WO2014073694A1

WO2014073694A1 - Surface-treated copper foil and laminate using same, copper-clad laminate, printed circuit board, and electronic device

Info

Publication number: WO2014073694A1
Application number: PCT/JP2013/080479
Authority: WO
Inventors: 新井　英太; 敦史三木; 康修新井; 嘉一郎中室
Original assignee: Jx日鉱日石金属株式会社
Priority date: 2012-11-09
Filing date: 2013-11-11
Publication date: 2014-05-15
Also published as: TWI484073B; KR101660663B1; CN104769165A; CN104769165B; KR20150070380A; TW201435153A

Abstract

Provided are a surface-treated copper foil which adheres favorably to resin and achieves excellent resin transparency after removing the copper foil by etching, a laminate using the same, a copper-clad laminate, a printed circuit board, and an electronic device. A surface-treated copper foil having rough particles formed on at least one surface thereof as a result of a roughening treatment, wherein: a copper foil is adhered to both surfaces of a polyimide resin substrate; the copper foil on both surfaces is removed by etching; printed matter on which a linear mark is printed is spread under the exposed polyimide substrate; and an observation point/brightness graph prepared by measuring the brightness at each observation point in a direction perpendicular to the direction in which the observed linear mark extends, in an image obtained by imaging the printed matter using a CCD camera through the polyimide substrate, illustrates that the difference ΔB (ΔB=Bt-Bb) between the top average value (Bt) and the bottom average value (Bb) of a brightness curve produced from the end of the mark to a section not having the mark is 40 or higher.

Description

Surface-treated copper foil and laminated board, copper-clad laminated board, printed wiring board and electronic device using the same

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

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

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

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

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

In Patent Document 1, a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency.
Moreover, in patent document 2, the roughening process is not made and the adhesive strength of copper foil and resin is low and inadequate in uses other than the flexible printed wiring board for COF.
Further, in the treatment method described in Patent Document 3, it was possible to finely process the copper foil with Cu—Co—Ni, but the resin after bonding the copper foil to the resin and removing it by etching was excellent. Transparency is not realized.
The present invention provides a surface-treated copper foil that adheres well to a resin and is excellent in resin transparency after removing the copper foil by etching, a laminate using the same, a copper-clad laminate, a printed wiring board, and Provide electronic equipment.

As a result of intensive studies, the inventors have placed a printed matter with a mark on the polyimide substrate from which the copper foil has been bonded and removed, and the mark portion taken by the CCD camera through the polyimide substrate. Paying attention to the lightness curve near the mark edge drawn in the observation point-lightness graph obtained from the image of the above, controlling the lightness curve is not affected by the type of substrate resin film or the thickness of the substrate resin film Furthermore, it has been found that the resin transparency after the copper foil is removed by etching is affected.

The present invention completed on the basis of the above knowledge, in one aspect, is a surface-treated copper foil in which roughened particles are formed on at least one surface by a roughening treatment, and the copper foil is disposed on both sides of a polyimide resin substrate. Then, the copper foils on both sides are removed by etching, and a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate, and the printed matter is photographed with a CCD camera through the polyimide substrate. In the observation point-brightness graph, the image obtained by the imaging was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends. The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the mark to the portion without the mark is 40. This is the surface-treated copper foil as described above.

In another embodiment of the surface-treated copper foil according to the present invention, a difference ΔB (ΔB = Bt−) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the mark to a portion without the mark. Bb) is 50 or more.

In still another embodiment of the surface-treated copper foil according to the present invention, a difference ΔB (ΔB = Bt) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the mark to a portion without the mark. -Bb) is 60 or more.

In still another embodiment of the surface-treated copper foil according to the present invention, in the observation point-brightness graph, a value indicating a position of an intersection closest to the line-shaped mark among the intersections of the brightness curve and Bt is set. t1 indicates the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt. When the value is t2, Sv defined by the following formula (1) is 3.5 or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)

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

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

In yet another embodiment of the surface-treated copper foil according to the present invention, the TD average roughness Rz of the roughened surface is 0.20 to 0.80 μm, and the roughened surface MD has a 60 ° gloss. The ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is 1.90-2. .40.

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

In yet another embodiment of the surface-treated copper foil according to the present invention, the average roughness Rz of the TD is 0.30 to 0.60 μm.

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

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

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

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

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

In yet another aspect, the present invention provides a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the ultrathin copper layer is the surface-treated copper foil of the present invention. is there.

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

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

In yet another aspect, the present invention is a laminated plate formed by laminating 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 copper foil with a carrier of the present invention.

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

In yet another aspect, the present invention provides a printed wiring board including an insulating resin substrate and a surface-treated copper foil that is laminated on the insulating substrate from the surface side where the surface treatment is performed and a copper circuit is formed. Then, when the copper circuit is photographed with a CCD camera through the insulating resin substrate laminated from the surface side where the surface treatment is performed, the copper circuit observed for the image obtained by the photographing is In the observation point-lightness graph prepared by measuring the lightness of each observation point along the direction perpendicular to the extending direction, the top average value Bt of the lightness curve generated from the end of the copper circuit to the portion without the copper circuit And the bottom average value Bb is a printed wiring board having a difference ΔB (ΔB = Bt−Bb) of 40 or more.

In still another aspect, the present invention provides a copper-clad laminate including an insulating resin substrate and a surface-treated copper foil laminated on the insulating substrate from the surface side on which the surface treatment is performed. When the surface-treated copper foil of the tension laminate is made into a line-shaped surface-treated copper foil by etching, and taken with a CCD camera through the insulating resin substrate laminated from the surface side where the surface treatment is performed, In the observation point-lightness graph, the image obtained by the photographing was prepared by measuring the lightness at each observation point along the direction perpendicular to the direction in which the observed surface-treated copper foil was extended. A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped surface-treated copper foil to a portion where the line-shaped surface-treated copper foil is absent is 40 This is the copper-clad laminate as described above.

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

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

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

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

In still another aspect of the present invention, a method for producing a printed wiring board, comprising at least a step of connecting a printed wiring board to which at least one printed wiring board of the present invention is connected or a printed wiring board of the present invention and a component. It is.

In yet another aspect of the present invention, the step of connecting at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, and
A method for producing a printed wiring board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board to which at least one printed wiring board of the present invention is connected or a printed wiring board of the present invention and a component. It is.

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

In yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

According to the present invention, a surface-treated copper foil that adheres well to a resin and is excellent in transparency of a resin after the copper foil is removed by etching, a laminate using the same, a copper-clad laminate, and a printed wiring A board and an electronic device can be provided.

It is a schematic diagram which defines Bt and Bb. It is a schematic diagram which defines t1, t2, and Sv. It is a schematic diagram showing the structure of an imaging device and the measuring method of the inclination of a lightness curve in the case of evaluation of the lightness curve inclination. It is a SEM observation photograph of the copper foil surface of (a) comparative example 1 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of (b) comparative example 3 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of (c) comparative example 5 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (d) comparative example 6 in the case of Rz evaluation. (E) It is a SEM observation photograph of the copper foil surface of Example 1 in the case of Rz evaluation. (F) It is a SEM observation photograph of the copper foil surface of Example 2 in the case of Rz evaluation. FIGS. 8A to 8C are schematic views of a cross section of a wiring board in a process up to circuit plating and resist removal according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. D to F are schematic views of the cross section of the wiring board in the process from the lamination of the resin and the second-layer copper foil with a carrier to the laser drilling according to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention. It is. GI are schematic views of the cross section of the wiring board in the steps from via fill formation to first layer carrier peeling, according to a specific example of the method for producing a printed wiring board using the copper foil with 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 bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. It is an external appearance photograph of the foreign material used in the Example. It is an external appearance photograph of the foreign material used in the Example.

[Form and manufacturing method of surface-treated copper foil]
The copper foil used in the present invention is useful for a copper foil used by making a laminate by bonding to a resin substrate 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 that adheres to the resin substrate, that is, the roughened surface, has a fist-like electric surface on the surface of the copper foil after degreasing in order to improve the peel strength of the copper foil after lamination. A roughening process is carried out to wear. Although the electrolytic copper foil has irregularities at the time of manufacture, the irregularities are further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. In the present invention, the roughening treatment is performed by alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating nickel-zinc alloy plating. Moreover, Preferably it can carry out by copper alloy plating. As the copper alloy plating bath, for example, a plating bath containing one or more elements other than copper and copper, more preferably any selected from the group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum It is preferable to use a plating bath containing at least one kind. And in this invention, the said roughening process makes a current density higher than the conventional roughening process, and shortens roughening processing time. Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off. In the present invention, including such pretreatment and finishing treatment, known treatments related to copper foil roughening are included as necessary, and are collectively referred to as roughening treatment.
The rolled copper foil according to the present invention includes 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, and B. Is also included. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The copper alloy foil may contain a total of elements other than copper of 0 mass% or more and 50 mass% or less, may contain 0.0001 mass% or more and 40 mass% or less, may contain 0.0005 mass% or more and 30 mass% or less, and 0.001 mass%. More than 20 mass% may be included.
Moreover, the copper foil with a carrier which has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order may be sufficient as the copper foil used in this invention. When using copper foil with a carrier in this invention, the said roughening process is performed to the ultra-thin copper layer surface. In addition, another embodiment of the copper foil with a carrier will be described later.

