formation to first layer carrier peeling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to formation of bumps and copper pillars according to a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention. It is an external appearance photograph of the foreign substance used in the Example. It is an external appearance photograph of the foreign substance used in the Example.

[Form and Method of Surface Treated Copper Foil]
The surface-treated copper foil which is one embodiment of the present invention is useful as a copper foil to be used by bonding it with a resin substrate to produce a laminate and removing it by etching.
The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. In general, the surface of the copper foil to be bonded to the resin substrate, that is, the roughened surface, has a rubbed-like electrode on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after lamination. A roughening process is performed to carry out the dressing. Although the electrodeposited copper foil has irregularities at the time of manufacture, the projections of the electrodeposited copper foil are strengthened by the roughening treatment to make the irregularities even larger. In the present invention, this roughening treatment is performed by alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, nickel-zinc alloy plating and the like. Moreover, Preferably it can carry out by copper alloy plating. The copper alloy plating bath is, 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 one or more kinds. In the present invention, the current density of the roughening process is made higher than that of the conventional roughening process, and the roughening process time is shortened. Hereinafter, in the present invention, the copper foil surface on which the roughening particles are formed by the roughening treatment is also referred to as a roughening treated surface S.

In the surface-treated copper foil of the present invention, one of the copper foil surfaces and / or both copper foil surfaces is a roughened surface S on which roughened particles are formed by the roughening treatment. Conventional copper plating and the like may be performed as pretreatment before the roughening treatment, and normal copper plating and the like may be performed as the finishing treatment after the roughening treatment to prevent detachment of the electrodeposit. In the present invention, such pretreatment and finishing may be performed.
The copper foil according to the present invention is also a copper alloy foil containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B, etc. included. When the concentration of the above elements becomes high (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 copper alloy foil may contain 0 mass% to 50 mass% in total of elements other than copper, may contain 0.0001 mass% to 40 mass%, may contain 0.0005 mass% to 30 mass%, and 0.001 mass%. More than 20 mass% may contain.
In addition, the copper foil used in the present invention may be a copper foil with carrier having a carrier, an intermediate layer, and a very thin copper layer in this order. In the case of using a copper foil with a carrier in the present invention, the roughening treatment is performed on the surface of the ultrathin copper layer. Note that another embodiment of the copper foil with carrier will be described later.
The copper foil used in the present invention has a predetermined surface roughness Rz (ten-point average roughness (based on JIS B 0601 1994)) and 60 as described later on the surface to be surface-treated before surface treatment It is necessary to have a degree of gloss.
In addition, the carrier of the copper foil with carrier used in the present invention has a predetermined Rz (ten-point average roughness (based on JIS B 0601 1994)) and 60 degree gloss on the surface on which the intermediate layer is provided, as described later. You must have a degree.
Although the thickness of the surface-treated copper foil according to the present invention is not particularly limited, it is typically 0.5 to 3000 μm, preferably 1.0 to 1000 μm, preferably 1.0 to 300 μm, and preferably 1 0 to 100 μm, preferably 1.0 to 75 μm, preferably 1.0 to 40 μm, preferably 1.5 to 20 μm, preferably 1.5 to 15 μm, preferably 1.5 to 12 μm, preferably 1.5 ~ 10 μm.

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

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

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

The copper-cobalt-nickel alloy plating as the roughening treatment for forming the roughened surface S is a copper-250-2000 μg / dm ² cobalt-50 with an adhesion amount of 15 to 40 mg / dm ² by electrolytic plating. It can be implemented to form a ternary alloy layer which is nickel of ̃1000 μg / dm ² . If the Co adhesion amount is less than 250 μg / dm ² , the heat resistance may be deteriorated and the etching property may be deteriorated. When the Co adhesion amount exceeds 2000 μg / dm ² , the transmission loss of the signal becomes large. In addition, etching spots may occur, and acid resistance and chemical resistance may be deteriorated. If the amount of Ni attached is less than 50 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the adhesion amount of Ni exceeds 1000 μg / dm ² , the transmission loss of the signal becomes large. In addition, the etching residue may be increased. The preferred amount of Co deposition is 300 to 1800 μg / dm ² , and the preferred amount of nickel deposition is 100 to 800 μg / dm ² . Here, the etching stain means that Co does not dissolve when etched with copper chloride, and the etching residue means that Ni does not dissolve when alkaline etching is performed with ammonium chloride. It means that.

An example of a plating bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10 to 20 g / L, Co 1 to 10 g / L, Ni 1 to 10 g / L
pH: 1 to 4
Temperature: 30 to 50 ° C
Current density D _k : 25 to 50 A / dm ²
Plating time: 0.2 to 3.0 seconds In one embodiment of the present invention, in the roughening treatment for forming the roughened surface S, the current of the roughening treatment is higher than that of the conventional roughening treatment conditions. Increase the density and reduce the roughening time.

After the roughening treatment, one or more types of layers selected from the group consisting of a heat-resistant layer, an anticorrosive layer, and a weather resistant layer may be provided on the roughened surface. Each layer may be a plurality of layers such as two layers, three layers, etc. The layers may be laminated in any order, and the layers may be laminated alternately.
In the surface-treated copper foil of the present invention, the "roughened surface" refers to the surface when the heat-resistant layer, the rustproof layer, the weather resistant layer, etc. are provided after the roughening treatment. It refers to the surface of the surface-treated copper foil after the treatment. When the surface-treated copper foil is an ultrathin copper layer of copper foil with a carrier, the "roughened surface" means that a heat-resistant layer, an antirust layer, a weather resistant layer, etc. are provided after the roughening treatment. When the surface treatment for the purpose is performed, it means the surface of the very thin copper layer after the surface treatment is performed.
Here, as the heat-resistant layer, a known heat-resistant layer can be used. Also, for example, the following surface treatment can be used.
A well-known heat-resistant layer and an antirust layer can be used as the heat-resistant layer and the antirust layer. For example, the heat resistant layer and / or the rustproof 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 Layer containing one or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements It may be a metal layer or an alloy layer composed of one or more elements selected from the group of iron and tantalum. In addition, the heat resistant layer and / or the rustproof 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. And oxides, nitrides, and silicides containing one or more elements selected from In addition, the heat resistant layer and / or the rustproof layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, excluding unavoidable 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 , and preferably 20 to 100 mg / m ² . Further, the ratio of the adhesion amount of nickel to the adhesion amount of zinc of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= adhesion amount of nickel / adhesion amount of zinc) is 1.5 to 10 Is preferred. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing It is more preferable that When the heat resistant layer and / or the rustproof 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 portion such as a through hole or a via hole contacts the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate. The rustproof layer may be a chromate treatment layer. A known chromate-treated layer can be used for the chromate-treated layer. For example, a chromate-treated layer refers to a layer treated with a solution containing chromic acid anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium and other elements (metals, alloys, oxides, nitrides, sulfides, etc.) May be included. As a specific example of a chromate treatment layer, a pure chromate treatment layer, a zinc chromate treatment layer, etc. are mentioned. In the present invention, a chromate-treated layer treated with an aqueous solution of chromic acid anhydride or potassium dichromate is referred to as a pure chromate-treated layer. In the present invention, a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate-treated layer.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt Or any one of the above. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 Is more preferred. The heat-resistant layer and / or the rust-preventive layer preferably have an adhesion amount of nickel in nickel or nickel alloy / an adhesion amount of tin of 0.25 to 10, and 0.33 to 3. More preferable. When the heat resistant layer and / or the rustproof layer are used, the copper foil with carrier is processed into a printed wiring board, and the peel strength of the circuit after that, the chemical resistance deterioration rate of the peel strength, etc. become good.
In addition, a cobalt-nickel alloy plated layer of cobalt with an adhesion amount of 200 to 2000 μg / dm ² and 50 to 700 μg / dm ² can be formed as a heat-resistant layer and / or an anticorrosive layer. This treatment can be regarded in a broad sense as a kind of rustproofing treatment. The cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesion strength between the copper foil and the substrate is not substantially reduced. When the cobalt deposition amount is less than 200 μg / dm ² , the heat resistant peel strength may be reduced, and the oxidation resistance and the chemical resistance may be deteriorated. As another reason, when the amount of cobalt is small, the treated surface becomes reddish, which is not preferable. If the cobalt deposition amount exceeds 2000 μg / dm ² , the transmission loss of the signal becomes large, which is not preferable. In addition, etching spots may occur, and acid resistance and chemical resistance may be deteriorated. As a heat-resistant layer and / or an anticorrosion layer, the preferable cobalt adhesion amount is 500 to 1000 μg / dm ² . On the other hand, when the nickel adhesion amount is less than 100 μg / dm ² , the heat resistant peel strength may be lowered, and the oxidation resistance and the chemical resistance may be deteriorated. When the nickel content exceeds 1000 μg / dm ² , the signal transmission loss increases. The preferable nickel adhesion amount is 100 to 600 μg / dm ² as the heat-resistant layer and / or the rustproof layer.

Moreover, an example of the conditions of cobalt-nickel alloy plating is as follows:
Plating bath composition: Co 1 to 20 g / L, Ni 1 to 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 to 4 seconds

Moreover, you may form the zinc-plating layer of 30-250 microgram / dm < ² > of adhesion amounts further on the said cobalt- nickel alloy plating. If the amount of zinc adhesion is less than 30 μg / dm ² , the effect of improving the thermal degradation rate may be lost. On the other hand, when the zinc adhesion amount exceeds 250 μg / dm ² , the hydrochloric acid resistance deterioration rate may extremely deteriorate. Preferably, the zinc coverage is 30 to 240 μg / dm ² , more preferably 80 to 220 μg / dm ² .

An example of the conditions of the above-mentioned galvanization is as follows:
Plating bath composition: Zn 100 to 300 g / L
pH: 3 to 4
Temperature: 50-60 ° C
Current density D _k : 0.1 to 0.5 A / dm ²
Plating time: 1 to 3 seconds

  In addition, you may form a zinc alloy plating layer such as zinc-nickel alloy plating instead of the zinc plating layer, and further, on the outermost surface, a rustproof layer or a weather resistant layer by chromate treatment or application of a silane coupling agent. You may form.

A well-known weathering layer can be used as a weathering layer. In addition, as the weather resistant layer, for example, a known silane coupling treated layer can be used, and a silane coupling treated layer formed using the following silane can be used.
A well-known silane coupling agent may be used for the silane coupling agent used for a silane coupling process, for example, an amino type silane coupling agent, an epoxy-type silane coupling agent, and a mercapto type silane coupling agent may be used. Further, as a silane coupling agent, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, It is also possible to use γ-mercaptopropyltrimethoxysilane or the like.

  The silane coupling treatment layer may be formed using a silane coupling agent such as epoxy based silane, amino based silane, methacryloxy based silane, mercapto based silane and the like. In addition, you may use such a silane coupling agent in mixture of 2 or more types. Among them, those formed using an amino-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

  As used herein, the term "amino-based silane coupling agent" means 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) phenethyl trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (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) to Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N Even selected from the group consisting of -β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane 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 atom. It is desirable to provide in the range of / m ² . In the case of the above-mentioned range, the adhesion between the base resin and the surface treated copper foil can be further improved.

[Surface roughness Rz]
The surface-treated copper foil of the present invention has a TD (direction perpendicular to the rolling direction (width direction of copper foil) measured with a contact-type roughness meter on the roughened surface S, and in the case of an electrolytic copper foil, it is an electrolytic copper foil It is preferable that ten-point average roughness Rz of the direction perpendicular | vertical to the foil passing direction of the copper foil in an apparatus is 0.20-0.80 micrometer. With such a configuration, the peel strength becomes high, the resin adheres well to the resin, and the degree of haze (haze value) of the resin after removing the copper foil by etching decreases, and the transparency becomes high. As a result, alignment at the time of mounting the IC chip and the like performed through the positioning pattern which is visually recognized through the resin becomes easy. In addition, since the surface unevenness is very small, the length of the surface-treated copper foil surface corresponding to the length of electron flow becomes short, and the transmission loss becomes small. If the ten-point average roughness Rz of TD is less than 0.20 μm, there may be a concern of manufacturing cost for producing an ultra-smooth copper foil. On the other hand, if the ten-point average roughness Rz of TD is more than 0.80 μm, the unevenness of the resin surface after removing the copper foil by etching may be large, and as a result, the haze value of the resin may be large. 0.30 to 0.70 μm is preferable, 0.30 to 0.60 μm is preferable, and 0.35 to 0.60 μm is more preferable, and the ten-point average roughness Rz of TD of the roughened surface S is preferably 0.35 -0.55 micrometer is still more preferable, and 0.35-0.50 micrometer is still more preferable.
In the case where the surface-treated copper foil of the present invention is used for applications where it is necessary to reduce Rz, the ten-point average roughness Rz of TD of the roughened surface S is 0.20 to 0.70 μm. Preferably, 0.25 to 0.60 μm is more preferable, 0.30 to 0.55 μm is still more preferable, and 0.30 to 0.50 μm is still more preferable.
In order to control the size and number density of the roughening particles as described above, the surface of the copper foil before surface treatment (in the case where the surface-treated copper foil is a carrier-attached copper foil, the carrier) as described later It is necessary to make the roughness Rz and the glossiness in a predetermined range, carry out roughing treatment plating by alloy plating, make the current density of the roughening treatment plating higher than before, and make the roughening treatment plating time shorter than before There is.
In the surface-treated copper foil of the present invention, one of the copper foil surfaces may be a roughened surface S, and the other copper foil surface may be surface-treated.

[Glossiness]
The glossiness at an angle of incidence of 60 degrees in the rolling direction (MD) of the roughened surface S of the surface-treated copper foil may greatly affect the transparency of the above-mentioned resin. That is, the transparency of the above-mentioned resin may be better as the glossiness of the roughened surface is larger. For this reason, in the surface-treated copper foil of the present invention, the glossiness of the roughened surface S is preferably 76 to 350%, preferably 80 to 350%, and more preferably 90 to 300%. Preferably, it is still more preferably 90 to 250% and even more preferably 100 to 250%.

  Here, in order to obtain the effect of the visibility of the present invention and the effect of transmission loss reduction, the surface on the treated side of the copper foil before the surface treatment (when the surface treated copper foil is an ultrathin copper layer of copper foil with carrier In the direction perpendicular to the rolling direction (the width direction of the copper foil), and in the case of the electrolytic copper foil, the copper foil in the electrolytic copper foil manufacturing apparatus Surface roughness (Rz (means ten-point average roughness Rz (JIS B0601 1994). The same applies in this specification)) and glossiness (60 degree glossiness (JIS). It is necessary to keep control of the same in this specification). Specifically, the surface roughness (Rz) of the TD of the copper foil before surface treatment (the carrier before formation of the intermediate layer when the surface treated copper foil is the ultrathin copper layer of the copper foil with carrier) is 0 30 to 0.80 μm, preferably 0.30 to 0.50 μm, and the incident angle 60 in the rolling direction (MD, in the case of an electrodeposited copper foil, the passing direction of the copper foil in the electrodeposited copper foil manufacturing apparatus) Degree of glossiness is 350 to 800%, preferably 500 to 800%, and a copper alloy plating bath (copper and copper other than copper and copper as plating for roughening treatment to form a further roughened surface S) A plating bath containing one or more elements, more preferably a plating bath containing copper and any one or more selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum) is used Current density of the roughening process Is made higher than the conventional roughening treatment, and the roughening treatment time is shortened than that of the conventional roughening treatment, the Sv value described later is 3.5, and after the surface treatment, the surface treated copper foil The glossiness at an incident angle of 60 degrees in the rolling direction (MD) is 76 to 350%, and the surface roughness Rz of the roughened surface S, the surface area A of the roughened particles, and the roughened particles are roughened The ratio A / B to the area B obtained when viewed in plan from the treated surface S side can be controlled within the predetermined range of the present invention. As such a copper foil (in the case where the surface-treated copper foil is a carrier-attached copper foil, this means a carrier). The rolling is performed by adjusting the oil film equivalent of rolling oil (high gloss rolling), or And chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Moreover, it can manufacture by manufacturing an electrolytic copper foil on a predetermined | prescribed electrolyte solution and predetermined | prescribed electrolysis conditions.

  If you want to make the gloss at an angle of incidence of 60 degrees in the rolling direction (MD) after surface treatment higher (for example, the degree of gloss at an angle of incidence of 60 degrees in the rolling direction (MD) = 350%), surface treatment The TD roughness (Rz) of the treated side surface of the previous copper foil is 0.18 to 0.80 μm, preferably 0.25 to 0.50 μm, and the gloss at a 60 ° incident angle in the rolling direction (MD) Copper alloy plating bath (plating containing one or more elements other than copper and copper) as plating for roughening treatment to form a roughened surface S, and having a degree of 350 to 800%, preferably 500 to 800% A bath, more preferably a plating bath comprising copper and at least one selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum), Current density rather than roughening treatment Increase the degree and shorten the roughening processing time.

High gloss rolling can be performed by setting the oil film equivalent defined by the following equation to 13,000 or more and 24,000 or less. In addition, high glossiness is desired when the glossiness at an incident angle of 60 degrees in the rolling direction (MD) after surface treatment is made higher (for example, the glossiness at an incident angle of 60 degrees in the rolling direction (MD) = 350%) The rolling is performed by setting the oil film equivalent defined by the following equation to 12,000 or more and 24,000 or less.
Oil film equivalent = {(rolled oil viscosity [cSt]) × (passing speed [mpm] + roll peripheral speed [mpm])} / {(roll bite angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is the kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 12000 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 for a long time with an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a lower concentration than usual.

Moreover, the manufacturing conditions etc. of the electrolytic copper foil which can be used for this invention are as follows.
-Electrolyte composition copper: 80 to 120 g / L
Sulfuric acid: 80 to 120 g / L
Chlorine: 30 to 100 ppm
Leveling agent 1 (bis (3 sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
The amine compound of the following chemical formula can be used for the above-mentioned amine compound.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of hydroxyalkyl group, ether group, aryl group, aromatic substituted alkyl group, unsaturated hydrocarbon group, alkyl group.)
The remainder of the treatment liquid used in the present invention for desmear treatment, electrolysis, surface treatment, plating, etc. is water unless otherwise specified.

