JP6537279B2 - 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 studies, the present inventors have made a mark on a polyimide substrate which is removed by bonding from the treated surface side a copper foil whose surface mean square height Rq is controlled to a predetermined range by surface treatment. The printed matter with the mark below is placed under, and attention is paid to the inclination of the lightness curve in the vicinity of the mark end portion drawn in the observation point-brightness graph obtained from the image of the marked portion Controlling the slope of the lightness curve affects resin transparency and signal transmission loss after etching away the copper foil without being affected by the type of substrate resin film and the thickness of the substrate resin film. I found out.
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.

The present invention completed based on the above findings is, in one aspect, a surface-treated copper foil in which one copper foil surface is the surface-treated surface S and the other copper foil surface is surface-treated. The laser light of the surface of the copper foil which is not the surface treated surface S is a root mean square height Rq of 0.14 to 0.63 μm measured by a laser microscope in which the wavelength of the laser light of the surface treated surface S is 405 nm. The ten-point average roughness Rz of TD measured with a laser microscope having a wavelength of 405 nm is 0.35 μm or more, and the copper foil is attached to both sides of the polyimide resin substrate from the surface treated surface S side and then etched. The copper foils on both sides were removed and the printed matter on which the line mark was printed was placed under the exposed polyimide substrate, and the printed matter was photographed by the CCD camera through the polyimide substrate When the mark obtained in the observation point-lightness graph is manufactured by measuring the lightness at 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. The difference between the top average Bt and the bottom average Bb of the lightness curve that occurs from the end of the area to the portion where the mark is not drawn is ΔB (ΔB = Bt−Bb), and the observation point—the lightness curve Of the points of intersection with Bt, a value indicating the position of the point of intersection closest to the line-shaped mark is t1, and the lightness curve is from the point of intersection of the lightness curve and Bt to the depth range of 0.1 ΔB with When the value indicating the position of the intersection closest to the linear mark among the intersections with 0.1 ΔB is t2, Sv defined by the following equation (1) is 3.5 or more, and the surface treatment is performed. Surface S is Ni, include any one or more elements selected from the group consisting of Co, when the treated surface S comprises Ni is deposited amount of Ni is less than 1400μg / dm ^2, the treated surface When S contains Co, the adhesion amount of Co is 2400 μg / dm ² or less.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In the present invention, in another aspect, one surface of the copper foil is a surface-treated surface S, and the other surface of the copper foil is surface-treated. Laser whose root mean square height Rq is 0.14 to 0.63 μm measured with a laser microscope whose wavelength of the laser light is 405 nm, and whose wavelength of the laser light on the copper foil surface which is not the surface treated surface S is 405 nm Arithmetic mean roughness Ra of TD measured with a microscope is 0.05 μm or more, and after bonding the copper foil to both sides of the polyimide resin substrate from the surface treated surface S side, the copper foils on both sides are removed by etching When the printed matter on which the line-shaped 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 the observation point-lightness graph prepared by measuring the lightness at each observation point along the direction perpendicular to the direction in which the observed line-like mark extends, the mark from the end of the mark Let ΔB (ΔB = Bt−Bb) be the difference between the top average Bt and the bottom average Bb of the lightness curve that occurs over the undrawn part, and in the observation point-lightness graph, within the intersection of the lightness curve and Bt, Assuming that the value indicating the position of the intersection closest to the linear mark is t1, the intersection of the lightness curve and 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB based on Bt Wherein, when the value indicating the position of the intersection closest to the linear mark is t2, Sv defined by the following equation (1) is 3.5 or more, and the surface treatment surface S is made of Ni, Co The Include any one or more elements selected from the group, the adhesion amount of Ni in the case where the treated surface S comprises Ni is less 1400μg / dm ^2, when the treated surface S contains Co The surface-treated copper foil has an adhesion amount of Co of 2400 μg / dm ² or less.
Sv = (ΔB × 0.1) / (t1-t2) (1)

In the present invention, according to still another aspect, the surface-treated copper foil is one surface-treated surface S and the other copper foil surface is surface-treated, the surface-treated surface S The wavelength of the laser beam at the surface of the copper foil which is not the surface treated surface S is 405 nm, the root mean square height Rq measured with a laser microscope having a wavelength of 405 nm is 0.14 to 0.63 μm. The root-mean-square height Rq of TD measured with a laser microscope is 0.08 μm or more, and after bonding the copper foil to both sides of the polyimide resin substrate from the surface treated surface S side, the copper foils on both sides by etching The printed matter on which the line mark has been printed is placed under the exposed polyimide substrate, and the printed matter is photographed with the CCD camera through the polyimide substrate. 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 observed line-like mark extends, the image obtained by Let ΔB (ΔB = Bt−Bb) be the difference between the top average Bt and the bottom average Bb of the lightness curve that occurs from the point to the portion where the mark is not drawn, and let ΔB (ΔB = Bt−Bb) Among the intersection points, a value indicating the position of the intersection point closest to the linear mark is t1, and the lightness curve and the 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB based on Bt When the value indicating the position of the intersection closest to the linear mark is t2 among the intersections with, the Sv defined by the following equation (1) is 3.5 or more, and the surface treated surface S is Ni, include any one or more elements selected from the group consisting of o, the adhesion amount of Ni in the case including the treated surface S of Ni is less than 1400μg / dm ^2, the treated surface S is Co In the case where the amount of Co attached is 2400 μg / dm ² or less.
Sv = (ΔB × 0.1) / (t1-t2) (1)

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

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

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

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

  In another embodiment of the surface-treated copper foil according to the present invention, the root mean square height Rq of the surface-treated surface S measured with a laser microscope having a wavelength of 405 nm is 0.25 to 0.60 μm. .

  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 surface-treated surface S is 0.20 to 0.64 μm.

  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 surface-treated surface S is 0.26 to 0.62 μm.

  In still another embodiment of the surface-treated copper foil according to the present invention, the ratio A / B of the three-dimensional surface area A to the two-dimensional surface area B of the surface treated surface S is 1.0 to 1.7.

  In still another embodiment of the surface-treated copper foil according to the present invention, the ratio A / B of the three-dimensional surface area A to the two-dimensional surface area B of the surface treated surface S is 1.0 to 1.6.

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

  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 surface-treated surface S is 405 nm is 0.05 μm or more is there.

  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 surface treated surface S is 405 nm is 0.08 μm or more It is.

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

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

  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 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.

  Another aspect of the present invention is an electronic device using the printed wiring board of the present invention or the copper foil with a carrier 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 one or more printed wiring boards 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, which comprises at least a step of connecting the printed wiring board produced by the method of the present invention and a component.

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.

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 another aspect of the present invention, 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 carrier is bonded to the resin layer. It is the manufacturing method of the printed wiring board which is a process of forming the said circuit using attached copper foil.