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: 90-110g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

<Production conditions>
Current density: 70-100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5m / sec
Electrolysis time: 0.5 to 10 minutes As an electrolytic copper foil that can be used in the present invention, HLP foil manufactured by JX Nippon Mining & Metals may be mentioned.

Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be a 15 ~ 40mg / dm ² of copper -100 ~ 3000μg / dm ² of cobalt -50 ~ 1500μg / dm ² of nickel A ternary alloy layer can be formed, and the adhesion amount is 15 to 40 mg / dm ² of copper—100 to 3000 μg / dm ² of cobalt—100 to 1500 μg / dm ² of nickel. It is preferable to carry out so as to form a ternary alloy layer. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 50 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

The plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating are as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1 to 4
Temperature: 30-50 ° C
Current density D _k : 25 to 50 A / dm ²
Plating time: 0.3 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased. By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.

The copper-nickel-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 10-50 g / L, Ni 3-20 g / L, P1-10 g / L
pH: 1 to 4
Temperature: 30-40 ° C
Current density D _k : 30 to 50 A / dm ²
Plating time: 0.3 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased. By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.

The copper-nickel-cobalt-tungsten alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 5-20 g / L, Ni 5-20 g / L, Co 5-20 g / L, W 1-10 g / L
pH: 1-5
Temperature: 30-50 ° C
Current density D _k : 30 to 50 A / dm ²
Plating time: 0.3 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased. By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.

The copper-nickel-molybdenum-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
Plating bath composition: Cu 5-20 g / L, Ni 5-20 g / L, Mo 1-10 g / L, P 1-10 g / L
pH: 1-5
Temperature: 30-50 ° C
Current density D _k : 30 to 50 A / dm ²
Plating time: 0.3 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased. By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.

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

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

For example, the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer with an adhesion amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and an adhesion amount of 1 mg / m ^2. A tin layer of ˜80 mg / m ² , preferably 5 mg / m ² ˜40 mg / m ² may be sequentially laminated. The nickel alloy layer may be nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. You may be comprised by any one of these. The heat-resistant layer and / or rust-preventing layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m ² to 150 mg / m ² and 10 mg / m ² to 70 mg / m ² . It is more preferable. In addition, the heat-resistant layer and / or the rust-preventing layer preferably has [amount of nickel deposited in nickel or nickel alloy] / [amount of tin deposited] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.
Further, as the heat-resistant layer and / or anticorrosive layer, coating weight of cobalt 200 ~ 2000μg / dm ² of cobalt -50 ~ 700 [mu] g / dm ² of nickel - can form a nickel alloy plating layer. This treatment can be regarded as a kind of rust prevention treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered. If the amount of cobalt adhesion is less than 200 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. As another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable.

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

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

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

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

In addition, a zinc alloy plating layer such as zinc-nickel alloy plating may be formed instead of the zinc plating layer, and a rust prevention layer and a weather resistance layer are applied to the outermost surface by chromate treatment or application of a silane coupling agent. It may be formed.

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

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

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

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

[Surface roughness Rz]
In the surface-treated copper foil of the present invention, it is preferable that roughened particles are formed on the surface of the copper foil by a roughening treatment, and that the average roughness Rz of TD on the roughened surface is 0.20 to 0.80 μm. . With such a configuration, the peel strength is increased and the resin is satisfactorily bonded to the resin, and the transparency of the resin after the copper foil is removed by etching is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin can be made easier. If the average roughness Rz of TD is less than 0.20 μm, there may be a concern about manufacturing costs for producing an ultra-smooth surface. On the other hand, if the average roughness Rz of TD is more than 0.80 μm, the unevenness of the resin surface after the copper foil is removed by etching may increase, resulting in a problem that the transparency of the resin becomes poor. There is a fear. The TD average roughness Rz of the roughened surface is more preferably 0.30 to 0.70 μm, still more preferably 0.35 to 0.60 μm, still more preferably 0.35 to 0.55 μm, and Even more preferred is 35 to 0.50 μm.
In addition, when the surface-treated copper foil of this invention is used for the use which needs to make Rz small, the average roughness Rz of TD of the roughening surface of the surface-treated copper foil of this invention is 0.20. To 0.70 μm, preferably 0.25 to 0.60 μm, more preferably 0.30 to 0.60 μm, still more preferably 0.30 to 0.55 μm, and 0.30 to 0.50 μm. Even more preferred.
In the surface-treated copper foil of the present invention, the term “roughened surface” means that when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, It means the surface of the surface-treated copper foil after the treatment. In addition, when the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the “roughened surface” means that a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided after the roughening treatment. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.

[Glossiness]
The glossiness at an incident angle of 60 degrees in the rolling direction (MD) of the roughened surface of the surface-treated copper foil greatly affects the transparency of the resin. That is, the greater the glossiness of the roughened surface, the better the transparency of the resin described above. Therefore, the surface-treated copper foil of the present invention preferably has a roughened surface having a glossiness of 76 to 350%, preferably 80 to 350%, more preferably 90 to 300%, It is still more preferably 90 to 250%, and even more preferably 100 to 250%.

Here, in order to obtain the effect of visibility of the present invention, the surface on the treatment side of the copper foil before the surface treatment (if the surface-treated copper foil is an ultrathin copper layer of the copper foil with carrier, an intermediate layer is formed. TD (direction perpendicular to the rolling direction (width direction of the copper foil) of the surface on the side where the intermediate layer of the previous carrier is provided or the surface of the ultrathin copper layer), in the case of electrolytic copper foil, copper foil in an electrolytic copper foil manufacturing apparatus Roughness (Rz) and glossiness in the direction perpendicular to the foil passing direction may be controlled. Specifically, the TD surface roughness (Rz) of the copper foil before the surface treatment is preferably 0.20 to 0.80 μm, preferably 0.30 to 0.80 μm, more preferably 0.30 to 0.8. The glossiness at an incident angle of 60 degrees in the rolling direction (MD) is preferably 350 to 800%, more preferably 500 to 800%, and the current density is higher than that of the conventional roughening treatment. If the roughening treatment time is shortened, the glossiness at an incident angle of 60 degrees in the rolling direction (MD) of the surface-treated copper foil after the surface treatment is 90 to 350%. Such a copper foil can be produced by adjusting the oil film equivalent of rolling oil (high gloss rolling), or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, it is easy to control the surface roughness (Rz) and the surface area of the copper foil after the treatment by setting the TD surface roughness (Rz) and the glossiness of the copper foil before the treatment within the above range. Can do.
When the surface roughness (Rz) of the copper foil after the surface treatment is desired to be smaller (for example, Rz = 0.20 μm), the TD roughness (Rz) of the treated side surface of the copper foil before the surface treatment is set. 0.18 to 0.80 μm, preferably 0.25 to 0.50 μm, and the glossiness at an incident angle of 60 degrees in the rolling direction (MD) is 350 to 800%, preferably 500 to 800%. The current density is made higher than that of the conventional roughening treatment, and the roughening treatment time is shortened.
Further, the copper foil before the roughening treatment preferably has a 60 degree gloss of MD of 500 to 800%, more preferably 501 to 800%, and still more preferably 510 to 750%. . If the 60 degree glossiness of MD of the copper foil before the roughening treatment is less than 500%, the transparency of the resin may be poorer than the case of 500% or more. The problem that it becomes difficult may arise.
The high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000 or less. When the surface roughness (Rz) of the copper foil after the surface treatment is desired to be smaller (for example, Rz = 0.20 μm), the oil film equivalent defined by the following formula is set to 12000 to 24000 for high gloss rolling. To do.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to make the oil film equivalent 12000 to 24000, a known method such as using a low viscosity rolling oil or slowing a sheet passing speed may be used.
Chemical polishing is performed with an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a lower concentration than usual and for a long time.