-Manufacturing conditions Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50 to 65 ° C
Electrolyte linear velocity: 1.5 to 5 m / sec
Electrolysis time: 0.5 to 10 minutes (Copper thickness to be deposited, adjusted by current density)
In addition, as an electrolytic copper foil that can be used in the present invention, an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metals Corporation can be used.

  The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD of the roughened surface S is 0.80 to 1 Preferably .40. If the ratio C between the 60 ° gloss of MD and the 60 ° gloss of TD on the roughened surface S is less than 0.80, the transparency of the resin may be lower than in the case of 0.80 or more. is there. In addition, when the ratio C is more than 1.40, the transparency of the resin may be lower than in the case where the ratio C is 1.40 or less. The ratio C is more preferably 0.90 to 1.35, and still more preferably 1.00 to 1.30.

[Slope of lightness curve]
In the surface-treated copper foil of the present invention, after bonding the roughened surface S of the surface-treated copper foil to both sides of the polyimide base resin, the copper foils on both sides were removed by etching, and line marks were printed. When a printed matter is placed under the exposed polyimide substrate and the printed matter is photographed with a CCD camera through the polyimide substrate, a direction perpendicular to the direction in which the observed line-shaped mark extends in the image obtained by photographing In the observation point-lightness graph produced by measuring the lightness at each observation point along the line, let Bt be the top average value of the lightness curve generated from the end of the mark to the part without the mark, and Bb be the bottom average value. As a difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb, in the observation point-lightness graph, among the intersections of the lightness curve and the Bt, A value indicating the position of the intersection closest to the linear mark is t1, and in the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with Bt as a reference, among the intersections of the lightness curve and 0.1 ΔB, When the value indicating the position of the intersection closest to the linear mark is t2, Sv defined by the above equation (1) is 3.5 or more. In the observation position-lightness graph, the horizontal axis represents position information (pixel × 0.1), and the vertical axis represents the value of lightness (tone).
Here, “top average value Bt of lightness curve”, “bottom average value Bb of lightness curve”, and “t1”, “t2”, and “Sv” described later will be described with reference to the drawings.
FIGS. 1A and 1B show schematic diagrams defining Bt and Bb when the width of the mark is about 0.3 mm. When the mark width is about 0.3 mm, it may be a V-shaped lightness curve as shown in FIG. 1A or a lightness curve having a bottom as shown in FIG. 1B. . In any case, “Top average value Bt of lightness curve” indicates the average value of lightness measured at five points (total ten points on both sides) at intervals of 30 μm from positions 50 μm away from the end positions on both sides of the mark. . On the other hand, “bottom average value Bb of lightness curve” indicates the lowest 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 of about 0.3 mm is shown. The width of the mark may be about 0.2 mm, 0.16 mm, and 0.1 mm. Furthermore, the “top average value Bt of the brightness curve” is 5 positions at intervals of 30 μm from the positions separated by 100 μm, 300 μm or 500 μm from the end positions on both sides of the mark (total 10 on both sides Location) It may be an average value of lightness when measured.
FIG. 2 shows a schematic diagram defining t1 and t2 and Sv. “T1 (pixel × 0.1)” is a value indicating the intersection closest to the line-like mark among the intersections of the lightness curve and Bt, and the position of the intersection (the value of the horizontal axis of the observation point-lightness graph ). “T2 (pixel × 0.1)” is the line-like mark of the intersections of the brightness curve and 0.1 ΔB in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt. And the value indicating the position of the intersection point (the value of the observation point-the horizontal axis of the lightness graph). At this time, the slope of the lightness curve indicated by the line connecting t1 and t2 is Sv (tone / pixel × 0.1) calculated by 0.1 ΔB in the y-axis direction and (t1-t2) in the x-axis direction. Defined in). Note that one pixel on the horizontal axis corresponds to 10 μm in length. Also, Sv measures both sides of the mark and adopts a small value. Furthermore, in the case where the shape of the lightness curve is unstable and there are a plurality of "intersections of the lightness curve and Bt", the intersection closest to the mark is adopted.
In the above-mentioned image taken by the CCD camera, the brightness is high in the part where the mark is not attached, but the brightness drops as soon as the mark end is reached. If the visibility of the polyimide substrate is good, such a decrease in brightness is clearly observed. On the other hand, if the visibility of the polyimide substrate is poor, the lightness does not drop sharply from "high" to "low" at once in the vicinity of the mark end, but the state of decline becomes moderate and the state of lightness is unclear It becomes.
On the basis of such findings, the present invention places the printed matter with a mark on the bottom of the polyimide substrate removed by bonding the surface-treated copper foil of the present invention, and the mark portion photographed with a CCD camera over the polyimide substrate. The inclination of the lightness curve in the vicinity of the end of the mark drawn in the observation point-lightness graph obtained from the image of (b) is controlled. More specifically, assuming that the top average value of the lightness curve is Bt and the bottom average value is Bb, and the difference ΔB (ΔB = Bt-Bb) between the top average value Bt and the bottom average value Bb, the observation point-lightness graph In the lightness curve and Bt, a value indicating the position of the intersection closest to the linear mark is taken as t1, and from the intersection of the lightness curve and Bt to a depth range of 0.1 ΔB with Bt as a reference When the value indicating the position of the intersection closest to the linear mark among the intersections of the lightness curve and 0.1ΔB is t2, Sv defined by the above equation (1) is 3.5 or more . According to such a configuration, the discriminating power of the mark over the polyimide by the CCD camera is improved without being affected by the type and thickness of the substrate resin. For this reason, a polyimide substrate excellent in visibility can be manufactured, positioning accuracy by marking in the case of performing predetermined processing on a polyimide substrate in an electronic substrate manufacturing process etc. is improved, and effects such as yield improvement are improved. can get. ΔB is preferably 40 or more, more preferably 50 or more. Sv is preferably 3.9 or more, more preferably 4.5 or more, more preferably 5.0 or more, more preferably 5.5 or more. The upper limit of ΔB is not particularly limited, but is, for example, 100 or less, 80 or less, or 70 or less. 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 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.
Therefore, when the copper foil which concerns on embodiment of this invention is used for a printed wiring board, when connecting one printed wiring board and another printed wiring board, a connection defect is reduced and a yield improves.
In addition, it is preferable that the polyimide film used for the measurement of the inclination of a brightness curve is a polyimide film whose value of (DELTA) B ((DELTA) B (PI)) before bonding to copper foil is 50 or more and 65 or less. It is because it becomes easier to measure Sv.

[Attachment amount of Ni and Co on the surface treated copper foil surface]
In the surface-treated copper foil of the present invention, when the roughened surface S contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the roughened surface S contains Co, the adhesion amount of Co Is less than or equal to 2400 μg / dm ² . Here, the adhesion amount of Ni and Co on the roughened surface S means the adhesion amount of the total of Ni and Co contained in all surface treatment layers formed on the copper foil surface. For example, when the surface of a copper foil is provided with a roughening treatment layer, a heat-resistant layer 1, a heat-resistant layer 2, a rustproof layer, and a weather resistant layer, the surface treatment layer formed on the surface of the copper foil is roughened It means the total adhesion amount of the adhesion amounts of Ni and Co contained in the treated layer, the heat resistant layer 1, the heat resistant layer 2, the rustproof layer, and the weather resistant layer.
As a result of studies by the inventors, it has been found that the adhesion amount of a predetermined metal in the surface treatment layer significantly affects the transmission loss. According to the study of the present inventor, it has been found that among such surface-treated metal species, Co and Ni, in particular, which have relatively high permeability and relatively low conductivity, affect transmission loss. Therefore, limiting the deposition amount of Ni and / or Co as described above is effective to reduce the transmission loss.
When the adhesion amount of Ni becomes larger than 1400 μg / dm ² , the transmission loss becomes large, which is not preferable. On the other hand, when the adhesion amount of Co is larger than 2400 μg / dm ² , the transmission loss becomes large, which is not preferable.
In order to further reduce transmission loss, when the roughened surface S contains Ni, the adhesion amount of Ni is preferably 1000 μg / dm ² or less, preferably 900 μg / dm ² or less, and 800 μg / dm ^2. preferably dm ² or less, more preferably 700 [mu] g / dm ² or less.
When the roughened surface S contains Ni, the adhesion amount of Ni is preferably 100 μg / dm ² or more, preferably 120 μg / dm ² or more, and 150 μg / dm ² or more. More preferable. If the adhesion amount of Ni is less than 100 μg / dm ² , the heat resistance may be deteriorated.
Order to further reduce the transmission loss, it is preferred that it is preferable that deposition amount of Co is less than 2000 [mu] g / dm ^2, at 1800 [mu] g / dm ² or less in the case of roughening treated surface S comprises Co, 1600μg / dm preferably ² or less, more preferably 1400μg / dm ² or less.
When the roughened surface S contains Co, the adhesion amount of Co is preferably 300 μg / dm ² or more, preferably 350 μg / dm ² or more, and 400 μg / dm ² or more. More preferable. If the adhesion amount of Co is less than 300 μg / dm ² , the heat resistance may deteriorate.
In addition, in order to control the adhesion amount of Ni and Co in the above-mentioned range, controlling the Ni and Co concentration in the surface treatment (plating) solution such as roughening treatment plating and heat resistant layer, and in the case of surface treatment It is effective to control the current density and surface treatment time. By increasing the concentration of Ni and Co in the surface treatment (plating) solution, the amount of Ni and Co adhesion can be increased. In addition, if the concentrations of Ni and Co are lowered, the amounts of Ni and Co deposited can be reduced. In addition, if the current density at the time of surface treatment is increased and / or the surface treatment time is lengthened, the amount of Ni and Co adhesion can be increased. In addition, if the current density at the time of surface treatment is lowered and / or the surface treatment time is shortened, the amount of Ni and Co adhesion can be reduced.

  The surface-treated copper foil of the present invention has a roughened surface S and / or a ten-point average roughness of TD measured by a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. It is preferable that Rz is 0.35 μm or more. Furthermore, it is more preferable that the copper foil surface which is not the roughening treatment surface S of the surface-treated copper foil of this invention is surface-treated. 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 in the lamination step with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention has a roughened surface S and / or a ten-point average roughness of TD measured by a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. Rz is more preferably 0.40 μm or more, still more preferably 0.50 μm or more, still more preferably 0.60 μm or more, and still more preferably 0.80 μm or more. In addition, the wavelength of the laser beam of the copper foil surface which is not the roughening treatment surface S and / or the roughening treatment surface S of the surface-treated copper foil of the present invention is 405 nm, and the ten point average of TD measured The upper limit of the roughness Rz is not particularly limited, but is typically 4.0 μm or less, more typically 3.0 μm or less, and more typically 2.5 μm or less. It is typically 2.0 μm or less.

  The surface-treated copper foil of the present invention has a roughened surface S and / or an arithmetic average roughness Ra of TD measured by a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. Is preferably 0.05 μm or more. Furthermore, it is more preferable that the copper foil surface which is not the roughening treatment surface S of the surface-treated copper foil of this invention is surface-treated. 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 in the lamination step with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention has a roughened surface S and / or an arithmetic average roughness Ra of TD measured by a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. Is more preferably 0.08 μm or more, 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 arithmetic mean roughness of TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface which is not the roughening process surface S and / or the roughening process surface S of the surface-treated copper foil of this invention is 405 nm. The upper limit of the thickness Ra is not particularly limited, but is typically 0.80 μm or less, more typically 0.65 μm or less, more typically 0.50 μm or less, and more typically Is 0.40 μm or less.

  The surface-treated copper foil of the present invention has a roughened surface S and / or a root-mean-square height of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. It is preferable that Rq is 0.08 μm or more. Furthermore, it is more preferable that the copper foil surface which is not the roughening treatment surface S of the surface-treated copper foil of this invention is surface-treated. 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 in the lamination step with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention has a roughened surface S and / or a root-mean-square height of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface other than the roughened surface S is 405 nm. Rq is more preferably 0.10 μm or more, still more preferably 0.15 μm or more, still more preferably 0.20 μm or more, and still more preferably 0.30 μm or more. The root mean square of TD of the surface-treated copper foil of the present invention measured with a laser microscope in which the wavelength of the laser light of the roughened surface S and / or the copper foil surface other than the roughened surface S is 405 nm. The upper limit of the height Rq is not particularly limited, but is typically 0.80 μm or less, more typically 0.60 μm or less, and more typically 0.50 μm or less, More typically, it is 0.40 μm or less.

The copper foil surface which is not the roughened surface S may be subjected to a treatment of providing a heat-resistant layer or a rustproof layer by plating (normal plating, plating not roughened plating) as surface treatment.
Moreover, the copper foil surface which is not roughening treatment surface S may be roughened as surface treatment. For the roughening treatment, for example, the roughening treatment may be performed using a plating solution containing copper sulfate and a sulfuric acid aqueous solution, or the roughening treatment may be performed using a plating solution composed of a copper sulfate and a sulfuric acid aqueous solution . Alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, nickel-zinc alloy plating, etc. may be used. Moreover, Preferably it can carry out by copper alloy plating. The copper alloy plating bath is, 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 one or more kinds.
Moreover, you may use roughening processes other than said roughening process with respect to the copper foil surface which is not roughening process surface S, and surface treatment other than said plating process may be used also when not roughening process. .
Moreover, the copper foil surface which is not roughening process surface S may be surface-treated for forming an unevenness | corrugation in the surface. As surface treatment for forming unevenness on the surface, surface treatment by electrolytic polishing may be performed. For example, by electropolishing the copper foil surface which is not the roughened surface S in a solution composed of copper sulfate and a sulfuric acid aqueous solution, unevenness can be formed on the copper foil surface which is not the roughened surface S. In general, the purpose of the electrolytic polishing is to smooth the surface, but in the surface treatment of the surface of the copper foil which is not the roughened surface S, since the irregularities are formed by the electrolytic polishing, the concept is the reverse of the ordinary. The method of forming the unevenness by electrolytic polishing may be performed by a known technique. As an example of the well-known technique of the electropolishing for forming the said unevenness | corrugation, the method as described in Unexamined-Japanese-Patent No. 2005-240132, Unexamined-Japanese-Patent No. 2010-059547, and Unexamined-Japanese-Patent No. 2010-047842 is mentioned. As specific conditions of the process which forms an unevenness | corrugation by electrolytic polishing, for example,
Processing solution: Cu: 20 g / L, H ₂ SO ₄ : 100 g / L, temperature: 50 ° C.
Electrolytic polishing current: 15 A / dm ²
Electrolytic polishing time: 15 seconds, etc. may be mentioned.
As surface treatment for forming unevenness in the copper foil surface which is not roughening processing surface S, for example, you may form unevenness by carrying out mechanical polish of the copper foil surface which is not roughening processing surface S. Mechanical polishing may be performed by known techniques.
In addition, you may provide a heat-resistant layer, a rustproof layer, and a weather resistant layer after surface treatment of the copper foil surface which is not roughening-treated surface S. The heat-resistant layer, the rust-preventive layer and the weather-resistant layer may be the methods described above or in the experimental examples, or may be methods of known techniques.

[Attachment amount of Ni, Co on the surface on the insulating resin substrate side of copper circuit of printed wiring board]
In the printed wiring board of the present invention, when the surface on the insulating resin substrate side of the copper circuit of the printed wiring board contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and the insulating resin of the copper circuit of the printed wiring board When the surface on the substrate side contains Co, the adhesion amount of Co is 2400 μg / dm ² or less. Here, the adhesion amounts of Ni and Co on the surface on the insulating resin substrate side of the copper circuit of the printed wiring board refer to all surface treatment layers formed on the surface of the insulating resin substrate on the copper circuit of the printed wiring board. It means the adhesion amount of the total of Ni and Co included. For example, in the case where the roughened layer, the heat-resistant layer 1, the heat-resistant layer 2, the rustproof layer, and the weather resistant layer are provided on the surface on the insulating resin substrate side of the copper circuit of the printed wiring board, the copper circuit of the printed wiring board The adhesion amount of the total of the adhesion amounts of Ni and Co contained in the roughening treatment layer, the heat-resistant layer 1, the heat-resistant layer 2, the rustproof layer, and the weather resistant layer which are surface treatment layers formed on the surface on the insulating resin substrate side Means
As a result of the inventors' investigation, it has been found that the amount of adhesion of a predetermined metal on the surface treatment layer on the surface of the copper circuit of the printed wiring board on the insulating resin substrate side significantly affects transmission loss. According to the study of the present inventor, it has been found that among such surface-treated metal species, Co and Ni, in particular, which have relatively high permeability and relatively low conductivity, affect transmission loss. Therefore, limiting the deposition amount of Ni and / or Co as described above is effective to reduce the transmission loss.
When the adhesion amount of Ni becomes larger than 1400 μg / dm ² , the transmission loss becomes large, which is not preferable. On the other hand, when the adhesion amount of Co is larger than 2400 μg / dm ² , the transmission loss becomes large, which is not preferable.
In order to further reduce the transmission loss, when the surface on the insulating resin substrate side of the copper circuit of the printed wiring board contains Ni, the adhesion amount of Ni is preferably 1000 μg / dm ² or less, and 900 μg / dm ² or less is preferably, it is preferably 800 [mu] g / dm ² or less, and more preferably 700 [mu] g / dm ² or less.
When the surface on the insulating resin substrate side of the copper circuit of the printed wiring board contains Ni, the adhesion amount of Ni is preferably 100 μg / dm ² or more, preferably 120 μg / dm ² or more, 150 μg It is more preferable that it is / dm ² or more. If the adhesion amount of Ni is less than 100 μg / dm ² , the heat resistance may be deteriorated.
Order to further reduce the transmission loss, it is preferable that deposition amount of Co is less than 2000 [mu] g / dm ² in the case where the insulating resin substrate-side surface of the copper circuit of the printed wiring board comprises Co, 1800 [mu] g / dm ² or less preferably there is preferably at 1600μg / dm ² or less, and more preferably 1400μg / dm ² or less.
When the surface on the insulating resin substrate side of the copper circuit of the printed wiring board contains Co, the adhesion amount of Co is preferably 300 μg / dm ² or more, preferably 350 μg / dm ² or more, 400 μg It is more preferable that it is / dm ² or more. If the adhesion amount of Co is less than 300 μg / dm ² , the heat resistance may deteriorate.
In addition, in order to control the adhesion amount of Ni and Co in the above-mentioned range, Ni in surface treatment (plating) liquid, such as roughening treatment plating and a heat-resistant layer, of copper foil before processed into the said copper circuit It is effective to control the Co concentration, and to control the current density during surface treatment and the surface treatment time. By increasing the concentration of Ni and Co in the surface treatment (plating) solution, the amount of Ni and Co adhesion can be increased. In addition, if the concentrations of Ni and Co are lowered, the amounts of Ni and Co deposited can be reduced. In addition, if the current density at the time of surface treatment is increased and / or the surface treatment time is lengthened, the amount of Ni and Co adhesion can be increased. In addition, if the current density at the time of surface treatment is lowered and / or the surface treatment time is shortened, the amount of Ni and Co adhesion can be reduced.

