TW201531173A - Surface-treated copper foil, and laminate, copper foil, printed wiring board and electronic device using the same, and method of manufacturing printed wiring board - Google Patents

Abstract

Provided are a surface-treated copper foil favorably adhered to resin, and having excellent transparency of resin after removing the copper foil by etching and a laminate using the same. The present invention relates to a surface-treated copper foil having roughening particles formed on one and/or both surfaces of the copper foil by roughening, wherein a 10-point average roughness Rz of TD of a roughened surface measured by a contact type roughness meter is 0.20-0.80 [mu]m, 60 DEG glossiness of MD of the roughened surface is 76-350 %, A/B, which is a ratio of a surface area A of roughening particles and an area B obtained when viewing the roughening particles on a flat surface from the copper foil surface, is 1.90-2.40, the roughened surface contains one or more elements selected from a group including Ni, and Co, the coating weight of Ni is equal to or less than 1,400 [mu]g/dm2 when the roughened surface includes Ni, and the coating weight of Co is equal to or less than 2,400 [mu]g/dm2 when the roughened surface includes Co.

Description

Surface-treated copper foil, copper foil with carrier, laminated board, printed wiring board, electronic equipment, and manufacturing method of printed wiring board

The present invention relates to a surface-treated copper foil, a laminated board using the same, a copper foil, a printed wiring board, an electronic device, and a method of manufacturing a printed wiring board, and more particularly to a resin suitable for requiring a residue after etching a copper foil. A surface-treated copper foil and a laminated board using the same, and a copper foil, a printed wiring board, an electronic device, and a manufacturing method of a printed wiring board.

In a small electronic device such as a smart phone or a tablet PC, a flexible printed wiring board (hereinafter referred to as FPC) is used in terms of ease of wiring or light weight. In recent years, with the high functionality of these electronic devices, the signal transmission speed has been increasing in speed, and impedance matching has become an important factor for FPC. As a countermeasure against impedance matching in which the signal capacity is increased, a resin insulating layer (for example, polyimide) which becomes a base of the FPC is developed in a thick layer direction. On the other hand, in FPC, processing such as bonding to a liquid crystal substrate or mounting of an IC wafer is performed. However, the alignment is performed by a positioning pattern which is transmitted through a copper foil and a resin insulating layer. Since the copper foil in the laminated board is visually recognized by the resin insulating layer remaining after etching, the visibility of the resin insulating layer becomes important.

Further, the copper clad laminate which is a laminate of the copper foil and the resin insulating layer can be produced by using a rolled copper foil having a roughened surface. The rolled copper foil is usually made of refined copper (oxygen content: 100 to 500 ppm by weight) or oxygen-free copper (oxygen content: 10 ppm by weight or less) as a raw material, and the ingots are hot rolled and then cold rolled. Manufactured by annealing to a specific thickness.

As such a technique, for example, Patent Document 1 discloses an invention of a copper-clad laminate in which a polyimide film and a low-roughness copper foil are laminated, and the film after etching the copper foil is transparent at a wavelength of 600 nm. The light rate is 40% or more, the haze (HAZE) is 30% or less, and the strength is 500 N/m or more.

Further, Patent Document 2 discloses an invention of a flexible printed wiring board for COF, which has an insulating layer in which a conductor layer formed of an electrolytic copper foil is laminated, and is etched in an etching region when the conductor layer is etched to form a circuit. A flexible printed wiring board for soft film flip chip (COF) having a light transmittance of 50% or more of the insulating layer, wherein the electrodeposited copper foil is provided with a rust preventive layer formed of a nickel-zinc alloy on the subsequent surface of the insulating layer. The layer is treated, and the surface roughness (Rz) of the bonding surface is 0.05 to 1.5 μm, and the specular gloss of the incident angle of 60° is 250 or more.

Further, Patent Document 3 discloses an invention for treating a copper foil for a printed circuit, which is a method for treating a copper foil for a printed circuit, characterized in that copper-cobalt-nickel alloy plating is performed on the surface of a copper foil. After the roughening treatment, a cobalt-nickel alloy plating layer is formed to form a zinc-nickel alloy plating layer.