The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD on the roughened surface is 0.80 to 1. 40 is preferred. If the ratio C between the 60 ° glossiness of MD and the 60 ° glossiness of TD on the roughened surface is less than 0.80, the transparency of the resin may be lower than when the ratio C is 0.80 or more. . Further, if the ratio C is more than 1.40, the transparency of the resin may be lower than when the ratio C is 1.40 or less. The ratio C is more preferably 0.90 to 1.35, and even more preferably 1.00 to 1.30.

[Brightness curve]
The surface-treated copper foil of the present invention is bonded to both surfaces of the polyimide resin substrate, and then the copper foil on both surfaces is removed by etching, and a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate. Then, when the printed matter is photographed with a CCD camera through the polyimide substrate, the brightness at each observation point is measured along the direction perpendicular to the direction in which the observed line-shaped mark extends with respect to the image obtained by photographing. The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the mark to the portion without the mark in the observation point-lightness graph produced in the above is 40 or more. is there.
Further, the surface-treated copper foil of the present invention has a lightness curve, Bt, and Bt, where t1 is a value indicating the position of the intersection closest to the line-shaped mark in the observation point-brightness graph. In the depth range from the intersection of Bt to 0.1ΔB, the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is t2. Sv defined by the following formula (1) is preferably 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 brightness (gradation).
Here, “top average value Bt of the lightness curve”, “bottom average value Bb of the lightness curve”, and “t1”, “t2”, and “Sv” described later will be described with reference to the drawings.
FIGS. 1A and 1B are schematic views for defining Bt and Bb when the mark width is about 0.3 mm. When the mark width is about 0.3 mm, a V-shaped brightness curve may be obtained as shown in FIG. 1A, or a brightness curve having a bottom as shown in FIG. 1B. . In any case, the “top average value Bt of the lightness curve” indicates the average value of lightness when measured at 5 locations (a total of 10 locations on both sides) at 30 μm intervals from the positions 50 μm away from the end positions on both sides of the mark. . On the other hand, the “bottom average value Bb of the lightness curve” indicates the minimum value of lightness at the tip of the V-shaped valley when the lightness curve is V-shaped as shown in FIG. When it has the bottom of (b), the value of the center part of about 0.3 mm is shown. The mark width may be about 0.2 mm, 0.16 mm, or 0.1 mm. Furthermore, the “top average value Bt of the lightness curve” is 5 points at 30 μm intervals from a position 100 μm apart, a position 300 μm apart, or a position 500 μm apart from the end positions on both sides of the mark (total 10 on both sides). Location) It may be the average value of brightness when measured.
FIG. 2 is a schematic diagram that defines t1, t2, and Sv. “T1 (pixel × 0.1)” is a value indicating an intersection point closest to the line-shaped mark among intersection points of the lightness curve and Bt and a position of the intersection point (value on the horizontal axis of the observation point-lightness graph) ). “T2 (pixel × 0.1)” is the line-shaped mark among the intersections of the lightness curve and 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt. And the value (the value on the horizontal axis of the observation point-lightness graph) indicating the closest intersection and the position of the intersection. At this time, regarding the slope of the brightness curve indicated by the line connecting t1 and t2, Sv (gradation / pixel × 0.1) calculated by 0.1ΔB in the y-axis direction and (t1−t2) in the x-axis direction. ). One pixel on the horizontal axis corresponds to a length of 10 μm. Further, Sv is measured on both sides of the mark, and a small value is adopted. Further, when the shape of the lightness curve is unstable and there are a plurality of the “intersections between the lightness curve and Bt”, the intersection closest to the mark is adopted.
In the image taken by the CCD camera, the brightness is high at the portion where the mark is not attached, but the brightness decreases as soon as the end of the mark is reached. If the visibility of the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the visibility of the polyimide substrate is poor, the lightness does not suddenly drop from “high” to “low” in the vicinity of the mark end, but the state of decline is slow and the state of lightness decline is unclear. End up.
Based on such knowledge, the present invention is based on such a polyimide substrate from which the surface-treated copper foil of the present invention is bonded and removed, and a mark printed matter is placed under the polyimide substrate and photographed with a CCD camera over the polyimide substrate. The brightness curve in the vicinity of the end of the mark drawn in the observation point-brightness graph obtained from the image is controlled. More specifically, the difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the mark to the portion without the mark is 40 or more. According to such a configuration, the discrimination 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, it is possible to produce a polyimide substrate with excellent visibility, and the positioning accuracy by marking when performing a predetermined treatment on the polyimide substrate in an electronic substrate manufacturing process or the like is improved, thereby improving the yield. can get.
ΔB (ΔB = Bt−Bb) is preferably 50 or more, and more preferably 60 or more. Sv is more preferably 3.9 or more, more preferably 4.5 or more, and more preferably 5.0 or more. The upper limit of ΔB is not particularly limited, but is, for example, 100 or less, 80 or less, or 70 or less. Further, the upper limit of Sv is not particularly limited, but is, for example, 15 or less and 10 or less. According to such a configuration, the boundary between the mark and the non-mark portion becomes clearer, the positioning accuracy is improved, the error due to the mark image recognition is reduced, and the alignment can be performed more accurately.

[Particle surface area]
The ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side greatly affects the transparency of the resin. That is, if the surface roughness Rz is the same, the smaller the ratio A / B, the better the transparency of the resin. For this reason, in the surface-treated copper foil of the present invention, the ratio A / B is preferably 1.90 to 2.40, and more preferably 2.00 to 2.20.

By controlling the current density and the plating time during grain formation, the shape and density of the grains are determined, and the top average value Bt and the bottom of the brightness curve generated from the end of the mark to the part where the mark is not drawn The difference ΔB from the average value Bb (ΔB = Bt−Bb), Sv, surface roughness Rz, glossiness, and particle area ratio A / B can be controlled.

As described above, the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan view from the copper foil surface side is controlled to 1.90 to 2.40. The roughness of the roughened surface is controlled to 0.20 to 0.80 μm to eliminate extremely rough portions, while the glossiness of the roughened surface is increased. It can be as high as 76 to 350%. By performing such control, in the surface-treated copper foil of the present invention, the particle size of the roughened particles on the roughened surface can be reduced. The particle size of the roughened particles affects the resin transparency after the copper foil is removed by etching, but such control means that the particle size of the roughened particles is reduced within an appropriate range. Therefore, the resin transparency after removing the copper foil by etching becomes better, and the peel strength becomes better.

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

[Transmission loss]
When the transmission loss is small, attenuation of the signal when performing signal transmission at a high frequency is suppressed, so that a stable signal transmission can be performed in a circuit that transmits the signal at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency. After bonding the 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 50Ω, and the network manufactured by HP When the transmission coefficient was measured using the analyzer HP8720C and the transmission loss at a frequency of 20 GHz was determined, 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. Even more preferred is less than 0.7 dB / 10 cm.

[Copper foil with carrier]
The carrier-attached copper foil according to another embodiment of the present invention includes a carrier, an intermediate layer, and an ultrathin copper layer in this order. And the said ultra-thin copper layer is the surface treatment copper foil which is one embodiment of the above-mentioned this invention.

<Career>
The carrier that can be used in the present invention is typically a metal foil or a resin film, for example, 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 alloy foil, insulating resin film (for example, polyimide film, liquid crystal polymer (LCP) film, polyethylene terephthalate (PET) film, polyamide film, polyester film, fluororesin film, etc.).
It is preferable to use a copper foil as a carrier that can be used in the present invention. This is because the copper foil has a high electrical conductivity, so that subsequent formation of an intermediate layer and an ultrathin copper layer is facilitated. The carrier is typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. 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 appropriately adjusted to a thickness suitable for serving as a carrier, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

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

<Intermediate layer>
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 hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
Moreover, a well-known organic substance can be used for the intermediate | middle layer as said organic substance, and it is preferable to use any 1 or more types of a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. For example, specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H, which are triazole compounds having a substituent. It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like.
As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
Further, for example, the intermediate layer can be constituted by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing 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 amount of chromium deposited on 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 a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.
If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer may affect the glossiness of the roughened surface of the ultrathin copper layer after the surface treatment and the size and number of roughened particles. 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 preferably 2 to 100 nm. More preferably, it is 3 to 60 nm.