[Attachment amount of Ni and Co on the surface on the insulating resin substrate side of copper foil of a copper clad laminate]
In the copper clad laminate of the present invention, when the surface on the insulating resin substrate side of the copper foil of the copper clad laminate contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and the copper clad laminate has When the surface on the insulating resin substrate side of the copper foil contains Co, the adhesion amount of Co is 2400 μg / dm ² or less. Here, the adhesion amount of Ni and Co on the surface on the insulating resin substrate side of the copper foil of the copper-clad laminate is the same as that of all the copper foil on the insulating resin substrate side of the copper-clad laminate. It means the adhesion amount of the total of Ni and Co contained in the surface treatment layer. For example, when a roughened layer, a heat-resistant layer 1, a heat-resistant layer 2, a rustproof layer, and a weather resistant layer are provided on the surface of the copper-clad laminate on the side of the insulating resin substrate of copper foil, the copper-clad laminate is Of the adhesion amount of Ni and Co contained in the roughening treated layer, the heat resistant layer 1, the heat resistant layer 2, the rustproof layer, and the weather resistant layer which are surface treatment layers formed on the surface on the insulating resin substrate side of the copper foil It means the total adhesion amount.
According to the inventors' investigations, it has been found that the adhesion amount of a predetermined metal in the surface treatment layer on the insulating resin substrate side of the copper foil of the copper clad laminate has a significant influence on the transmission loss. According to the study of the present inventor, it has been found that among such surface-treated metal species, Co and Ni, in particular, which have relatively high permeability and relatively low conductivity, affect transmission loss. Therefore, limiting the deposition amount of Ni and / or Co as described above is effective to reduce the transmission loss.
When the adhesion amount of Ni becomes larger than 1400 μg / dm ² , the transmission loss becomes large, which is not preferable. On the other hand, when the adhesion amount of Co is larger than 2400 μg / dm ² , the transmission loss becomes large, which is not preferable.
In order to further reduce the transmission loss, when the surface on the insulating resin substrate side of the copper foil of the copper clad laminate contains Ni, the adhesion amount of Ni is preferably 1000 μg / dm ² or less, 900 μg / dm 2 preferably ² or less, it is preferably 800 [mu] g / dm ² or less, and more preferably 700 [mu] g / dm ² or less.
When the surface on the insulating resin substrate side of the copper foil of the copper-clad laminate contains Ni, the adhesion amount of Ni is preferably 100 μg / dm ² or more, and preferably 120 μg / dm ² or more And more preferably 150 μg / dm ² or more. If the adhesion amount of Ni is less than 100 μg / dm ² , the heat resistance may be deteriorated.
Order to further reduce the transmission loss, it is preferred that it is preferable that deposition amount of Co is less than 2000 [mu] g / dm ^2, at 1800 [mu] g / dm ² or less in the case of roughening treated surface S comprises Co, 1600μg / dm preferably ² or less, more preferably 1400μg / dm ² or less.
When the surface on the insulating resin substrate side of the copper foil of the copper-clad laminate contains Co, the adhesion amount of Co is preferably 300 μg / dm ² or more, and preferably 350 μg / dm ² or more And more preferably 400 μg / dm ² or more. If the adhesion amount of Co is less than 300 μg / dm ² , the heat resistance may deteriorate.
In addition, in order to control the adhesion amount of Ni and Co in the above-mentioned range, Ni, Co concentration in surface treatment (plating) liquid of roughening treatment plating of a copper foil used for a copper clad laminate, heat resistant layer, etc. It is effective to control the current density during surface treatment, and to control the surface treatment time. By increasing the concentration of Ni and Co in the surface treatment (plating) solution, the amount of Ni and Co adhesion can be increased. In addition, if the concentrations of Ni and Co are lowered, the amounts of Ni and Co deposited can be reduced. In addition, if the current density at the time of surface treatment is increased and / or the surface treatment time is lengthened, the amount of Ni and Co adhesion can be increased. In addition, if the current density at the time of surface treatment is lowered and / or the surface treatment time is shortened, the amount of Ni and Co adhesion can be reduced.

Particle surface area
The ratio A / B of the surface area A of the roughening particles to the area B obtained when the roughening particles are viewed in plan from the roughening treated surface S greatly affects the transparency of the above-mentioned resin. That is, when the surface roughness Rz is the same, the transparency of the above-mentioned resin becomes better as the ratio A / B is smaller. Therefore, in the surface-treated copper foil of the present invention, the ratio A / B is preferably 1.90 to 2.40, and more preferably 2.00 to 2.20.

  By controlling the current density at the time of particle formation and the plating time, the morphology and formation density of the particles are determined, and the surface roughness Rz, the degree of gloss and the area ratio A / B of the particles can be controlled.

  As described above, in the surface-treated copper foil of the present invention, the ratio A / B of the surface area A of the roughening particles to the area B obtained when the roughening particles are viewed in plan from the roughening treated surface S is 1 It is controlled to .90 to 2.40, and surface irregularities are present to some extent. Moreover, since the ten-point average roughness Rz of TD on the roughened surface is controlled to 0.20 to 0.80 μm, there is no extremely rough portion on the surface. On the other hand, the glossiness of the roughened surface is as high as 76 to 350%. When these are considered, it turns out that the surface-treated copper foil of this invention is controlled so that the particle size of the roughening particle | grains in the roughening process surface is small. Although the particle size of the roughening particles affects the resin transparency after the copper foil is etched away, the surface-treated copper foil of the present invention has the surface ten points on the side adhering to the resin substrate in this manner. Controlling the average roughness Rz, the glossiness, and the ratio of the surface area of the roughened particles to the area obtained when the roughened particles are viewed in plan from the roughened surface S side is within the scope of the present invention. This means that the particle diameter of the conversion particles is reduced within an appropriate range, and therefore, the resin transparency after etching removal of the copper foil is good, and the peel strength is also good. Since the grain size of the roughening particles is small within an appropriate range, surface irregularities are present to a certain extent, but not so large, so that the length of the surface-treated copper foil corresponding to the length of electrons flow becomes short and transmission loss Becomes smaller.

[Etching factor]
When the value of the etching factor at the time of forming a circuit using copper foil is large, since the bottom of the bottom of the circuit generated at the time of etching becomes small, the space between circuits can be narrowed. Therefore, a larger etching factor is preferable because it is suitable for forming a circuit with a fine pattern. In the surface-treated copper foil of the present invention, for example, the etching factor value is preferably 1.8 or more, preferably 2.0 or more, and preferably 2.2 or more, 2.3 or more. Is preferably, and more preferably 2.4 or more.
In the printed wiring board or copper-clad laminate, the above-mentioned surface roughness (Rz), particle area ratio (A / B), glossiness of the copper circuit or copper foil surface are obtained by dissolving and removing the resin. The degree can be measured.

[Transmission loss]
When the transmission loss is small, signal attenuation at the time of signal transmission at high frequency is suppressed, so that stable signal transmission can be performed in a circuit that performs signal transmission at high frequency. Therefore, it is preferable that the value of the transmission loss is small because it is suitable for use in a circuit application that performs signal transmission at high frequency. After bonding a surface-treated copper foil to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm, manufactured by Kuraray Co., Ltd.), a microstrip line is formed by etching so that the characteristic impedance is 50 Ω, and a network made by HP When the transmission coefficient is measured using the analyzer HP8720C and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is obtained, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm, more preferably less than 4.1 dB / 10 cm Preferably, less than 4.0 dB / 10 cm is more preferred, and less than 3.7 dB / 10 cm is even more preferred.

[Heat-resistant]
When the heat resistance is high, the adhesion between the surface-treated copper foil and the resin is less likely to deteriorate even in a high temperature environment, and therefore it is preferable because it can be used in a high temperature environment.
In the present invention, the heat resistance is evaluated by the peel strength retention rate. After laminating the surface-treated side of the surface-treated copper foil to a polyimide film with a thermosetting adhesive for lamination (thickness: 50 μm, Upirex made by Ube Industries, Ltd.) and after heating at 150 ° C for 168 hours, IPC-TM In accordance with -650, normal peel strength and peel strength after heating at 150 ° C for 168 hours were measured by a tensile tester Autograph 100.
And the peeling strength retention represented by following Formula was computed.
Peel strength retention (%) = 150 ° C after heating for 168 hours Peel strength (kg / cm) / Normal peel strength (kg / cm) × 100
And, the peel strength retention rate is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more.

[Copper foil with carrier]
A copper foil with a carrier, which is another embodiment of the present invention, comprises a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. And the said ultra-thin copper layer is the surface-treated copper foil which is one embodiment of the above-mentioned this invention. In addition, the copper foil with carrier may be provided with a carrier, an intermediate layer and a very thin copper layer in this order. The copper foil with carrier may have a surface treatment layer such as a roughening treatment layer on either or both of the surface on the carrier side and the surface on the very thin copper layer side. In addition, the copper foil with carrier may have a surface-treated surface such as a roughened surface S or the like on the carrier-side surface of the ultrathin copper layer and / or the surface opposite to the carrier side. In order to improve working efficiency, it is preferable that the copper foil with carrier has a surface-treated surface such as a roughened surface S on the surface of the ultrathin copper layer opposite to the carrier side.
When a roughening treatment layer is provided on the surface of the carrier side of the copper foil with carrier, when laminating the copper foil with carrier from the surface side of the carrier to a support such as a resin substrate, the support such as a carrier and a resin substrate It has the advantage that it becomes difficult to peel off.

<Carrier>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum It is provided in the form of an alloy foil, an insulating resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluorine resin film, etc.).
It is preferable to use a copper foil as a carrier that can be used in the present invention. Since the copper foil has high electrical conductivity, the subsequent formation of the intermediate layer and the extremely thin copper layer is facilitated. The carrier is typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, an electrolytic copper foil is manufactured by electrolytically depositing copper on a drum of titanium or stainless steel from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating plastic working and heat treatment by rolling rolls. As a material of the copper foil, besides copper of high purity such as tough pitch copper and oxygen free copper, copper containing Sn, copper containing Ag, copper alloy to which Cr, Zr, Mg or the like is added, Corson type to which Ni, Si or the like is added Copper alloys such as copper alloys can also be used.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be suitably adjusted to a thickness suitable for serving as a carrier, for example, 12 μm or more. However, if it is too thick, the production cost will increase, so in general, the thickness is preferably 35 μm or less. Thus, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

  Further, as described above, the carrier used in the present invention needs to control the surface roughness Rz on the side where the intermediate layer is formed and the glossiness. This is to control the Sv of the ultrathin copper layer after surface treatment.

<Middle class>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is difficult to peel from the carrier prior to the lamination step on the insulating substrate with the copper foil with carrier, while the ultrathin copper layer from the carrier is after the lamination step on the insulating substrate The configuration is not particularly limited as long as the configuration is such that it can be peeled off. For example, the intermediate layer of the copper foil with a carrier according to the present invention may be made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, their alloys, their hydrates, their oxides, One or more selected from the group consisting of organic substances may be included. Also, the intermediate layer may be a plurality of layers.
Also, for example, the intermediate layer is a single metal layer consisting of a kind of element selected from the group of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side Or form an alloy layer composed of one or more elements selected from the group of elements composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer comprising a hydrate or oxide of one or more elements selected from the group of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Can be configured.
In the intermediate layer, a known organic substance can be used as the organic substance, and it is preferable to use any one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid. For example, as specific nitrogen-containing organic compounds, 1,2,3-benzotriazole which is a triazole compound having a substituent, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole or the like.
As the sulfur-containing organic compound, mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol and the like are preferably used.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and among them, it is preferable to use oleic acid, linoleic acid, linolenic acid and the like.
Also, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on the carrier. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, when peeling off the very thin copper layer, it peels off at the interface between the very thin copper layer and the chromium. In addition, a barrier effect is expected in the nickel of the intermediate layer to prevent the diffusion of the copper component from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the adhesion amount of chromium in the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide an anticorrosive layer such as a Ni plating layer on the opposite side of the carrier.
If the thickness of the intermediate layer is too large, the thickness of the intermediate layer may affect the gloss of the roughened surface of the ultrathin copper layer after surface treatment and the size and number of roughened particles, so The thickness of the intermediate layer on the roughened surface of the thin copper layer is preferably 1 to 1000 nm, preferably 1 to 500 nm, preferably 2 to 200 nm, and more preferably 2 to 100 nm, More preferably, it is 3 to 60 nm. Intermediate layers may be provided on both sides of the carrier.

<Ultra-thin copper layer>
An ultra-thin copper layer is provided on the middle layer. Other layers may be provided between the intermediate layer and the very thin copper layer. Also, ultra-thin copper layers may be provided on both sides of the carrier. The ultrathin copper layer having the carrier is a surface-treated copper foil according to an embodiment of the present invention. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, and more typically 1.5 to 5 μm. Also, prior to providing the ultrathin copper layer on the intermediate layer, strike plating with a copper-phosphorus alloy may be performed to reduce pinholes in the ultrathin copper layer. The strike plating includes copper pyrophosphate plating solution and the like.
The roughened surface S may be provided on either or both of the surface of the ultrathin copper layer opposite to the surface on the carrier side and / or the surface of the ultrathin copper layer on the carrier side. In addition, it is preferable to provide the roughened surface S on the surface opposite to the surface on the carrier side of the ultrathin copper layer.
In addition, the ultrathin copper layer of the present invention is formed under the following conditions. By forming a smooth ultrathin copper layer, the size and the number of particles of the roughening treatment, and the glossiness after the roughening treatment are controlled.
-Electrolyte composition copper: 80 to 120 g / L
Sulfuric acid: 80 to 120 g / L
Chlorine: 30 to 100 ppm
Leveling agent 1 (bis (3 sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
The amine compound of the following chemical formula can be used for the above-mentioned amine compound.

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

-Manufacturing conditions Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50 to 65 ° C
Electrolyte linear velocity: 1.5 to 5 m / sec
Electrolysis time: 0.5 to 10 minutes (Copper thickness to be deposited, adjusted by current density)

[Resin layer on roughened surface S]
A resin layer may be provided on the roughened surface S of the surface-treated copper foil of the present invention. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive or may be an insulating resin layer in a semi-cured state (B-stage state) for bonding. In the semi-cured state (B-stage state), there is no sticky feeling even when the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when heat treatment is further performed. Including.

  The resin layer may be an adhesive resin, that is, an adhesive, or may be an insulating resin layer in an adhesive semi-cured state (B-stage state). In the semi-cured state (B-stage state), there is no sticky feeling even when the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when heat treatment is further performed. Including.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton and the like. In addition, the resin layer may be formed of, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent No. 3184485, WO Nos. WO 97/02728, Patent No. 3676375, JP-A 2000-43188, Patent No. 3612594, JP-A 2002-179772, JP-A 2002-359444, JP-A 2003-304068, JP 3992225, JP-A 2003 No. 249739, Patent No. 4136509, Japanese Patent No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent No. 20 Patent No. 5-53218, Patent No. 3949676, Patent No. 4178415, International Publication No. WO 2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Publication No. 2007-326923, Japanese Patent Publication No. 2008-111169, Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, JP2009-67029, International Publication No. WO2006 / 134868, Patent No. 5046927, JP2009-173017, International Publication No. WO2007 / 105635, Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Application Publication No. 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, JP-A-2013-19056 (a resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeletal material, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyether sulfone (also referred to as polyether sulfone or polyether sulfone), polyether sulfone (also referred to as polyether sulfone or polyether sulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamide imide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, anhydride of carboxylic acid, anhydride of polyvalent carboxylic acid, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2, 2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane modified polyamideimide resin, cyano ester resin, phosphazene resin, Select from the group of rubber modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, high molecular weight epoxy, aromatic polyamide, fluorocarbon resin, bisphenol, block copolymer polyimide resin and cyano ester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin may be used without particular problems as long as it has two or more epoxy groups in the molecule and can be used for electrical and electronic materials. The epoxy resin is preferably an epoxy resin which is epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, ortho cresol novolac epoxy resin, rubber modified bisphenol A epoxy resin, glycidyl amine epoxy resin, triglycidyl isocyanurate, N, N Glycidyl amine compounds such as -diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl It may be used by mixing one or two or more selected from the group consisting of phenyl novolac epoxy resin, trishydroxyphenylmethane epoxy resin, tetraphenylethane epoxy resin, or a hydrogenated product of the above epoxy resin or Halogenated products can be used.
A phosphorus-containing epoxy resin known as the phosphorus-containing epoxy resin can be used. Also, the phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

  The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After naphthoquinone and hydroquinone were reacted to form a compound represented by the following chemical formula 4 (HCA-NQ) or chemical formula 5 (HCA-HQ), the OH group portion was reacted with an epoxy resin to obtain a phosphorus-containing epoxy resin It is a thing.

