JP2015061934A - Surface-treated copper foil and laminated board, copper foil with carrier, printed wiring board and electronic device using same, as well as method for producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated copper foil which adheres suitably to a resin, is excellent in transparency of a resin after removing the copper foil by etching and has less transmission loss of signal and to provide a laminated board using the same.SOLUTION: There is provided a surface-treated copper foil in which roughened particles are formed on one surface of the copper foil and/or both surfaces of the copper foil by a roughening treatment, wherein in roughened particles on the roughening-treated surface, 50 pieces/μmor more of roughened particles having a major diameter of 100 nm or less per unit surface area are formed and the 60-degree glossiness of MD of the roughening-treated surface is 76 to 350%, the roughening-treated surface contains one or more elements selected from the group consisting of Ni and Co, when the roughening-treated surface contains Ni, the adhesion amount of Ni is 1400 μg/dmor less and when the roughening-treated surface contains Co, the adhesion amount of Co is 2400 μg/dmor less.

Description

  TECHNICAL FIELD The present invention relates to a surface-treated copper foil and a laminate using the same, a copper foil with a carrier, a printed wiring board, an electronic device, and a method for producing a printed wiring board, and in particular, the remaining resin after etching the copper foil. The present invention relates to a surface-treated copper foil suitable for a field requiring transparency, a laminated board using the same, a copper foil with a carrier, a printed wiring board, an electronic device, and a method for manufacturing a printed wiring board.

  In a small electronic device such as a smartphone or a tablet PC, a flexible printed wiring board (hereinafter referred to as FPC) is adopted because of easy 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. 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.

  Moreover, the copper clad laminated board which is a laminated board of copper foil and a resin insulating layer can also be manufactured even if it uses the rolled copper foil by which roughening plating was given to the 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 has 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, and an invention relating to a flexible printed wiring board for COF is disclosed.
Moreover, in patent document 3, in the processing method of the copper foil for printed circuits, after the roughening process by copper-cobalt-nickel alloy plating on the surface of copper foil, a cobalt-nickel alloy plating layer is formed, and also 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.

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

  Patent Document 4 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is a concavo-convex surface having a surface roughness of 2 to 4 μm made of bump-shaped protrusions. And according to this, it describes that the electrolytic copper foil excellent in the high frequency transmission characteristic can be provided.

JP 2004-98659 A WO2003 / 096776 Japanese Patent No. 2849059 JP 2004-244656 A

In Patent Document 1, a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency.
Moreover, in patent document 2, the roughening process is not made and the adhesive strength of copper foil and resin is low and inadequate in uses other than the flexible printed wiring board for COF.
Furthermore, in the processing method described in Patent Document 3, Cu-Co-Ni fine processing on the copper foil was possible, but the resin after bonding the copper foil with the resin and removing it by etching was excellent. Transparency is not realized.
In Patent Documents 1 to 3, reduction of transmission loss cannot be realized.
In Patent Document 4, excellent transparency cannot be realized for the resin after the copper foil is bonded to the resin and removed by etching.
The present invention provides a surface-treated copper foil that adheres well to a resin, has excellent resin transparency after removing the copper foil by etching, and has a small signal transmission loss, and a laminate using the surface-treated copper foil.

As a result of intensive research, the present inventors have determined that the number density of the roughened particles having a predetermined major axis on the surface of the roughened surface and the glossiness in the copper foil in which the roughened particles are formed on the surface by the roughening treatment. Has found that it affects the resin transparency and signal transmission loss after etching away the copper foil.
In addition, the inventors of the present invention are factors in which the surface treatment metal species of the copper foil and the amount of adhesion thereof affect the signal transmission loss, and these factors together with the number density and glossiness of the roughened particles on the copper foil surface It has been found that, by controlling, a surface-treated copper foil with a small signal transmission loss can be obtained even when used for a high-frequency circuit board.

The present invention completed on the basis of the above knowledge, in one aspect, roughening particles are formed by roughening treatment on one copper foil surface and / or both copper foil surfaces, and the roughening treatment surface has the roughening surface. As for the roughened particles, rough particles having a major axis of 100 nm or less are formed at 50 particles / μm ² or more per unit area, and the 60 ° glossiness of MD on the roughened surface is 76 to 350%. When the surface contains one or more elements selected from the group consisting of Ni and Co, and the roughened surface contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and the roughened surface When Co contains Co, it is a surface-treated copper foil in which the adhesion amount of Co is 2400 μg / dm ² or less.

In one embodiment of the surface-treated copper foil according to the present invention, roughened particles are formed on one copper foil surface by a roughening treatment, and the roughened particles on the roughened surface have a major axis of 100 nm or less. 50 / μm ² or more per unit area is formed, the 60 ° glossiness of MD on the roughened surface is 76 to 350%, and the roughened surface is selected from the group consisting of Ni and Co. In addition, when one or more elements are included and the roughened surface contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the roughened surface contains Co, the adhesion amount of Co Is 2400 μg / dm ² or less, and the surface of the other copper foil is surface-treated.

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

In still another embodiment of the surface-treated copper foil according to the present invention, when the roughened surface contains Ni, the adhesion amount of Ni is 100 μg / dm ² or more and 1000 μg / dm ² or less.

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

In yet another embodiment of the surface-treated copper foil according to the present invention, when the roughening treatment surface comprises a Co is deposited amount of Co is 300 [mu] g / dm ² or more 2000 [mu] g / dm ² or less.

In one embodiment of the surface-treated copper foil according to the present invention, the roughened particles on the roughened surface are formed with 90 / μm ² or more of roughened particles having a major axis of 200 nm or less per unit area.

In another embodiment of the surface-treated copper foil according to the present invention, the roughened particles on the roughened surface are formed with rough particles having a major axis exceeding 100 nm and not more than 150 nm at a rate of 50 particles / μm ² or less per unit area. Has been.

  In still 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 still another embodiment of the surface-treated copper foil according to the present invention, the wavelength of the laser light on the surface of the copper foil that has been subjected to the roughening treatment and / or the surface of the copper foil that has not been subjected to the roughening treatment. The ten-point average roughness Rz of TD measured with a laser microscope of 405 nm is 0.35 μm or more.

  In still another embodiment of the surface-treated copper foil according to the present invention, the wavelength of the laser light on the surface of the copper foil that has been subjected to the roughening treatment and / or the surface of the copper foil that has not been subjected to the roughening treatment. The arithmetic average roughness Ra of TD measured with a laser microscope of 405 nm is 0.05 μm or more.

  In still another embodiment of the surface-treated copper foil according to the present invention, the wavelength of the laser light on the surface of the copper foil that has been subjected to the roughening treatment and / or the surface of the copper foil that has not been subjected to the roughening treatment. The root mean square height Rq of TD measured with a laser microscope of 405 nm is 0.08 μm or more.

  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 still another embodiment of the surface-treated copper foil according to the present invention, the ratio A 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. / B is 1.90-2.40.

  In another embodiment of the surface-treated copper foil which concerns on this invention, said A / B is 2.00-2.20.

  In still another embodiment of the surface-treated copper foil according to the present invention, the copper foil is bonded to both surfaces of a 50 μm thick resin substrate from the roughened surface side, and then the copper foils on both sides are etched. When removed, the haze value of the resin substrate is 20 to 70%.

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

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

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

  In still 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 according to the present invention. It is a foil.

  In one embodiment, the carrier-attached copper foil of the present invention is obtained by bonding the carrier-attached copper foil to both surfaces of a 50 μm thick resin substrate from the roughened surface side of the ultrathin copper layer of the carrier-attached copper foil. After removing the carrier of the copper foil with carrier, when the ultrathin copper layer bonded to both surfaces of the resin substrate is removed by etching, the haze value of the resin substrate becomes 20 to 70%.

  In another embodiment, the copper foil with a carrier of the present invention comprises the ultrathin copper layer on both sides of the carrier.