<Ultra thin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer having the carrier is a surface-treated copper foil that is one 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. Typically 0.5 to 12 μm, more typically 1.5 to 5 μm. Further, before the ultrathin copper layer is provided on the intermediate layer, strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.
The ultra-thin copper layer of the present application is formed under the following conditions. This is for controlling the size and number of particles of the roughening treatment and the glossiness after the roughening treatment by forming a smooth ultrathin copper layer.
Electrolyte composition Copper: 80 to 120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

[Resin layer on roughened surface]
A resin layer may be provided on the roughened surface of the surface-treated copper foil of the present invention. The resin layer may be an insulating resin layer. The resin layer may be provided on part or all of the roughened surface of the surface-treated copper foil of the present invention. In the surface-treated copper foil of the present invention, the term “roughened surface” means that when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, It means the surface of the surface-treated copper foil after the treatment. In addition, when the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the “roughened surface” means that a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided after the roughening treatment. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.

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

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

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, 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 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179721, Japanese Patent Application Laid-Open No. 2002-309444, Japanese Patent Application Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Application Laid-Open No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, and Japanese Patent Application Laid-Open No. 4570070. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO2006 / 028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication No. WO 2008/114858, International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, 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, acrylic resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin , Aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismale Midtriazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, 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, cyanoester resin, phosphazene Resin, rubber modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin and cyanoester It can be mentioned resins containing at least one selected from the group of fat as preferable.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, 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 type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. 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.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (commonly called PZT), PbLaTiO3 / PbLaZrO (commonly known as PLZT), SrBi2Ta2O9 (commonly known as SBT), and the like. Dielectric powder is used.

The dielectric (dielectric filler) may be in powder form. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are such that the particle size is in the range of 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

For example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether is used as the resin and / or resin composition and / or compound contained in the resin layer. , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). The surface-treated copper foil is coated on the roughened surface by, for example, a roll coater method, and then heated and dried as necessary to remove the solvent to obtain a B-stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C. The resin layer composition 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 is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. It is preferable to use a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples were sampled from a surface-treated copper foil with resin with a resin thickness of 55 μm. In a state where the samples are stacked (laminate), the values calculated based on Equation 1 from the results of measuring the resin outflow weight at the press temperature of 171 ° C., the press pressure of 14 kgf / cm 2, and the press time of 10 minutes. is there.

The surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

Using this surface-treated copper foil with resin makes it possible to reduce the number of prepreg materials used when manufacturing a multilayer printed wiring board. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. 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 becomes thinner than 0.1 μm, the adhesive strength is reduced, and when this surface-treated copper foil with resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is greater than 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
When the surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.

Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier according to the present invention are shown.

In one embodiment of a 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, and with the carrier After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate Laminating the copper foil with carrier and the insulating substrate, then peeling off the carrier of the copper foil with carrier, etching the exposed ultrathin copper layer with a corrosive solution such as an acid. The process of removing everything by methods such as
A step of providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching, a step of performing a desmear process on a region including the through hole or / and the blind via, the resin and the A step of providing an electroless plating layer in a region including a through hole or / and a blind via, a step of providing a plating resist on the electroless plating layer, a region where a circuit is formed after the plating resist is exposed to light The step of removing the plating resist, the step of providing an electrolytic plating layer in the region where the circuit from which the plating resist has been removed is formed, the step of removing the plating resist, and the region other than the region where the circuit is formed Remove a certain electroless plating layer by flash etching etc. Process, including the,.

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 and an insulating substrate according to the present invention, the copper foil with a carrier and the insulating substrate Laminating the copper foil with carrier and the insulating substrate, then peeling off the carrier of the copper foil with carrier, etching the exposed ultrathin copper layer with a corrosive solution such as an acid. Removing all by a method such as plasma or plasma, providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching, and providing a plating resist on the electroless plating layer A step of exposing the plating resist, and then removing the plating resist in a region where a circuit is formed, the plating resist The step of providing an electrolytic plating layer in the region where the removed circuit is formed, the step of removing the plating resist, and flushing the electroless plating layer and the ultrathin copper layer in the region other than the region where the circuit is formed Removing by etching or the like.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulation A step of laminating the substrate, a step of peeling the carrier of the copper foil with carrier and the insulating substrate after laminating the carrier-attached copper foil, a through-hole or / and in the insulating substrate and the ultrathin copper layer exposed by peeling the carrier A step of providing a blind via, a step of performing a desmear process on the region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, and exposing the substrate by peeling off the carrier The step of providing a plating resist on the surface of the ultrathin copper layer, the plating resist After digits, including the step of forming a circuit by electroplating, removing the plating resist, a step, is removed by flash etching ultrathin copper layer exposed by removing the plating resist.

In addition, the step of forming a circuit on the resin layer includes bonding another copper foil with a carrier on the resin layer from the ultrathin copper layer side, and using the copper foil with a carrier bonded to the resin layer. It may be a step of forming a circuit. Moreover, the copper foil with a carrier of the present invention may be another copper foil with a carrier to be bonded onto the resin layer. Further, the step of forming a circuit on the resin layer may be performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. Moreover, the copper foil with a carrier which forms a circuit on the said surface may have a board | substrate or a resin layer on the surface of the carrier of the said copper foil with a carrier.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulation A step of laminating the substrate, a step of laminating the carrier-attached copper foil and an insulating substrate, a step of peeling the carrier of the copper foil with carrier, a step of 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 formed; providing an electrolytic plating layer in a region where the circuit where the plating resist is removed; Step of removing resist, flash etching of electroless plating layer and ultrathin copper layer in regions other than the region where the circuit is formed, etc. A step of further removing including,.

In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening 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 partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via; a step of performing a desmear process on a region including the through hole or / and a blind via; a step of applying a catalyst nucleus in a region including the through hole or / and a blind via; and an electrode exposed by peeling off the carrier Providing an etching resist on the surface of the thin copper layer; A step of forming a circuit pattern, removing the ultrathin copper layer and the catalyst nuclei by a method such as etching or plasma using a corrosive solution such as acid to form a circuit, and removing the etching resist A step of 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 nuclei by a method such as etching or plasma using a corrosive solution such as an acid, the solder Providing an electroless plating layer in a region where no resist or plating resist is provided.

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

Therefore, in one embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate, Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer A step of providing an electroplating layer, an electroplating layer and / or a surface of the ultrathin copper layer. A step of providing a ching resist, a step of exposing the etching resist to form a circuit pattern, etching or plasma using a corrosive solution such as an acid on the ultrathin copper layer, the electroless plating layer, and the electrolytic plating layer. And a step of forming a circuit by removing the etching resist, and a step of removing the etching resist.

In another 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 and an insulating substrate according to the present invention, the copper foil with a carrier and the insulating substrate Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer Forming a mask on the surface of the electroless plating layer on which the mask is not formed. A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer, a step of exposing the etching resist to form a circuit pattern, the ultrathin copper layer and the electroless plating The method includes a step of forming a circuit by removing the layer by a method such as etching using a corrosive solution such as acid or plasma, and a step of removing the etching resist.

¡Through holes and / or blind vias and subsequent desmear steps may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown in FIG. 5-A, a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
Next, as shown in FIG. 5-B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 5C, after circuit plating is formed, the resist is removed to form circuit plating having a predetermined shape.
Next, as shown in FIG. 6-D, an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier attachment. A copper foil (second layer) is bonded from the ultrathin 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. 6-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 7G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 7H, 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 copper foil with carrier.
Next, as shown in FIG. 8J, the ultrathin copper layers on both surfaces are 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, the printed wiring board using the copper foil with a carrier of this invention is produced.

The other carrier-attached copper foil (second layer) may be the carrier-attached copper foil of the present invention, a conventional carrier-attached copper foil, or a normal copper foil. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 7-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin 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 according to the present invention is controlled so that the color difference of the roughened surface of the ultrathin copper layer satisfies the following (1). In the surface-treated copper foil of the present invention, the term “roughened surface” means that when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, It means the surface of the surface-treated copper foil (ultra thin copper layer) after the treatment. In addition, when the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the “roughened surface” means that a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided after the roughening treatment. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.
(1) As for the formula difference on the surface of the ultrathin copper layer, the color difference ΔE * ab based on JISZ8730 is 45 or more.

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

The above-described 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 rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughening layer, the current density is higher than that in the past (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm2), and can be adjusted by shortening the processing time (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni—W alloy plating, Ni—Co—P alloy plating, Ni—Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm ² ), and the processing time can be set long (20 to 40 seconds).