In addition, in the case where the signal transmission speed is increasing in the direction of high speed, the high-frequency substrate is required to reduce the transmission loss of the high-frequency substrate in order to ensure the quality of the output signal. The transmission loss mainly includes dielectric loss due to the resin (substrate side) and conductor loss due to the conductor (copper foil side). Regarding dielectric loss, The smaller the dielectric constant and dielectric loss tangent of the resin, the more the dielectric loss is reduced. In high-frequency signals, the main reason for conductor loss is that the higher the frequency, the smaller the cross-sectional area through which the current flows due to the skin effect of the current flowing only on the surface of the conductor, and the higher the resistance.

Patent Document 4 discloses an electrolytic copper foil characterized in that one of the surfaces of the copper foil is an uneven surface having a round-like projection having a surface roughness of 2 to 4 μm. Further, it is described that an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-98659

[Patent Document 2] WO2003/096776

[Patent Document 3] Japanese Patent No. 2849059

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-244656

In Patent Document 1, the low-roughness copper foil obtained by the improvement of the adhesiveness by the organic treatment agent after the blackening treatment or the plating treatment has a bending property for the copper-clad laminate, and is fatigued. In the case of wire breakage, and there is a case where the resin has poor transparency.

Further, in Patent Document 2, the roughening treatment is not performed, and in applications other than the flexible printed wiring board for COF, the adhesion strength between the copper foil and the resin is not sufficient.

Further, in the treatment method described in Patent Document 3, the copper foil may be subjected to fine treatment using Cu-Co-Ni, but the copper foil and the resin are subsequently removed by etching to remove the copper foil. In words, excellent transparency is not achieved.

Further, in Patent Documents 1 to 3, the reduction in transmission loss is not achieved.

In Patent Document 4, excellent transparency is not achieved for a resin obtained by subsequently removing the copper foil and the resin by etching.

The present invention provides a surface-treated copper foil excellent in transparency of a resin which is excellent in adhesion to a resin and which is removed by etching, and which has a small transmission loss of a signal, and a laminated board using the same.

As a result of intensive research, the inventors of the present invention found that the surface roughness of the surface of the copper foil having the roughened particles formed on the surface by the roughening treatment is Rz, gloss, and coarseness on the side of the resin substrate. The ratio of the surface area of the particles to the area obtained when the roughened particles are viewed from the surface side of the copper foil affects the transparency of the resin after the copper foil is removed and the transmission loss of the signal.

In addition, the inventors have found that the type of surface-treated metal of the copper foil and the amount of adhesion thereof affect the transmission loss of the signal, by the factors and the number density of the roughened particles on the surface of the copper foil and The gloss is controlled at the same time, and a surface-treated copper foil having a small transmission loss of a signal even for a high-frequency circuit substrate can be obtained.

The present invention based on the above findings is a surface-treated copper foil which is roughened to form roughened particles on the surface of a copper foil and/or on the surface of two copper foils, and the surface of the roughened surface is utilized. The ten-point average roughness Rz of the TD measured by the roughness meter is 0.20-0.80 μm, and the 60-degree gloss of the MD of the roughened surface is 76-350%, and the surface area A of the roughened particles is as described above. The ratio A/B of the area B obtained when the surface of the copper foil is viewed from the surface of the roughened particles is 1.90 to 2.40, and the surface of the roughened surface contains an element selected from the group consisting of Ni and Co, and is coarsened. When the surface of the treatment surface contains Ni, the adhesion amount of Ni is 1400 μg/dm ² or less, and when Co is included in the roughening treatment surface, the adhesion amount of Co is 2400 μg/dm ² or less.