  In yet another embodiment, the carrier-attached copper foil of the present invention includes a roughening treatment layer on the opposite side of the carrier from the ultrathin copper layer.

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

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

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

  In still another aspect, the present invention is a method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards 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 still another aspect, the present invention is an electronic apparatus using one or more printed wiring boards to which at least one printed wiring board manufactured by the method of the present invention is connected.

  In still another aspect, the present invention is a method for manufacturing a printed wiring board, comprising at least a step of connecting a printed wiring board manufactured by the method of the present invention and a component.

  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 of manufacturing a printed wiring board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board of the present invention or a printed wiring board having two or more printed wiring boards of the present invention connected thereto and a component. It is.

In 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 another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

  In another aspect of the present invention, in the step of forming a circuit on the resin layer, another carrier-attached copper foil is bonded to the resin layer from the ultrathin copper layer side and bonded to the resin layer. It is a manufacturing method of the printed wiring board which is the process of forming the said circuit using an attached copper foil.

  In another aspect of the present invention, there is provided a method for producing a printed wiring board, wherein another carrier-attached copper foil to be bonded onto the resin layer is the carrier-attached copper foil of the present invention.

  In another aspect of the present invention, the process for forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. Is the method.

  In another aspect of the present invention, the copper foil with carrier for forming a circuit on the surface has a substrate or a resin layer on the surface on the carrier side or the surface on the ultrathin copper layer side of the copper foil with carrier. It is a manufacturing method.

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

4 is a SEM observation photograph of the copper foil surface of Example 4. 4 is a SEM observation photograph of the copper foil surface of Comparative Example 1. 10 is a SEM observation photograph of the copper foil surface of Comparative Example 7. AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil 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.

[Form and manufacturing method of surface-treated copper foil]
The surface-treated copper foil which is one embodiment of 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, copper-nickel-phosphorus alloy plating, or 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 the roughening treatment, and ordinary copper plating or the like may be performed as a finishing treatment after the roughening treatment in order to prevent the electrodeposit from falling off. In the present invention, such pretreatment and finishing treatment may be performed.
The 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, and V. . 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.
The copper foil used in the present invention has a predetermined surface roughness Rz (10-point average roughness (based on JIS B0601 1994)) and 60 on the surface to be surface-treated before the surface treatment, as described later. Need to have high glossiness.
Further, the carrier of the copper foil with carrier used in the present invention has a predetermined Rz (10-point average roughness (conforming to JIS B0601 1994)) and 60 degree gloss as described later on the surface on which the intermediate layer is provided. Must have a degree.
The thickness of the surface-treated copper foil according to the present invention is not particularly limited, but is typically 0.5 to 3000 μm, preferably 1.0 to 1000 μm, preferably 1.0 to 300 μm, preferably 1 0.0-100 μm, preferably 1.0-75 μm, preferably 1.0-40 μm, preferably 1.5-20 μm, preferably 1.5-15 μm, preferably 1.5-12 μm, preferably 1.5 10 μm.

Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be the 15~40mg / dm ² of copper -250~2000μg / dm ² of cobalt -50~1000μg / dm ² of nickel It can be carried out so as to form a ternary alloy layer. When the Co adhesion amount is less than 250 μg / dm ² , the heat resistance may be deteriorated, and the etching property may be deteriorated. When the amount of Co deposition exceeds 2000 μg / dm ² , signal transmission loss increases. In addition, 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, if the Ni adhesion amount exceeds 1000 μg / dm ² , the signal transmission loss increases. In addition, etching residue may increase. A preferable Co adhesion amount is 300 to 1800 μg / dm ² , and a preferable nickel adhesion amount is 100 to 800 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.

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

After the roughening treatment, one or more of 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.
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 after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.
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 . Further, 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 nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing 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 such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate. The rust prevention layer may be a chromate treatment layer. A known chromate treatment layer can be used for the chromate treatment layer. For example, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 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 the rust-preventing layer, a cobalt-nickel alloy plating layer of nickel having an adhesion amount of 200 to 2000 μg / dm ² and 50 to 700 μg / dm ² can be formed. 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 reduced. 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. If the amount of deposited cobalt exceeds 2000 μg / dm ² , signal transmission loss increases, which is not preferable. In addition, etching spots may occur, and acid resistance and chemical resistance may deteriorate. As a heat-resistant layer and / or a rust-preventing layer, a preferable cobalt adhesion amount is 500 to 1000 μg / dm ² . On the other hand, when the nickel adhesion amount is less than 100 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. When nickel exceeds 1000 μg / dm ² , signal transmission loss increases. As a heat-resistant layer and / or a rust-preventing layer, a preferable nickel adhesion amount is 100 to 600 μg / dm ² .

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

Moreover, you may form the zinc plating layer of 30-250 microgram / dm < ² > of the adhesion amount further on the said 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 adhesion amount is 30 to 240 μg / dm ² , more preferably 80 to 220 μg / 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: 1-3 seconds

  A zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer 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 an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. 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, N (2-Aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, 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 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.

[Number density of coarse particles]
In the surface-treated copper foil of the present invention, roughened particles are formed by roughening treatment on one copper foil surface and / or both copper foil surfaces, and the major diameter of the roughened particles on the roughened surface is 100 nm. The following roughened particles are formed at 50 particles / μm ² or more per unit area. 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 after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed. With such a configuration, the peel strength becomes high and the resin adheres well to the resin, and the degree of haze (haze value) of the resin after the copper foil is removed by etching is reduced and the transparency is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin are facilitated. In addition, since the size of the roughened particles is very small, the surface unevenness is reduced, the length of the surface-treated copper foil surface corresponding to the length of the electron flow is shortened, and the transmission loss is reduced. When the number of roughened particles having a major axis of 100 nm or less is less than 50 / μm ² per unit area, the surface of the copper foil is not sufficiently roughened and cannot be sufficiently bonded to the resin. When the particle diameter is more than 100 nm and the number of particles per unit volume is small, the adhesion to the resin is ensured, but the degree of haze (haze value) of the resin after the copper foil is removed by etching. Increases and decreases transparency. Roughened particles having a major axis of 100 nm or less are preferably formed at 60 particles / μm ² or more per unit area, more preferably 150 particles / μm ² or more. Although it is not necessary to set an upper limit in particular, examples of the upper limit of the number of coarse particles having a major axis of 100 nm or less include 2500 particles / μm ² or less.
In the surface-treated copper foil of the present invention, roughened particles are formed on one copper foil surface by a roughening treatment, and the roughened particles on the roughened surface have a major axis of 100 nm or less as a unit. 50 / μm ² or more are formed per area, the 60 ° glossiness of MD on the roughened surface is 76 to 350%, and the roughened surface is any one selected from the group consisting of Ni and Co. When the roughening surface contains Ni or more and the roughening surface contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the roughening treatment surface contains Co, the adhesion amount of Co is 2400 μg / dm 2. ² or less, and the surface of the other copper foil may be surface-treated.

In the surface-treated copper foil of the present invention, the roughened particles on the surface of the roughened surface are preferably formed with 90 / μm ² or more of roughened particles having a major axis of 200 nm or less per unit area. With such a configuration, the peel strength becomes high and the resin adheres well to the resin, and the degree of haze (haze value) of the resin after the copper foil is removed by etching is reduced and the transparency is increased. As a result, an effect of facilitating alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin is produced. In addition, since the size of the roughened particles is very small, the surface unevenness is reduced, the length of the surface-treated copper foil surface corresponding to the length of the electron flow is shortened, and the transmission loss is reduced. When the number of roughened particles having a major axis of 200 nm or less is less than 90 particles / μm ² per unit area, the surface of the copper foil is not sufficiently roughened and may not be sufficiently bonded to the resin. In addition, when the particle diameter is more than 200 nm and the number of particles per unit volume is small, adhesion with the resin is ensured, but the degree of haze (haze value) of the resin after removing the copper foil by etching is high. There is a possibility that the problem of increased transparency and low transparency may occur. Roughened particles having a major axis of 200 nm or less are preferably formed at least 100 particles / μm ² per unit area, more preferably at least 150 particles / μm ² . There is no particular need to set an upper limit, but examples of the upper limit of the number of coarse particles having a major axis of 200 nm or less include 2500 particles / μm ² or less.