When the color difference ΔE * ab based on JISZ8730 is 45 or more when the formula difference on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, As a result, the visibility is improved and the circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JISZ8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and even 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. Accordingly, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 5C, it is possible to form the circuit plating at a predetermined position with high accuracy. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, the ultrathin copper layer is removed by flash etching as shown in FIG. 8J, for example. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 8J and 8K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating is recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

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

The surface-treated copper foil of the present invention can be bonded to a resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film, Teflon for FPC A (registered trademark) film, a fluororesin film, or the like can be used. In addition, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the surface-treated copper foil is etched to form a copper circuit, and then the copper circuit is covered with a cover lay to cover the film and the copper The circuit is difficult to peel off, and peeling of the film and the copper circuit due to a decrease in peel strength can be prevented.
Resins with good dielectric properties (low dielectric loss tangent (for example, dielectric loss tangent is 0.008 or less) and / or low relative dielectric constant (for example, 3 or less when the signal frequency is 25 GHz)) or low dielectric resin (Resin having a small relative dielectric constant (for example, 3 or less when the signal frequency is 25 GHz)) has a small dielectric loss. Therefore, copper-clad laminates, printed wiring boards, and printed circuit boards using a resin, low dielectric resin or low dielectric loss resin with good dielectric properties and the surface-treated copper foil according to the present invention are high frequency circuits (signals at high frequencies). Suitable for transmission circuit). Here, the low dielectric loss resin refers to a resin having a dielectric loss smaller than that of polyimide conventionally used for a copper clad laminate. Further, 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 suitable for high-frequency circuit applications. Examples of the resin having good dielectric characteristics, the low dielectric resin, or the low dielectric loss resin include a liquid crystal polymer (LCP) film and a fluororesin film.
In addition, the surface-treated copper foil of this invention can be used suitably for all the uses. For example, it can be used for printed wiring boards, printed circuit boards, printed wiring boards for high frequency circuits, printed circuit boards, semiconductor package substrates, secondary batteries, capacitor electrodes, and the like.

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

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

The printed wiring board of the present invention is a printed wiring board composed of an insulating resin substrate and a surface-treated copper foil on which a copper circuit is formed by being laminated on the insulating substrate from the surface side where the surface treatment is performed. When a copper circuit is photographed with a CCD camera through an insulating resin substrate laminated from the surface side where the surface treatment is performed, the image obtained by photographing is perpendicular to the direction in which the observed copper circuit extends. In the observation point-lightness graph produced by measuring the lightness at each observation point along a certain direction, the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the copper circuit to the portion without the copper circuit Difference ΔB (ΔB = Bt−Bb) is 40 or more. When such a printed wiring board is used, the printed wiring board can be positioned more accurately. Therefore, when one printed wiring board and another printed wiring board are connected, it is considered that the 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, connection via soldering or anisotropic conductive film (ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used.
The copper-clad laminate of the present invention is a copper-clad laminate composed of an insulating resin substrate and a surface-treated copper foil laminated on the insulating substrate from the surface side where the surface treatment is performed. When the surface-treated copper foil of the tension laminate is made into a line-shaped surface-treated copper foil by etching, and taken with a CCD camera through the insulating resin substrate laminated from the surface side where the surface treatment is performed, In the observation point-lightness graph prepared for the obtained image, the lightness at each observation point was measured along the direction perpendicular to the direction in which the observed surface treated copper foil was extended. The difference ΔB (ΔB = Bt−Bb) between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the treated copper foil to the portion where the line-shaped surface-treated copper foil is not present is 40 or more. When a printed wiring board is manufactured using such a copper-clad laminate, the printed wiring board can be positioned more accurately. Therefore, when one printed wiring board and another printed wiring board are connected, it is considered that the 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, connection via soldering or anisotropic conductive film (ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used.
In the present invention, the “printed wiring board” includes a printed wiring board and a printed board on which components are mounted.

[Lamination board and printed wiring board positioning method using the same]
A method for positioning the laminate of the surface-treated copper foil and the resin substrate of the present invention will be described. First, a laminate of a surface-treated copper foil and a resin substrate is prepared. As a specific example of the laminate of the surface-treated copper foil and the resin substrate according to the present invention, at least one of a main substrate, an attached circuit substrate, and a resin substrate such as polyimide used for electrically connecting them. In an electronic device composed of a flexible printed circuit board with copper wiring formed on the surface, a laminated board manufactured by accurately positioning the flexible printed circuit board and crimping it to the wiring ends of the main circuit board and the attached circuit board Is mentioned. That is, in this case, the laminate is a laminate in which the wiring end portions of the flexible printed circuit board and the main body substrate are bonded together by pressure bonding, or the wiring edge portions of the flexible printed circuit board and the circuit board are bonded together by pressure bonding. Laminated board. The laminated board has a mark formed of a part of the copper wiring and a separate material. The position of the mark is not particularly limited as long as it can be photographed by photographing means such as a CCD camera through the resin constituting the laminated plate. Here, the mark refers to a mark used to detect, position, or align the position of a laminated board, printed wiring board, or the like.

In the thus prepared laminated plate, when the above-mentioned mark is photographed by the photographing means through the resin, the position of the mark can be detected well. And the position of the said mark can be detected in this way, and based on the position of the said detected mark, the positioning of the laminated board of surface-treated copper foil and a resin substrate can be performed favorably. Similarly, when a printed wiring board is used as the laminated board, the photographing 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, it is considered that when one printed wiring board and another printed wiring board are connected, the connection failure is reduced and the yield is improved. In addition, as a method for connecting one printed wiring board and another printed wiring board, soldering, connection through an anisotropic conductive film (Anisotropic Conductive Film, ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. Moreover, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring. Furthermore, the printed wiring board of the present invention may be connected to a component 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. A printed wiring board in which two or more printed wiring boards are connected may be manufactured by connecting two or more printed wiring boards and components. Here, “components” include connectors, LCDs (Liquid Crystal Display), electronic components such as glass substrates used in LCDs, ICs (Integrated Circuits), LSIs (Large Scale Integrated Circuits), VLSIs (Very Large Circuits). ), Electronic components including semiconductor integrated circuits such as ULSI (Ultra-Large Scale Integration) (for example, IC chips, LSI chips, VLSI chips, ULSI chips), components for shielding electronic circuits and covers on printed wiring boards Examples include parts necessary for fixing.

The positioning method according to the embodiment of the present invention may include a step of moving a laminated board (including a laminated board of 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, may be moved by a moving device provided with an arm mechanism, or may be moved by floating a laminated plate using gas. It may be moved by a moving means, a moving device or moving means (including a roller or a bearing) that moves a laminated plate by rotating an object such as a substantially cylindrical shape, a moving device or moving means that uses hydraulic pressure as a power source, Moving devices and moving means powered by air pressure, moving devices and moving means powered by motors, gantry moving linear guide stages, gantry moving air guide stages, stacked linear guide stages, linear motor drive stages, etc. It may be moved by a moving device or moving means having a stage. Moreover, you may perform the movement process by a well-known moving means. In the step of moving the laminated plate, the laminated plate can be moved for alignment. Then, it is considered that by performing alignment, connection failure is reduced and yield is improved when one printed wiring board is connected to another printed wiring board or components.
The positioning method according to the embodiment of the present invention may be used for a surface mounter or a chip mounter.
Moreover, the printed wiring board which has the circuit provided on the resin board and the said resin board may be sufficient as the laminated board of the surface treatment copper foil and the resin board which are positioned in this invention. In that case, the mark may be the circuit.

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

As Examples 1 to 35 and Comparative Examples 1 to 14, various copper foils shown in Table 2 were prepared, and one surface was subjected to a plating treatment under the conditions shown in Table 1 as a roughening treatment.
For Examples 31 to 35, various carriers shown in Table 2 were prepared, an intermediate layer was formed on the surface of the carrier, and an ultrathin copper layer was formed on the surface of the intermediate layer under the following conditions. And the surface of the ultra-thin copper layer was plated on the conditions described in Table 1 as a roughening treatment.

Example 31
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer having an adhesion amount of 1000 μg / dm ² was formed on the carrier by electroplating with a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270 to 280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²
(2) Cr layer (electrolytic chromate treatment)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm 2 is continuously formed on the Ni layer on the roll-to-roll type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the conditions of.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 ° C
Current density: 2 A / dm ²
<Ultra thin copper layer>
Next, after the surface of the Cr layer formed in (2) is washed with water and pickled, an ultrathin copper layer having a thickness of 1.5 μm is continuously formed on the Cr layer on a roll-to-roll-type continuous plating line. It was formed by electroplating under the following conditions to produce an ultrathin copper foil with a carrier.
Copper concentration: 90-110 g / L
Sulfuric acid concentration: 90-110 g / L
Chloride ion concentration: 50-90ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
In addition, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm ²
Electrolyte linear velocity: 1.5-5m / sec
The surface roughness of TD on the surface of the ultrathin copper layer was 0.55 μm, and the 60 ° glossiness of MD was 519%.