In one embodiment of the surface-treated copper foil of the present invention, coarsened particles are formed on the surface of a copper foil by roughening treatment, and a ten-point average of TD measured by a contact roughness meter is used for roughening the surface. The roughness Rz is 0.20 to 0.80 μm, and the 60 degree gloss of the MD of the roughened surface is 76 to 350%, and the surface area A of the roughened particles and the surface of the copper foil are as viewed from the surface of the copper foil. The ratio A of the area B is 1.90 to 2.40, and the surface of the roughening treatment contains an element selected from the group consisting of Ni and Co. When the surface of the roughened surface contains Ni, the adhesion amount of Ni is 1400μg / dm ² or less, while in the case of roughened surface contains Co, the deposition amount of Co was 2400μg / dm ² or less, and the other surface of the copper foil surface treatment.

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

In still another embodiment of the surface-treated copper foil of the present invention, when Ni is contained on the surface of the roughening treatment, 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 of the present invention, when Co is included in the surface of the roughening treatment, the adhesion amount of Co is 2000 μg/dm ² or less.

In still another embodiment of the surface-treated copper foil of the present invention, when Co is included in the surface of the roughening treatment, the adhesion amount of Co is 300 μg/dm ² or more and 2000 μg/dm ² or less.

In still another embodiment of the surface-treated copper foil of the present invention, the MD has a 60-degree gloss of 90 to 250%.

In still another embodiment of the surface-treated copper foil of the present invention, 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 measured by a laser microscope having a laser wavelength of 405 nm. The ten-point average roughness Rz of the obtained TD is 0.35 μm or more.

In still another embodiment of the surface-treated copper foil of the present invention, 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 measured by a laser microscope having a laser wavelength of 405 nm. The arithmetic mean roughness Ra of the obtained TD is 0.05 μm or more.

In still another embodiment of the surface-treated copper foil of the present invention, 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 measured by a laser microscope having a laser wavelength of 405 nm. The radix height Rq of the obtained TD is 0.08 μm or more.

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

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

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

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

In still another embodiment of the surface-treated copper foil of the present invention, the copper foil is bonded to both surfaces of the resin substrate having a thickness of 50 μm from the roughened surface side, and then the copper foil of the both surfaces is removed by etching. The haze value of the resin substrate is 20 to 70%.

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

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

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

In another aspect, the invention provides a copper foil with carrier, which is provided with a carrier copper foil with a carrier, an intermediate layer and an extremely thin copper layer, and the ultra-thin copper layer is the surface-treated copper foil of the invention.

In one embodiment of the copper foil with a carrier of the present invention, the copper foil with a carrier is bonded to the both sides of the resin substrate having a thickness of 50 μm from the roughened surface side of the ultra-thin copper layer of the copper foil with the carrier. When the carrier with the carrier copper foil is removed, and then the extremely thin 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%.

In another embodiment of the copper foil with a carrier of the present invention, the ultra-thin copper layer is provided on both sides of the carrier.

In still another embodiment of the copper foil with a carrier of the present invention, a roughened layer is provided on a side of the carrier opposite to the ultra-thin copper layer.

In another aspect of the invention, a surface-treated copper foil is formed on the surface of the copper foil by roughening treatment, and the copper foil is bonded to the both sides of the resin substrate having a thickness of 50 μm from the surface of the roughened surface. When the copper foil of the both surfaces is removed by etching, the haze value of the resin substrate is 20 to 70%.

In still another aspect, the present invention provides a laminated board comprising a surface-treated copper foil of the present invention or a copper foil with a carrier of the present invention and a resin substrate.

Still another aspect of the invention is a copper foil prior to roughening treatment for use in the surface treated copper foil of the present invention.

In one embodiment of the copper foil prior to the roughening treatment of the present invention, the 60 degree gloss of MD is 500 to 800%.

The invention is further characterized by a copper foil having a 60 degree gloss of MD of 501 to 800%.

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.

The present invention is on the other hand an electronic machine using the printed wiring board of the present invention.

In still another aspect of the invention, there is provided 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.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board to which two or more printed wiring boards are connected includes the steps of: at least one printed wiring board of the present invention, and another printed wiring board of the present invention or The printed wiring board which does not belong to the printed wiring board of this invention is connected.

Still another aspect of the invention is an electronic device 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 provides a method of manufacturing a printed wiring board comprising at least the step of connecting a printed wiring board manufactured by the method of the present invention to a component.