  The phosphorus-containing epoxy resin which is the component E obtained using the above-mentioned compound as a raw material is used by mixing one or two kinds of compounds having the structural formula shown in any one of chemical formulas 6 to 8 shown below. Is preferred. It is because it is excellent in the stability of the resin quality in a semi-hardened state, and at the same time the flame retardancy effect is high.

Further, as the brominated (brominated) epoxy resin, a known brominated (brominated) epoxy resin can be used. For example, the brominated (brominated) epoxy resin is a brominated epoxy resin having a structural formula shown in Chemical formula 9 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, It is preferable to use 1 type or 2 types of brominated epoxy resin provided with Structural formula shown to, mixing.

As the maleimide resin or the aromatic maleimide resin or the maleimide compound or the polymaleimide compound, a known maleimide resin or an aromatic maleimide resin or a maleimide compound or a polymaleimide compound can be used. For example, as a maleimide resin or an aromatic maleimide resin or a maleimide compound or a polymaleimide compound, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,4 It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, and polymers obtained by polymerizing the above-mentioned compound and the above-mentioned compound or other compounds. The maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or an aromatic polyamine It may be a polymerized adduct obtained by polymerizing
As the polyamine or the aromatic polyamine, known polyamines or aromatic polyamines can be used. For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane as a polyamine or an aromatic polyamine, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone 4,4'-Diaminodiphenyl sulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4 ' -Diaminodiphenylmethane, 3,3'-diethyl-4 4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis (3- Methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3 -Dimethyl-4-aminophenyl) phenylethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the above compound and the above compound or other compounds were polymerized A polymer etc. can be used. In addition, one or more known polyamines and / or aromatic polyamines or the above-mentioned polyamines or aromatic polyamines can be used.
A well-known phenoxy resin can be used as said phenoxy resin. Moreover, as said phenoxy resin, what is synthesize | combined by reaction of a bisphenol and a bivalent epoxy resin can be used. As an epoxy resin, a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
As the bisphenol, known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- A bisphenol etc. obtained as an adduct of 10-Phosphaphenanthrene-10-Oxide) and quinones, such as hydroquinone and naphthoquinone, can be used.
As the linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group such as a hydroxyl group or a carboxyl group that contributes to the curing reaction of the epoxy resin. The linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C. to 200 ° C. Specific examples of the linear polymer having a functional group as referred to herein include polyvinyl acetal resin, phenoxy resin, polyether sulfone resin, polyamide imide resin and the like.
The resin layer may contain a crosslinking agent. A well-known crosslinking agent can be used for a crosslinking agent. For example, a urethane resin can be used as the crosslinking agent.
The rubber resin can be a known rubber resin. For example, the rubber resin is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( (Acrylic acid ester copolymer), polybutadiene rubber, isoprene rubber and the like. Furthermore, in order to secure the heat resistance of the resin layer to be formed, it is also useful to select and use heat-resistant synthetic rubber such as nitrile rubber, chloroprene rubber, silicone rubber, urethane rubber and the like. With regard to these rubbery resins, in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin, it is desirable to have various functional groups at both ends. In particular, it is useful to use CTBN (carboxy-terminated butadiene nitrile). Moreover, among the acrylonitrile butadiene rubbers, when it is a carboxyl-modified product, it is possible to take a crosslinked structure with an epoxy resin and improve the flexibility of the resin layer after curing. As the carboxyl modified product, carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), and carboxy-modified nitrile butadiene rubber (C-NBR) can be used.
A well-known polyimide amide resin can be used as said polyamide imide resin. Moreover, as the polyimide amide resin, for example, trimellitic acid anhydride, benzophenone tetracarboxylic acid anhydride and bitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. Resin, trimellitic acid anhydride, diphenylmethane diisocyanate and carboxyl group-terminated acrylonitrile-butadiene rubber by heating in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide What is obtained can be used.
A known rubber-modified polyamideimide resin can be used as the rubber-modified polyamideimide resin. The rubber modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubbery resin. The reaction of the polyamideimide resin and the rubber resin is carried out for the purpose of improving the flexibility of the polyamideimide resin itself. That is, a polyamideimide resin and a rubbery resin are reacted to substitute a part of an acid component (such as cyclohexanedicarboxylic acid) of the polyamideimide resin with a rubber component. A well-known polyamide imide resin can be used for a polyamide imide resin. In addition, as the rubbery resin, a known rubbery resin or the above-mentioned rubbery resin can be used. Examples of solvents used to dissolve the polyamideimide resin and the rubber resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane and tetrahydrofuran. It is preferable to use cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone or the like singly or in combination of two or more.
A known phosphazene resin can be used as the phosphazene resin. The phosphazene resin is a resin containing phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve the flame retardant performance by the synergetic effect of nitrogen and phosphorus in the molecule. Also, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it stably exists in the resin, and the effect of preventing the occurrence of migration can be obtained.
A well-known fluorine resin can be used as said fluorine resin. Moreover, as a fluorine resin, for example, PTFE (polytetrafluoroethylene (tetrafluorinated), PFA (tetrafluoroethylene-perfluoroalkylvinylether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (4.6) Fluorinated), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluorinated)), PCTFE (polychlorotrifluoroethylene (trifluorinated)), polyallyl sulfone, aromatic You may use the fluorine resin etc. which consist of any at least 1 sort (s) of thermoplastic resin and fluorine resin which are chosen from polysulfide and aromatic polyether.
Further, the resin layer may contain a resin curing agent. A well-known resin curing agent can be used as a resin curing agent. For example, as resin curing agents, amines such as dicyandiamide, imidazoles, aromatic amines, phenols such as bisphenol A, brominated bisphenol A, novolaks such as phenol novolac resin and cresol novolac resin, acid anhydride such as phthalic anhydride , A biphenyl type phenol resin, a phenol aralkyl type phenol resin and the like can be used. Moreover, the said resin layer may also contain 1 type, or 2 or more types of the above-mentioned resin hardening agent. These hardeners are particularly effective for epoxy resins.
The specific example of the said biphenyl type phenol resin is shown to Chemical formula 11.

  Further, a specific example of the above-mentioned phenol aralkyl type phenol resin is shown in Chemical formula 12.

As the imidazoles, known ones can be used. For example, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-yl Hydroxymethyl imidazole etc. are mentioned, These can be used individually or in mixture.
Further, among them, it is preferable to use an imidazole having a structural formula shown in the following chemical formula 13. By using the imidazoles of the structural formula shown in Formula 13, the moisture absorption resistance of the resin layer in the semi-cured state can be remarkably improved, and the long-term storage stability is excellent. The imidazoles function as a catalyst for curing the epoxy resin, and contribute as an initiator that causes the self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

Well-known amines can be used as a resin hardening agent of the said amines. Further, as the resin curing agent of the above-mentioned amines, for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides and these are obtained by polymerizing or condensing these with epoxy resin or polyvalent carboxylic acid. One or more selected from the group of amine adducts may be used. Moreover, as a resin curing agent for the above-mentioned amines, 4,4'-diaminodiphenylene sulfone, 3,3'-diaminodiphenylene sulfone, 4,4-diaminodiphenylel, 2,2-bis [4 It is preferable to use any one or more of-(4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone.
The resin layer may contain a curing accelerator. A well-known hardening accelerator can be used as a hardening accelerator. For example, as a curing accelerator, tertiary amines, imidazoles, urea-based curing accelerators and the like can be used.
The resin layer may contain a reaction catalyst. A well-known reaction catalyst can be used as a reaction catalyst. For example, finely ground silica, antimony trioxide or the like can be used as a reaction catalyst.

  The polyvalent carboxylic acid anhydride is preferably a component that contributes as a curing agent for the epoxy resin. Further, the anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine It is preferable that it is an acid, methyl nadic acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than the epoxy resin and polymerizable alcoholic hydroxyl group.
The polyvinyl acetal resin may have a functional group capable of polymerizing with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group. The polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into its molecule.
As said aromatic polyamide resin polymer, what is obtained by making an aromatic polyamide resin and rubbery resin react is mentioned. Here, the aromatic polyamide resin is one synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, m-xylenediamine, 3,3'-oxydianiline or the like is used. And, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and the like are used.
A known rubbery resin or the above-mentioned rubbery resin can be used as the rubbery resin to be reacted with the aromatic polyamide resin.
This aromatic polyamide resin polymer is used for the purpose of not being damaged by an etching solution by an etching solution when the copper foil after being processed into a copper-clad laminate is etched.

  The resin layer is a cured resin layer ("cured resin layer" means a cured resin layer) in order from the copper foil side (that is, the very thin copper layer side of the copper foil with carrier). It may be a resin layer in which a cured resin layer is sequentially formed. The said cured resin layer may be comprised by the resin component in any one of the polyimide resin whose thermal expansion coefficient is 0 ppm / degrees C-25 ppm / degrees C, polyamidoimide resin, and these composite resin.

  In addition, a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C. to 50 ppm / ° C. after curing may be provided on the cured resin layer. In addition, the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less. The cured resin layer may have a glass transition temperature of 300 ° C. or higher. The semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. The epoxy resin can be a known epoxy resin or the epoxy resin described in the present specification. In addition, maleimide resin, aromatic maleimide resin, known maleimide resin as a linear polymer having a crosslinkable functional group, aromatic maleimide resin, linear polymer having a crosslinkable functional group, or the maleimide resin described above Aromatic maleimide resins, linear polymers having crosslinkable functional groups can be used.

Moreover, when providing the copper foil with a carrier which has a resin layer suitable for a three-dimensional molded printed wiring board manufacture use, it is preferable that the said cured resin layer is a polymeric polymer layer which has hardened | cured flexibility. The polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so as to withstand the solder mounting process. The polymer layer is preferably made of one or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin and a polyamide imide resin. Moreover, it is preferable that the thickness of the said high molecular polymer layer is 3 micrometers-10 micrometers.
The polymer layer preferably contains one or more of an epoxy resin, a maleimide resin, a phenol resin, and a urethane resin. Moreover, it is preferable that the said semi-hardened resin layer is comprised with a 10 micrometers-50 micrometers-thick epoxy resin composition.

Moreover, it is preferable that the said epoxy resin composition is what contains each component of the following A component-E component.
Component A: An epoxy resin consisting of one or more selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin which has an epoxy equivalent of 200 or less and is liquid at room temperature.
Component B: High heat resistant epoxy resin.
Component C: A phosphorus-containing flame retardant resin which is a resin obtained by mixing any one or a mixture of a phosphorus-containing epoxy resin and a phosphazene resin.
Component D: A rubber-modified polyamideimide resin modified with a liquid rubber component having a solubility in a solvent having a boiling point in the range of 50 ° C to 200 ° C.
E component: resin curing agent.

The component B is a "high heat resistant epoxy resin" having a high so-called glass transition point Tg. The “high heat resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as novolac epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin and the like.
The phosphorus-containing epoxy resin described above can be used as the C-component phosphorus-containing epoxy resin. Moreover, the above-mentioned phosphazene resin can be used as phosphazene resin of C component.
The rubber-modified polyamideimide resin described above can be used as the rubber-modified polyamideimide resin of the component D. The above-mentioned resin curing agent can be used as a resin curing agent of E component.

  A solvent is added to the resin composition shown above and it uses as a resin varnish, and forms a thermosetting resin layer as an adhesive layer of a printed wiring board. The said resin varnish adds a solvent to the above-mentioned resin composition, prepares resin solid content in the range of 30 wt%-70 wt%, and the resin flow when it measures based on MIL-P-13949G in MIL specification It is possible to form a semi-cured resin film in the range of 5% to 35%. As the solvent, known solvents or the above-mentioned solvents can be used.

  The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer positioned on the surface of the first thermosetting resin layer in order from the copper foil side, The curable resin layer is formed of a resin component which does not dissolve in chemicals during desmearing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmearing in the wiring board manufacturing process. It may be formed using a resin that can be removed by washing. The first thermosetting resin layer may be formed using a resin component in which one or two or more of a polyimide resin, a polyether sulfone, and a polyphenylene oxide are mixed. The second thermosetting resin layer may be formed using an epoxy resin component. For the thickness t1 (μm) of the first thermosetting resin layer, the roughened surface roughness of the copper foil with carrier is Rz (μm), and the thickness of the second thermosetting resin layer is t2 (μm) Preferably, t1 is a thickness satisfying the condition of Rz <t1 <t2.

  The resin layer may be a prepreg in which a skeleton material is impregnated with a resin. It is preferable that the resin impregnated in the frame material is a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for producing a printed wiring board.

The framework may comprise aramid fibers or glass fibers or wholly aromatic polyester fibers. The framework is preferably a non-woven fabric or a woven fabric of aramid fibers or glass fibers or wholly aromatic polyester fibers. The wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer is 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid. It has an acid polymer as a main component. Since this wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, it has excellent performance as a constituent material of the electrical insulation layer and can be used like glass fiber and aramid fiber. is there.
In addition, in order to improve the wettability with the resin of the surface, it is preferable to perform the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric. At this time, known silane coupling agents such as amino type and epoxy type or the above-mentioned silane coupling agents can be used as the silane coupling agent depending on the purpose of use.

  The prepreg is a non-woven fabric using aramid fibers or glass fibers having a nominal thickness of 70 μm or less, or a prepreg in which a thermosetting resin is impregnated into a skeleton made of glass cloth having a nominal thickness of 30 μm or less. It is also good.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may contain a dielectric (dielectric filler).
When a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for forming a capacitor layer to increase the electric capacity of the capacitor circuit. As the dielectric (dielectric filler), BaTiO ₃ , SrTiO ₃ , Pb (Zr-Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), etc. The dielectric powder of complex oxide having a pebroskite structure is used.

The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in the form of powder, the powder characteristics of the dielectric (dielectric filler) first have a particle diameter of 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It must be in range. Since the particle diameter said here forms a certain secondary aggregation state which powder particles have a certain fixed, it is indirect such that an average particle diameter is estimated from measurement values, such as a laser diffraction scattering type particle size distribution measuring method and BET method. It can not be used because the accuracy becomes poor in measurement, and dielectrics (dielectric fillers) are directly observed with a scanning electron microscope (SEM), and mean particle diameter obtained by image analysis of the SEM image It is. In the present specification, the particle size at this time is indicated as DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed using the scanning electron microscope (SEM) in the present specification is circularity using IP-1000PC manufactured by Asahi Engineering Co., Ltd. The circular particle analysis is performed with a threshold value of 10 and an overlap degree of 20, and the average particle diameter DIA is determined.
According to the above-described embodiment, the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric is improved, and the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent The carrier-attached copper foil can be provided.

The resin and / or resin composition and / or compound contained in the aforementioned resin layer may be, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether The resin solution (resin varnish) is dissolved in a solvent such as dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc. The surface-treated copper foil is coated, for example, by a roll coater method on the roughened surface S, and then dried by heating if necessary to remove the solvent to obtain a B-stage state. For drying, for example, a hot air drying furnace may be used, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt% It may be a resin liquid. In addition, it is most preferable at the present stage from the environmental point of view to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 degreeC-200 degreeC for a solvent.
Moreover, it is preferable that the said resin layer is a semi-hardened resin film which has a resin flow in the range of 5%-35% when it measures based on MIL-P-13949G in MIL specification.
In the present specification, resin flow refers to four 10 cm square samples from a resin-coated surface-treated copper foil having a resin thickness of 55 μm in accordance with MIL-P-13949G in the MIL standard. A value calculated based on equation 1 based on the result of measuring resin outflow weight at the time of laminating the samples (laminate) in a press temperature of 171 ° C, a press pressure of 14 kgf / cm ² and a press time of 10 minutes. It is.

  The surface-treated copper foil provided with the resin layer (surface-treated copper foil with resin) is made by laminating the resin layer on a substrate and then thermocompression bonding the whole to thermally cure the resin layer, and then the surface-treated copper foil When the carrier is an ultrathin copper layer of copper foil with carrier, the carrier is peeled off to expose the ultrathin copper layer (naturally, it is the surface on the middle layer side of the ultrathin copper layer) It is used in the aspect of forming a predetermined | prescribed wiring pattern from the surface on the opposite side to the side by which the roughening process of the surface treatment copper foil is carried out.

  By using this surface-treated copper foil with resin, it is possible to reduce the number of used prepreg materials at the time of manufacturing a multilayer printed wiring board. In addition, the thickness of the resin layer can be made such that interlayer insulation can be secured, or a copper-clad laminate can be manufactured without using any prepreg material. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the surface smoothness.

In the case where a prepreg material is not used, the material cost of the prepreg material is saved, and the lamination process is simplified, which is economically advantageous. Furthermore, the multilayer printed wiring board manufactured by the thickness of the prepreg material The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of this resin layer is preferably 0.1 to 120 μm.

When the thickness of the resin layer is smaller than 0.1 μm, the adhesive force is reduced, and when the resin-coated surface-treated copper foil is laminated on a substrate provided with an inner layer material without interposing a prepreg material, the circuit of the inner layer material It may be difficult to secure interlayer insulation between them. On the other hand, if the thickness of the resin layer is greater than 120 μm, it may be difficult to form the resin layer of the desired thickness in one application step, which may be economically disadvantageous because extra material costs and man-hours are required.
In addition, when the surface-treated copper foil which has a resin layer is used for manufacturing an ultra-thin multilayer printed wiring board, the thickness of the said resin layer is 0.1 micrometer-5 micrometers, More preferably, 0.5 micrometer-5 micrometers, More preferably, the thickness is 1 μm to 5 μm to reduce the thickness of the multilayer printed wiring board.
When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, more preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, and 10 μm to 60 μm. Is more preferable. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 μm to 55 μm, preferably 7 μm to 55 μm, and more preferably 15 to 115 μm. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board, and if it is less than 5 μm, it becomes easy to form a thin multilayer printed wiring board, but the insulating layer between the inner layer circuits This is because the resin layer may be too thin, which may make the insulation between the circuits in the inner layer unstable. In addition, when the thickness of the cured resin layer is less than 2 μm, it may be necessary to consider the surface roughness of the roughened surface S of the surface-treated copper foil. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes large.