In the surface-treated copper foil of the present invention, the roughened particles on the surface of the roughened surface are preferably formed with roughened particles having a major axis exceeding 100 nm and not more than 150 nm at a rate of 50 particles / μm ² or less per unit area. With such a configuration, the degree of haze (haze value) of the resin after removing the copper foil by etching is increased while ensuring the adhesiveness with the resin, and an effect is obtained that good transparency is obtained. In addition, since the size of the roughened particles is very small, the surface unevenness is reduced, the length of the surface-treated copper foil surface corresponding to the length of the electron flow is shortened, and the transmission loss is reduced. If the rough particle having a major axis of more than 100 nm and not more than 150 nm is 50 particles / μm ² or more per unit area, the degree of haze (haze value) of the resin after removing the copper foil by etching increases, and transparency is increased. There is a risk that the problem of lowering may occur. Roughened particles having a major axis exceeding 100 nm and not more than 150 nm are preferably formed at 30 particles / μm ² or less per unit area, more preferably at 10 particles / μm ² or less. Although there is no particular need to limit the lower limit, the lower limit of the number of particles having a major axis exceeding 100 nm and not more than 150 nm is 0 / μm ² or more.
In addition, in order to control the size and number density of the roughened particles as described above, the surface of the copper foil before the surface treatment (the carrier when the surface-treated copper foil is a copper foil with a carrier) is used as described later. It is necessary to set the roughness Rz and the glossiness within the predetermined ranges, further perform roughening plating by alloy plating, increase the current density of the roughening plating, and shorten the roughening plating time. There is.

[Amount of adhesion of Ni and Co on the surface treated copper foil surface]
In the surface-treated copper foil of the present invention, when the roughened surface contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less, and when the roughened surface contains Co, the adhesion amount of Co is 2400 μg. / Dm ² or less. Here, the adhesion amount of Ni and Co on the roughened surface means the total adhesion amount of Ni and Co contained in all the surface treatment layers formed on the surface of the copper foil. For example, when a roughened layer, a heat-resistant layer 1, a heat-resistant layer 2, a rust-proof layer, and a weather-resistant layer are provided on the surface of the copper foil, the roughened surface-treated layer formed on the surface of the copper foil It means the total adhesion amount of the adhesion amounts of Ni and Co contained in the treatment layer, the heat resistance layer 1, the heat resistance layer 2, the rust prevention layer, and the weather resistance layer.
According to the inventors' investigation, it has been found that the amount of the predetermined metal deposited on the surface treatment layer significantly affects the transmission loss. As a result of studies by the present inventors, it has been found that among such surface-treated metal species, Co and Ni, which have a relatively high magnetic permeability and a relatively low conductivity, affect transmission loss. Therefore, limiting the adhesion amount of Ni and / or Co as described above is effective for reducing transmission loss.
If the adhesion amount of Ni is greater than 1400 μg / dm ² , transmission loss increases, which is not preferable. On the other hand, it is not preferable that the adhesion amount of Co is larger than 2400 μg / dm ² because transmission loss increases.
In order to further reduce transmission loss, when the roughened surface contains Ni, the adhesion amount of Ni is preferably 1000 μg / dm ² or less, preferably 900 μg / dm ² or less, and 800 μg / dm. ² or less is preferable, and 700 μg / dm ² or less is more preferable.
Further, when the roughened surface contains Ni, the Ni adhesion amount is preferably 100 μg / dm ² or more, more preferably 120 μg / dm ² or more, and more preferably 150 μg / dm ² or more. preferable. This is because when the adhesion amount of Ni is less than 100 μg / dm ² , the heat resistance may deteriorate.
Order to further reduce the transmission loss, it is preferred that it is preferable that deposition amount of Co is less than 2000 [mu] g / dm ^2, at 1800 [mu] g / dm ² or less in the case of roughening treated surface comprises Co, 1600μg / dm ² Or less, more preferably 1400 μg / dm ² or less.
Further, when the roughened surface contains Co, the adhesion amount of Co is preferably 300 μg / dm ² or more, more preferably 350 μg / dm ² or more, and more preferably 400 μg / dm ² or more. preferable. This is because the heat resistance may be deteriorated when the adhesion amount of Co is less than 300 μg / dm ² .
In order to control the adhesion amount of Ni and Co within the above-mentioned range, the concentration of Ni and Co in the surface treatment (plating) solution such as roughening plating and heat-resistant layer is controlled, and the surface treatment is performed. It is effective to control the current density and surface treatment time. Increasing the concentration of Ni and Co in the surface treatment (plating) solution can increase the adhesion amount of Ni and Co. Further, when the Ni and Co concentrations are lowered, the amount of Ni and Co attached can be reduced. Further, if the current density during the surface treatment is increased and / or the surface treatment time is lengthened, the amount of deposited Ni and Co can be increased. Further, if the current density during the surface treatment is lowered and / or the surface treatment time is shortened, the amount of Ni and Co attached can be reduced.

  The surface-treated copper foil of the present invention has a TD measured by a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The point average roughness Rz is preferably 0.35 μm or more. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention has a TD measured by a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The point average roughness Rz is more preferably 0.40 μm or more, still more preferably 0.50 μm or more, still more preferably 0.60 μm or more, and 0.80 μm or more. Even more preferred. In addition, TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface by which the surface treatment copper foil of this invention was roughened, and / or the copper foil surface which has not been roughened is 405 nm. The upper limit of the ten-point average roughness Rz is not particularly limited, but is typically 4.0 μm or less, more typically 3.0 μm or less, and more typically 2.5 μm. Or less, more typically 2.0 μm or less.

  The surface-treated copper foil of the present invention is a TD arithmetic measured with a laser microscope whose wavelength of laser light is 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The average roughness Ra is preferably 0.05 μm or more. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention is a TD arithmetic measured with a laser microscope whose wavelength of laser light is 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The average roughness Ra is more preferably 0.08 μm or more, even more preferably 0.10 μm or more, even more preferably 0.20 μm or more, and further preferably 0.30 μm or more. Is more preferable. In addition, TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface by which the surface treatment copper foil of this invention was roughened, and / or the copper foil surface which has not been roughened is 405 nm. The upper limit of the arithmetic average roughness Ra is not particularly limited, but is typically 0.80 μm or less, more typically 0.65 μm or less, and more typically 0.50 μm or less. More typically, it is 0.40 μm or less.

  The surface-treated copper foil of the present invention is a square of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The average square root height Rq is preferably 0.08 μm or more. With such a configuration, by further increasing the contact area between the copper foil and the protective film, the problem of the protective film sticking to the copper foil during the lamination process with the resin substrate is better suppressed. be able to. The surface-treated copper foil of the present invention is a square of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil that has been roughened and / or the surface of the copper foil that has not been roughened. The average square root height Rq is more preferably 0.10 μm or more, still more preferably 0.15 μm or more, still more preferably 0.20 μm or more, and preferably 0.30 μm or more. Even more preferred. In addition, TD measured with the laser microscope whose wavelength of the laser beam of the copper foil surface by which the surface treatment copper foil of this invention was roughened, and / or the copper foil surface which has not been roughened is 405 nm. The upper limit of the root mean square height Rq is not particularly limited, but is typically 0.80 μm or less, more typically 0.60 μm or less, and more typically 0. It is 50 μm or less, and more typically 0.40 μm or less.