  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 another aspect of the present invention, a printed wiring board is manufactured, wherein the step of forming a circuit on the resin layer is performed by any of a semi-additive method, a subtractive method, a partory additive method or a modified semi-additive method. It is a method.

  In another aspect of the present invention, there is provided a printed wiring in which a copper foil with a carrier forming 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. It is a manufacturing method of a board.

  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 comparative example 1 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 1 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 2 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 3 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 4 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of Example 5 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 6 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 7 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of Example 8 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of Example 9 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of comparative example 2 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of comparative example 3 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. Usually, the surface of the copper foil to be bonded to the resin substrate, that is, the surface on the surface treatment side, is shaped like a bump on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after lamination. The roughening process which performs electrodeposition of these may be given. Although the electrodeposited copper foil has irregularities at the time of manufacture, the projections can be reinforced by the roughening treatment to make the asperity larger. In the present invention, when the roughening treatment is performed, the 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. And in this invention, when performing a roughening process, a current density is made higher than the conventional roughening process, and the roughening process time is shortened. Hereinafter, in the present invention, the copper foil surface on which the surface treatment including such treatment is performed is also referred to as a surface-treated surface S.

In the surface-treated copper foil of the present invention, one copper foil surface and / or both copper foil surfaces are the surface-treated surface S. 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 a finishing treatment after the roughening to prevent detachment of the electrodeposit. In the present invention, such pretreatment and finishing may be performed. Moreover, surface treatment may be carried out to both copper foil surfaces.
In the surface-treated copper foil of the present invention, one copper foil surface may be the surface-treated surface S, and the other copper foil surface may be surface-treated.

The surface-treated copper foil which is one embodiment of the present invention is provided with a heat-resistant (plating) layer or a rust-preventing (plating) layer on the surface after the roughening treatment is performed or the roughening treatment is omitted. It may be done. When the heat-resistant layer and the rust-preventive layer are provided by omitting the roughening treatment, the current density is made higher than in the conventional normal plating conditions, and the plating time is shortened.
The thickness of the copper foil used in the present invention is not particularly limited, but is, for example, 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, for example, 3000 μm or less, 1500 μm or less, 800 μm or less, 300 μm or less, 150 μm or less 100 μm or less, 70 μm or less, 50 μm or less, and 40 μm or less.
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 and performing the above-mentioned roughening treatment, the above-mentioned roughening treatment is performed on the surface of the ultrathin copper layer. In addition, the copper foil with a carrier which is another embodiment of this invention is mentioned later.
In the present invention, the copper foil used in the present invention has a predetermined surface roughness Rz (ten-point average roughness (the ten-point average roughness (see below)) as described later on the surface to be surface-treated before surface treatment to form the surface-treated surface S. According to JIS B0601 1994)) and 60 degree glossiness.
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.)
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 60 ° C
Electrolyte linear velocity: 3 to 5 m / sec
Electrolysis time: 0.5 to 10 minutes

Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be the 15~40mg / dm ² of copper -250~2400μg / dm ² of cobalt -50~1400μg / dm ² of nickel It can be implemented to form a ternary ternary alloy layer. 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 deposition amount exceeds 2400 μg / dm ² , the signal transmission loss increases. 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 1400 μg / dm ² , the transmission loss of the signal becomes large. In addition, the etching residue may be increased. The preferred Co deposition amount is 300 to 2000 μg / dm ² , the more preferred Co deposition amount is 300 to 1800 μg / dm ² , the preferred nickel deposition amount is 100 to 1000 μg / dm ² , and the more preferred nickel deposition amount is 100. It is ̃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 to end up.

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 surface treatment surface S, the current density of the roughening treatment is higher than that of the conventional roughening treatment conditions. To reduce roughening processing 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 "surface-treated surface" refers to the surface treatment when roughening treatment is followed by surface treatment for providing a heat-resistant layer, an antirust layer, a weather resistant layer, etc. Surface of the surface-treated copper foil after In the case where the surface-treated copper foil is an ultrathin copper layer of copper foil with a carrier, the "surface-treated surface" is to provide a heat-resistant layer, an anticorrosive layer, a weather resistant layer, etc. after roughening treatment. When the surface treatment is performed, it means the surface of the ultrathin copper layer after the surface treatment.
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.
Further, as the heat-resistant layer and / or anticorrosive layer, cobalt nickel adhesion amount of 200~2400μg / dm ² of cobalt -50~1400μg / dm ² - nickel alloy plating layer, more preferably the amount of deposition is 200～2000Myug / dm ² cobalt-50 to 1000 μg / dm ² of nickel-cobalt-nickel alloy plating layer of nickel, more preferably cobalt-nickel alloy plating of 200 to 2000 μg / dm ² of cobalt-50 to 700 μg / dm ² of nickel Layers can be formed. 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 2400 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 50 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 1400 μg / dm ² , the transmission loss of the signal increases. As a heat-resistant layer and / or an anticorrosion layer, the preferable nickel adhesion amount is 50 to 600 μg / dm ² , and the more preferable nickel adhesion amount is 100 to 600 μg / dm ² .

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 : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

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 : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

  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.

Moreover, the metal-plating process by Ni-plating bath of the following conditions can be used as a process which abbreviate | omits a roughening process and gives a heat-resistant plating layer and a rust-prevention plating layer on the surface.
Ni: 15 to 25 g / L
pH: 2.5
Temperature: 35-45 ° C
Current density D _k : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

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.

In the surface-treated copper foil of the present invention, when the surface treatment for forming the surface-treated surface S is not roughened, the current density is lower than that of the roughening treatment so that the plated film can not be uneven as described above And by processing in a shorter time than normal plating at a higher current density than normal plating, and by using a high current density in the case of performing a roughening treatment, the size of the roughened particles can be reduced. And plating in a short time enables surface treatment with a small roughness, thereby controlling the root mean square height Rq of the surface.
In the present invention, "normal plating" refers to plating that is not roughening plating (burnt plating).