When the thickness of the resin layer is 0.1 μm to 5 μm, the heat-resistant layer and / or the roughened surface S of the surface-treated copper foil is used to improve the adhesion between the resin layer and the surface-treated copper foil. Alternatively, after providing an anticorrosive layer and / or a weather resistant layer, it is preferable to form a resin layer on the heat resistant layer or the anticorrosive layer or the weather resistant layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in ten arbitrary points.

  Furthermore, as another product form in the case where this resin-coated surface-treated copper foil is an ultra-thin copper layer of a carrier-attached copper foil, the above-mentioned ultra-thin copper layer (surface-treated copper foil) is roughened on the surface S After the resin layer is provided and the resin layer is in a semi-cured state, it is also possible to peel off the carrier and manufacture it in the form of a resin-attached ultrathin copper layer (surface-treated copper foil) without a carrier.

  Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, with the carrier After laminating the copper foil and the insulating substrate so that the very thin copper layer side faces the insulating substrate, the carrier of the copper foil with carrier is removed to form a copper-clad laminate, and then the semi-additive method, modified semi Forming a circuit by any of an additive method, a partory additive method and a subtractive method. The insulating substrate may be one including an inner layer circuit.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing the carrier and removing the exposed very thin copper layer by etching using a corrosive solution such as acid or plasma, etc .;
Providing a through hole or / and a blind via in the resin exposed by removing the very thin copper layer by etching;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist and then removing the plating resist in a region where a circuit is to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing the carrier and removing the exposed very thin copper layer by etching using a corrosive solution such as acid or plasma, etc .;
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist and then removing the plating resist in a region where a circuit is to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, in the modified semi-additive method, a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, copper plating of the circuit forming portion is performed by electrolytic plating, and then the resist is removed. And a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit formation portion by (flash) etching.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling off the carrier;
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultrathin copper layer exposed by removing the plating resist by flash etching;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist and then removing the plating resist in a region where a circuit is to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, in the partly additive method, a catalyst core is provided on a substrate provided with a conductor layer, and a substrate provided with holes for through holes and via holes as necessary, and a conductor circuit is formed by etching. And a method of manufacturing a printed wiring board by providing a solder resist or a plating resist as necessary, and thickening the through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the partory additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Applying catalytic nuclei to the area including the through holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling off the carrier;
Exposing the etching resist to form a circuit pattern;
Forming a circuit by removing the ultra-thin copper layer and the catalyst core by a method such as etching using a corrosive solution such as acid or plasma,
Removing the etching resist;
Providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching using a corrosive solution such as acid or plasma;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided;
including.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Providing an electrolytic plating layer on the surface of the electroless plating layer;
Providing an etching resist on the surface of the electrolytic plating layer or / and the very thin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer, the electroless plating layer and the electrolytic plating layer by a method such as etching using a corrosive solution such as acid or plasma to form a circuit;
Removing the etching resist;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Forming a mask on the surface of the electroless plating layer;
Providing an electrolytic plating layer on the surface of the electroless plating layer where the mask is not formed;
Providing an etching resist on the surface of the electrolytic plating layer or / and the very thin copper layer;
Exposing the etching resist to form a circuit pattern;
Forming a circuit by removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as acid;
Removing the etching resist;
including.

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

Here, a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. In addition, although the copper foil with a carrier which has the ultrathin copper layer in which the roughening process layer was formed is demonstrated to an example here, it is not restricted to this, The carrier which has the ultrathin copper layer in which the roughening process layer is not formed Even when using the attached copper foil, the following method for producing a printed wiring board can be carried out similarly.
First, as shown to FIG. 5-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer by which the roughening process layer was formed in the surface is prepared.
Next, as shown in FIG. 5B, a resist is applied on the roughened layer of the extremely thin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 5C, plating for a circuit is formed, and then the resist is removed to form a circuit plating of a predetermined shape.
Next, as shown in FIG. 6-D, the embedded resin is provided on the ultrathin copper layer to cover the circuit plating (so that the circuit plating is buried), and the resin layer is laminated, and then another carrier is attached. Bond the copper foil (second layer) from the very thin copper layer side.
Next, as shown in FIG. 6E, the carrier is peeled off from the second layer of copper foil with carrier.
Next, as shown in FIG. 6F, laser drilling is performed at a predetermined position of the resin layer to expose circuit plating and form a blind via.
Next, as shown in FIG. 7G, copper is buried in the blind vias to form a via fill.
Next, as shown in FIG. 7-H, circuit plating is formed on the via fill as shown in FIGS. 5-B and 5-C.
Next, as shown in FIG. 7I, the carrier is peeled off from the first layer of copper foil with carrier.
Next, as shown in FIG. 8J, the ultrathin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 8K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with carrier of the present invention is produced.

  The other copper foil with carrier (second layer) may use the copper foil with carrier of the present invention, may use a conventional copper foil with carrier, and may further use a normal copper foil. Further, one or more layers of circuits may be further formed on the circuit of the second layer shown in FIG. 7-H, and these circuits may be formed by semi-additive method, subtractive method, party additive method or modified semi-conductor. It may be carried out by any of the additive methods.

It is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the ultra-thin copper layer surface may satisfy following (1). In the present invention, the "color difference on the surface of the very thin copper layer" refers to the color difference on the surface of the very thin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, it is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the roughening process surface of an ultra-thin copper layer may satisfy following (1). In the surface-treated copper foil of the present invention, the "roughened surface" refers to the surface when the heat-resistant layer, the rustproof layer, the weather resistant layer, etc. are provided after the roughening treatment. It refers to the surface of the surface-treated copper foil after the treatment. When the surface-treated copper foil is an ultrathin copper layer of copper foil with a carrier, the "roughened surface" means that a heat-resistant layer, an antirust layer, a weather resistant layer, etc. are provided after the roughening treatment. When the surface treatment for the purpose is performed, it means the surface of the very thin copper layer after the surface treatment is performed.
(1) The difference in formula of the surface of the ultrathin copper layer is 45 or more in color difference ΔE * ab based on JIS Z8730.

  Here, the color differences ΔL, Δa, Δb are each measured with a color difference meter, are added black / white / red / green / yellow / blue, and are shown using the L * a * b color system based on JIS Z8730. It is a comprehensive index and is expressed as ΔL: black and white, Δa: red-green, Δb: yellow-blue. Further, ΔE * ab is expressed by the following equation using these color differences.

The above color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow velocity of the plating solution.
The color difference described above can also be adjusted by roughening the surface of the very thin copper layer and providing a roughened layer. In the case of providing the roughened layer, the current density is made higher (for example, 40 to 60 A) by using an electrolytic solution containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / Dm < ² > and it can adjust by shortening processing time (for example, 0.1-1.3 second). When a roughening treatment layer is not provided on the surface of the ultrathin copper layer, a plating bath in which the concentration of Ni is twice or more that of other elements is used to form an ultrathin copper layer or heat resistant layer or a rustproof layer or chromate Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the treated layer or silane coupling treated layer has a lower current density (0.1 to 1. This can be achieved by setting the processing time to be longer (20 seconds to 40 seconds) at 3 A / dm ² ).

  If the color difference ΔE * ab based on JIS Z8730 is 45 or more, for example, when forming a circuit on the surface of an ultrathin copper layer of a copper foil with a carrier, The contrast becomes clear, and as a result, the visibility is improved, and the circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more.

  When the color difference on the surface of the ultrathin copper layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, in the manufacturing process as shown, for example to FIG. 5-C of the above printed wired boards, it becomes possible to form circuit plating in a predetermined | prescribed position accurately. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, the removal of the ultrathin copper layer by flash etching as shown in FIG. In this case, the circuit plating is protected by the resin layer and its shape is maintained, thereby facilitating the formation of the fine circuit. In addition, since the circuit plating is protected by the resin layer, the migration resistance is improved and the conduction of the wiring of the circuit is well suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIG. 8-J and FIG. 8-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a concaved shape from the resin layer, so bumps are formed on the circuit plating. Further, copper pillars can be easily formed thereon, and the manufacturing efficiency is improved.

  In addition, well-known resin and a prepreg can be used for embedding resin (resin). For example, a prepreg which is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. In addition, the resin layer and / or the resin and / or the prepreg described in the present specification can be used as the embedding resin (resin).

  Further, the copper foil with carrier used in the first layer may have a substrate or a resin layer on the surface of the copper foil with carrier. By having the said board | substrate or a resin layer, since the copper foil with a carrier used for a first layer is supported and it becomes difficult to get wrinkled, there exists an advantage that productivity improves. As the substrate or the resin layer, any substrate or resin layer can be used as long as it has the effect of supporting the copper foil with carrier used in the first layer. For example, the carrier described in the specification as the substrate or resin layer, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, Foils of organic compounds can be used.

The surface-treated copper foil of the present invention can be bonded to a resin substrate from the roughened surface S side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board etc. For example, for rigid PWB, paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin , Glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin, glass cloth base epoxy resin, etc., polyester film or polyimide film for FPC, liquid crystal polymer (LCP) film, fluorine Resin, Teflon (registered trademark) film, etc. can be used. In addition, when a liquid crystal polymer (LCP) film, a fluororesin film, or a Teflon (registered trademark) film is used, the peel strength of the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. . Therefore, when a liquid crystal polymer (LCP) film or a fluorine resin film is used, after the copper circuit is formed, the film and the copper circuit are less likely to be peeled off by covering the copper circuit with a coverlay, and the peel strength is reduced. Peeling between the film and the copper circuit can be prevented.
In addition, since a liquid crystal polymer (LCP) film or a fluorine resin film has a small dielectric loss tangent, a copper-clad laminate using a liquid crystal polymer (LCP) film or a fluorine resin film and the surface-treated copper foil according to the present invention Boards and printed circuit boards are suitable for high frequency circuits (circuits that transmit signals at high frequencies). In addition, the surface-treated copper foil according to the present invention has a small surface roughness Rz and a high glossiness, so that the surface is smooth and is suitable for high frequency circuit applications.
In the present invention, a "printed wiring board" includes a printed wiring board on which components are mounted, a printed circuit board and a printed circuit board.

In the case of a rigid PWB, a method of bonding is to impregnate a base material such as a glass cloth with a resin and prepare a prepreg in which the resin is cured to a semi-cured state. It can be carried out by overlapping the copper foil from the roughened surface S onto the prepreg and heating and pressing it. In the case of FPC, lamination adhesion is carried out to copper foil under high temperature and high pressure through a base material such as a polyimide film through an adhesive or without using an adhesive, or a polyimide precursor is applied / dried / cured etc. Can produce a laminate.
The thickness of the polyimide base resin is not particularly limited, but generally 25 μm or 50 μm.

  The laminate of the present invention can be used for various printed wiring boards (PWBs), and is not particularly limited. For example, from the viewpoint of the number of conductor pattern layers, single-sided PWBs, double-sided PWBs, multilayer PWBs (3 The present invention is applicable to rigid PWBs, flexible PWBs (FPCs), and rigid flex PWBs 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. In addition, two or more printed wiring boards of the present invention can be connected to produce a printed wiring board in which two or more printed wiring boards are connected, and at least one printed wiring board of the present invention and another Two printed wiring boards according to the present invention or printed wiring boards not corresponding to the printed wiring board according to the present invention can be connected, and electronic devices can be manufactured using such printed wiring boards.

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 substrate, and the copper circuit is photographed by a CCD camera through the insulating resin substrate. 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 circuit extends in the image obtained by the photographing; Let Bt be the top average value of the lightness curve generated from the part to the part without the copper circuit and Bb be the bottom average value, and the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb In the observation point-brightness graph, among the points of intersection of the lightness curve and Bt, a value indicating the position of the point of intersection closest to the copper circuit is t1, and from the point of intersection of the lightness curve and Bt, 0. 0 based on Bt. In the depth range up to 1ΔB, when the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and 0.1ΔB is t2, Sv defined by equation (1) is 3 .5 or more.
Furthermore, the printed wiring board of the present invention is a printed wiring board comprising an insulating resin substrate, and a surface treated copper foil laminated on the insulating substrate from the surface side on which surface treatment is performed, and on which a copper circuit is formed. And the copper circuit observed for an image obtained by the photographing when the copper circuit is photographed by a CCD camera through the insulating resin substrate laminated from the surface side on which the surface treatment is performed. In the observation point-brightness graph produced by measuring the lightness at each observation point along the direction perpendicular to the direction in which the eaves extend, the top average value of the lightness curve generated from the end of the copper circuit to the portion without the copper circuit Let Bt be the bottom average value Bb, and the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb in the observation point-brightness graph be the lightness curve and the Bt Among the points of intersection with the lightness curve, the value indicating the position of the intersection closest to the copper circuit is t1, and the lightness curve and 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with Bt as a reference When the value indicating the position of the intersection closest to the copper circuit is t2 among the intersections with, the Sv defined by the equation (1) is 3.5 or more.
When such a printed wiring board is used, the printed wiring board can be positioned more accurately. Therefore, when connecting one printed wiring board to another printed wiring board, it is considered that connection failure is reduced and the yield is improved.

The copper-clad laminate of the present invention is a copper-clad laminate having an insulating resin substrate and a copper foil, and after the copper foil of the copper-clad laminate has been etched into a line-shaped copper foil When the image obtained by the photographing is photographed by the CCD camera through the insulating resin substrate, the brightness of each observation point is measured along the direction perpendicular to the extending direction of the observed linear copper foil. In the observation point-lightness graph produced, the top average value of the lightness curve generated from the end of the linear copper foil to the portion without the linear copper foil is Bt, and the bottom average is Bb, and As the difference ΔB between the top average Bt and the bottom average Bb (ΔB = Bt−Bb), in the observation point-brightness graph, of the intersections of the lightness curve and Bt, it is closest to the line-shaped surface-treated copper foil Position of intersection point In the depth range from the point of intersection of the brightness curve and Bt to 0.1 ΔB on the basis of Bt, with the value indicating the position being t1, of the points of intersection of the brightness curve and 0.1 ΔB, the linear surface-treated copper foil When the value indicating the position of the intersection point closest to is denoted by t2, Sv defined by the equation (1) is 3.5 or more.
Furthermore, the copper-clad laminate of the present invention is a copper-clad laminate composed of an insulating resin substrate and a surface-treated copper foil laminated to the insulating substrate from the surface side on which surface treatment is performed, The surface-treated copper foil of the copper-clad laminate was formed into a line-shaped surface-treated copper foil by etching, and then photographed with a CCD camera through the insulating resin substrate laminated from the surface side on which the surface treatment is performed. When the observation point-brightness graph is produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the line-like surface-treated copper foil is observed, with respect to the image obtained by the photographing. The top average value of the brightness curve generated from the end of the line-shaped surface-treated copper foil to the portion without the line-shaped surface-treated copper foil is Bt, the bottom average is Bb, and the top average value Bt and In the observation point-brightness graph, the difference ΔB (ΔB = Bt-Bb) from the average value Bb indicates the position of the intersection closest to the line-shaped surface-treated copper foil among the intersections of the brightness curve and Bt. Assuming that the value is t1, in the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB on the basis of Bt, among the intersections of the lightness curve and 0.1 ΔB, it is closest to the line-shaped surface-treated copper foil When the value indicating the position of the intersection point is t2, Sv defined by equation (1) is 3.5 or more.
When a printed wiring board is manufactured using such a copper-clad laminate, the printed wiring board can be positioned more accurately. Therefore, when connecting one printed wiring board to another printed wiring board, it is considered that connection failure is reduced and the yield is improved.

(Positioning method of laminate)
A method of positioning a laminate of metal and resin according to the present invention (including a laminate of copper and resin and a printed wiring board) 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 the laminate is formed by bonding the metal to the resin. As a specific example of the laminate of metal and resin according to the present invention, at least one surface of resin such as polyimide used to electrically connect the main substrate and the attached circuit substrate, etc. In an electronic device configured with a flexible printed circuit board on which a metal wiring is formed, a laminate manufactured by accurately positioning the flexible printed circuit board and pressing the flexible printed circuit board to the wiring end of the main circuit board and the attached circuit board Be That is, in this case, in the laminate, the laminate obtained by bonding the flexible printed circuit board and the wiring end of the main body substrate by pressure bonding, or the wiring end of the flexible printed circuit and the circuit substrate is bonded by pressure bonding Become a laminated body. The laminate has a part of the metal wiring and a mark separately formed of a material. The position of the mark is not particularly limited as long as it can be photographed by a photographing means such as a CCD camera through the resin constituting the laminate. In the case where the surface-treated copper foil of the present invention is an ultrathin copper layer (an ultrathin copper layer having a carrier) of a copper foil with a carrier, a laminate of the surface treated copper foil and a resin substrate may be used as needed. Remove the carrier.
As a method of connecting one printed wiring board and another printed wiring board, soldering, connection through an anisotropic conductive film (ACF), or anisotropic conductive paste (Anisotropic Conductive Paste,) A known connection method such as connection via ACP) or connection via an adhesive having conductivity can be used.
In the present invention, "copper circuit" includes copper wiring.

The positioning method according to the embodiment of the present invention may include the step of moving the laminate (including a laminate 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, or may be moved by a moving device provided with an arm mechanism, or a moving device which moves by floating the laminate using a gas It may be moved by a moving means, a moving device or moving means (including rollers, bearings, etc.) for moving the laminate by rotating an approximately cylindrical object or the like, a moving device or moving means using hydraulic pressure as a power source, Moving devices and moving means powered by air pressure, moving devices and moving means powered by motor, gantry moving linear guide stage, gantry moving air guide stage, stacked linear guide stage, linear motor drive stage, etc. It may be moved by a moving device having a stage or moving means. Further, the moving step may be performed by a 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.
Further, the laminate of the metal and the resin positioned in the present invention may be a resin board and a printed wiring board having a circuit provided on the resin board. Also, in this case, the mark may be the circuit.