The surface of the copper foil that has not been roughened may be subjected to a treatment for providing a heat-resistant layer or a rust-preventing layer by plating (plating that is not normal plating or roughening plating).
As for the roughening treatment, for example, the roughening treatment may be performed using a plating solution containing copper sulfate and an aqueous sulfuric acid solution, or the roughening treatment may be performed using a plating solution comprising copper sulfate and an aqueous sulfuric acid solution. . Alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or nickel-zinc alloy plating may also be used. Moreover, Preferably it can carry out by copper alloy plating. As the copper alloy plating bath, for example, a plating bath containing one or more elements other than copper and copper, more preferably any selected from the group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum It is preferable to use a plating bath containing at least one kind.
Moreover, roughening processes other than said roughening process may be used, and when it is not a roughening process, surface treatments other than said plating process may be used.
As a surface treatment for forming irregularities on the surface, a surface treatment by electropolishing may be performed. For example, unevenness can be formed on the other surface of the copper foil by electropolishing the other surface of the copper foil in a solution composed of copper sulfate and an aqueous sulfuric acid solution. In general, electropolishing aims at smoothing, but the other surface treatment of the present invention forms concavities and convexities by electropolishing. The method for forming the irregularities by electrolytic polishing may be performed by a known technique. Examples of known techniques of electropolishing for forming the unevenness include the methods described in JP-A-2005-240132, JP-A-2010-059547, and JP-A-2010-047842. As specific conditions for the treatment for forming irregularities by electrolytic polishing, for example,
Treatment solution: Cu: 20 g / L, H ₂ SO ₄ : 100 g / L, temperature: 50 ° C.
-Electropolishing current: 15 A / dm ²
-Electropolishing time: 15 seconds etc. are mentioned.
As the surface treatment for forming the unevenness on the other surface, for example, the unevenness may be formed by mechanically polishing the other surface. Mechanical polishing may be performed by a known technique.
In addition, you may provide a heat-resistant layer, a rust prevention layer, and a weather resistant layer after the other surface treatment in the surface-treated copper foil of this invention. The heat-resistant layer, the rust-proof layer, and the weather-resistant layer may be the method described in the above description or experimental example, or may be a known technique.

[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 haze value of the resin. That is, the haze value of the above-mentioned resin becomes smaller as the copper foil has a higher glossiness on the roughened surface. For this reason, the surface-treated copper foil of the present invention has a roughened surface with a glossiness of 76 to 350%, preferably 80 to 350%, preferably 90 to 300%, and 90 to 250%. It is more preferable that it is 100 to 250%.

  Here, in order to obtain the effect of visibility and the effect of reducing transmission loss of the present invention, the surface on the treatment side of the copper foil before the surface treatment (when the surface-treated copper foil is an ultrathin copper layer of the copper foil with carrier) Includes a TD (surface perpendicular to the rolling direction (width direction of the copper foil) of the carrier before forming the intermediate layer), and in the case of an electrolytic copper foil, a copper foil in an electrolytic copper foil manufacturing apparatus. ) Roughness (Rz (meaning ten-point average roughness Rz (meaning JIS B0601 1994)) and glossiness (60 degree glossiness (JIS)). It is necessary to control (measured in accordance with Z8741). Specifically, the surface roughness (Rz) of TD of the copper foil before the surface treatment (or the carrier before forming the intermediate layer when the surface-treated copper foil is an ultrathin copper layer of the copper foil with carrier) is 0. .30 to 0.80 μm, preferably 0.30 to 0.50 μm, and incident angle 60 in the rolling direction (MD, in the case of electrolytic copper foil, the foil passing direction of the copper foil in the electrolytic copper foil manufacturing apparatus). The gloss at 350 degrees is 350 to 800%, preferably 500 to 800%, and further a copper alloy plating bath (plating bath containing one or more elements other than copper and copper, as plating for roughening treatment, More preferably, a plating bath containing copper and one or more selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese, and molybdenum is used. Higher density than conventional roughening treatment If the roughening treatment time is shortened compared to the conventional roughening treatment, 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 76 to 350%. In addition, the particle size and density of the roughened surface can be controlled within a predetermined range. As such a copper foil (meaning a carrier when the surface-treated copper foil is a copper foil with a carrier, the same applies hereinafter), rolling is performed by adjusting the oil film equivalent of the rolling oil (high gloss rolling), or It can be produced by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Moreover, it is producible by manufacturing electrolytic copper foil with a predetermined electrolyte solution and predetermined electrolysis conditions.

  When the glossiness at an incident angle of 60 degrees in the rolling direction (MD) after the surface treatment is desired to be higher (for example, the glossiness at an incident angle of 60 degrees in the rolling direction (MD) = 350%), the surface treatment is performed. Gloss at an incident angle of 60 degrees in the rolling direction (MD) with a TD roughness (Rz) of the treatment side surface of the previous copper foil of 0.18 to 0.80 μm, preferably 0.25 to 0.50 μm. The degree is 350 to 800%, preferably 500 to 800%. Further, as a plating for roughening treatment, a copper alloy plating bath (a plating bath containing one or more elements other than copper and copper, more preferably copper and cobalt). A plating bath containing at least one selected from the group consisting of nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum), and the current density of the roughening treatment is higher than that of the conventional roughening treatment. Increase the roughening time To shorten.

The high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000. When the glossiness at the incident angle of 60 degrees in the rolling direction (MD) after the surface treatment is desired to be higher (for example, the glossiness at the incident angle of 60 degrees in the rolling direction (MD) = 350%), the glossiness is high. Rolling is performed by setting the oil film equivalent defined by the following formula to 12000 or more and 24000 or less.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 12000 to 24000, a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used.
Chemical polishing is performed over a long period of time using an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a concentration lower than usual.

Moreover, the manufacturing conditions etc. of the electrolytic copper foil which can be used for this invention are as follows.
-Electrolyte composition Copper: 80-120 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.

(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.)
The balance of the treatment liquid used in the present invention for desmear treatment, electrolysis, surface treatment or plating is water unless otherwise specified.

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

  The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and 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 haze value may be higher than when the ratio C is 0.80 or more. Further, if the ratio C is greater than 1.40, the haze value may be higher 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.

[Haze value]
As described above, the surface-treated copper foil of the present invention is controlled in the average roughness Rz and glossiness of the roughened surface as described above. Therefore, after being bonded to the resin substrate, the portion of the resin substrate where the copper foil is removed The haze value decreases. Here, the haze value (%) is a value calculated by (diffuse transmittance) / (total light transmittance) × 100. Specifically, the surface-treated copper foil of the present invention has a haze value of the resin substrate when the copper foil is removed by etching after being bonded to both surfaces of a 50 μm thick resin substrate from the roughened surface side. It is preferably 20 to 70%, more preferably 30 to 55%.

[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 haze value of the resin. That is, if the surface roughness Rz is the same, the haze value of the above-described resin decreases as the copper foil having a smaller ratio A / B. For this reason, as for the surface-treated copper foil of this invention, the said ratio A / B is 1.90-2.40, It is preferable that it is 2.00-2.20.

  By controlling the current density and the plating time during particle formation, the particle morphology and formation density are determined, and the surface roughness Rz, glossiness, and particle area ratio A / B can be controlled.

[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 a printed wiring board or copper-clad laminate, by dissolving and removing the resin, the area ratio (A / B), glossiness, and rough particle number density of the above-mentioned particles on the copper circuit or copper foil surface. 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 a network manufactured by HP When the transmission coefficient is measured using the analyzer HP8720C and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is determined, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm, and more preferably less than 4.1 dB / 10 cm. Preferably, less than 3.7 dB / 10 cm is even more preferable.

[Heat-resistant]
When the heat resistance is high, the adhesiveness between the surface-treated copper foil and the resin hardly deteriorates even in a high temperature environment, which is preferable because it can be used in a high temperature environment.
In this application, heat resistance is evaluated by peel strength retention. After laminating the surface of the surface-treated copper foil on the polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Upilex manufactured by Ube Industries) and after heating at 150 ° C. for 168 hours, IPC-TM In accordance with -650, the normal peel strength and the peel strength after heating for 168 hours were measured with a tensile tester Autograph 100.
And the peel strength retention represented by following Formula was computed.
Peel strength retention (%) = 150 ° C., 168 hours after heating peel strength (kg / cm) / normal peel strength (kg / cm) × 100
The peel strength retention is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.