In another aspect of the invention, a printing of two or more printed wiring boards is connected A method of manufacturing a brushed wiring board comprising the steps 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 belonging to the printed wiring board of the present invention And a step of connecting the printed wiring board of the present invention or the printed wiring board to which the two or more printed wiring boards of the present invention are connected, and the components.

The invention is a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and After the carrier-attached copper foil is laminated with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then, by semi-additive method, subtractive method, partial addition method or modification The step of forming a circuit by any of the methods of semi-additive.

The invention is directed to a method of manufacturing a printed wiring board comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention or the side surface of the carrier; a step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier or the side surface of the carrier; forming a circuit on the resin layer; after forming a circuit on the resin layer, the carrier or a step of peeling off the ultra-thin copper layer; and after removing the carrier or the ultra-thin copper layer, removing the ultra-thin copper layer, thereby burying the surface of the ultra-thin copper layer or the side surface of the carrier Above tree The step of exposing the circuit of the lipid layer.

The invention is directed to a method of manufacturing a printed wiring board, wherein the step of forming a circuit on the resin layer is a step of bonding another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer. The above circuit is formed using a copper foil with a carrier attached to the above resin layer.

In another aspect of the invention, a method of manufacturing a printed wiring board, wherein another copper foil with a carrier adhered to the resin layer is a copper foil with a carrier of the invention.

The present invention is directed to a method of manufacturing a printed wiring board, wherein the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method is carried out.

According to still another aspect of the invention, there is provided a method of producing a printed wiring board, wherein a copper foil with a carrier on the surface forming circuit has a substrate or a resin layer on a carrier side surface or an extremely thin copper layer side surface of the carrier copper foil.

According to the present invention, it is possible to provide a surface-treated copper foil which is excellent in transparency of a resin which is excellently adhered to a resin and which is removed by etching, and which has a small transmission loss of a signal, and a laminated board using the same.

Fig. 1a is a SEM observation photograph of the surface of the copper foil of Comparative Example 1 (a) at the time of Rz evaluation.

Fig. 1b is a SEM observation photograph of the surface of the copper foil of Comparative Example 2 in (b) at the time of Rz evaluation.

Fig. 1c is a SEM observation photograph of the surface of the copper foil of Comparative Example 3 (c) at the time of Rz evaluation.

Fig. 1d is a SEM observation photograph of the surface of the copper foil of Comparative Example 4 (d) at the time of Rz evaluation.

Fig. 1e is a SEM observation photograph of the surface of the copper foil of Example 1 in (e) at the time of Rz evaluation.

Fig. 1f is a SEM observation photograph of the surface of the copper foil of Example 2 in (f) when Rz was evaluated.

2A to 2C are schematic views showing a cross section of a wiring board in a step of circuit plating-removing a resist in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

3D to 3F are schematic views showing a cross section of a wiring board in a step from a build-up resin and a second-layer carrier-attached copper foil to a laser opening in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention; .

4G to 1I are schematic views showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier in the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

5J to K are schematic views showing a cross section of a wiring board in a step from rapid etching to formation of a bump-copper pillar in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

[Formation 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 which is formed by laminating a resin substrate and is removed by etching.

The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. In general, in order to increase the peeling strength of the copper foil after lamination, the rough surface of the copper foil and the resin substrate may be subjected to roughening treatment of the surface of the copper foil after degreasing. The electrolytic copper foil has irregularities at the time of manufacture, but the convex portion of the electrolytic copper foil is enlarged by the roughening treatment to make the concave The convexity becomes larger. In the present invention, the roughening treatment can be carried out by alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating or nickel-zinc alloy plating. Further, it is preferably carried out by a copper plating alloy. As the copper alloy plating bath, for example, a plating bath containing copper and one or more elements other than copper is preferably used, and more preferably contains copper and is selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese, and Any one or more of the plating baths of the group consisting of molybdenum. Further, in the present invention, the current density of the roughening treatment is made higher than the current density of the conventional roughening treatment, and the roughening treatment time is shortened.