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

Various copper foils listed in Table 2 and Table 3 are prepared as Examples 1 to 30 and 36 to 42 and Comparative Examples 1 to 14, and plating is performed on one surface under the conditions described in Table 1 as roughening treatment. I did the processing.
In Examples 31 to 35, various carriers described in Table 2 were prepared, an intermediate layer was formed on the surface of the carrier under the following conditions, and an ultrathin copper layer was formed on the surface of the intermediate layer. And it plated on the conditions of Table 1 as a roughening process on the surface of an ultra-thin copper layer.

Example 31
<Middle class>
(1) Ni layer (Ni plating)
The carrier was electroplated on a continuous roll-to-roll plating line under the following conditions to form a 1000 μg / dm ² adhesion amount Ni layer. Specific plating conditions are described below.
Nickel sulfate: 270 to 280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10 to 20 g / L
Boric acid: 30 to 40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55 to 75 ppm
pH: 4 to 6
Bath temperature: 55 to 65 ° C
Current density: 10A / dm ²
(2) Cr layer (electrolytic chromate treatment)
Next, after washing the surface of the Ni layer formed in (1) with water and pickling, a Cr layer of 11 μg / dm ² deposited on the Ni layer on a continuous roll-to-roll plating line. It was made to adhere by carrying out an electrolytic chromate process on condition of the following.
Potassium dichromate 1 to 10 g / L, zinc 0 g / L
pH: 7 to 10
Liquid temperature: 40 to 60 ° C
Current density: 2A / dm ²
<Ultra-thin copper layer>
Next, after washing and pickling the surface of the Cr layer formed in (2), a 1.5 μm-thick ultra-thin copper layer is subsequently formed on the Cr layer on a roll-to-roll type continuous plating line. It formed by electroplating on condition of the following, and produced the carrier with ultra-thin copper foil.
Copper concentration: 90 to 110 g / L
Sulfuric acid concentration: 90 to 110 g / L
Chloride ion concentration: 50 to 90 ppm
Leveling agent 1 (bis (3 sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
The following amine compound was used as leveling agent 2.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of hydroxyalkyl group, ether group, aryl group, aromatic substituted alkyl group, unsaturated hydrocarbon group, alkyl group.)
Electrolyte temperature: 50-80 ° C
Current density: 100A / dm ²
Electrolyte linear velocity: 1.5 to 5 m / sec

Examples 32, 33
<Middle class>
(1) Ni-Mo layer (nickel-molybdenum alloy plating)
The carrier was electroplated on a continuous roll-to-roll plating line under the following conditions to form a Ni-Mo layer with a loading of 3000 μg / dm ² . Specific plating conditions are described below.
(Liquid composition) Nitric acid sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds <very thin copper layer>
An ultra-thin copper layer was formed on the Ni-Mo layer formed in (1). An ultrathin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultrathin copper layer was 3 μm.

Example 34
<Middle class>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in Example 31.
(2) Organic matter layer (organic matter layer formation processing)
Next, the surface of the Ni layer formed in (1) is washed with water and acid, and subsequently, the solution temperature contains 1 to 30 g / L of carboxybenzotriazole (CBTA) with respect to the surface of the Ni layer under the following conditions. The organic layer was formed by showering and spraying an aqueous solution at 40 ° C. and pH 5 for 20 to 120 seconds.
<Ultra-thin copper layer>
An ultrathin copper layer was formed on the organic layer formed in (2). An ultrathin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultrathin copper layer was 2 μm.

Example 35
<Middle class>
(1) Co-Mo layer (cobalt molybdenum alloy plating)
The carrier was electroplated on a continuous roll-to-roll plating line under the following conditions to form a Co-Mo layer with a loading of 4000 μg / dm ² . Specific plating conditions are described below.
(Liquid composition) sulfuric acid Co: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds <very thin copper layer>
An ultra-thin copper layer was formed on the Co-Mo layer formed in (1). An ultrathin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultrathin copper layer was 5 μm.

After the plating treatment (described in Table 1) was performed as the above-mentioned roughening treatment, the following heat resistance was applied to Examples 1 to 10, 12 to 27, 32 to 42, and Comparative Examples 3, 4, 6, and 9 to 14 Plating treatment was performed to form a layer and an anticorrosion layer. In addition, "Ni-Co", "Ni-Co (2)", "Ni-Co (3)", "Ni-P", "Ni-Zn", "Ni--" described in Tables 4 and 5 Zn (2) "," Ni-Zn (3) "," Ni-W "," chromate ", and" silane coupling treatment "mean the following surface treatment.
The formation conditions of the heat-resistant layer 1 are shown below.
・ Heat resistant layer 1
[Ni-Co]: Nickel-cobalt alloy plating solution composition: Nickel 5 to 20 g / L, cobalt 1 to 8 g / L
pH: 2 to 3
Liquid temperature: 40 to 60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 10 to 20 As / dm ²
[Ni-Co (2)]: Nickel-cobalt alloy plating solution composition: 5 to 20 g / L of nickel, 1 to 8 g / L of cobalt
pH: 2 to 3
Liquid temperature: 40 to 60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 35 to 50 As / dm ²
[Ni-Co (3)]: Nickel-cobalt alloy plating solution composition: 5 to 20 g / L of nickel, 1 to 8 g / L of cobalt
pH: 2 to 3
Liquid temperature: 40 to 60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 25 to 35 As / dm ²
[Ni-P]: Nickel-phosphorus alloy plating solution composition: 5 to 20 g / L of nickel, 2 to 8 g / L of phosphorus
pH: 2 to 3
Liquid temperature: 40 to 60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 10 to 20 As / dm ²
・ Heat resistant layer 2
[Ni-Zn]: Nickel-Zinc Alloy Plating The heat-resistant layer 2 was formed on the copper foil on which the above-described heat-resistant layer 1 was applied. In Comparative Examples 5, 7 and 8, roughening plating was not performed, and the heat-resistant layer 2 was directly formed on the prepared copper foil. The formation conditions of the heat-resistant layer 2 are shown below.
Liquid composition: Nickel 2 to 30 g / L, zinc 2 to 30 g / L
pH: 3 to 4
Liquid temperature: 30 to 50 ° C
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 1 to ^{2 As} / dm ²
[Ni-Zn (2)]: Nickel-zinc alloy plating solution composition: 2 to 30 g / L of nickel, 2 to 30 g / L of zinc
pH: 3 to 4
Liquid temperature: 30 to 50 ° C
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 3 to 4 As / dm ²
[Ni-Zn (3)]: Nickel-zinc alloy plating solution composition: 2 to 30 g / L of nickel, 2 to 30 g / L of zinc
pH: 3 to 4
Liquid temperature: 30 to 50 ° C
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 2-3 As / dm ²
[Ni-W]: Nickel-tungsten alloy plating solution composition: 2 to 30 g / L of nickel, 0.5 to 20 g / L of tungsten
pH: 3 to 4
Liquid temperature: 30 to 50 ° C
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 1 to ^{2 As} / dm ²
Anticorrosion Layer [Chromate]: Chromate Treatment An anticorrosion layer was further formed on the copper foil on which the heat resistant layers 1 and 2 were applied. The formation conditions of the anticorrosion layer are shown below.
Liquid composition: Potassium dichromate 1 to 10 g / L, zinc 0 to 5 g / L
pH: 3 to 4
Liquid temperature: 50 to 60 ° C
Current density: 0 to ^{2 A} / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)
A weather resistant layer was further formed on the heat-resistant layers 1 and 2 and the copper foil on which the anticorrosion layer was applied. The formation conditions are shown below.
As a silane coupling agent having an amino group, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Examples 17, 24 to 27), N-2- (aminoethyl) -3-aminopropyltriol Ethoxysilane (Examples 1-16, 32-36, Comparative Examples 2-14), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (Examples 18, 28, 29, 30), 3- Aminopropyltrimethoxysilane (Example 19), 3-aminopropyltriethoxysilane (Examples 20, 21), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Example 22) Coating and drying were performed with N-phenyl-3-aminopropyltrimethoxysilane (Example 23) to form a weather resistant layer. These silane coupling agents can also be used in combination of 2 or more types. Similarly, in Comparative Examples 1 to 14, coating and drying were performed with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane to form a weather resistant layer.
In addition, the surface-treated copper foil which surface-treated in Table 10 in the other surface was manufactured also about the surface-treated copper foil obtained in Examples 1-29 and Comparative Example 6. Here, "Example No.-number" in Table 10 means that the surface treatment described in Table 10 was performed on the other surface of the surface-treated copper foil obtained in the example. For example, in Table 10, “Example 2-1” and “Example 2-2” are obtained by performing the surface treatment described in Table 10 on the other surface of Example 2, respectively.

In addition, the rolled copper foil was manufactured as follows. After manufacturing the copper ingot of the composition shown in Table 2, after hot-rolling, annealing and cold rolling of a 300-800 degreeC continuous annealing line were repeated, and the rolling board of 1-2 mm thickness was obtained. The rolled sheet was annealed and recrystallized in a continuous annealing line at 300 to 800 ° C., and finally cold rolled to the thickness shown in Table 2 under the conditions described in Table 2 to obtain a copper foil. "Tough pitch copper" in the column of "Type" in Table 2 indicates tough pitch copper specified in JIS H3100 C1100, and "Oxygen-free copper" indicates oxygen-free copper specified in JIS H3100 C1020. Moreover, "tough pitch copper + Ag: 100 ppm" means that 100 mass ppm of Ag was added to tough pitch copper.
The electrolytic copper foil used the electrolytic copper foil HLP foil by JX Nippon Mining & Metals company. In addition, about Example 27, Example 31, and Comparative Example 12, a predetermined surface treatment, an intermediate layer, and an extremely thin surface are performed on the deposition surface (the surface on the opposite side to the surface in contact with the electrolytic drum at the time of electrolytic copper foil manufacture). A copper layer was formed. In addition, for the electrodeposited copper foils in Tables 2 and 3, the surface roughness Rz and the degree of gloss on the deposition surface side are described. When electrolytic polishing or chemical polishing was performed, the plate thickness after electrolytic polishing or chemical polishing was described.
In addition, the point of the copper foil preparation process before surface treatment was described in Table 2. "High gloss rolling" means that the final cold rolling (cold rolling after final recrystallization annealing) was performed at the value of the oil film equivalent value described. "Normal rolling" means that the final cold rolling (cold rolling after final recrystallization annealing) was performed at the value of the oil film equivalent value described. "Chemical polishing" and "electrolytic polishing" mean that it was performed under the following conditions.
The “chemical polishing” uses an etching solution of 1 to 3% by mass of H ₂ SO ₄ , 0.05 to 0.15% by mass of H ₂ O ₂ , and the balance water, and the polishing time is 1 hour.
The “electropolishing” was conducted under the conditions of 67% phosphoric acid + 10% sulfuric acid + 23% water, with a voltage of 10 V / cm ² , for the time shown in Table 2 (electrolytic polishing for 10 seconds, the polishing amount is 1 to 2 μm It went in).

Various evaluations were performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
(1-1) Measurement of surface roughness (Rz);
Ten-point average roughness was measured on the roughened surface according to JIS B0601-1994 using Kosaka Research Institute Ltd. contact roughness meter Surfcorder SE-3C. Perpendicular to the rolling direction under the conditions of measurement standard length 0.8 mm, evaluation length 4 mm, cut-off value 0.25 mm, feed speed 0.1 mm / sec The measurement position was changed vertically (that is, in the width direction) ten times, and the average value of ten measurements was taken as the value of the surface roughness (Rz). When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
In addition, surface roughness (Rz) was similarly calculated | required about the copper foil before surface treatment.

(3-2) Measurement of surface roughness of the other surface (surface of copper foil which is not roughened surface S);
Non-contact method is used for the other surface of each example and comparative example (copper foil surface not roughened surface S) (the other surface after surface treatment when the other surface is subjected to surface treatment) It is preferred to use it to measure the surface roughness. Specifically, the condition of the other surface after the surface treatment of each example and comparative example is evaluated by the value of roughness measured with a laser microscope. This is because the surface condition can be evaluated in more detail.

・ Measurement of surface roughness (Rz);
The surface roughness of the other surface of each of the surface-treated copper foils of the examples and the comparative examples (the other surface after the surface treatment when the other surface is subjected to the surface treatment) was subjected to surface roughness using a laser microscope OLS4000 manufactured by Olympus Corporation. (Ten-point average roughness) Rz was measured in accordance with JIS B0601 1994. Using a 50 × objective lens, evaluation length of 258 μm in observation of copper foil surface, with a cutoff value of zero, for a rolled copper foil by measurement in the direction (TD) perpendicular to the rolling direction, or electrolytic copper About foil, each value was calculated | required by measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of an electrolytic copper foil. In addition, the measurement environmental temperature of surface roughness Rz by a laser microscope was 23-25 degreeC. Rz was arbitrarily measured at 10 points, and the average value of the 10 points of Rz was taken as the value of surface roughness (ten-point average roughness) Rz. Moreover, the wavelength of the laser beam of the laser microscope used for measurement was 405 nm. The same measurement was performed on the roughened surface S as well.

・ Measurement of root mean square height Rq of surface;
The other surface of the surface-treated copper foil of each example and comparative example (the other surface after the surface treatment when the other surface is subjected to the surface treatment) is a copper foil surface with a laser microscope OLS4000 manufactured by Olympus Corporation. The root mean square height Rq of was measured in accordance with JIS B0601 2001. Using a 50 × objective lens, evaluation length of 258 μm in observation of copper foil surface, with a cutoff value of zero, for a rolled copper foil by measurement in the direction (TD) perpendicular to the rolling direction, or electrolytic copper About foil, each value was calculated | required by measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of an electrolytic copper foil. In addition, the measurement environmental temperature of the root mean square height Rq of the surface by a laser microscope was 23-25 degreeC. Rq was arbitrarily measured at 10 points, and the average value of 10 points of Rq was taken as the value of root mean square height Rq. Moreover, the wavelength of the laser beam of the laser microscope used for measurement was 405 nm. The same measurement was performed on the roughened surface S as well.

・ Measurement of surface arithmetic mean roughness Ra;
The surface roughness Ra of the other surface of each of the surface-treated copper foils of Examples and Comparative Examples (the other surface after the surface treatment when the other surface is subjected to surface treatment) conforms to JIS B0601-1994. Then, it was measured with an Olympus Olympus laser microscope OLS4000. Electrolyzed copper by measurement (direction TD perpendicular to the rolling direction) for rolled copper foil under the condition of evaluation length of 258 μm in observation of copper foil surface and cutoff value of zero using objective lens 50 times About foil, each value was calculated | required by measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of an electrolytic copper foil. In addition, the measurement environmental temperature of arithmetic mean roughness Ra of the surface by a laser microscope was 23-25 degreeC. Ra was arbitrarily measured at 10 points, and the average value of 10 points of the Ra was taken as the value of the arithmetic average roughness Ra. Moreover, the wavelength of the laser beam of the laser microscope used for measurement was 405 nm. The same measurement was performed on the roughened surface S as well.

(2) Particle area ratio (A / B);
The surface area of the roughened particles was measured using a laser microscope. Three-dimensional surface area A is measured by measuring the three-dimensional surface area A at 100 × 100 μm equivalent area B (9982.52 μm ^{2 in} actual data) at a magnification of 2000 times of the roughened surface using a laser microscope VK 8500 manufactured by Keyence Corporation. The setting was performed by the method of setting two-dimensional surface area B = area ratio (A / B). When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(3) glossiness;
Using a gloss meter handy gloss meter PG-1 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z8741, a rolling direction (MD, a passing direction in the case of electrolytic copper foil) and a direction perpendicular to the rolling direction (TD, In the case of the electrodeposited copper foil, measurement was made on the roughened surface of the surface-treated copper foil at an incident angle of 60 ° in each of the directions perpendicular to the foil passing direction. When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
In addition, glossiness was similarly calculated | required about the surface by which the surface treatment of the copper foil before surface treatment is carried out, and the surface in which the intermediate layer of a carrier is provided.