[Copper foil with carrier]
The copper foil with a carrier which is another embodiment of the present invention includes a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. And the said ultra-thin copper layer is the surface treatment copper foil which is one embodiment of the above-mentioned this invention. Moreover, the copper foil with a carrier may include a carrier, an intermediate layer, and an ultrathin copper layer in this order. The copper foil with a carrier may have a surface treatment layer such as a roughening treatment layer on one or both of the surface on the carrier side and the surface on the ultrathin copper layer side.
When a roughening treatment layer is provided on the carrier-side surface of the carrier-attached copper foil, when the carrier-attached copper foil is laminated on the support such as a resin substrate from the carrier-side surface side, the carrier and the support such as the resin substrate Has the advantage that it becomes difficult to peel off.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of 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 becomes easy. 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, 12 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 have controlled surface roughness Rz and 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 and 3-amino-1H-1,2,4-triazole.
For 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 configured 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 1-1000 nm, preferably 1-500 nm, preferably 2-200 nm, preferably 2-100 nm, More preferably, it is 3-60 nm. An intermediate layer may be provided on both sides of the carrier.

<Ultrathin 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. Further, an ultrathin copper layer may be provided on both sides of the carrier. 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, it is 0.5 to 12 μm, and more typically 1.5 to 5 μm. Further, strike plating with a copper-phosphorus alloy may be performed before reducing the pinholes in the ultrathin copper layer before providing the ultrathin copper layer on the intermediate 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: 80-120 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.

(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.)

Manufacturing conditions Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-65 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to 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. 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 after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. 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 an adhesive semi-cured (B stage state) insulating resin layer. 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 may be 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 Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 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, Japanese Patent Application Laid-Open No. 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. WO 2006/028207, 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 Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (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, 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, bismaleimide triazine tree Fat, 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, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

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 -Glycidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins , Biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a mixture of two or more types, or a hydrogenated product of the epoxy resin Or a halogenated compound 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.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , 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 composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It 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. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
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 are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. In a state where the samples were stacked (laminated body), bonding was performed under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm ² , and a press time of 10 minutes, and the resin outflow weight at that time was measured. Value.

  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.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. 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 the 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.
In addition, when the surface-treated copper foil having a resin layer is used for manufacturing 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.
When the resin layer includes a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness with the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, more preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. Moreover, it is preferable that the thickness of a semi-hardened resin layer is 3 micrometers-55 micrometers, it is preferable that they are 7 micrometers-55 micrometers, and it is more desirable that it is 15-115 micrometers. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 μm, it may be necessary to consider the surface roughness of the roughened surface of the surface-treated copper foil. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.

In addition, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve adhesion between the resin layer and the surface-treated copper foil, a heat-resistant layer and a surface treated with the roughened surface of the surface-treated copper foil are provided. After providing the rust preventive layer and / or the weather resistant layer, it is preferable to form a resin layer on the heat resistant layer, the rust preventive layer or the weather resistant layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.

  Furthermore, as another product form when this surface-treated copper foil with resin is the ultrathin copper layer of the copper foil with carrier, on the roughened surface of the ultrathin copper layer (surface-treated copper foil) After the resin layer is provided and the resin layer is in a semi-cured state, the carrier is then peeled off and can be manufactured in the form of an ultrathin copper layer with a resin (surface-treated copper foil) having no carrier.

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

  In one embodiment of 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 a 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,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

  In the present invention, 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,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

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

  In the present invention, 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 a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
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 core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

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

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

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may not be performed.

Moreover, the manufacturing method of the printed wiring board of the present invention includes a step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit being exposed may be used.

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 to FIG. 4-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown to FIG. 4-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and image development are performed, and a resist is etched to a defined shape.
Next, as shown in FIG. 4C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 5-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 to FIG. 5-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 5-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. 6-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 6-H, circuit plating is formed on the via fill as shown in FIGS. 4-B and 4-C.
Next, as shown to FIG. 6-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 7-J, 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. 7K, 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.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 6-H, and these circuits may be formed by the semi-additive method, the subtractive method, the partial additive method, or the 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 a surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, the surface 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 after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.
(1) The color difference on the surface of the ultrathin copper layer has a color difference ΔE * ab based on JIS Z8730 of 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 treatment layer, the current density is made higher than conventional (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. / Dm ² ), and the processing time can be shortened (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).

  If the color difference ΔE * ab based on JIS Z8730 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 can be accurately aligned. The color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface 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. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 4-C, the circuit plating can be accurately formed at a predetermined position. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. 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. 7-J and 7-K, when the ultra-thin 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).

  Moreover, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface on the carrier side or the surface on the ultrathin copper layer side of the copper foil with carrier. 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, fluorine for FPC A resin 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 copper circuit is covered with a coverlay after the copper circuit is formed, so that the film and the copper circuit are not easily peeled off, and the peel strength is reduced. The film can be prevented from peeling off from the copper circuit.
In addition, since a liquid crystal polymer (LCP) film or a fluororesin film has a small dielectric loss tangent, a copper-clad laminate using a liquid crystal polymer (LCP) film or a fluororesin film and the surface-treated copper foil according to the present invention, printed wiring Boards and printed circuit boards are suitable for high-frequency circuits (circuits that transmit signals at high frequencies). In addition, the surface-treated copper foil according to the present invention has a smooth surface because it has a small particle size for roughening treatment and a high glossiness, and is suitable for high-frequency circuit applications.

  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 the copper foil on the prepreg from the surface subjected to the roughening treatment and heating and pressing it. 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 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.

[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 addition, when the surface-treated copper foil of this invention is the ultra-thin copper layer (ultra-thin copper layer which has a carrier) of copper foil with a carrier, from the laminated board of surface-treated copper foil and a resin substrate as needed Remove the carrier.

  In the laminated plate thus prepared, when the above-described mark is photographed by the photographing means through the resin, the position of the mark can be detected satisfactorily. 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, 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, a printed circuit board, and a printed board on which components are mounted. Also, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring. 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, as “components”, 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 scale 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 23, 28 to 35 and Comparative Examples 1 to 13, various copper foils described in Table 9 were prepared, and plating treatment was performed on one surface under the conditions described in Tables 1 to 8 as a roughening treatment. Went.
Moreover, about Examples 24-27, the various carriers described in Table 9 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 it plated on the conditions of Table 1 and Table 2 as a roughening process on the surface of an ultra-thin copper layer.

Example 24
<Intermediate layer>
(1) Ni layer (Ni plating)
An Ni layer having an adhesion amount of 1000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / 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 a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
<Ultrathin 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: 1.5-5 m / sec

Example 25
<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 to 4 A / 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 24 except that the thickness of the ultrathin copper layer was 3 μm.

Example 26
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in Example 24.
(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 after 20 to 120 seconds of showering.
<Ultrathin 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 24 except that the thickness of the ultrathin copper layer was 2 μm.