In the case of normal copper plating or the like, pretreatment before roughening may be performed, and in order to prevent the electrodeposited material from falling off, normal copper plating or the like may be performed as a final processing after the roughening treatment. In the present invention, such pretreatment and final processing can also be performed.

Further, the copper foil of the invention of the present application also 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 is high (for example, 10% by mass or more in total), the electrical conductivity may be lowered. The electrical 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 0 mass% or more and 50 mass% or less of the elements other than copper, and may contain 0.0001 mass% or more and 40 mass% or less, and may contain 0.0005 mass% or more and 30 mass% or less, and may contain 0.001 mass% or more and 20 mass%. the following.

Further, the copper foil used in the present invention may be a copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order. In the case where the carrier copper foil is used in the present invention, the above roughening treatment is performed on the surface of the ultra-thin copper layer. Further, another embodiment of the copper foil with a carrier will be described in detail below.

Further, regarding the copper foil used in the present invention, the surface to be subjected to the surface treatment before the surface treatment must have a specific surface roughness Rz (ten-point average roughness) (according to JIS B0601 1994). )) and 60 degree gloss.

Further, with respect to the carrier with the carrier copper foil used in the present invention, for the surface on the side on which the intermediate layer is provided, it is necessary to have a specific Rz (ten-point average roughness) as follows (according to JIS) B0601 1994)) and 60 degree gloss.

Further, the thickness of the surface-treated copper foil of the invention of the present application is not particularly limited, and is typically 0.5 to 3000 μm, preferably 1.0 to 1000 μm, preferably 1.0 to 300 μm, preferably 1.0 to 100 μm, preferably. It is 1.0 to 75 μm, preferably 1.0 to 40 μm, preferably 1.5 to 20 μm, preferably 1.5 to 15 μm, preferably 1.5 to 12 μm, preferably 1.5 to 10 μm.

As the roughening treatment of copper - cobalt - nickel alloy plating may be formed by electrolytic plating deposition amount as 15 ~ 40mg / dm ² of copper -250 ~ 2000μg / dm ² of cobalt -50 ~ 1000μg / dm ² of The implementation of the ternary alloy layer of nickel. When the Co adhesion amount is less than 250 μg/dm ² , the heat resistance is deteriorated and the etching property is deteriorated. When the Co adhesion amount exceeds 2000 μg/dm ² , the transmission loss of the signal becomes large. In addition, there are cases where etching spots are generated, or acid resistance and chemical resistance are deteriorated. If the Ni adhesion amount is less than 50 μg/dm ² , heat resistance may be deteriorated. On the other hand, if the Ni adhesion amount exceeds 1000 μg/dm ² , the transmission loss of the signal becomes large. In addition, there are cases where the etching residue is increased. The Co adhesion amount is preferably 300 to 1800 μg/dm ² , and the nickel adhesion amount is preferably 100 to 800 μg/dm ² . Here, the etching spot refers to a case where Co is not dissolved and remains in the case of etching with copper chloride, and the term "etching residue" refers to a case where alkaline etching is performed using ammonium chloride, and Ni is not Dissolved and left.

One of the plating baths and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows: plating bath composition: Cu 10~20g/L, Co 1~10g/L, Ni 1~10g/ L

pH: 1~4

Temperature: 30~50°C

Current density D _k : 25~50A/dm ²

Plating time: 0.2~3.0 seconds

In one embodiment of the present invention, in the roughening treatment, the current density of the roughening treatment is higher than the current density of the conventional roughening treatment conditions, and the roughening treatment time is shortened.

After the roughening treatment, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, and a weather-resistant layer may be provided on the roughened surface. In addition, each layer may also be a plurality of layers of 2 layers, 3 layers, etc., and the order of the layers may be in any order, or the layers may be alternately laminated.

In the surface-treated copper foil of the present invention, the term "roughening surface" refers to a case where a surface treatment such as a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like is performed after the roughening treatment. The surface of the surface treated copper foil after the surface treatment. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the term "roughened surface" refers to a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after the roughening treatment. In the case of surface treatment, the surface of the ultra-thin copper layer after the surface treatment is performed.