-Example 32
<Intermediate layer>
(1) Ni-Mo layer (nickel molybdenum alloy plating)
A Ni—Mo layer having an adhesion amount of 3000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Ni 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 ~ 4A / dm ²
(Energization time) 3 to 25 seconds <Ultra thin copper layer>
An ultrathin copper layer was formed on the Ni—Mo layer formed in (1). An ultrathin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultrathin copper layer was 3 μm. The surface roughness of TD on the surface of the ultrathin copper layer was 0.26 μm, and the 60 ° glossiness of MD was 770%.

Examples 33 and 34
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in Example 31.
(2) Organic layer (organic layer formation treatment)
Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and subsequently contains carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L with respect to the Ni layer surface under the following conditions. An organic layer was formed by spraying an aqueous solution of 40 ° C. and pH 5 by spraying for 20 to 120 seconds.
<Ultra thin copper layer>
An ultrathin copper layer was formed on the organic layer formed in (2). An ultrathin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultrathin copper layer was 2 μm. The surface roughness of TD on the surface of the ultrathin copper layer was 0.40 μm, and the 60 ° glossiness of MD was 528%.

Example 35
<Intermediate layer>
(1) Co-Mo layer (cobalt molybdenum alloy plating)
The carrier, to form a Co-Mo layer deposition amount of 4000μg / dm ² by electroplating in a continuous plating line of the roll-to-roll type under the following conditions. Specific plating conditions are described below.
(Liquid composition) Co sulfate 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 ~ 4A / dm ²
(Energization time) 3 to 25 seconds <Ultra thin copper layer>
An ultrathin copper layer was formed on the Co—Mo layer formed in (1). An ultrathin copper layer was formed under the same conditions as in Example 31, except that the thickness of the ultrathin copper layer was 8 μm. The surface roughness of TD on the surface of the ultrathin copper layer was 0.75 μm, and the 60 ° glossiness of MD was 453%.

After performing the above-described rough plating treatment, Examples 1 to 10, 12 to 27, 32 to 35 and Comparative Examples 3, 4, 6, and 9 to 14 are plated for forming the following heat-resistant layer and rust-preventing layer. Processed.
The conditions for forming the heat-resistant layer 1 are shown below.
Liquid composition: Nickel 5-20 g / L, Cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
A heat-resistant layer 2 was formed on the copper foil provided with the heat-resistant layer 1. For Comparative Examples 5, 7, and 8, the rough plating treatment was not performed, and the heat-resistant layer 2 was directly formed on the prepared copper foil. The conditions for forming the heat-resistant layer 2 are shown below.
Liquid composition: Nickel 2-30 g / L, Zinc 2-30 g / L
pH: 3-4
Liquid temperature: 30-50 ° C
Current density: 1 to 2 A / dm ²
Coulomb amount: 1 to ^{2 As} / dm ²
On the copper foil which gave the said heat-resistant layers 1 and 2, the antirust layer was further formed. The conditions for forming the rust preventive layer are shown below.
Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 ° C
Current density: 0-2A / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)
On the copper foil which gave the said heat-resistant layers 1 and 2 and a rust prevention layer, the weathering layer was further formed. The formation conditions are shown below.
As a silane coupling agent having an amino group, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Examples 17, 24-27), N-2- (aminoethyl) -3-aminopropyltri Ethoxysilane (Examples 1 to 16, 32 to 35), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (Examples 18, 28, 29, 30), 3-aminopropyltrimethoxysilane ( Example 19), 3-aminopropyltriethoxysilane (Examples 20 and 21), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Example 22), N-phenyl-3 -Aminopropyltrimethoxysilane (Example 23) was applied and dried to form a weather-resistant layer. These silane coupling agents can be used in combination of two or more. Similarly, in Comparative Examples 1 to 14, coating and drying were performed with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane to form a weather resistant layer.

In addition, the rolled copper foil was manufactured as follows. After producing a copper ingot having the composition shown in Table 2 and performing 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. This rolled sheet was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thickness shown in Table 2 to obtain a copper foil. “Tough pitch copper” in the “Type” column of Table 2 indicates tough pitch copper standardized in JIS H3100 C1100, and “Oxygen-free copper” indicates oxygen-free copper standardized in JIS H3100 C1020. “Tough pitch copper + Ag: 100 ppm” means that 100 mass ppm of Ag is added to tough pitch copper.
Except for Example 35, electrolytic copper foil HLP foil made by JX Nippon Mining & Metals was used as the electrolytic copper foil. For Example 35, electrolytic copper foil JTC foil manufactured by JX Nippon Mining & Metals was used as the electrolytic copper foil. When electrolytic polishing or chemical polishing was performed, the plate thickness after electrolytic polishing or chemical polishing was described.
Table 2 shows the points of the copper foil or carrier manufacturing process before the surface treatment. “High gloss rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the value of the oil film equivalent. “Normal rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the oil film equivalent value described. “Chemical polishing” and “electropolishing” mean the following conditions.
“Chemical polishing” was performed using an etching solution of 1 to 3% by mass of H ₂ SO ₄ , 0.05 to 0.15% by mass of H ₂ O ₂ , and the remaining water, and the polishing time was 1 hour.
“Electropolishing” is a condition of 67% phosphoric acid + 10% sulfuric acid + 23% water, a voltage of 10 V / cm ² , and a time shown in Table 2 (the amount of polishing is 1 to 2 μm when electrolytic polishing is performed for 10 seconds) ).

Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
(1) Measurement of surface roughness (Rz);
Ten-point average roughness was measured on the roughened surface in accordance with JIS B0601-1994, using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory. Measurement standard length 0.8mm, evaluation length 4mm, cut-off value 0.25mm, feed rate 0.1mm / sec. The measurement position was changed 10 times (perpendicularly), and the values for 10 measurements were obtained.
In addition, the surface roughness (Rz) was calculated | required similarly about the copper foil before surface treatment.
Further, the surface roughness (Rz) was similarly determined for the surface on the side where the carrier intermediate layer is provided and the surface of the ultrathin copper layer.
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(2) Particle area ratio (A / B);
The surface area of the roughened particles was measured by a laser microscope. Using a laser microscope VK8500 manufactured by Keyence Co., Ltd., measuring the three-dimensional surface area A in an area B equivalent to 100 × 100 μm at a magnification of 2000 times the roughened surface (actual data: 9982.52 μm ² ) Setting was performed by a method of setting a two-dimensional surface area B = area ratio (A / B).
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(3) Glossiness;
Using Nippon Denshoku Industries Co., Ltd. gloss meter handy gloss meter PG-1 conforming to JIS Z8741, rolling direction (MD, foil direction in the case of electrolytic copper foil) and direction perpendicular to the rolling direction (TD, In the case of an electrolytic copper foil, the roughened surface was measured at an incident angle of 60 degrees in a direction perpendicular to the direction of foil passing).
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
In addition, the glossiness was calculated | required similarly about the copper foil before surface treatment.
Further, the glossiness of the surface of the copper foil before the surface treatment, the surface on the side where the carrier intermediate layer is provided, and the surface of the ultrathin copper layer were determined in the same manner.