Example 27
<Intermediate layer>
(1) Co-Mo layer (cobalt molybdenum alloy plating)
A Co—Mo layer having an adhesion amount of 4000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll type continuous plating line 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 to 4 A / 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 24 except that the thickness of the ultrathin copper layer was 5 μm.
After performing the plating treatment (described in Tables 1 to 8) as the roughening treatment described above, Examples 1 to 12, 14 to 19, 21 to 23, 25 to 27, 30 to 35, Comparative Examples 2, 4, and 7 No. 10 to 10 were subjected to a plating treatment for forming the following heat-resistant layer and rust-proof layer. In Table 10, “Ni—Co”, “Ni—Co (2)”, “Ni—Co (3)”, “Ni—P”, “Ni—Zn”, “Ni—Zn ( “2)”, “Ni—Zn (3)”, “Ni—W”, “chromate” and “silane coupling treatment” mean the following surface treatment.
The conditions for forming the heat-resistant layer 1 are shown below.
・ Heat resistant layer 1
[Ni-Co]: Nickel-cobalt alloy plating solution composition: nickel 5-20 g / L, cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
[Ni-Co (2)]: nickel-cobalt alloy plating solution composition: nickel 5-20 g / L, cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 35-50 As / dm ²
[Ni-Co (3)]: Nickel-cobalt alloy plating solution composition: nickel 5-20 g / L, cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 25-35 As / dm ²
[Ni-P]: Nickel-phosphorus alloy plating Liquid composition: Nickel 5-20 g / L, phosphorus 2-8 g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
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. In Comparative Examples 3, 5, and 6, 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.
・ Heat resistant layer 2
[Ni-Zn]: Nickel-zinc alloy plating Liquid composition: Nickel 2-30 g / L, zinc 2-30 g / L
pH: 3-4
Liquid temperature: 30-50 degreeC
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 1-2 As / dm ²
[Ni-Zn (2)]: Nickel-zinc alloy plating solution composition: nickel 2-30 g / L, zinc 2-30 g / L
pH: 3-4
Liquid temperature: 30-50 degreeC
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 3-4 As / dm ²
[Ni-Zn (3)]: Nickel-zinc alloy plating solution composition: nickel 2-30 g / L, zinc 2-30 g / L
pH: 3-4
Liquid temperature: 30-50 degreeC
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 2-3 As / dm ²
[Ni-W]: Nickel-tungsten alloy plating solution composition: nickel 2-30 g / L, tungsten 0.5-20 g / L
pH: 3-4
Liquid temperature: 30-50 degreeC
Current density: 1 to ^{2 A} / dm ²
Coulomb amount: 1-2 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.
Rust prevention layer [chromate]: Chromate treatment Liquid composition: Potassium dichromate 1-10 g / L, Zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0 to ^{2 A} / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)
A weather-resistant layer was further formed on the copper foil to which the heat-resistant layers 1 and 2 and the rust-proof layer were applied or on the copper foil to which the heat-resistant layers 1 and 2 and the rust-proof layer were not applied. The formation conditions are shown below.
Weatherproof layer [Silane coupling treatment]: Silane coupling treatment As a silane coupling agent having an amino group, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Example 16), N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane (Examples 1-12, 14, 15, 23, 25-32 Comparative Examples 2-10), N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane (Example 17), 3-aminopropyltrimethoxysilane (Example 18), 3-aminopropyltriethoxysilane (Examples 19, 33-35), 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine (Example 21), N-phenyl-3-aminopropyltrimethoxysilane (Example 22) Cloth was dried and a weather resistant layer was formed. These silane coupling agents can be used in combination of two or more.
In addition, about the surface treatment copper foil obtained in Examples 1-22 and the comparative example 4, the surface treatment copper foil which performed the surface treatment of Table 13 on the other surface was also manufactured. Here, "Example No.-number" in Table 13 means that the other surface of the surface-treated copper foil obtained in the example was subjected to the surface treatment described in Table 13. For example, in Table 13, “Example 1-1”, “Example 1-2”, and “Example 1-3” were each subjected to the surface treatment described in Table 13 on the other surface of Example 1. "Example 2-1" and "Example 2-2" are obtained by performing the surface treatment described in Table 13 on the other surface of Example 2, respectively.

In addition, the rolled copper foil was manufactured as follows. After manufacturing the copper ingot of the composition shown in Table 9 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 plate was annealed and recrystallized in a continuous annealing line at 300 to 800 ° C., and finally cold-rolled to the thickness shown in Table 9 to obtain a copper foil. “Tough pitch copper” in the “Type” column of Table 9 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.
The electrolytic copper foil used was an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metals. In addition, in Example 20, Example 24, and Comparative Example 10, a predetermined surface treatment, intermediate layer, and ultrathin film were formed on the precipitation surface (the surface opposite to the surface in contact with the electrolytic drum when the electrolytic copper foil was manufactured). A copper layer was formed. When electrolytic polishing or chemical polishing was performed, the plate thickness after electrolytic polishing or chemical polishing was described.
Table 9 shows the points of the copper foil preparation 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 phosphoric acid 67% + sulfuric acid 10% + water 23%, voltage 10 V / cm ² , and the time shown in Table 9 (when electropolishing for 10 seconds, the polishing amount is 1 to 2 μm. ).

  Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.

(1) 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 of the roughened surface (in the actual data, 9982.52 μm ² ), the three-dimensional surface area A ÷ 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.

(2) Glossiness;
Using Nippon Denshoku Industries Co., Ltd. gloss meter handy gloss meter PG-1 in accordance with 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 surface of the roughened surface was measured at an incident angle of 60 degrees in a direction perpendicular to the direction of threading. 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, glossiness was similarly calculated | required also about the surface by which surface treatment of the copper foil before surface treatment and the surface by which the intermediate | middle layer of a carrier is provided.

(3-1) Measurement of surface roughness (Rz);
Using a contact roughness meter Surfcoder SE-3C manufactured by Kosaka Laboratory Ltd., the 10-point average roughness Rz was measured for the copper foil before the surface treatment in accordance with JIS B0601-1994. Moreover, when the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the ten-point average roughness Rz was measured for the carrier in the same manner as described above. Measurement standard length 0.8mm, evaluation length 4mm, cut-off value 0.25mm, feed rate 0.1mm / sec. Perpendicular to rolling direction (in TD, in case of electrolytic copper foil, in foil passing direction) The measurement position was changed 10 times (perpendicularly), and the values for 10 measurements were obtained.

(3-2) Measurement of surface roughness after surface treatment of the other surface;
About the other surface after surface treatment of each Example and a comparative example, it is preferable to measure the surface roughness using a non-contact-type method. Specifically, the state of the other surface after the surface treatment of each example and comparative example is evaluated by the roughness value measured with a laser microscope. This is because the state of the surface can be evaluated in more detail.

-Measurement of surface roughness (Rz);
About the other surface of the surface-treated copper foil, surface roughness (ten-point average roughness) Rz was measured based on JIS B0601 1994 with an Olympus laser microscope OLS4000. Using an objective lens 50 times, in the observation of the copper foil surface, the evaluation length is 258 μm, the cut-off value is zero, and the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction or electrolytic copper About foil, the value was calculated | required by the measurement of the direction (TD) perpendicular | vertical to the advancing direction of the electrolytic copper foil in the manufacturing apparatus of electrolytic copper foil, respectively. In addition, the measurement environmental temperature of surface roughness Rz by a laser microscope was 23-25 degreeC. Rz was arbitrarily measured at 10 locations, and the average value at 10 locations of Rz was defined as the value of surface roughness (10-point average roughness) Rz. Further, the wavelength of the laser beam of the laser microscope used for the measurement was 405 nm.

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

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

(4) haze value;
Roughened surface of the surface-treated copper foil is coated with a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex (Upilex (registered trademark) -VT, BPDA (biphenyltetracarboxylic dianhydride)) (BPDA -PDA (paraphenylenediamine) -based polyimide resin substrate)) was bonded to both surfaces, and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A haze value of a sample film was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory based on JIS K7136 (2000). 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.

(5) Visibility (resin transparency);
The surface of the surface-treated copper foil is bonded to both surfaces of a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex), and the surface-treated copper foil is etched (ferric chloride aqueous solution). ) To obtain 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). 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.