[Root mean square height Rq of surface treated copper foil surface]
The surface-treated copper foil of the present invention has a root-mean-square height Rq of 0.14 to 0.63 μm, which is measured with a laser microscope in which the wavelength of laser light on the surface-treated surface S is 405 nm. With such a configuration, the peel strength is increased to adhere well to the resin, and the transparency of the resin after the copper foil is removed by etching is increased. 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 root mean square height Rq is less than 0.14 μm, the degree of irregularities on the surface of the copper foil will be insufficient, resulting in the problem that the resin can not be sufficiently adhered. On the other hand, if the root mean square height Rq is more than 0.63 μm, the irregularities on the resin surface after removing the copper foil by etching become large, resulting in a problem that the transparency of the resin becomes poor. As for root mean square height Rq measured with a laser microscope whose wavelength of a laser beam of surface treatment side S is 405 nm, 0.25-0.60 micrometers is more preferred, and 0.32-0.56 micrometers is still more preferred.
Here, the root mean square height Rq of the surface is the degree of unevenness in the surface roughness measurement with a noncontact roughness meter (laser microscope having a laser beam having a wavelength of 405 nm) according to JIS B 0601 (2001). The surface roughness is represented by the following equation, and is the height of unevenness (mountain) in the Z-axis direction of the surface roughness, and is the root mean square of the mountain height Z (x) at the reference length lr .
Root-mean-square height Rq of mountain height at reference length lr:
√ {(1 / lr) x ∫ Z ² (x) dx (where integral is an integrated value from 0 to lr)}

[Ten-point average roughness Rz of surface-treated copper foil surface]
The surface-treated copper foil of the present invention may be a non-roughened treated copper foil or a roughened treated copper foil on which roughened particles are formed, and the TD measured in the contact direction roughness meter of the surface treated surface S (in the rolling direction The ten-point average roughness Rz (JIS B0601 1994) in the vertical direction (width direction of the copper foil) and in the direction perpendicular to the foil passing direction of the copper foil in the electrolytic copper foil manufacturing apparatus in the case of the electrodeposited copper foil is 0. It is preferable that it is 20-0.64 micrometer. With such a configuration, the peel strength is further enhanced, and the resin adheres well to the resin, and the transparency of the resin after the copper foil is removed by etching is further enhanced. As a result, the 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 easier. 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, the degree of irregularities on the surface of the copper foil may be insufficient, and there may be a problem that the resin can not be sufficiently adhered. On the other hand, if the ten-point average roughness Rz of TD is more than 0.64 μm, the unevenness of the resin surface after removing the copper foil by etching may become large, and as a result, the transparency of the resin becomes poor. May occur. The ten-point average roughness Rz of TD measured by the contact-type roughness meter of the surface-treated surface S is more preferably 0.26 to 0.62 μm, and still more preferably 0.40 to 0.55 μm.

Here, in order to obtain the effect of visibility of the present invention and the effect of reduction of transmission loss, the surface on the treated side of the copper foil before the surface treatment for forming the surface treated surface S In the case of an ultrathin copper layer of foil, the direction TD (direction of the copper foil width) measured with a contact-type roughness meter on the surface of the carrier on which the intermediate layer is to be provided before formation of the intermediate layer In the case of an electrodeposited copper foil, it means the roughness (Rz (ten-point average roughness Rz (JIS B0601 1994)) of the direction perpendicular to the foil passing direction of the copper foil in the electrodeposited copper foil manufacturing apparatus). It is necessary to control the same in the specification) and gloss (meaning 60 degree gloss (measured in accordance with JIS Z8741); the same in this specification). Specifically, the TD of the copper foil before surface treatment (in the case where the surface treated copper foil is the ultrathin copper layer of the copper foil with carrier, the carrier before formation of the intermediate layer) The surface roughness (ten-point average roughness Rz) is 0.20 to 0.55 μm, preferably 0.20 to 0.42 μm.
In addition, the copper foil before surface treatment for forming the surface treated surface S has a TD 60 degree glossiness of 400 to 710%, and more preferably 500 to 710%. If the 60 degree gloss of the TD of the copper foil before surface treatment is less than 400%, the transparency of the above-mentioned resin may be worse than in the case of 400% or more, and the transmission loss of the signal may be increased. There is. If it exceeds 710%, there may be a problem that it becomes difficult to manufacture. 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 rolling Roll roughness can be adjusted to perform rolling, or it can be produced by chemical polishing such as chemical etching or electropolishing 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.

High gloss rolling can be performed by setting the oil film equivalent defined by the following equation to 8500 to 24000 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 8500 to 24000, a known method may be used, such as using a low viscosity rolling oil, or slowing the threading speed.
The surface roughness of a rolling roll can be 0.01-0.25 micrometer by arithmetic mean roughness Ra (JIS B0601 1994), for example. When the value of the arithmetic average roughness Ra of the rolling rolls is large, the TD roughness (Rz) of the surface of the copper foil before the surface treatment for forming the surface treated surface S becomes large, and the copper foil before the surface treatment There is a tendency for the 60 degree gloss of the surface TD to be low. In addition, when the value of the arithmetic average roughness Ra of the rolling rolls is small, the TD roughness (Rz) of the surface of the copper foil before surface treatment becomes small, and the 60 degree gloss of the TD of the surface of the copper foil before surface treatment The degree tends to be high.
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.)

-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.

[Slope of lightness curve]
In the surface-treated copper foil of the present invention, after bonding the surface-treated copper foil to both sides of the polyimide base resin from the surface-treated surface S side, 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, which is produced by measuring the lightness of each observation point along the line, 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 where the mark is not drawn Let the difference be ΔB (ΔB = Bt−Bb), and in the observation point-lightness graph, among the intersections of the lightness curve and Bt, the intersection closest to the line mark is t1. Then, in the depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt, when the intersection closest to the linear mark is t2 among the intersections of the brightness curve and 0.1 ΔB. In addition, Sv defined by equation (1) is 3.5 or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)
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 near the end of the mark drawn in the observation point-lightness graph obtained from the image of (b) is controlled. More specifically, the difference between the top average Bt and the bottom average Bb of the lightness curve is ΔB (ΔB = Bt−Bb), and in the observation point-lightness graph, the line among the intersections of the lightness curve and Bt. Assuming that the value indicating the position of the intersection closest to the shape mark (the value of the observation point-the horizontal axis of the lightness graph) is t1, 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 line-like mark (the observation point-the value of the horizontal axis of the lightness graph) of the intersections of the lightness curve and 0.1ΔB is t2, Sv defined by 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. Sv is preferably 3.9 or more, more preferably 4.5 or more, still more preferably 5.0 or more, and still more preferably 5.5 or more. Although the upper limit of Sv does not need to be specifically limited, it is 70 or less, 30 or less, 15 or less, 10 or less, for example. 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 values of (DELTA) B ((DELTA) B (PI)) before bonding to a copper foil are 50 or more and 65 or less for the polyimide film used for measurement of the inclination of a brightness curve. 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 surface-treated surface S contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the surface-treated surface S 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 treated surface S means the adhesion amount of the total of Ni and Co contained in all the 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, an antirust layer, and a weather resistant layer, the roughening treatment layer which is a surface treatment layer formed on the surface of the copper foil, a heat resistant layer It means the adhesion amount of the sum total of the adhesion amounts of Ni and Co contained in 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 the transmission loss, when the surface-treated 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 ² or less, more preferably 700 [mu] g / dm ² or less.
When the surface-treated 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 more preferably 150 μg / dm ² or 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, the adhesion amount of Co in the case of surface treatment the surface S comprises a Co is preferably not more than 2000 [mu] g / dm ^2, is preferably 1800 [mu] g / dm ² or less, 1600μg / dm ² It is preferable that it is the following and it is more preferable that it is 1400 microgram / dm < ² > or less.
When the surface-treated 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 more preferably 400 μg / dm ² or 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 ten-point average roughness TD measured by a laser microscope in which the wavelength of the laser light of the surface-treated surface S and / or the copper foil surface other than the surface-treated 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 surface-treated 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 ten-point average roughness TD measured by a laser microscope in which the wavelength of the laser light of the surface-treated surface S and / or the copper foil surface other than the surface-treated 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 surface-treated surface S of the surface-treated copper foil of the present invention and / or the laser light on the surface of the copper foil other than the surface-treated surface S is 405 nm 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 an arithmetic average roughness Ra of TD measured with a laser microscope in which the wavelength of the laser light of the surface-treated surface S and / or the copper foil surface other than the surface-treated 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 surface-treated 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 an arithmetic average roughness Ra of TD measured with a laser microscope in which the wavelength of the laser light of the surface-treated surface S and / or the copper foil surface other than the surface-treated 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 said surface-treated surface S and / or the said surface-treated 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.