(4) Inclination of lightness curve The surface-treated copper foil is bonded to both surfaces of a polyimide film (Kaneka thickness 25 μm or 50 μm or Toray DuPont thickness 50 μm) from the roughened surface side of the surface-treated copper foil. Was removed by etching (ferric chloride aqueous solution) to prepare a sample film. In addition, about the copper foil which performed the roughening process, the surface which carried out the roughening process of copper foil was bonded together to the above-mentioned polyimide film, and the above-mentioned sample film was produced. In addition, if the surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the copper foil surface or without the roughening treatment, the heat-resistant layer, rust-proof The surface-treated copper foil after the surface treatment of the layer, weather resistant layer, etc. is bonded to both surfaces of the polyimide film from the surface-treated surface side, and the surface-treated copper foil is etched (ferric chloride aqueous solution) Removed to create a sample film. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the carrier-attached copper foil is bonded to both surfaces of the polyimide film from the roughened surface side of the ultrathin copper layer, and then the carrier is peeled off. Later, the ultrathin copper layer was removed by etching (ferric chloride aqueous solution) to prepare a sample film. Subsequently, a printed material on which a line-shaped black mark is printed is laid under the sample film, and the printed material is photographed with a CCD camera (line CCD camera of 8192 pixels) through the sample film. In an 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-shaped marks extend, ΔB and t1, t2, and Sv were measured from the lightness curve. FIG. 3 is a schematic diagram showing the configuration of the photographing apparatus used at this time and the measurement method of the brightness curve.
Further, ΔB, t1, t2, and Sv were measured by the following photographing apparatus as shown in FIG.
The above-mentioned “printed matter printed with a line-shaped black mark” is printed on white glossy paper having a glossiness of 43.0 ± 2 according to JIS P8208 (1998) (a copy of the measurement table of dust) and JIS P8145 (2011) ( Annex JA (normative) Visual foreign substance comparison chart Figure JA.1-Copy of visual foreign substance comparison chart) Dirt with various lines printed on the transparent film shown in Fig. 9 (Contamination) (Product name: Choyokai Co., Ltd., product name: “Measurement chart of dust-full size”, product number: JQA160-20151-1 (manufactured by the National Printing Bureau)) was used. .
The glossiness of the glossy paper was measured at an incident angle of 60 degrees using a gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741.
The photographing device has a CCD camera, a stage (white) on which a polyimide substrate is placed with a marked paper underneath, an illumination power source that irradiates light onto the photographing portion of the polyimide substrate, and a paper with a mark to be photographed. A transporter (not shown) for transporting the evaluation polyimide substrate placed below onto the stage is provided. The main specifications of the camera are as follows:
・ Photographing device: Sheet inspection device Mujken manufactured by Nireco Corporation
Line CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits)
・ Power supply for lighting: High frequency lighting power supply (power supply unit x 2)
・ Illumination: fluorescent lamp (30W, model name: FPL27EX-D, twin fluorescent lamp)
Line for Sv measurement was used a line indicated by an arrow drawn on the contaminants 9 of 0.7 mm ^2. The width of the line is 0.3 mm. Further, the line CCD camera field of view is arranged in a dotted line in FIG.
When shooting with a line CCD camera, the signal is confirmed at 256 gradations on the full scale, and the place where the black mark of the printed matter does not exist (on the white glossy paper above) without placing the polyimide film (polyimide substrate) to be measured. The lens aperture was adjusted so that the peak gradation signal of 230 ± 5 falls within the range (when a portion outside the mark printed on the contaminants is measured with a CCD camera from the transparent film side). The camera scan time (the time when the camera shutter is open and the time when light is captured) is fixed at 250 μs, and the lens aperture is adjusted so that it falls within the above gradation.
In the case of measuring ΔB and Sv using a line-shaped copper foil as a mark for a printed wiring board and a copper-clad laminate, a white gloss with a glossiness of 43.0 ± 2 is provided on the back surface of the line-shaped copper foil. Cover the paper, photograph with a CCD camera (line CCD camera of 8192 pixels) through the polyimide film, and for the image obtained by photographing, for each observation point along the direction perpendicular to the direction in which the observed copper foil extends In the observation point-lightness graph produced by measuring the lightness, the above “line-shaped black mark” is used except that ΔB, t1, t2, and Sv are measured from the lightness curve generated from the end of the mark to the portion without the mark. It is the same as the conditions for measuring ΔB and Sv using the “printed matter printed”.
For the lightness shown in FIG. 3, 0 means “black”, lightness 255 means “white”, and the gray level from “black” to “white” (black and white shading, gray scale) Is divided into 256 gradations for display.

(5) Visibility (resin transparency);
The surface-treated surface of the surface-treated copper foil is bonded to both sides of a polyimide film (Kaneka thickness 25 μm or 50 μm, or Toray Dupont thickness 50 μm), and the copper foil is removed by etching (ferric chloride aqueous solution). A sample film was prepared. In addition, about the copper foil which performed the roughening process, the surface which carried out the roughening process of copper foil was bonded together to the above-mentioned polyimide film, and the above-mentioned sample film was produced. In addition, if the surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the copper foil surface or without the roughening treatment, the heat-resistant layer, rust-proof The surface-treated copper foil after the surface treatment of the layer, weather resistant layer, etc. is bonded to both surfaces of the polyimide film from the surface-treated surface side, and the surface-treated copper foil is etched (ferric chloride aqueous solution) Removed to create a sample film. When the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the carrier-attached copper foil is bonded to both surfaces of the polyimide film from the roughened surface side of the ultrathin copper layer, and then the carrier is peeled off. Later, the ultrathin copper layer was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A printed material (black circle with a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer. “◎” indicates that the outline of the black circle of the printed material is clear when the length is 90% or more of the circumference, and “Clear” indicates that the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. “O” (passed above), a black circle with a clear outline of 0 to less than 80% of the circumference and a broken outline were evaluated as “x” (failed).

(6) Peel strength (adhesive strength);
After the surface-treated surface of the surface-treated copper foil is laminated on a polyimide film (Kaneka thickness 25 μm or 50 μm, or Toray DuPont thickness 50 μm), in accordance with IPC-TM-650, tensile tester Autograph The normal peel strength was measured at 100, and the normal peel strength of 0.7 N / mm or more could be used for laminated substrate applications. In Examples 31 to 35, after the surface-treated surface of the surface-treated copper foil was laminated on a polyimide film (Kaneka thickness 25 μm or 50 μm, or Toray DuPont thickness 50 μm), the carrier was peeled off. The peel strength was measured after copper plating was performed such that the ultrathin copper layer laminated with the polyimide film had a thickness of 12 μm. In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(7) Solder heat resistance evaluation;
The surface-treated surface of the surface-treated copper foil was bonded to both surfaces of a polyimide film (Kaneka thickness 25 μm or 50 μm, or Toray DuPont thickness 50 μm). In addition, about the copper foil which performed the roughening process, the surface which roughened the copper foil was bonded together to the above-mentioned polyimide film. About the obtained double-sided laminated board, the test coupon based on JISC6471 was created. The prepared test coupon was exposed to high temperature and high humidity of 85 ° C. and 85% RH for 48 hours, and then floated in a solder bath at 300 ° C. to evaluate solder heat resistance. After the solder heat resistance test, at the interface between the copper foil roughening surface and the polyimide resin adhesion surface, the area where the interface discolored due to blistering in an area of 5% or more of the copper foil area in the test coupon is x (failed), area When the color change was less than 5%, the case was evaluated as ◯, and the case where no color change occurred was evaluated as ◎.
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(8) Yield The surface of the surface-treated copper foil is bonded to both sides of a polyimide film (Kaneka thickness 25 μm or 50 μm, or Toray DuPont thickness 50 μm), and the copper foil is etched (ferric chloride). FPC having a circuit width of L / S of 30 μm / 30 μm was prepared. In addition, about the copper foil which performed the roughening process, the surface which roughened the copper foil was bonded together to the above-mentioned polyimide film. After that, an attempt was made to detect a 20 μm × 20 μm square mark with a CCD camera through polyimide. “◎” if 9 or more out of 10 times can be detected, “○” if 7 to 8 times can be detected, “△” if 6 times can be detected, or if 5 times or less can be detected. Is “×”.
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the copper foil surface or without performing the roughening treatment, the heat-resistant layer, rust-proof Said evaluation was performed about the surface of the surface treatment copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(9) Circuit shape by etching (fine pattern characteristics)
The surface-treated surface of the surface-treated copper foil was bonded to both sides of a polyimide film with a thermosetting adhesive for lamination (Kaneka thickness 25 μm or 50 μm, or Toray DuPont thickness 50 μm). In order to evaluate the fine pattern circuit formability, it is necessary to make the copper foil thickness the same. That is, when the thickness was thicker than 12 μm, the thickness was reduced to 12 μm by electrolytic polishing. On the other hand, when the thickness was thinner than 12 μm, the thickness was increased to 12 μm by copper plating. For one side of the resulting double-sided laminate, the fine pattern circuit is printed by the photosensitive resist coating and exposure process on the copper foil glossy side of the laminate, and unnecessary portions of the copper foil are etched under the following conditions, A fine pattern circuit having L / S = 20/20 μm was formed. Here, the circuit width was set such that the bottom width of the circuit cross section was 20 μm.
(Etching conditions)
Equipment: Spray type small etching equipment Spray pressure: 0.2 MPa
Etching solution: Ferric chloride aqueous solution (specific gravity 40 Baume)
Liquid temperature: 50 ° C
After forming the fine pattern circuit, the photosensitive resist film was peeled off by dipping in a 45 ° C. NaOH aqueous solution for 1 minute.

(10) Calculation of etching factor (Ef) The fine pattern circuit sample obtained above was observed from the top of the circuit at a magnification of 2000 using a scanning electron micrograph S4700 manufactured by Hitachi High-Technologies Corporation. The top width (Wa) at the top and the bottom width (Wb) at the bottom of the circuit were measured. The copper foil thickness (T) was 12 μm. The etching factor (Ef) was calculated by the following formula.
Etching factor (Ef) = (2 × T) / (Wb−Wa)
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.