(6) Peel strength (adhesive strength);
After laminating the surface of the surface-treated copper foil on the polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Upilex manufactured by Ube Industries), the tensile tester auto is compliant with IPC-TM-650. The normal peel strength was measured with the graph 100. The normal peel strength of 0.7 N / mm or more can be used for laminated substrates.
The lamination conditions of the surface-treated copper foil and the polyimide film were the conditions recommended by the polyimide film manufacturer. In addition, about Examples 24-27, after laminating | stacking the surface of the surface-treated side of the surface treatment copper foil on the polyimide film with a thermosetting adhesive for lamination (thickness 50 micrometers, Ube Industries Upilex), peeling a carrier 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) heat resistance;
After laminating the surface of the surface-treated copper foil on the polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Upilex manufactured by Ube Industries) and after heating at 150 ° C. for 168 hours, IPC-TM In accordance with -650, the normal peel strength and the peel strength after heating for 168 hours were measured with a tensile tester Autograph 100.
And the peel strength retention represented by following Formula was computed.
Peel strength retention (%) = 150 ° C., 168 hours after heating peel strength (kg / cm) / normal peel strength (kg / cm) × 100
When the peel strength retention is 70% or more, the heat resistance is “◎”, and when the peel strength retention is 60% or more and less than 70%, the heat resistance is “◯” and the peel strength retention is 50% or more 60. When it was less than%, the heat resistance was “Δ”, and when the peel strength retention was less than 50%, the heat resistance was “x”. In addition, about Examples 24-27, after laminating | stacking the surface of the surface-treated side of the surface treatment copper foil on the polyimide film with a thermosetting adhesive for lamination (thickness 50 micrometers, Ube Industries Upilex), peeling a carrier 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.

(8) rough particle number density;
Using scanning electron micrograph S4700 manufactured by Hitachi High-Technologies Corporation, the roughened particles of the surface-treated copper foil were observed at a magnification of 80,000 times (observation area: 1.58 μm × 1.19 μm = 1.88 μm ² ), The number of particles was counted for each particle size. In addition, when a straight line was drawn on the particle | grains of the scanning electron micrograph, the length of the particle | grain of the part with the longest length of the straight line crossing particle | grains was made into the major axis of the particle | grains. The number of particles observed is divided by the observation area of 1.88 μm ² and is shown in the table as the number of particles per unit area. 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 The surface density of the roughened particles was measured on the surface of the surface-treated copper foil after the surface treatment of the layer, the weather resistant layer and the like. 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 surfaces of a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex). In order to perform fine pattern circuit formation, it is necessary to make the copper foil thickness the same, and here, a thickness of 12 μm copper foil was used as a reference. 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) Evaluation of solder heat resistance;
The surface-treated surface of the surface-treated copper foil was bonded to both surfaces of a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex). 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.

(12) Measurement of transmission loss For each sample, after bonding with 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, 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. As an evaluation of transmission loss at a frequency of 20 GHz, を is less than 3.7 dB / 10 cm, を is 3.7 dB / 10 cm or more and less than 4.0 dB / 10 cm, ○ is 4.0 dB / 10 cm or more and less than 4.1 dB / 10 cm. 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm was evaluated as Δ, and 5.0 dB / 10 cm or more was evaluated as x.
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.

(13) Nickel and cobalt adhesion on the surface of the roughened surface Nickel adhesion and cobalt adhesion were determined by dissolving the sample with nitric acid having a concentration of 20% by mass and using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. It was measured by performing quantitative analysis by atomic absorption method. The size of the sample for measuring nickel and cobalt adhesion in the examples and comparative examples was 50 mm × 50 mm. In addition, the measurement of the adhesion amount of the said nickel and cobalt was performed as follows. After prepreg (FR4) is heat-pressed and laminated on the surface of the surface-treated copper foil that has not been surface-treated, the surface of the surface-treated copper foil that has been surface-treated is dissolved by 2 μm in thickness. The adhesion amount of nickel and cobalt adhering to the surface of the copper foil subjected to the surface treatment was measured. And the adhesion amount of the obtained nickel and cobalt was made into the adhesion amount of nickel and cobalt of the roughening process surface, respectively. It should be noted that the thickness of the surface-treated copper foil on the surface-treated side need not be exactly 2 μm, and it is clear that the entire surface-treated surface portion is dissolved (for example, 1.5-2.5 μm) and may be measured after dissolution. In addition, when the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, first, the surface treatment of the ultrathin copper layer is performed after the prepreg (FR4) is first laminated on the surface on the carrier side by thermocompression bonding. Only the vicinity of the surface is dissolved (if the thickness of the ultra-thin copper layer is 1.4 μm or more, the surface of the ultra-thin copper layer is treated with a surface of 0. When the thickness of the ultrathin copper layer that dissolves only 5 μm thickness is less than 1.4 μm, only 20% of the thickness of the ultrathin copper layer dissolves from the surface on the surface treated with the ultrathin copper layer. The amount of nickel and cobalt deposited on the surface of the ultrathin copper layer that has been surface-treated is measured. And the adhesion amount of the obtained nickel and cobalt was made into the adhesion amount of nickel and cobalt of the roughening process surface, respectively.
In addition, the said adhesion amount of nickel and cobalt says the adhesion amount (mass) of nickel and cobalt per sample unit area (1 dm < ² >).

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

In addition, after roughening the copper foil surface or the ultrathin copper layer surface of the copper foil with carrier, surface treatment is performed to provide a heat-resistant layer, rust-proof layer, weather-resistant layer, etc. without roughening treatment. In this case, the above measurement was performed on the surface of the surface-treated copper foil after the surface treatment of the heat-resistant layer, the rust-proof layer, the weather-resistant layer and the like.
The conditions and evaluation results of the above tests are shown in Tables 1-13.

  In Table 10, "-" in the column of heat-resistant layer 1, heat-resistant layer 2, rust-proof layer, and weather-resistant layer is treatment for forming the heat-resistant layer 1, heat-resistant layer 2, rust-proof layer, and weather-resistant layer. Indicates not to go.

〔Evaluation results〕
Examples 1 to 35 all had good haze values, visibility, peel strength, and transmission loss.
Comparative Examples 1-2, 4, 7-11 and 13 had remarkably high haze values and poor visibility.
In Comparative Examples 3, 5, 6, and 12, the visibility was excellent, but the peel strength was insufficient and the substrate adhesion was poor.
In Example 4, the 60 degree glossiness of MD and the surface area ratio A / B are substantially the same values as in Example 14, but the 60 degree glossiness of MD and 60 degrees of TD on the roughened surface of Example 4 are the same. Example 14 in which the value of C was outside the range of 0.75 and 0.80 to 1.40 because the value of the ratio C to gloss was within the range of 0.84 and 0.80 to 1.40 The haze value became smaller.
For the same reason, the haze value of Example 15 was smaller than that of Example 16.
In addition, the surface treatment is performed on both sides of the copper foil under the same conditions using the same copper foil as each of the above examples and comparative examples, and both sides of the carrier under the same conditions using the same carrier as the above examples, After the formation of the intermediate layer and the ultrathin copper layer, the same surface treatment was performed to produce a surface-treated copper foil, and as a result, the same evaluation results as in the above-mentioned Examples and Comparative Examples were obtained on both sides. When electrolytic polishing or chemical polishing was performed on the copper foil or carrier, surface treatment was performed after electrolytic polishing or chemical polishing was performed on both surfaces. Moreover, about Example 20, Example 24, and the comparative example 10, by performing electrolytic polishing and / or chemical polishing about the glossy surface of copper foil (surface on the side in contact with the drum at the time of electrolytic copper foil production) A predetermined surface treatment or formation of an intermediate layer or the like was performed after setting the roughness Rz and glossiness of TD to be the same as the deposition surface.
When surface treatment such as roughening treatment is performed on both surfaces of the copper foil, the surface treatment may be performed on both surfaces simultaneously, or the surface treatment may be separately performed on one surface and the other surface. In addition, when performing surface treatment on both surfaces simultaneously, it is good to perform surface treatment using the surface treatment apparatus (plating apparatus) which provided the anode on both surfaces side of copper foil. In this example, surface treatment was performed on both sides simultaneously.
The ten-point average roughness Rz of TD measured with a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper foil subjected to the roughening treatment in each example was 0.35 μm or more. Moreover, arithmetic mean roughness Ra of TD measured with the laser microscope whose wavelength of the laser beam of the roughened copper foil surface of each Example was 405 nm was all 0.05 micrometer or more. Moreover, the root mean square height Rq of TD measured with the laser microscope whose wavelength of the laser beam of the roughened copper foil surface of each Example was 405 nm was 0.08 micrometer or more in all.
FIG. 1 shows an SEM observation photograph of the surface of the copper foil of Example 4, FIG. 2 shows Comparative Example 1 and FIG. 3 shows Comparative Example 7.