  In the surface-treated copper foil of 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 copper foil surface other than the surface-treated surface S is 405 nm is 0.08 μm or more Is preferred. Furthermore, it is more preferable that the copper foil surface which is not the surface-treated 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. In the surface-treated copper foil of 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 copper foil surface other than the surface-treated surface S is 405 nm is 0.10 μm or more Is 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 upper limit of the root mean square height Rq of TD of the surface-treated copper foil of the present invention measured by a laser microscope whose wavelength of the laser light on the surface of the copper foil other than the surface S is 405 nm is particularly limited. Although not necessary, it is typically 0.80 μm or less, more typically 0.60 μm or less, more typically 0.50 μm or less, and more typically 0.40 μm or less. is there.

The surface of the copper foil which is not the surface treated surface S may be subjected to a treatment of providing a heat-resistant layer or an anticorrosive layer by plating (normal plating, plating not roughening plating) as surface treatment. Moreover, the copper foil surface which is not the said surface 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 surface treatment surface S, and when not roughening process, you may use surface treatments other than said plating process.
Moreover, the copper foil surface which is not the said surface treatment 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 surface treatment surface S in a solution composed of copper sulfate and a sulfuric acid aqueous solution, irregularities can be formed on the copper foil surface which is not the surface treatment 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 surface treated surface S of the present invention, irregularities are formed by the electrolytic polishing. 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 on the copper foil surface which is not the surface treatment surface S, for example, the unevenness may be formed by mechanically polishing the copper foil surface which is not the surface treatment 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 the surface-treated surface S in the surface-treated copper foil of this invention. 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.

[Area ratio of copper foil surface]
The ratio A / B of the three-dimensional surface area A to the two-dimensional surface area B of the surface treated surface S of the copper foil 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 1.0 to 1.7, and more preferably 1.0 to 1.6. Here, the ratio A / B of the three-dimensional surface area A of the roughened particles to the two-dimensional surface area B of the surface treated surface S is, for example, the surface area A of the roughened particles and copper when the surface is roughened. It can be said that the ratio A / B to the area B obtained when the foil is viewed in plan from the surface treated surface S side.

  By controlling the current density of the surface treatment and the plating time at the time of surface treatment such as roughening particle formation, the surface condition of the surface treatment surface S of the copper foil after surface treatment and the form and formation density of roughening particles are determined. The above root mean square heights Rq and Sv, surface roughness Rz, glossiness, and area ratio A / B of the copper foil surface can be controlled.

[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. Polyimide film with a thermosetting adhesive for lamination (surface thickness S: 50 μm, UPI REX made by Ube Industries, Ltd.) {Eupirex (registered trademark)-VT, BPDA (biphenyl tetracarboxylic acid dianhydride) type After laminating on a polyimide resin substrate of BPDA-PDA (para-phenylenediamine) and after heating at 150 ° C. for 168 hours, the tensile tester autograph 100 conforms to normal peel strength in accordance with IPC-TM-650. The peel strength was measured after heating at 150 ° C. for 168 hours.
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 surface treated surface S or the like on the surface on the carrier side of the ultrathin copper layer and / or the surface opposite to the carrier side. In addition, it is preferable in order to improve working efficiency that the copper foil with carrier has a surface-treated surface such as the surface-treated surface S on the surface opposite to the carrier side of the ultrathin copper layer.
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 root mean square heights Rq and Sv, the surface roughness Rz, the glossiness and the area ratio A / B of the copper foil surface of the surface on which the surface treatment of the ultrathin copper layer is performed.

<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 surface treatment surface S may be provided on either or both of the surface of the ultrathin copper layer opposite to the carrier side and / or the surface of the ultrathin copper layer on the carrier side. Moreover, it is preferable to provide the surface treatment surface S on the surface on the opposite side 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 root mean square height Rq, Sv of the surface treated surface S after surface treatment of the ultrathin copper layer, surface roughness Rz, glossiness, and area ratio of copper foil surface This is to control A / B.
-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 surface treatment surface S]
A resin layer may be provided on the surface-treated 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 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 polyamideimide 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 on its surface-treated surface S by, for example, a roll coater method, and then dried by heating if necessary to remove the solvent and put it in 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. When the thickness of the cured resin layer is less than 2 μm, it may be necessary to consider the surface roughness of the surface-treated 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 surface-treated surface S of the surface-treated copper foil are used to improve the adhesion between the resin layer and the surface-treated copper foil. After providing the rustproof layer and / or the weather resistant layer, it is preferable to form a resin layer on the heat resistant layer or the rustproof 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 copper foil with a carrier, it is formed on the surface-treated surface S of the ultra-thin copper layer (surface-treated copper foil). 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 color difference on 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 surface-treated 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 surface treatment surface S on 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.

(Laminated board and method of positioning printed wiring board using the same)
The method of positioning the laminate of the surface-treated copper foil of the present invention and the resin substrate will be described. First, a laminate of surface-treated copper foil and a resin substrate is prepared. Specific examples of the laminate of the surface-treated copper foil and the resin substrate of the present invention include at least one of the main substrate and the attached circuit substrate, and a resin substrate such as polyimide used to electrically connect them. In an electronic device configured of a flexible printed circuit board having a copper wiring formed on the surface, a laminated board manufactured by correctly 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 Can be mentioned. That is, in this case, in the laminated board, a laminate obtained by bonding the flexible printed circuit board and the wiring end of the main substrate by pressure bonding, or the wiring end of the flexible printed circuit and the circuit board is bonded by pressure bonding Become a laminated board. The laminate has a part of the copper wiring and a mark formed of a separate 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.