(4) Slope of brightness curve Polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), adhesive layer for copper-clad laminates) from the roughened surface side of the surface-treated copper foil Polyimide film with polyimide, PMDA (Pyramellitic anhydride) -based polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA ( (Pyramellitic anhydride) -based polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film))) is bonded to both sides, and the surface-treated copper foil is etched (ferric chloride aqueous solution) It removed and produced the sample film. When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust The surface-treated copper foil after surface treatment such as a layer and a weather resistant layer is pasted on both sides of the polyimide film from the surface-treated side, and the surface-treated copper foil is etched (ferric chloride aqueous solution) It removed and produced the sample film. When the surface-treated copper foil is the ultrathin copper layer of the copper foil with carrier, the copper foil with carrier was attached to both sides of the polyimide film from the roughened surface side of the ultrathin copper layer, and then the carrier was peeled off. Thereafter, the ultrathin copper layer was removed by etching (ferric chloride aqueous solution) to prepare a sample film. Subsequently, the printed matter on which the line-like black mark is printed is placed under the sample film, and the printed matter is photographed through the sample film with a CCD camera (line CCD camera of 8192 pixels). In the observation point-lightness graph produced by measuring the lightness at each observation point along the direction perpendicular to the direction in which the observed line-like mark extends, ΔB and t1, t2, and Sv were measured from the lightness curve. FIG. 3 is a schematic view showing the configuration of the photographing apparatus used at this time and the method of measuring the lightness curve.
In addition, ΔB and t1, t2 and Sv were measured by the following imaging apparatus as shown in FIG. Note that one pixel on the horizontal axis corresponds to 10 μm in length. Sv measures both sides of the mark and adopts a small value.
In addition, as a polyimide film used for the measurement of the inclination of a brightness curve, as long as the value of (DELTA) B ((DELTA) B (PI)) before bonding to copper foil is 50 or more and 65 or less, you may use what kind of polyimide film. In addition, the value of (DELTA) B (PI) of the polyimide film used for the present Example and the comparative example was 50-65 (for example, 59).
The above-mentioned "printed matter on which a line-like black mark is printed" is formed on a white glossy paper having a gloss of 43.0 ± 2 according to JIS P8208 (1998) (Fig. 1 copy of the measurement chart of foreign matters) and JIS P 8145 (2011) Contamination with various lines printed on the transparent film shown in Fig. 9 which is adopted in any of Annex JA (Standard) visual method foreign matter comparison chart Fig. JA 1-Copy of visual method foreign matter comparison chart) (Miscellaneous materials) (Product name of Chaoseikai Co., Ltd. Product name: "Kyoto miscellaneous materials measurement chart-full size size" Part number: JQA 160-20151-1 (manufactured by the National Administrative Agency, Independent Administrative Agency)) .
The glossiness of the glossy paper was measured at an incident angle of 60 degrees using a glossmeter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS Z8741.
The imaging device includes a CCD camera, a stage (white) on which a polyimide substrate with a mark-marked paper (glossy paper on which foreign matter is placed) is placed down (white), an illumination power source for irradiating light to the imaging unit of the polyimide substrate, imaging There is provided a conveyer (not shown) for conveying the evaluation polyimide substrate on which the paper marked with the object of interest is placed on the stage. The main specifications of the imaging device are as follows:
・ Photographing device: Sheet inspection device Mujiken made by Nireko Co., Ltd.
Line CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits)
・ Lighting power supply: High frequency lighting power supply (power supply unit x 2)
・ Lighting: Fluorescent lamp (30 W, Model name: FPL27EX-D, Twin fluorescent lamp)
The line for Sv measurement used the line shown by the arrow drawn to the contaminant of FIG. 9 of 0.7 mm ² . The width of the line is 0.3 mm. In addition, the line CCD camera field of view is arranged in a dotted line in FIG.
In shooting with a line CCD camera, the signal is checked at full scale 256 gradations, and the place where the black mark of the printed matter does not exist in the state where the polyimide film (polyimide substrate) to be measured is not placed The above-mentioned transparent film was placed on the lens, and the lens aperture was adjusted so that the peak gray scale signal of the area out of the mark printed on the foreign matter from the transparent film side was measured by a CCD camera within 230 ± 5. The camera scan time (the time when the shutter of the camera is open, the time when light is taken in) was fixed at 250 μsec, and the lens aperture was adjusted to be within the above gradation.
In the case of measuring ΔB and Sv with a line-shaped copper foil as a mark for printed wiring boards and copper-clad laminates, a white gloss of 43.0 ± 2 in glossiness is formed on the back of the line-shaped copper foil. A sheet of paper is taken and photographed with a CCD camera (line CCD camera of 8192 pixels) through the polyimide film, and an image obtained by the photographing is observed for each observation point along the direction perpendicular to the direction in which the observed copper foil extends. In the observation point-lightness graph prepared by measuring lightness, the above-mentioned “line-shaped black mark except that ΔB and t1, t2, and Sv are measured from the lightness curve generated from the end of the mark to the unmarked portion Is the same as the conditions under which ΔB and Sv were measured using the “printed matter printed”.
In the lightness shown in FIG. 3, 0 means "black" and lightness 255 means "white", and the degree of gray from "black" to "white" (black and white shades, gray scale) Is divided into 256 gradations.

(5) Visibility (resin transparency);
The surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm, and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminates, PMDA (pyromellitic anhydride) ) Polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film)), Toray Du Pont made 50 μm thick (Kapton (registered trademark), PMDA (pyromellitic anhydride) polyimide film ( A sample film was prepared by laminating on both sides of PMDA-ODA (4, 4′-diaminodiphenyl ether) based polyimide film)) and removing the surface-treated copper foil by etching (ferric chloride aqueous solution). In addition, about the copper foil which performed the roughening process, the surface which carried out the roughening process of copper foil was bonded together to the above-mentioned polyimide film, and the above-mentioned sample film was produced. Printed matter (black circle with a diameter of 6 cm) was attached to one side of the obtained resin layer, and the visibility of the printed matter was judged from the opposite side through the resin layer. If the outline of the black circle of the printed matter is clear when the length is 90% or more of the circumference, "」 ", the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. (Circle or more pass), what the outline of a black circle clarified in the length less than 0-80% of circumference, and what the outline broke was evaluated as "x" (reject). When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(6) Peel strength (adhesive strength);
The surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm, and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminates, PMDA (pyromellitic anhydride) ) Polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film)), Toray Du Pont made 50 μm thick (Kapton (registered trademark), PMDA (pyromellitic anhydride) polyimide film ( After laminating on a PMDA-ODA (4, 4′-diaminodiphenyl ether) -based polyimide film)), the normal peel strength was measured with a tensile tester autograph 100 in accordance with IPC-TM-650. And, the above normal peel strength should be 0.7 N / mm or more for use in laminated substrate applications.
The conditions for laminating the surface-treated copper foil and the polyimide film were the conditions recommended by the polyimide film manufacturer. In Examples 31 to 34, the surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), adhesive layer for copper-clad laminate) Polyimide film, polyimide film of PMDA (pyromellitic anhydride) type (Polyimide film of PMDA-ODA (4, 4'-diaminodiphenyl ether) type), 50 μm thick made by Toray DuPont (Kapton (registered trademark), PMDA (piro After laminating on a polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film) based on melitic acid anhydride), the carrier is peeled off, and ultra-thin copper laminated with the polyimide film Peel strength after copper plating to a layer thickness of 12 μm It was measured. When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(7) Heat resistance;
The surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm, and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminates, PMDA (pyromellitic anhydride) ) Polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film)), Toray Du Pont made 50 μm thick (Kapton (registered trademark), PMDA (pyromellitic anhydride) polyimide film ( In accordance with IPC-TM-650, after being laminated on PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film))) and after heating at 150 ° C. for 168 hours, tensile tester autograph 100 Measure normal peel strength and peel strength after heating at 150 ° C for 168 hours The
And the peeling strength retention represented by following Formula was computed.
Peel strength retention (%) = 150 ° C after heating for 168 hours Peel strength (kg / cm) / Normal peel strength (kg / cm) × 100
And, when the peel strength retention rate is 70% or more, the heat resistance is “、”, and when the peel strength retention rate is 60% or more and less than 70%, the heat resistance is “〇”, the peel strength retention rate is 50% or more 60 When it is less than%, the heat resistance is "Δ", and when the peel strength retention is less than 50%, the heat resistance is "X". In Examples 31 to 34, the surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), adhesive layer for copper-clad laminate) Polyimide film, polyimide film of PMDA (pyromellitic anhydride) type (Polyimide film of PMDA-ODA (4, 4'-diaminodiphenyl ether) type), 50 μm thick made by Toray DuPont (Kapton (registered trademark), PMDA (piro After laminating on a polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film) based on melitic acid anhydride), the carrier is peeled off, and ultra-thin copper laminated with the polyimide film Peel strength after copper plating to a layer thickness of 12 μm It was measured. When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(8) Solder heat resistance evaluation;
The surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm, and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminates, PMDA (pyromellitic anhydride) ) Polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film)), Toray Du Pont made 50 μm thick (Kapton (registered trademark), PMDA (pyromellitic anhydride) polyimide film ( Polyimide film of PMDA-ODA (4, 4'-diaminodiphenyl ether) system) was bonded to both sides of the film. The test coupon based on JISC6471 was created about the obtained double-sided laminated board. The test coupons were exposed for 48 hours under high temperature and high humidity conditions of 85 ° C. and 85% RH, and then floated in a solder bath at 300 ° C. to evaluate solder heat resistance characteristics. After the solder heat resistance test, at the interface between the copper foil roughened surface and the polyimide resin adhesion surface, the discolored interface due to swelling in the area of 5% or more of the copper foil area in the test coupon is x (failed), area In the case of blistering of less than 5%, the case of blistering was evaluated as ○, and the case where blistering did not occur at all was evaluated as 。.
When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(9) Yield The surface-treated side of the surface-treated copper foil is a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper clad laminate, PMDA (Piro) Melt acid anhydride) polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film)), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA (pyromellitic anhydride) type) Paste on both sides of polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) based polyimide film) and etch the copper foil (ferric chloride aqueous solution) to make L / S 30 μm / 30 μm The circuit width of the FPC was created. In Examples 31 to 34, after laminating the surface of the surface-treated copper foil on the surface-treated side to a polyimide film (Kaneka thickness 25 μm and 50 μm, Toray DuPont thickness 50 μm), the carrier is peeled off. Then, a 20 μm × 20 μm square mark was tried to be detected by a CCD camera through polyimide. "◎" if detected 9 or more out of 10 times, "○" if detected 7 to 8 times, "○" if detected 6 times if "Δ", detected 5 times or less Was "X".
When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said evaluation was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
In the printed wiring board or copper-clad laminate, the resin is dissolved and removed to obtain the above-mentioned (1) surface roughness (Rz), (2) area ratio of particles (Copper circuit or copper foil surface). A / B), (3) Gloss can be measured.

(10) Circuit shape by etching (fine pattern characteristics)
Thermosetting adhesive-laminated polyimide film for lamination (thickness 50 μm, UPI REX manufactured by Ube Industries, Ltd.) from the side of the surface-treated surface (roughened surface S) of a surface-treated copper foil (UPILEX (registered trademark)-VT, BPDA ( It bonded together on both surfaces of the polyimide resin substrate of a biphenyl tetracarboxylic acid dianhydride type | system | group (BPDA-PDA (paraphenylene diamine) type | system | group). In order to form a fine pattern circuit, it is necessary to make copper foil thickness the same, and made 12 micrometers copper foil thickness into reference here. That is, when the thickness was larger than 12 μm, the thickness was reduced to 12 μm by electrolytic polishing. On the other hand, when the thickness was thinner than 12 μm, the thickness was increased to 12 μm by copper plating treatment. When the surface-treated copper foil is an ultrathin copper layer of copper foil with carrier, after the copper foil with carrier is attached to both sides of the above-mentioned polyimide film with thermosetting adhesive for lamination from the ultrathin copper layer side The carrier was peeled off, and then the thickness was increased by copper plating until the total thickness of the ultrathin copper layer and the copper plating became 12 μm. A fine pattern circuit is printed on the copper foil shiny side of the laminate by a photosensitive resist application and exposure process on one side of the double-sided laminate obtained, and unnecessary portions of the copper foil are etched under the following conditions, A fine pattern circuit was formed such that L / S = 20/20 μm. Here, the circuit width was such that the bottom width of the circuit cross section was 20 μm.
(Etching conditions)
Equipment: Spray type small etching equipment Spray pressure: 0.2MPa
Etching solution: ferric chloride aqueous solution (specific gravity 40 Bome)
Liquid temperature: 50 ° C
After forming the fine pattern circuit, the photosensitive resist film was peeled by immersing in a 45 ° C. NaOH aqueous solution for 1 minute.

(11) Calculation of etching factor (Ef) The fine pattern circuit sample obtained above is observed from the top of the circuit at a magnification of 2000 using a scanning electron micrograph S4700 manufactured by Hitachi High-Technologies Corporation, and the circuit is obtained. The top width at the top (Wa) and the bottom width at the bottom of the circuit (Wb) were measured. The copper foil thickness (T) was 12 μm. The etching factor (Ef) was calculated by the following equation.
Etching factor (Ef) = (2 x T) / (Wb-Wa)
Those that did not exist were evaluated as ◎.

(12) Measurement of transmission loss About each sample, after pasting together with a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm made by Kuraray Co., Ltd.), a microstrip line is formed by etching so that the characteristic impedance is 50Ω, The transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was determined. As evaluation of the transmission loss at a frequency of 20 GHz, 未 満 for 3.7 dB / 10 cm or less, 3.7 3.7 dB / 10 cm or more and 4.0 dB / 10 cm or less ○, 4.0 dB / 10 cm or more and 4.1 dB / 10 cm or less cm Δ of 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm, and X of 5.0 dB / 10 cm or more.
When surface treatment is performed to provide a heat-resistant layer, an antirust layer, a weather resistant layer, etc. after roughening the copper foil surface or without providing a roughening treatment, the heat resistant layer, antirust Said measurement was performed about the surface of the surface-treated copper foil after surface treatment of a layer, a weather resistant layer, etc. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(13) Adhesion amount of nickel and cobalt on the roughened surface The adhesion amount of nickel and cobalt on the roughened surface is determined by dissolving the sample in nitric acid with a concentration of 20% by mass and using a VARIAN atomic absorption spectrophotometer ( It measured by performing quantitative analysis by atomic absorption method using model: AA240FS. The size of the measurement sample of the nickel and cobalt adhesion amount of the example and the comparative example was 50 mm × 50 mm.
In addition, the measurement of the adhesion amount of nickel and cobalt on the said roughening process surface was performed as follows. After laminating the prepreg (FR4) on the non-surface-treated side of the surface-treated copper foil by thermocompression bonding, the surface-treated side of the surface-treated copper foil is dissolved in a thickness of 2 μm for surface treatment The amount of adhesion of nickel and cobalt adhering to the surface of the surface-treated side of the copper foil was measured. And the adhesion amount of the obtained nickel and cobalt was made into the adhesion amount of nickel and cobalt on the roughening process surface, respectively. In addition, the melt | dissolution thickness of the side by which the said surface treatment is carried out of the surface-treated copper foil does not need to be exactly 2 micrometers, and it is clear that all the surface parts which are surface-treated melt | dissolve (for example, thickness , 1.5 to 2.5 μm) may be dissolved and measured. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, first, a prepreg (FR4) is heat-pressed and laminated on the surface on the carrier side, and then the surface treatment of the ultrathin copper layer is performed. The surface on the side where it is made is dissolved only in the vicinity of the surface (if the thickness of the ultrathin copper layer is 1.4 μm or more, 0. When the thickness of the ultrathin copper layer is less than 1.4 μm, only 20% of the thickness of the ultrathin copper layer is dissolved from the surface of the ultrathin copper layer that is surface-treated. The amount of nickel and cobalt deposited on the surface of the ultrathin copper layer on which the surface is treated is measured. And the adhesion amount of the obtained nickel and cobalt was made into the adhesion amount of nickel and cobalt on the roughening process surface, respectively.
In addition, the adhesion amount of the said nickel and cobalt says the thing of the adhesion amount (mass) of nickel and cobalt per sample unit area (1 dm < ² >).

(14) Evaluation of copper foil wrinkles etc. by lamination;
The surface-treated copper foils of Examples and Comparative Examples are laminated on both surfaces of a 25 μm-thick polyimide resin from the side of one surface (roughened surface S), and the other surface of each surface-treated copper foil A state in which a 125 μm thick protective film (made of polyimide) is laminated on the (surface opposite to roughened surface S) side, that is, protective film / surface treated copper foil / polyimide resin / surface treated copper foil / protection In the state made into five layers of films, lamination processing was performed while applying heat and pressure from the outside of both protective films using heat and pressure, and surface treated copper foil was laminated on both sides of polyimide resin. . Then, after peeling off the protective film on both surfaces, the other surface of the surface-treated copper foil is visually observed to confirm the presence or absence of wrinkles or streaks, and when no wrinkles or streaks are generated, ◎, copper foil length When only one wrinkle or streak was observed per 5 m was evaluated as ○, when two or more wrinkles or streaks were observed per 5 m of copper foil was evaluated as x.

After roughening the copper foil surface or the ultrathin copper layer surface of the copper foil with a carrier, or performing a roughening treatment, surface treatment is performed to provide a heat-resistant layer, an anticorrosion layer, a weather resistant layer, etc. In this case, the above-mentioned measurement was performed on the surface of the surface-treated copper foil after the surface treatment of the heat-resistant layer, the rustproof layer, the weather resistant layer and the like.
Tables 1 to 10 show production conditions, evaluation results and the like of Examples and Comparative Examples.

  In addition, "-" in the column of the heat resistant layer 1, the heat resistant layer 2, the rustproof layer, and the weather resistant layer in Tables 4 and 5 forms the heat resistant layer 1, the heat resistant layer 2, the rust proofed layer, the weather resistant layer. It means that processing has not been performed.