Here, as the heat-resistant layer, a known heat-resistant layer can be used. In addition, for example, the following surface treatment can be used.

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat-resistant layer and/or the rust-preventing layer may also contain a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. The layer of one or more elements of the group of iron and antimony may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver. A metal layer or an alloy layer composed of one or more elements selected from the group consisting of platinum group elements, iron, and antimony. In addition, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements of the group of iron and antimony. 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 rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may also be a nickel-zinc alloy layer containing 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , more preferably 20 to 100 mg/m ² . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the adhesion amount of zinc (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-preventing layer is a layer containing a nickel-zinc alloy, when the inner wall portion of the through hole or the guide hole or the like is in contact with the desmear liquid, the interface between the copper foil and the resin substrate is hardly affected by the glue removal. The slag liquid is corroded, and the adhesion between the copper foil and the resin substrate is improved. The rustproof layer may also be a chromate treatment layer. A chromate treatment layer can be used with a known chromate treatment layer. For example, a chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (may also be metals, alloys, oxides, nitrides, sulfides). Any form of matter). Specific examples of the chromate treatment layer include a pure chromate treatment layer or a zinc chromate treatment layer. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer having a deposition amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and adhesion. The heat-resistant layer and/or the rust-proof layer formed by a tin layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² , and the nickel alloy layer may also be composed of nickel-molybdenum and nickel. - Any of zinc, nickel-molybdenum-cobalt. Further, the total adhesion amount of the nickel or nickel alloy of the heat-resistant layer and/or the rust-preventing layer to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel adhered in nickel or a nickel alloy] / [the amount of tin adhesion] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the peeling strength of the circuit after the copper foil with a carrier is processed into a printed wiring board, and the chemical-resistant deterioration rate of the peeling strength, etc. are favorable.

Further, the amount of deposition of 200 ~ 2000μg / dm ² of cobalt -50 ~ 700μg / dm ² of nickel, cobalt - nickel alloy plated layer as the heat-resistant layer and / or layer of rust. This treatment can be regarded as a rust-proof treatment in a broad sense. The cobalt-nickel alloy plating layer must be carried out to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 μg/dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance are deteriorated. Further, as another reason, if the amount of cobalt is small, the treated surface is reddish, which is not preferable. When the cobalt adhesion amount exceeds 2000 μg/dm ² , the transmission loss of the signal becomes large, which is not preferable. In addition, there are cases where etching spots are generated, and in addition, acid resistance and chemical resistance are deteriorated. The cobalt adhesion amount is preferably 500 to 1000 μg/dm ² as the heat-resistant layer and/or the rust-preventive layer. 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 are deteriorated. If the nickel exceeds 1000 μg/dm ² , the transmission loss of the signal becomes large. The nickel adhesion amount is preferably from 100 to 600 μg/dm ² as the heat-resistant layer and/or the rust-preventive layer.

In addition, one of the plating conditions of the cobalt-nickel alloy is as follows: plating bath composition: Co 1~20g/L, Ni 1~20g/L

pH: 1.5~3.5

Temperature: 30~80°C

Current density D _k : 1.0~20.0A/dm ²

Plating time: 0.5~4 seconds

Further, a zinc plating layer having an adhesion amount of 30 to 250 μg/dm ² may be further formed on the cobalt-nickel alloy plating layer. When the amount of zinc adhesion is less than 30 μg/dm ² , the effect of improving the heat-resistant deterioration rate disappears. On the other hand, when the amount of zinc adhesion exceeds 250 μg/dm ² , the rate of deterioration of hydrochloric acid resistance is extremely deteriorated. The zinc adhesion amount is preferably from 30 to 240 μg/dm ² , more preferably from 80 to 220 μg/dm ² .