  In the laminate prepared as above, when the above mark is photographed by the photographing means through the resin, the position of the mark can be detected favorably. And the position of the said mark can be detected in this way, and the positioning of the laminated board of a surface-treated copper foil and a resin substrate can be performed favorably based on the position of the said detected mark. Also, even when a printed wiring board is used as a laminate, similarly, the imaging means can detect the position of the mark well by such a positioning method, and 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. In addition, as a method of connecting one printed wiring board and another printed wiring board, soldering, connection via an anisotropic conductive film (Anisotropic Conductive Film, ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via an adhesive having conductivity can be used. 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 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. In the present invention, "copper circuit" includes copper wiring. Furthermore, the printed wiring board of the present invention may be connected to components to produce a printed wiring board. Further, at least one printed wiring board of the present invention is connected to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, and the printed wiring board of the present invention A printed wiring board in which two or more printed wiring boards are connected may be manufactured by connecting a printed wiring board connected with one or more components and a component. Here, "parts" include electronic parts such as connectors, LCDs (Liquid Cristal Display), glass substrates used for LCDs, Integrated Circuits (ICs), Large scale integrated circuits (LSI), Very Large scale integrated circuits (VLSI). ), Electronic components including semiconductor integrated circuits such as ULSI (Ultra-Large Scale Integrated circuits) (for example, IC chips, LSI chips, VLSI chips, ULSI chips), components for shielding electronic circuits, covers for printed wiring boards, etc. Parts required to fix the

The positioning method according to the embodiment of the present invention may include the step of moving a laminate (including a laminate of a copper foil and a resin substrate 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 gas. It may be moved by a moving means, or 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.
Moreover, the printed wiring board which has a circuit board provided on the resin board and the said resin board may be sufficient as the laminated board of the surface-treated copper foil and the resin substrate which are positioned in this invention. 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”.
In the printed wiring board, a circuit on the printed wiring board can be used as a mark instead of the mark on the printed matter, and the circuit can be photographed with a CCD camera through resin to measure the value of Sv. In addition, for copper-clad laminates, copper is made into a line by etching, and then the line-shaped copper is taken as a mark instead of the printed mark, and the line-shaped copper is photographed with a CCD camera. The value of Sv can be measured.

The copper foils described in Table 1 are prepared as Examples 1 to 10, Examples 15 to 20, and Comparative Examples 1 to 5, and plating treatment is performed on one surface under the conditions described in Table 2 as surface treatment. went.
In Examples 11 to 14, various carriers described in Table 1 were prepared, and 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. Then, the surface treatment described in Table 2 was performed on the surface of the ultrathin copper layer.
In addition, the surface-treated copper foil which does not perform a roughening process was also prepared. "None" in the "roughening treatment" column of "surface treatment" in Table 2 indicates that the surface treatment is not roughening treatment, and "presence" indicates that the surface treatment is roughening treatment.
Example 11
<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
Example 12
<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 11 except that the thickness of the ultrathin copper layer was 3 μm.
Example 13
<Middle class>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in Example 11.
(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 11 except that the thickness of the ultrathin copper layer was 2 μm.
Example 14
<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 11 except that the thickness of the ultrathin copper layer was 5 μm.

In addition, rolled copper foil ("tough pitch copper" of the "type" column of Table 1 shows that it is a rolled copper foil.) Was manufactured as follows. After predetermined copper ingots were produced and subjected to hot rolling, annealing and cold rolling of a continuous annealing line at 300 to 800 ° C. were repeated to obtain a rolled sheet having a thickness of 1 to 2 mm. 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 1 under the conditions described in Table 1 to obtain a copper foil. "Tough pitch copper" of Table 1 shows tough pitch copper standardized to JIS H3100 C1100.
In addition, the point of the copper foil preparation process before surface treatment was described in Table 1. "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. In Examples 1 and 2, copper foils having thicknesses of 6 μm, 12 μm, and 35 μm were also produced.
The leveling agent 1 and the leveling agent 2 in Example 2 are the leveling agent 1 and the leveling agent 2 used in the plating bath at the time of forming the ultrathin copper layer in Examples 11 to 14 described above. Same.
Moreover, about Example 2, predetermined | prescribed surface treatment was performed to the precipitation surface (surface on the opposite side to the surface on the side which is in contact with the electrolytic drum at the time of electrolytic copper foil manufacture). In addition, for the electrodeposited copper foil of Table 1, the surface roughness Rz and the degree of gloss on the deposition surface side are described.
In addition, the surface-treated copper foil which surface-treated in Table 4 in the other surface was manufactured also about the surface-treated copper foil obtained by Examples 1-3, Examples 5-10, and the comparative example 1 was also manufactured. . Here, "Example No.-number" in Table 4 means that the surface treatment described in Table 4 was performed on the other surface of the surface-treated copper foil obtained in the example. For example, in Table 4, “Example 1-1” is the other surface of Example 1 subjected to the surface treatment described in Table 4, and “Example 2-1” is the same as Example 2. The other surface was subjected to the surface treatment described in Table 4.

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);
About the copper foil after the surface treatment of each example and comparative example, the Kosaka research institute Co., Ltd. product contact-type roughness meter Surfcorder SE-3C is used and surface treatment of ten-point average roughness is carried out based on JIS B0601-1994. The surface was measured. 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, for rolled copper foil, the direction perpendicular to the rolling direction Travel direction: Change the measurement position to TD, that is, the width direction, or, for electro-deposited copper foil, measure position in the direction (TD, ie, the width direction) perpendicular to the travel direction of electro-deposited copper foil in the electrolytic copper foil manufacturing equipment Was changed ten times each, and the average value of ten measurements was taken as the value of the surface roughness (Rz). When the surface-treated copper foil is the ultrathin copper layer of the copper foil with carrier, the above measurement was performed on the surface-treated surface of the ultrathin copper layer.
In addition, surface roughness (Rz) was similarly calculated | required about the copper foil before surface treatment.

(1-2) Measurement of the root mean square height Rq of the surface;
About the surface treatment surface of the copper foil after surface treatment of each Example and a comparative example, root mean square height Rq of the copper foil surface was measured with Olympus Corporation laser microscope OLS4000. Evaluation length 647μm, with a cutoff value of zero, for rolled copper foil, measurement in the direction (TD) perpendicular to the rolling direction, or for electrodeposited copper foil, progress of electrodeposited copper foil in a device for producing electrodeposited copper foil Each value was determined by measurement in the direction (TD) perpendicular to the direction. In addition, the measurement environmental temperature of the root mean square height Rq of the surface by a laser microscope was 23-25 degreeC. When the surface-treated copper foil is the ultrathin copper layer of the copper foil with carrier, the above measurement was performed on the surface-treated surface of the ultrathin copper layer.

(2) Measurement of surface roughness of the other surface (copper foil surface not surface treated surface S);
It is preferable to measure surface roughness using the non-contact method about the other surface of each Example and a comparative example. 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 for the surface treated surface S.

・ 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 for the surface treated surface S.