(Evaluation results)
In all of Examples 1 to 42, visibility, peel strength, solder heat resistance evaluation and yield were good. Moreover, in Examples 1 to 36, the transmission loss was also small and good.
In Comparative Examples 1 to 4, 6 and 9 to 14, since the value of Sv was less than 3.5, the visibility was poor.
Comparative Examples 5, 7 and 8 had excellent visibility but poor substrate adhesion. Moreover, the comparative examples 1-14 were inferior in solder heat-resistant evaluation.
In addition, surface treatment is performed on both sides of the copper foil under the same conditions using the same copper foil as the respective examples and comparative examples, and on both sides of the carrier under the same conditions using the same carriers as the respective examples. After the formation of the intermediate layer and the ultrathin copper layer, the same surface treatment was performed to manufacture and evaluate a surface-treated copper foil. As a result, the same evaluation results as those of the respective examples and comparative examples were obtained on both sides. In addition, when electropolishing or chemical polishing was performed about copper foil or a carrier, surface treatment was performed after performing electropolishing or chemical polishing on both surfaces. In Example 27, Example 31, and Comparative Example 12, electrolytic polishing and / or chemical polishing is performed on the shiny side of the copper foil (the side which is in contact with the drum at the time of production of the electrolytic copper foil). After making the roughness Rz of TD and the glossiness the same as the deposition surface, 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, surface treatment may be simultaneously performed on both surfaces, or surface treatment may be separately performed on one surface and the other surface. In addition, when surface-treating simultaneously on both surfaces, it is good to surface-treat using the surface treatment apparatus (plating apparatus) which provided the anode on both surfaces side of copper foil. In addition, in the present Example, surface treatment was performed to both surfaces simultaneously.
In addition, the ten-point average roughness Rz of TD measured by a laser microscope in which the wavelength of the laser light of the copper foil surface (roughened surface S) subjected to the roughening treatment of each example is 405 nm is all 0. It was 35 μm or more. Moreover, as for the arithmetic mean roughness Ra of all of TD measured by the laser microscope whose wavelength of the laser beam of the copper foil surface (roughened surface S) which the roughening process of each Example was 405 nm, 0.05 micrometer in all. It was over. In addition, the root mean square height Rq of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface (roughened surface S) roughened in each example is 405 nm is all 0. It was over 08 μm.
In FIG. 4, (a) Comparative Example 1, (b) Comparative Example 3, (c) Comparative Example 5, (d) Comparative Example 6, (e) Example 1, (f) Example in the case of the above Rz evaluation. The SEM observation photograph of the copper foil surface of Example 2 is each shown.
In each of the above embodiments, the width of the mark is 0.3 mm to 0.16 mm (the third mark from the side closer to the 0.5 description of the area 0.5 mm ² of the sheet of the foreign matter (arrow in FIG. 10 is The same Sv value was measured by changing the mark to the mark)), but in each case, the Sv value was the same value as when the mark width was 0.3 mm.
Furthermore, in each of the above embodiments, with respect to “top average value Bt of lightness curve”, positions separated 50 μm from the end positions on both sides of the mark are positions separated by 100 μm, positions separated by 300 μm, and positions separated 500 μm. The same Sv value was measured by changing to the average value of lightness when measured at five locations (total of 10 locations on both sides) from each position at intervals of 30 μm, but in all cases, the Sv value is the end of both sides of the mark The average value of lightness measured at 5 points (10 points on both sides) at 30 μm intervals from the position 50 μm away from the part position was the same value as the Sv value when “top average value Bt of lightness curve” .

Claims (56)

One of the copper foil surfaces is a roughened surface S on which roughened particles are formed by the roughening treatment, and the other copper foil surface is a surface-treated copper foil having a surface treatment,
The ten-point average roughness Rz of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface which is not the roughened surface S is 405 nm is 0.35 μm or more,
After the roughened surface S is bonded to both sides of a polyimide resin substrate, the copper foils on both sides are removed by etching.
When a printed matter on which a linear mark is printed is placed under the exposed polyimide substrate, and the printed matter is photographed by the CCD camera through the polyimide substrate,
In an observation point-lightness graph produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed line-like mark extends, with respect to the image obtained by the photographing,
Let Bt be the top average value of the lightness curve generated from the end of the mark to the portion without the mark, and Bb be the bottom average value, and the difference ΔB between the top average value Bt and the bottom average value Bb (ΔB = Bt−Bb In the observation point-lightness graph, a value indicating the position of the intersection point closest to the line-like mark among the intersection points of the lightness curve and Bt is taken as t1, and Bt is used as a reference from the intersection point of the lightness curve and Bt. In the depth range up to 0.1ΔB, when the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is t2, it is defined by the following equation (1) Sv is 3.5 or more, the roughened surface S contains at least one element selected from the group consisting of Ni and Co, and the roughened surface S includes Ni. The adhesion amount of Ni is 14 0 Pg / dm ² or less, a surface-treated copper foil attached amount of Co is less than 2400μg / dm ² in the case where the roughening treated surface S comprises Co.
Sv = (ΔB × 0.1) / (t1-t2) (1) One of the copper foil surfaces is a roughened surface S on which roughened particles are formed by the roughening treatment, and the other copper foil surface is a surface-treated copper foil having a surface treatment,
Arithmetic average roughness Ra of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface which is not the roughened surface S is 405 nm is 0.05 μm or more.
After the roughened surface S is bonded to both sides of a polyimide resin substrate, the copper foils on both sides are removed by etching.
When a printed matter on which a linear mark is printed is placed under the exposed polyimide substrate, and the printed matter is photographed by the CCD camera through the polyimide substrate,
In an observation point-lightness graph produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed line-like mark extends, with respect to the image obtained by the photographing,
Let Bt be the top average value of the lightness curve generated from the end of the mark to the portion without the mark, and Bb be the bottom average value, and the difference ΔB between the top average value Bt and the bottom average value Bb (ΔB = Bt−Bb In the observation point-lightness graph, a value indicating the position of the intersection point closest to the line-like mark among the intersection points of the lightness curve and Bt is taken as t1, and Bt is used as a reference from the intersection point of the lightness curve and Bt. In the depth range up to 0.1ΔB, when the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is t2, it is defined by the following equation (1) Sv is 3.5 or more, the roughened surface S contains at least one element selected from the group consisting of Ni and Co, and the roughened surface S includes Ni. The adhesion amount of Ni is 14 0 Pg / dm ² or less, a surface-treated copper foil attached amount of Co is less than 2400μg / dm ² in the case where the roughening treated surface S comprises Co.
Sv = (ΔB × 0.1) / (t1-t2) (1) One of the copper foil surfaces is a roughened surface S on which roughened particles are formed by the roughening treatment, and the other copper foil surface is a surface-treated copper foil having a surface treatment,
The root mean square height Rq of TD measured with a laser microscope in which the wavelength of the laser light of the copper foil surface which is not the roughened surface S is 405 nm is 0.08 μm or more.
After the roughened surface S is bonded to both sides of a polyimide resin substrate, the copper foils on both sides are removed by etching.
When a printed matter on which a linear mark is printed is placed under the exposed polyimide substrate, and the printed matter is photographed by the CCD camera through the polyimide substrate,
In an observation point-lightness graph produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed line-like mark extends, with respect to the image obtained by the photographing,
Let Bt be the top average value of the lightness curve generated from the end of the mark to the portion without the mark, and Bb be the bottom average value, and the difference ΔB between the top average value Bt and the bottom average value Bb (ΔB = Bt−Bb In the observation point-lightness graph, a value indicating the position of the intersection point closest to the line-like mark among the intersection points of the lightness curve and Bt is taken as t1, and Bt is used as a reference from the intersection point of the lightness curve and Bt. In the depth range up to 0.1ΔB, when the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is t2, it is defined by the following equation (1) Sv is 3.5 or more, the roughened surface S contains at least one element selected from the group consisting of Ni and Co, and the roughened surface S includes Ni. The adhesion amount of Ni is 14 0 Pg / dm ² or less, a surface-treated copper foil attached amount of Co is less than 2400μg / dm ² in the case where the roughening treated surface S comprises Co.
Sv = (ΔB × 0.1) / (t1-t2) (1) The surface-treated copper foil according to any one of claims 1 to 3, wherein the adhesion amount of Ni is 1000 μg / dm ² or less when the roughened surface S contains Ni. The surface-treated copper foil according to any one of claims 1 to 4, wherein the adhesion amount of Ni is 100 μg / dm ² or more when the roughened surface S contains Ni. The surface-treated copper foil according to any one of claims 1 to 5, wherein the adhesion amount of Co is 2000 μg / dm ² or less when the roughened surface S contains Co. The surface-treated copper foil according to any one of claims 1 to 6, wherein the adhesion amount of Co is 300 μg / dm ² or more when the roughened surface S contains Co.   The difference ΔB (ΔB = Bt−Bb) between the top average Bt and the bottom average Bb of the lightness curve which occurs from the end of the mark to the portion without the mark is 40 or more. The surface-treated copper foil as described in a term.   The surface-treated copper foil according to claim 8, wherein ΔB is 50 or more in the observation point-lightness graph produced from the image obtained by the photographing.   The surface-treated copper foil as described in any one of Claims 1-9 whose Sv defined by (1) Formula in the said brightness curve becomes 3.9 or more.   The surface-treated copper foil according to claim 10, wherein Sv defined by equation (1) in the lightness curve is 5.0 or more. The ten-point average roughness Rz of TD measured by the contact-type roughness meter of the roughened surface S is 0.20 to 0.80 μm, and the 60 degree gloss of the MD of the roughened surface S is 76 to 350%,
The ratio A / B of the surface area A of the roughening particles to the area B obtained when the roughening particles are viewed in plan from the roughening treated surface S side is 1.90 to 2.40. The surface-treated copper foil as described in any one of -11.   The 60-degree glossiness of MD of said roughened surface S is 90 to 250%, The surface-treated copper foil as described in any one of Claims 1-12.   The surface-treated copper foil according to any one of claims 1 to 13, wherein the ten-point average roughness Rz of TD measured by the contact-type roughness meter of the roughened surface S is 0.30 to 0.60 μm. .   The ratio A / B of the surface area A of the roughening particles to the area B obtained when the roughening particles are viewed in plan from the roughening treated surface S side is 2.00 to 2.20. The surface-treated copper foil as described in any one of -14.   The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD of the roughened surface S is 0.80 to The surface-treated copper foil according to any one of claims 1 to 15, which is 1.40.   The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD of the roughened surface S is 0.90 to 90 The surface-treated copper foil according to claim 16, which is 1.35.   The surface according to any one of claims 1 to 17, wherein a ten-point average roughness Rz of TD measured by a laser microscope in which the wavelength of the laser light of the roughened surface S is 405 nm is 0.35 μm or more. Treated copper foil.   The surface treatment according to any one of claims 1 to 18, wherein an arithmetic average roughness Ra of TD measured by a laser microscope in which the wavelength of the laser light of the roughened surface S is 405 nm is 0.05 μm or more. Copper foil.   The surface according to any one of claims 1 to 19, wherein a root mean square height Rq of TD measured by a laser microscope having a laser beam wavelength of 405 nm on the roughened surface S is 0.08 μm or more. Treated copper foil.   The roughened surface S includes any one or more selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. Surface-treated copper foil as described.   The surface-treated copper foil as described in any one of Claims 1-2 which equips the said roughening process surface S with a resin layer.   The surface-treated copper foil according to claim 22, wherein the resin layer contains a dielectric.   A copper foil with a carrier comprising a carrier, an intermediate layer and an ultrathin copper layer in this order, wherein the ultrathin copper layer is a surface-treated copper foil according to any one of claims 1 to 23. .   The copper foil with carrier according to claim 24, wherein the ultrathin copper layer is provided on both sides of the carrier.   The copper foil with a carrier according to claim 24, further comprising: a roughened layer on the surface of the carrier opposite to the very thin copper layer side.   The laminated board manufactured by laminating | stacking the surface-treated copper foil as described in any one of Claims 1-20, or the copper foil with a carrier as described in any one of Claims 24-26, and a resin substrate.   The printed wiring board using the surface-treated copper foil as described in any one of Claims 1-23, or the copper foil with a carrier as described in any one of Claims 24-26.   An electronic device using the printed wiring board according to claim 28. A printed wiring board comprising an insulating resin substrate and a copper circuit provided on the insulating substrate,
When the copper circuit is photographed by a CCD camera through the insulating resin substrate,
In an observation point-lightness graph produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed copper circuit extends, with respect to the image obtained by the photographing,
Let Bt be the top average value of the brightness curve generated from the end of the copper circuit to the portion without the copper circuit be Bt and the bottom average value be Bb, and the difference ΔB between the top average value Bt and the bottom average value Bb (ΔB = Bt Among the intersections of the lightness curve and Bt in the observation point-lightness graph, a value indicating the position of the intersection closest to the copper circuit is taken as t1, and Bt is used as a reference from the intersection of the lightness curve and Bt. In the depth range up to 0.1 ΔB, 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 defined as t2, it is defined by the following equation (1) Sv is 3.5 or more, and the surface on the insulating resin substrate side of the copper circuit contains one or more elements selected from the group consisting of Ni and Co, and the surface on the insulating resin substrate side of the copper circuit is Adhesion of Ni when it contains Ni Not more than 1400μg / dm ^2, the printed wiring board attached amount of Co is less than 2400μg / dm ² in the case where the insulating resin substrate side of the surface of the copper circuit comprises Co.
Sv = (ΔB × 0.1) / (t1-t2) (1) The printed wiring board according to claim 30, wherein when the surface on the insulating resin substrate side of the copper circuit contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less. The printed wiring board according to claim 30 or 31, wherein the adhesion amount of Ni is 100 μg / dm ² or more when the surface on the insulating resin substrate side of the copper circuit contains Ni. The printed wiring board according to any one of claims 30 to 32, wherein when the surface on the insulating resin substrate side of the copper circuit contains Co, the adhesion amount of Co is 2000 μg / dm ² or less. The printed wiring board according to any one of claims 30 to 33, wherein when the surface on the insulating resin substrate side of the copper circuit contains Co, the adhesion amount of Co is 300 μg / dm ² or more. A copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating substrate,
When the copper foil of the copper-clad laminate is made into a line-shaped copper foil by etching and then photographed with a CCD camera through the insulating resin substrate,
In an observation point-lightness graph produced by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed line-like copper foil extends, with respect to the image obtained by the photographing,
Let Bt be the top average value of the lightness curve generated from the end of the line-like copper foil to the portion without the line-like copper foil be Bt, and let the bottom average be Bb. As a difference ΔB (ΔB = Bt−Bb), in the observation point-lightness graph, among the intersections of the lightness curve and Bt, the value indicating the position of the intersection closest to the linear surface-treated copper foil is taken as t1. A value indicating the position of the closest intersection point to the line-shaped surface-treated copper foil among the intersection points of the brightness curve and 0.1ΔB in the depth range from the intersection of the curve and Bt to 0.1ΔB on the basis of Bt When t is t, Sv defined by the following equation (1) is 3.5 or more, and the surface of the copper foil on the insulating resin substrate side is at least one selected from the group consisting of Ni and Co. Of the copper foil, containing If the surface of the substrate side comprising the Ni is deposited amount of Ni is less than 1400μg / dm ^2, the adhesion amount of Co in the case where the insulating resin substrate side of the surface of the copper foil containing Co is 2400μg / dm ² Copper-clad laminates that are less.
Sv = (ΔB × 0.1) / (t1-t2) (1) The copper clad laminate according to claim 35, wherein when the surface on the insulating resin substrate side of the copper foil contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less. The copper clad laminate according to claim 35 or 36, wherein the adhesion amount of Ni is 100 μg / dm ² or more when the surface of the copper foil on the insulating resin substrate side contains Ni. The copper clad laminate according to any one of claims 35 to 37, wherein when the surface on the insulating resin substrate side of the copper foil contains Co, the adhesion amount of Co is 2000 μg / dm ² or less. The copper clad laminate according to any one of claims 35 to 38, wherein when the surface on the insulating resin substrate side of the copper foil contains Co, the adhesion amount of Co is 300 μg / dm ² or more.   The electronic device using the printed wiring board as described in any one of Claims 30-34.   A printed wiring board using the copper clad laminate according to any one of claims 35 to 39.   An electronic device using the copper clad laminate according to any one of claims 35 to 39.   A method for 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 28, 30 to 34 and 41.   42. At least one printed wiring board according to any one of claims 28, 30 to 34 and 41 and another printed wiring board or claim according to any one of claims 28, 30 to 34 and 41 The method to manufacture the printed wiring board which two or more printed wiring boards connected including the process of connecting with the printed wiring board which does not correspond to the printed wiring board in any one of claim 28, 30 to 34 and 41.   An electronic device using a printed wiring board to which at least one printed wiring board according to any one of claims 28, 30 to 34 and 41 is connected.   A printed circuit board according to any one of claims 28, 30 to 34 and 41, or a printed circuit board produced by the method according to claim 43 or 44, and at least a step of connecting a component How to manufacture a wiring board. 42. At least one printed wiring board according to any one of claims 28, 30 to 34 and 41 and another printed wiring board or claim according to any one of claims 28, 30 to 34 and 41 A process of manufacturing a printed wiring board A by connecting a printed wiring board not corresponding to the printed wiring board according to any one of items 28, 30 to 34, and 41, and
A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected, comprising at least a step of connecting the printed wiring board A and a component. 42. A printed wiring board according to any one of claims 28, 30 to 34 and 41,
A printed wiring board produced by the method according to claim 43 or 44, and
A printed wiring board which does not correspond to any of the printed wiring board according to any one of claims 28, 30 to 34 and 41 or the printed wiring board produced by the method according to claim 43 or 44,
And at least one printed wiring board selected from the group consisting of
A printed wiring board manufactured by the method according to claim 46,
A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting   The surface-treated copper foil used for the printed wiring board as described in any one of Claims 30-34.   The surface-treated copper foil used for the copper clad laminated board as described in any one of Claims 35-39. A process of preparing the copper foil with carrier according to any one of claims 24 to 26 and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier.
And then forming a circuit by any of a semi-additive method, a subtractive method, a partial additive method or a modified semi-additive method. A process of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 24 to 26,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is embedded;
Forming a circuit on the resin layer;
Separating the carrier or the ultrathin copper layer after forming a circuit on the resin layer;
After peeling off the carrier or the ultrathin copper layer, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. Method of producing a printed wiring board including the step of exposing the circuit.   In the step of forming a circuit on the resin layer, another copper foil with a carrier is bonded to the resin layer from the very thin copper layer side, and the copper foil with a carrier bonded to the resin layer is used to form the circuit. The method for manufacturing a printed wiring board according to claim 52, which is a forming step.   The method for producing a printed wiring board according to claim 53, wherein the other carrier-attached copper foil to be attached onto the resin layer is the carrier-attached copper foil according to any one of claims 24 to 26.   The print according to any one of claims 52 to 54, wherein the step of forming a circuit on the resin layer is performed by any of a semi-additive method, a subtractive method, a partly additive method or a modified semi-additive method. Wiring board manufacturing method.   The copper foil with a carrier which forms a circuit on the surface has a substrate or a resin layer on the surface on the carrier side of the copper foil with a carrier or the surface on the very thin copper layer side. The manufacturing method of the printed wiring board as described.