One of the above conditions for galvanizing is as follows: Plating bath composition: Zn 100~300g/L

pH: 3~4

Temperature: 50~60°C

Current density D _k : 0.1~0.5A/dm ²

Plating time: 1~3 seconds

Further, instead of the zinc plating layer, a galvannealed alloy layer such as a zinc-nickel alloy plating layer may be formed, and a rustproof layer or a weather resistant layer may be formed on the outermost surface by a chromate treatment or a coating of a decane coupling agent.

A known weather resistant layer can be used as the weather resistant layer. Further, as the weather resistant layer, for example, a known decane coupling treatment layer can be used, and a decane coupling treatment layer formed by the following decane can be used.

As the decane coupling agent to be used in the decane coupling treatment, a known decane coupling agent can be used. For example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, the decane coupling agent may also be a vinyl trimethoxy decane, a vinyl phenyl trimethoxy decane, a γ-methyl propylene methoxy propyl trimethoxy decane or a γ-glycidoxy propyl trimethoxy group. Basear, 4-epoxypropylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer may be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, a decane coupling treatment layer formed using an amine decane coupling agent or an epoxy decane coupling agent is preferred.

The amino decane coupling agent herein may also be selected from N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2- Aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, Aminopropyl Trimethoxy decane, N-methylaminopropyltrimethoxy decane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3 -Aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropyl)trimethoxydecane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylamino) Propyl)trimethoxydecane, aminophenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxynonane, 3-amino group Propyltris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxy Decane, 3-(2-N-benzyl Ethylethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-aminopropyl) Trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxy Decane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(amine Benzyl)-γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane An amine-based decane coupling agent in the group consisting of.

The decane coupling treatment layer is preferably 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 ruthenium atom. Set within the range of /m ² . When it is in the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

[surface roughness Rz]

The surface-treated copper foil of the present invention forms roughened particles on the surface of one copper foil and/or two copper foils by roughening treatment, and the TD (measured by a contact type roughness meter) is used for roughening the surface. The average roughness Rz of the direction perpendicular to the rolling direction (the width direction of the copper foil) in the direction perpendicular to the advance direction of the copper foil in the electrolytic copper foil manufacturing apparatus when the surface-treated copper foil is an electrolytic copper foil is 0.20~ 0.80 μm. With such a configuration, the peeling strength is increased, and the resin is satisfactorily adhered to, and the haze (haze value) of the resin after the copper foil is removed by etching is reduced, and the transparency is increased. As a result, it is easier to position the IC wafer during mounting by the positioning pattern viewed through the resin. Further, since the unevenness of the surface is extremely small, the length of the surface of the surface-treated copper foil corresponding to the length through which the electrons flow is shortened, and the transmission loss becomes small. If the ten-point average roughness Rz of the TD is less than 0.20 μm, there is a concern that the manufacturing cost of manufacturing the ultra-smooth copper foil is high. On the other hand, when the ten-point average roughness Rz of the TD exceeds 0.80 μm, the unevenness of the surface of the resin after the copper foil is removed by etching increases, and as a result, the haze value of the resin becomes large. The ten-point average roughness Rz of the TD of the roughened surface is preferably from 0.30 to 0.70 μm, more preferably from 0.35 to 0.60 μm, still more preferably from 0.35 to 0.55 μm, and still more preferably from 0.35 to 0.50 μm. Further, in the surface-treated copper foil of the present invention, the "roughening treatment surface" means a heat-resistant layer after the roughening treatment. In the case of surface treatment of a rust layer, a weather resistant layer or the like, the surface of the surface-treated copper foil after the surface treatment is performed. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the term "roughening surface" means a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after the roughening treatment. In the case of surface treatment, the surface of the ultra-thin copper layer after the surface treatment is performed.

Further, when the surface-treated copper foil of the present invention is used for the application in which Rz must be reduced, the ten-point average roughness Rz of the TD of the roughened surface is preferably 0.20 to 0.70 μm, more preferably 0.25~ 0.60 μm, more preferably 0.30 to 0.55 μm, still more preferably 0.30 to 0.50 μm.