・ Measurement of surface arithmetic mean roughness Ra;
Based on JIS B0601-1994, the surface roughness Ra of the other surface of the copper foil of each Example and Comparative Example (the other surface after surface treatment when the other surface is subjected to surface treatment) , And a laser microscope OLS4000 manufactured by Olympus Corporation. 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 for the surface treated surface S.

(3) Area ratio of copper foil surface (A / B);
The surface area of the copper foil surface was measured by a laser microscope. The surface treated surface of the copper foil after the surface treatment of each example and comparative example, using a laser microscope OLS4000 manufactured by Olympus, has an area B equivalent to 647 μm × 646 μm at 20 times magnification of the treated surface (actual data is 417, 953 μm ² ) The three-dimensional surface area A in was measured, and the setting was performed by the method of three-dimensional surface area A / two-dimensional surface area B = area ratio (A / B). In addition, the measurement environmental temperature of the three-dimensional surface area A by a laser microscope was 23-25 degreeC. When the surface-treated copper foil is the ultrathin copper layer of the copper foil with carrier, the above measurement was performed on the surface-treated surface of the ultrathin copper layer.

(4) glossiness;
Glossmeter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z8741 is used. For rolled copper foils, the glossiness at an incident angle of 60 degrees in the direction (TD) perpendicular to the rolling direction, or For the electrodeposited copper foil, the glossiness at an incident angle of 60 degrees in the direction (TD) perpendicular to the traveling direction of the electrodeposited copper foil in the production apparatus of the electrodeposited copper foil was measured for each of the copper foils before surface treatment.

(5) Inclination of lightness curve From the surface side of the surface-treated copper foil, a polyimide film (Kaneka thickness 50 μm (PixEo for two-layer copper-clad laminates (polyimide type: FRS), copper) Bonded to both sides of polyimide film with adhesive layer for tension laminates, PMDA (pyromellitic anhydride) -based polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film)), and surface treatment The copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. When the surface-treated copper foil is an ultrathin copper layer of copper foil with carrier, the copper foil with carrier is attached to both sides of the polyimide film from the surface side where the surface treatment of the ultrathin copper layer is performed, Then, after peeling off the carrier, the ultrathin copper layer was removed by etching (aqueous ferric chloride 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). Observation point-brightness 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, occurs from the end of the mark to the part where the mark is not drawn The slope (angle) of the lightness curve was measured. FIG. 3 is a schematic view showing the configuration of the photographing apparatus used at this time and the method of measuring the inclination of 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.
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.

(6) Visibility (resin transparency);
Surface-treated copper foil, from the surface side where the surface treatment is performed Polyimide film (Kaneka thickness 50 μm (Pixeo for two-layer copper-clad laminate (PIDEO) (polyimide type: FRS), with adhesive layer for copper-clad laminate) Polyimide film, bonded to both sides of PMDA (Pyramellitic anhydride) -based polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) -based polyimide film)), surface-treated copper foil was etched The sample film was prepared by removing with aqueous diiron solution). When the surface-treated copper foil is an ultrathin copper layer of copper foil with carrier, the copper foil with carrier is attached to both sides of the polyimide film from the surface side where the surface treatment of the ultrathin copper layer is performed, Then, after peeling off the carrier, the ultrathin copper layer was removed by etching (aqueous ferric chloride solution) to prepare a sample film. 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).

(7) Peel strength (adhesive strength);
According to IPC-TM-650, the normal-state peel strength was measured by a tensile tester autograph 100, and the above-mentioned normal-state peel strength of 0.7 N / mm or more could be used for laminated substrate applications. In addition, the measurement of peel strength measured copper foil thickness as 12 micrometers. About copper foil whose thickness is less than 12 micrometers, copper plating was performed and copper foil thickness was 12 micrometers. Moreover, when thickness was larger than 12 micrometers, it etched and copper foil thickness was 12 micrometers. For the measurement of this peel strength, a 50 μm thick polyimide film made of Kaneka (Pixio for two-layer copper-clad laminates (PIXEO) (polyimide type: FRS), polyimide film with an adhesive layer for copper-clad laminates, PMDA (Mellitic acid anhydride) polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) polyimide film))) and the surface-treated surface of the surface-treated copper foil according to the examples and comparative examples of the present invention The bonded sample was used. Also, at the time of measurement, the polyimide film is fixed to a hard base material (stainless steel plate or synthetic resin plate (do not deform during peel strength measurement)) with double-sided tape or by using an instant adhesive. did. In Examples 11 to 14, the surface-treated copper foil (very thin copper layer) was coated with a polyimide film (Kaneka thickness 50 μm (Pixeo for two-layer copper-clad laminate) from the surface side on which the surface treatment was performed. ) (Polyimide type: FRS), polyimide film with adhesive layer for copper clad laminate, polyimide film of PMDA (pyromellitic anhydride) type (polyimide film of PMDA-ODA (4, 4'-diaminodiphenyl ether) type))) The carrier was peeled off, copper plating was performed so that the thickness of the ultrathin copper layer laminated with the polyimide film was 12 μm, and then the peel strength was measured.

(8) Heat resistance;
Surface-treated copper foil, from the surface side where the surface treatment is performed Polyimide film (Kaneka thickness 50 μm (Pixeo for two-layer copper-clad laminate (PIDEO) (polyimide type: FRS), with adhesive layer for copper-clad laminate) After lamination to a polyimide film, a polyimide film of PMDA (pyromellitic anhydride) (PMDA-ODA (4, 4′-diaminodiphenyl ether) polyimide film), IPC after heating at 150 ° C. for 168 hours In accordance with -TM-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, 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 11 to 14, after the surface-treated copper foil (very thin copper layer) is bonded to a polyimide film (50 μm made by Kaneka) from the surface side on which the surface treatment is performed, the carrier is peeled off, Peeling strength was measured after copper plating so that the thickness of the said ultra-thin copper layer laminated | stacked with the polyimide film might be 12 micrometers in thickness.

(9) Solder heat resistance evaluation;
Surface-treated copper foil, from the surface side where the surface treatment is performed Polyimide film (Kaneka thickness 50 μm (Pixeo for two-layer copper-clad laminate (PIDEO) (polyimide type: FRS), with adhesive layer for copper-clad laminate) A polyimide film and a polyimide film of PMDA (pyromellitic anhydride) (PMDA-ODA (4, 4′-diaminodiphenyl ether) polyimide film) were laminated to each other. 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 。.

(10) Yield surface-treated copper foil, from the surface side where the surface treatment is performed Polyimide film (Kaneka thickness 50 μm (Pixeo for double-layer copper-clad laminate (PIDEO) (polyimide type: FRS), copper-clad laminate) Adhesive film with adhesive layer, PMDA (pyromellitic anhydride) based polyimide film (PMDA-ODA (4, 4'-diaminodiphenyl ether) based polyimide film) bonded on both sides, and etching the copper foil ( A ferric chloride aqueous solution was used to prepare an FPC with a circuit width of 30 μm / 30 μm for L / S. After that, an attempt was made to detect a 20 μm × 20 μm square mark through a polyimide with a CCD camera. "◎" 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".
In Examples 11 to 14, a surface-treated copper foil (very thin copper layer) is bonded to both sides of a polyimide film (50 μm made by Kaneka) from the surface side on which surface treatment is performed, and the carrier is peeled off. The yield was evaluated in the same manner as described above.