(11) Measurement of transmission loss For each sample, the surface treated side surface of the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), and then etched to give characteristics. A microstrip line was formed so that the impedance was 50Ω, and a transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. In addition, in order to arrange evaluation conditions as much as possible, after bonding surface-treated copper foil and liquid crystal polymer resin, copper foil thickness was 18 micrometers. That is, when the thickness of the copper foil was thicker than 18 μm, the thickness was reduced to 18 μm by electrolytic polishing. On the other hand, when the thickness was thinner than 18 μm, the thickness was increased to 18 μm by copper plating. As an evaluation of transmission loss at a frequency of 20 GHz, 未満 less than 3.7 dB / 10 cm, ◎ 3.7 dB / 10 cm or more and less than 4.1 dB / 10 cm, 、４ 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm, △, 5.0 dB / 10 cm or more was defined as x.
In addition, in the surface treatment copper foil which has a printed wiring board, a copper clad laminated board, or a resin layer, it is (1) surface roughness (Rz) mentioned above about a copper circuit or a copper foil surface by melt | dissolving and removing resin. (2) Particle area ratio (A / B), (3) Glossiness, (4) Lightness curve slope (ΔB and t1, t2, Sv) can be measured.
In addition, when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. When the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
Tables 1 to 5 show the conditions and evaluation of each test.

(Evaluation results)
Examples 1 to 35 all had good visibility, peel strength, solder heat resistance evaluation and yield. Examples 1 to 35 were all good because of a large etching factor and a small transmission loss.
Comparative Examples 1 to 4, 6, and 9 to 14 had poor visibility because ΔB was less than 40.
In Comparative Examples 5, 7, and 8, the visibility was excellent, but the substrate adhesion was poor. In Comparative Examples 1 to 14, the solder heat resistance evaluation was poor.
For the surface-treated copper foils of Examples 10 to 12, 14, 32, and 35, an acrylic resin having a thickness of 1 μm was applied to the roughened surface, and the above evaluation was performed. As a result, the same evaluation results as those of the surface-treated copper foils of Examples 10 to 12, 14, 32, and 35 were obtained.
FIG. 4 shows (a) Comparative Example 1, (b) Comparative Example 3, (c) Comparative Example 5, (d) Comparative Example 6, (e) Example 1, and (f) in the Rz evaluation. The SEM observation photograph of the copper foil surface of Example 2 is shown, respectively.
Further, in Examples 1 to 35, the mark width is 0.3 mm to 0.16 mm (the third mark from the side closest to the description of 0.5 of 0.5 mm ² in the area of the contaminant sheet (see FIG. 10). The same ΔB value and Sv value were measured by changing to the mark indicated by the arrow)), but both ΔB value and Sv value were the same as when the mark width was 0.3 mm.
Further, in Examples 1 to 35 above, with respect to the “top average value Bt of the lightness curve”, a position 50 μm away from the end positions on both sides of the mark is defined as a position 100 μm apart, a position 300 μm apart, and a position 500 μm apart. From this position, the same ΔB value and Sv value were measured by changing to the average value of the brightness when measured at 5 locations (total of 10 locations on both sides) at 30 μm intervals. The value is the value when the average value of brightness when measuring 5 locations at 30 μm intervals from a position 50 μm away from the end positions on both sides of the mark (10 locations in total on both sides) is “top average value Bt of the brightness curve” The values were the same as the ΔB value and the Sv value.

Claims

A surface-treated copper foil in which roughened particles are formed by roughening treatment on at least one surface,
After laminating the copper foil on both sides of the polyimide resin substrate, the copper foil on both sides is removed by etching,
When a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate, and the printed matter is photographed with a CCD camera through the polyimide substrate,
For the image obtained by the photographing, the observation point-lightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends,
A surface-treated copper foil in which a difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the mark to a portion without the mark is 40 or more.
2. The surface-treated copper according to claim 1, wherein a difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the mark to a portion without the mark is 50 or more. Foil.
3. The surface-treated copper according to claim 2, wherein a difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a lightness curve generated from an end portion of the mark to a portion without the mark is 60 or more. Foil.
In the observation point-lightness graph, a value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and Bt is defined as t1, and the intersection of the lightness curve and Bt is set to 0. In the depth range up to 1ΔB, the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is defined by the following equation (1). The surface-treated copper foil according to any one of claims 1 to 3, wherein Sv is 3.5 or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)
The surface-treated copper foil according to claim 4, wherein Sv defined by the formula (1) in the lightness curve is 3.9 or more.
The surface-treated copper foil according to claim 5, wherein Sv defined by the formula (1) in the brightness curve is 5.0 or more.
The TD average roughness Rz of the roughened surface is 0.20 to 0.80 μm, and the 60 degree gloss of MD of the roughened surface is 76 to 350%.
The ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is 1.90 to 2.40. The surface-treated copper foil in any one of.
The surface-treated copper foil according to claim 7, wherein the MD has a 60-degree glossiness of 90 to 250%.
The surface-treated copper foil according to claim 7 or 8, wherein the average roughness Rz of the TD is 0.30 to 0.60 µm.
The surface-treated copper foil according to any one of claims 7 to 9, wherein the A / B is 2.00 to 2.20.
The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD on the roughened surface is 0.80 to 1. The surface-treated copper foil according to any one of claims 7 to 10, which is 40.
The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of 0.90 to 1.60 of the 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface. The surface-treated copper foil according to claim 11, which is 35.
The surface-treated copper foil according to any one of claims 1 to 12, further comprising a resin layer on the roughened surface.
The surface-treated copper foil according to claim 13, wherein the resin layer contains a dielectric.
A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the ultrathin copper layer is the surface-treated copper foil according to any one of claims 1 to 14. .
A laminate comprising a laminate of the surface-treated copper foil according to any one of claims 1 to 14 and a resin substrate.
A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 14.
A laminate comprising a laminate of the carrier-attached copper foil according to claim 15 and a resin substrate.
A printed wiring board using the copper foil with a carrier according to claim 15.
An electronic device using the printed wiring board according to claim 17 or 19.
A printed wiring board composed of an insulating resin substrate and a surface-treated copper foil on which a copper circuit is formed, which is laminated on the insulating substrate from the surface side where surface treatment is performed,
When the copper circuit is photographed with a CCD camera through the insulating resin substrate laminated from the surface side where the surface treatment is performed,
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit extends,
A printed wiring board in which a difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the copper circuit to a portion without the copper circuit is 40 or more.
A copper-clad laminate composed of an insulating resin substrate and a surface-treated copper foil laminated on the insulating substrate from the surface side where the surface treatment is performed,
The surface-treated copper foil of the copper-clad laminate was photographed with a CCD camera through the insulating resin substrate laminated from the surface side where the surface treatment was performed after making the surface-treated copper foil into a line-like surface by etching. When
For the image obtained by the photographing, in the observation point-brightness graph, which was prepared by measuring the brightness for each observation point along the direction perpendicular to the direction in which the observed surface treated copper foil extends,
A difference ΔB (ΔB = Bt−Bb) between a top average value Bt and a bottom average value Bb of a brightness curve generated from an end portion of the line-shaped surface-treated copper foil to a portion where the line-shaped surface-treated copper foil is not present is 40. This is the copper-clad laminate.
A printed wiring board using the copper clad laminate according to claim 22.
An electronic device using the printed wiring board according to claim 21 or 23.
A method for manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to claim 17, 19, 21, or 23.
24. At least one printed wiring board according to claim 17, 19, 21, or 23, another printed wiring board according to claim 17, 19, 21 or 23, or claim 17, 19, 21, or 23. A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected, including a step of connecting a printed wiring board not corresponding to the printed wiring board.
27. An electronic device using one or more printed wiring boards according to claim 17, 19, 21 or 23, wherein two or more printed wiring boards according to claim 25 or 26 are connected.
A printed wiring board in which two or more printed wiring boards according to claim 25 or 26 are connected or a printed wiring board including at least a step of connecting a printed wiring board according to claim 17, 19, 21 or 23 and a component. A method of manufacturing a board.
24. At least one printed wiring board according to claim 17, 19, 21, or 23, another printed wiring board according to claim 17, 19, 21 or 23, or claim 17, 19, 21, or 23. Connecting a printed wiring board not corresponding to the printed wiring board of
A printed wiring board in which two or more printed wiring boards according to claim 25 or 26 are connected or a printed wiring board including at least a step of connecting a printed wiring board according to claim 17, 19, 21 or 23 and a component. A method of manufacturing a printed wiring board in which two or more boards are connected.
Preparing a copper foil with a carrier according to claim 15 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
Forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to claim 15;
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.