Claims (38)

Roughened particles are formed by roughening treatment on one copper foil surface and / or both copper foil surfaces, and the roughened particles having a major axis of 100 nm or less are unit areas of the roughened particles on the roughened surface. 50 / μm ² or more per surface, the 60 ° glossiness of the MD of the roughened surface is 76 to 350%, and the roughened surface is any one selected from the group consisting of Ni and Co When the above-described elements are included and the roughened surface contains Ni, the amount of Ni deposited is 1400 μg / dm ² or less, and when the roughened surface contains Co, the amount of Co deposited is 2400 μg / dm ^2. The surface-treated copper foil which is the following. Roughening particles are formed on the surface of one copper foil by roughening treatment, and the roughening particles on the roughening treatment surface are formed with 50 or more μm ^{2 of} roughening particles having a major axis of 100 nm or less per unit area. The 60 degree glossiness of the MD of the roughened surface is 76 to 350%, and the roughened surface contains one or more elements selected from the group consisting of Ni and Co, and the roughened surface When Ni contains Ni, the adhesion amount of Ni is 1400 μg / dm ² or less. When the roughened surface contains Co, the adhesion amount of Co is 2400 μg / dm ² or less. The surface-treated copper foil according to claim 1, wherein the surface treatment is performed. 3. The surface-treated copper foil according to claim 1, wherein when the roughened surface contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less. 4. The surface-treated copper foil according to claim 3, wherein when the roughened surface contains Ni, the adhesion amount of Ni is 100 μg / dm ² or more and 1000 μg / dm ² or less. The surface-treated copper foil according to any one of claims 1 to 4, wherein when the roughened surface contains Co, the adhesion amount of Co is 2000 µg / dm ² or less. Surface treated copper foil according to claim 5 attached amount of Co is 300 [mu] g / dm ² or more 2000 [mu] g / dm ² or less in the case of containing the roughening treatment surface Co. The surface-treated copper according to any one of claims 1 to 6, wherein the roughened particles on the roughened surface are formed with 90 / μm ² or more of roughened particles having a major axis of 200 nm or less per unit area. Foil. For the roughening particles of roughening the surface, the major axis is according to any one of claims 1 to 7, 100nm greater and 150nm or less of the roughening particles are formed by 50 / [mu] m ² or less per unit area Surface treated copper foil.   The surface-treated copper foil according to any one of claims 1 to 8, wherein the MD has a 60-degree glossiness of 90 to 250%.   The ten-point average roughness Rz of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the copper foil surface subjected to the roughening treatment and / or the copper foil surface not subjected to the roughening treatment, It is 0.35 micrometer or more, The surface treatment copper foil as described in any one of Claims 1-9.   Arithmetic average roughness Ra of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the surface of the copper foil subjected to the roughening treatment and / or the surface of the copper foil not subjected to the roughening treatment is 0. The surface-treated copper foil according to claim 1, wherein the surface-treated copper foil is at least 0.05 μm.   The root mean square height Rq of TD measured with a laser microscope having a wavelength of laser light of 405 nm on the copper foil surface subjected to the roughening treatment and / or the copper foil surface not subjected to the roughening treatment, It is 0.08 micrometer or more, The surface-treated copper foil as described in any one of Claims 1-11.   The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface is 0.80 to 1. It is 40, The surface-treated copper foil as described in any one of Claims 1-12.   The ratio C (C = (60 ° gloss of MD) / (60 ° gloss of TD)) of the 60 ° gloss of MD and 60 ° gloss of TD on the roughened surface is 0.90 to 1. The surface-treated copper foil according to claim 13, which is 35.   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 as described in any one of these.   The surface-treated copper foil according to claim 15, wherein the A / B is 2.00 to 2.20.   After the copper foil is bonded to both surfaces of a 50 μm thick resin substrate from the surface of the roughened surface, when the copper foil on both surfaces is removed by etching, the haze value of the resin substrate becomes 20 to 70%. The surface-treated copper foil as described in any one of Claims 1-16.   The roughening-treated surface includes any one or more selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. Surface treated copper foil.   The surface-treated copper foil as described in any one of Claims 1-18 which equips the said roughening process surface with a resin layer.   The surface-treated copper foil of Claim 19 in which the said resin layer contains a dielectric material.   The copper foil with a carrier which has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order, Comprising: The said ultra-thin copper layer is the surface-treated copper foil as described in any one of Claims 1-20. .   After laminating the copper foil with carrier on both surfaces of a 50 μm thick resin substrate from the roughened surface side of the ultrathin copper layer of the copper foil with carrier, after removing the carrier of the copper foil with carrier, The copper foil with a carrier according to claim 21, wherein when the ultrathin copper layer bonded to both surfaces of the resin substrate is removed by etching, the haze value of the resin substrate is 20 to 70%.   The copper foil with a carrier according to claim 21 or 22, wherein the ultrathin copper layer is provided on both surfaces of the carrier.   The copper foil with a carrier of Claim 21 or 22 provided with the roughening process layer on the opposite side to the said ultra-thin copper layer of the said carrier.   The laminated board manufactured by laminating | stacking the surface-treated copper foil as described in any one of Claims 1-20, or the copper foil with a carrier as described in any one of Claims 21-24, and a resin substrate.   The printed wiring board using the surface-treated copper foil as described in any one of Claims 1-20, or the copper foil with a carrier as described in any one of Claims 21-24.   The electronic device using the printed wiring board of Claim 26.   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 26. At least one printed wiring board according to claim 26;
Another printed wiring board according to claim 26 or a printed wiring board not corresponding to the printed wiring board according to claim 26;
The method of manufacturing the printed wiring board which two or more printed wiring boards connected including the process of connecting.   An electronic device using one or more printed wiring boards to which at least one printed wiring board manufactured by the method according to claim 28 or 29 is connected.   30. A method for producing a printed wiring board, comprising at least a step of connecting a printed wiring board produced by the method according to claim 28 or 29 and a component. Connecting at least one printed wiring board according to claim 26 with another printed wiring board according to claim 26 or a printed wiring board not corresponding to the printed wiring board according to claim 26; and
27. A printed wiring board comprising at least a step of connecting a printed wiring board according to claim 26 or two or more printed wiring boards manufactured by the method according to claim 29 and a component. A method of manufacturing a printed wiring board in which two or more are connected. A step of preparing the carrier-attached copper foil according to any one of claims 21 to 24 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. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 21 to 24,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected.   The step of forming a circuit on the resin layer includes attaching another carrier-attached copper foil on the resin layer from the ultrathin copper layer side, and using the carrier-attached copper foil attached to the resin layer to form the circuit. The method for producing a printed wiring board according to claim 34, wherein the method is a forming step.   36. The method for producing a printed wiring board according to claim 35, wherein another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier according to any one of claims 21 to 24.   37. The print according to any one of claims 34 to 36, wherein the step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, and a modified semi-additive method. A method for manufacturing a wiring board.   The copper foil with a carrier for forming a circuit on the surface has a substrate or a resin layer on the surface on the carrier side or the surface on the ultrathin copper layer side of the copper foil with carrier. Manufacturing method of printed wiring board.