(11) Measurement of transmission loss After bonding a surface-treated copper foil to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm, manufactured by Kuraray Co., Ltd.) from the surface side where the surface treatment is performed, the characteristic impedance is obtained by etching. A microstrip line was formed to be 50 Ω, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP Co., and 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.
In addition, when the surface-treated copper foil is an ultrathin copper layer of copper foil with a carrier, the above-mentioned measurement was performed about the surface where surface treatment of an ultrathin copper layer is performed.

(12) Adhesion amount of nickel and cobalt on the surface of the surface-treated copper foil The nickel adhesion amount and the cobalt adhesion amount of the surface on which the surface treatment is performed are prepared by dissolving the sample with nitric acid having a concentration of 20% by mass. It measured by performing quantitative analysis by atomic absorption spectrometry using an atomic absorption spectrophotometer (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 of the surface in which the said surface treatment is performed 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 nickel and cobalt which were obtained was made into the adhesion amount of nickel and cobalt of the surface in which the surface treatment of the surface-treated copper foil is performed, 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 nickel and cobalt which were obtained was made into the adhesion amount of nickel and cobalt of the surface in which the surface treatment of the surface-treated copper foil is performed, 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 >).
In the printed wiring board or copper-clad laminate, the resin is dissolved and removed to remove the surface (1) surface roughness (Rz) and (2) root mean square of the surface of the copper circuit or copper foil surface. It is possible to measure height Rq, (3) area ratio of copper foil surface (A / B), and (12) adhesion amount of nickel and cobalt on the surface of the surface-treated copper foil or copper circuit.

(13) Evaluation of copper foil wrinkles 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 one surface (surface-treated surface S) side, and the other surface of each surface-treated copper foil ( In the state where a 125 μm thick protective film (made of polyimide) is laminated on the surface opposite to the surface-treated surface S, ie, protective film / surface treated copper foil / polyimide resin / surface treated copper foil / protective film In the state made into five layers, lamination processing was performed (lamination processing), applying heat and pressure from the outer side of both protective films using a lamination roll, and surface-treated copper foil was bonded together on both surfaces 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.
The conditions and evaluation results of each of the above tests are shown in Tables 1 to 4.

(Evaluation results)
In Examples 1 to 20, in all cases, the root mean square height Rq of the surface is in the range of 0.14 to 0.63 μm, Sv is 3.5 or more, and the surface treatment is performed. When the surface contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the surface of the surface on which the surface treatment is performed contains Co, the adhesion amount of Co is 2400 μg / dm ² or less There were good visibility, peel strength, solder heat resistance evaluation and yield. Also, the transmission loss was small and good. Moreover, also about the copper foil which is about 6 micrometers, 12 micrometers, and 35 micrometers in thickness manufactured about Example 1 and 2, the thickness of Example 1 and 2 became the same result as the case where it is 18 micrometers. That is, the copper foils having thicknesses of 6 μm, 12 μm, and 35 μm manufactured for Examples 1 and 2 all have a root mean square height Rq of 0.14 to 0.63 μm on the surface, and Sv is It was 3.5 or more, and the visibility, the peel strength, the solder heat resistance evaluation and the yield were good.
In Comparative Example 1, the root mean square height Rq of the surface was less than 0.14 μm, and the peel strength and the solder heat resistance were poor.
In Comparative Examples 2 to 5, the root mean square height Rq of the surface exceeded 0.63 μm, Sv was less than 3.5, and the visibility was poor.
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 Example 2, by performing electropolishing and / or chemical polishing on the shiny side of the copper foil (the side which is in contact with the drum at the time of production of the electrodeposited copper foil), its TD roughness Rz and glossiness After making the same as the deposition surface, predetermined surface treatment 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.
Moreover, as for the ten-point average roughness Rz of TD measured by the laser microscope whose wavelength of the laser beam of the copper foil surface (surface-treated surface S) surface-treated in Examples 4-20 is 405 nm, all were 0. It was 35 μm or more. Moreover, as for the arithmetic mean roughness Ra of all of TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface (surface-treated surface S) surface-treated in Examples 4-20 is 405 nm, all are 0.05 micrometer. It was over. Moreover, the root mean square height Rq of TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface (surface-treated surface S) surface-treated in Examples 4-20 is 405 nm is all 0. It was over 08 μm.
In FIG. 4, (a) Comparative Example 1, (b) Example 1, (c) Example 2, (d) Example 3, (e) Example 4, (f) Example in the case of the above Rz evaluation. Example 5, (g) Example 6, (h) Example 7, (i) Example 8, (j) Example 9, (k) Comparative Example 2, (l) SEM of Surface of Copper Foil of Comparative Example 3 The observation photographs are shown respectively.
In Examples 1 to 20, 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 (FIG. 10 The same Sv value was measured by changing to the mark indicated by the arrow)), but in each case, the Sv value was the same value as when the mark width was 0.3 mm.
Furthermore, in the above Examples 1 to 20, 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 by 500 μm The same Sv value was measured by changing to the average value of lightness when measured at five points (total ten points on both sides) at intervals of 30 μm from the position respectively, but both Sv values were measured on both sides of the mark The same value as the Sv value when the average value of brightness when measured at 5 locations (10 locations on both sides) at intervals of 30 μm from the position 50 μm away from the end position of the “top average value Bt of brightness curve” became.

Claims (38)

One surface of the copper foil is a surface-treated surface S, and the other surface of the copper foil is surface-treated, and
The root mean square height Rq measured with a laser microscope having a wavelength of 405 nm of the laser light of the surface treated surface S is 0.14 to 0.63 μm,
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 other than the surface treated surface S is 405 nm is 0.35 μm or more.
After bonding the said copper foil to both surfaces of a polyimide resin substrate from the surface treatment surface S side, the copper foil of the said both surfaces is 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 ΔB (ΔB = Bt−Bb) be the difference between the top average Bt and the bottom average Bb of the lightness curve generated from the end of the mark to the portion where the mark is not drawn, and Of the points of intersection of the curve and Bt, the value indicating the position of the point of intersection closest to the linear mark is t1, and the lightness in the depth range from the point of intersection of the lightness curve and Bt to 0.1 ΔB based on Bt When the value indicating the position of the intersection closest to the linear mark among the intersections of the curve and 0.1ΔB is t2, Sv defined by the following equation (1) becomes 3.5 or more, The surface-treated surface S contains any one or more elements selected from the group consisting of Ni and Co, and when the surface-treated surface S contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, The surface treatment surface S is treated copper foil attached amount of Co is less than 2400μg / dm ² in the case of containing o.
Sv = (ΔB × 0.1) / (t1-t2) (1) One surface of the copper foil is a surface-treated surface S, and the other surface of the copper foil is surface-treated, and
The root mean square height Rq measured with a laser microscope having a wavelength of 405 nm of the laser light of the surface treated surface S is 0.14 to 0.63 μm,
Arithmetic mean 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 surface treated surface S is 405 nm is 0.05 μm or more,
After bonding the said copper foil to both surfaces of a polyimide resin substrate from the surface treatment surface S side, the copper foil of the said both surfaces is 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 ΔB (ΔB = Bt−Bb) be the difference between the top average Bt and the bottom average Bb of the lightness curve generated from the end of the mark to the portion where the mark is not drawn, and Of the points of intersection of the curve and Bt, the value indicating the position of the point of intersection closest to the linear mark is t1, and the lightness in the depth range from the point of intersection of the lightness curve and Bt to 0.1 ΔB based on Bt When the value indicating the position of the intersection closest to the linear mark among the intersections of the curve and 0.1ΔB is t2, Sv defined by the following equation (1) becomes 3.5 or more, The surface-treated surface S contains any one or more elements selected from the group consisting of Ni and Co, and when the surface-treated surface S contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, The surface treatment surface S is treated copper foil attached amount of Co is less than 2400μg / dm ² in the case of containing o.
Sv = (ΔB × 0.1) / (t1-t2) (1) One surface of the copper foil is a surface-treated surface S, and the other surface of the copper foil is surface-treated, and
The root mean square height Rq measured with a laser microscope having a wavelength of 405 nm of the laser light of the surface treated surface S is 0.14 to 0.63 μm,
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 other than the surface treated surface S is 405 nm is 0.08 μm or more
After bonding the said copper foil to both surfaces of a polyimide resin substrate from the surface treatment surface S side, the copper foil of the said both surfaces is 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 ΔB (ΔB = Bt−Bb) be the difference between the top average Bt and the bottom average Bb of the lightness curve generated from the end of the mark to the portion where the mark is not drawn, and Of the points of intersection of the curve and Bt, the value indicating the position of the point of intersection closest to the linear mark is t1, and the lightness in the depth range from the point of intersection of the lightness curve and Bt to 0.1 ΔB based on Bt When the value indicating the position of the intersection closest to the linear mark among the intersections of the curve and 0.1ΔB is t2, Sv defined by the following equation (1) becomes 3.5 or more, The surface-treated surface S contains any one or more elements selected from the group consisting of Ni and Co, and when the surface-treated surface S contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, The surface treatment surface S is treated copper foil attached amount of Co is less than 2400μg / dm ² in the case of containing o.
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 1,000 μg / dm ² or less when the surface treated 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 surface treatment 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 surface-treated 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 surface-treated surface S contains Co.   The surface treatment according to any one of claims 1 to 7, wherein the root mean square height Rq measured with a laser microscope having a wavelength of 405 nm of the laser beam on the surface treatment surface S is 0.25 to 0.60 μm. Copper foil.   The surface-treated copper foil as described in any one of Claims 1-8 which Sv defined by (1) Formula in the said brightness curve becomes 3.9 or more.   The surface-treated copper foil according to claim 9, wherein Sv defined by equation (1) in the lightness curve is 5.0 or more.   The surface-treated copper foil according to any one of claims 1 to 10, wherein the ten-point average roughness Rz of TD measured by the contact-type roughness meter of the surface-treated surface S is 0.20 to 0.64 μm.   The surface-treated copper foil according to claim 11, wherein the ten-point average roughness Rz of TD measured by the contact-type roughness meter of the surface-treated surface S is 0.26 to 0.62 μm.   The surface treated copper foil according to any one of claims 1 to 12, wherein the ratio A / B of the three-dimensional surface area A to the two-dimensional surface area B of the surface treated surface S is 1.0 to 1.7.   The surface-treated copper foil according to claim 13, wherein a ratio A / B of the three-dimensional surface area A to the two-dimensional surface area B of the surface treated surface S is 1.0 to 1.6.   The surface treatment according to any one of claims 1 to 14, wherein a ten-point average roughness Rz of TD measured by a laser microscope having a laser beam wavelength of 405 nm on the surface treatment surface S is 0.35 μm or more. Copper foil.   The surface treated copper according to any one of claims 1 to 15, wherein an arithmetic average roughness Ra of TD measured by a laser microscope having a wavelength of laser light of 405 nm on the surface treated surface S is 0.05 μm or more. Foil.   The surface treatment according to any one of claims 1 to 16, wherein a root mean square height Rq of TD measured by a laser microscope having a laser beam wavelength of 405 nm on the surface treatment surface S is 0.08 μm or more. Copper foil.   18. The surface-treated surface S according to any one of claims 1 to 17, which contains at least one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. Surface treated copper foil.   The surface-treated copper foil as described in any one of Claims 1-18 provided with the resin layer in the said surface treatment surface S.   The surface-treated copper foil according to claim 19, 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 20 .   22. The copper foil with carrier according to claim 21, wherein the ultrathin copper layer is provided on both sides of the carrier.   22. The copper foil with a carrier according to claim 21, 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 21-23, and a resin substrate.   The printed wiring board using 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 21-23.   An electronic device using the printed wiring board according to claim 25.   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 claim 25.   At least a step of connecting at least one printed wiring board according to claim 25 with a printed wiring board not corresponding to the printed wiring board according to claim 25 or the printed wiring board according to claim 25. , A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected.   An electronic device using one or more printed wiring boards manufactured by the method according to claim 27 or 28.   A method for producing a printed wiring board, comprising at least a step of connecting the printed wiring board according to claim 25 or a printed wiring board produced by the method according to claim 27 or 28 with a component. A printed wiring board by connecting at least one printed wiring board according to claim 25 and a printed wiring board not corresponding to the printed wiring board according to claim 25 or the printed wiring board according to claim 25 A process of producing A, 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. The printed wiring board according to claim 25,
A printed wiring board produced by the method according to claim 27 or 28, and
A printed wiring board which does not correspond to any of the printed wiring board according to claim 25 or the printed wiring board produced by the method according to claim 27 or 28;
And at least one printed wiring board selected from the group consisting of
A printed wiring board manufactured by the method according to claim 30;
A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting A process of preparing a copper foil with a carrier according to any one of claims 21 to 23 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 for forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier according to any one of claims 21 to 23,
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 34, which is a forming step.   The method for manufacturing a printed wiring board according to claim 34, wherein the other copper foil with carrier attached to the resin layer is the copper foil with carrier according to any one of claims 21 to 23.   The print according to any one of claims 34 to 36, wherein the step of forming a circuit on the resin layer is performed by any of a semi-additive method, a subtractive method, a partory 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.