Further, in order to control the size and the number density of the roughened particles as described above, it is necessary to roughen the surface of the copper foil before the surface treatment (in the case where the surface-treated copper foil is a carrier-attached copper foil) as described below. The degree Rz and the gloss are set to a specific range, and further, roughening treatment by alloy plating is performed, and the current density of the roughening plating is higher than the current density of the conventional roughening treatment, and the plating time of the roughening treatment is performed. Shorter than conventional roughing treatment plating time.

[Adhesion of Ni and Co on the surface of copper foil]

In the surface-treated copper foil of the present invention, when Ni is contained on the roughened surface, the adhesion amount of Ni is 1400 μg/dm ² or less, and when Co is included in the roughened surface, the adhesion amount of Co is 2400 μg/dm. ² or less. Here, the adhesion amount of Ni and Co in the roughened surface refers to 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 the roughened layer, the heat-resistant layer 1, the heat-resistant layer 2, the rustproof layer, and the weather-resistant layer are provided on the surface of the copper foil, it means a roughened layer as a surface treatment layer formed on the surface of the copper foil, The total adhesion amount of the adhesion amount of Ni and Co contained in the heat-resistant layer 1, the heat-resistant layer 2, the rust-preventive layer, and the weather-resistant layer.

By the study of the inventors and others, it is clarified that the amount of adhesion of a specific metal in the surface treatment layer is Transmission losses have a significant impact. According to the research of the present inventors, it has been clarified that among the surface-treated metal species, in particular, Co and Ni having relatively high magnetic permeability and relatively low conductivity have an influence on transmission loss. Therefore, in order to reduce the transmission loss, it is effective to limit the adhesion amount of Ni and/or Co as described above.

When the adhesion amount of Ni becomes more than 1400 μg/dm ² , the transmission loss becomes large, which is not preferable. Further, when the adhesion amount of Co becomes more than 2400 μg/dm ² , the transmission loss becomes large, which is not preferable.

In order to further reduce the transmission loss, in the case of roughened surface contains Ni, the Ni deposition amount is preferably of 1000μg / dm ² or less, preferably 900μg / dm ² or less, preferably 800μg / dm ² or less, more preferably It is 700 μg/dm ² or less.

Further, when Ni is contained on the surface of the roughening treatment, the adhesion amount of Ni is preferably 100 μg/dm ² or more, preferably 120 μg/dm ² or more, and more preferably 150 μg/dm ² or more. The reason for this is that when the adhesion amount of Ni is less than 100 μg/dm ² , heat resistance is poor.

In order to further reduce the transmission loss, in the roughened surface of the case containing Co, the deposition amount of Co is preferably 2000μg / dm ² or less, preferably 1800μg / dm ² or less, preferably 1600μg / dm ² or less, more preferably It is 1400 μg/dm ² or less.

In addition, in the roughened surface of the case containing Co, the deposition amount of Co is preferably 300μg / dm ² or more, preferably 350μg / dm ² or more, more preferably 400μg / dm ² or more. The reason for this is that when the adhesion amount of Co is less than 300 μg/dm ² , heat resistance is poor.

In addition, in order to control the adhesion amount of Ni and Co within the above range, it is effective to control the Ni and Co concentrations in the surface treatment (plating) liquid such as the roughening treatment plating or the heat-resistant layer, and the surface treatment. Current density, surface treatment time. When the concentration of Ni and Co in the surface treatment (plating) liquid is increased, the adhesion amount of Ni and Co can be increased. In addition, if the concentration of Ni and Co is lowered, Then, the adhesion amount of Ni and Co can be reduced. Further, when the current density at the time of surface treatment is increased and/or the surface treatment time is made longer, the adhesion amount of Ni and Co can be increased. Further, when the current density at the time of surface treatment is lowered and/or the surface treatment time is shortened, the amount of adhesion of Ni and Co can be reduced.

Further, in the surface-treated copper foil of the present invention, roughened particles can be formed on the surface of one copper foil by roughening treatment, and the ten-point average roughness of the TD measured by the contact type roughness meter on the roughened surface is obtained. Rz is 0.20 to 0.80 μm, the 60-degree gloss of the MD of the roughened surface is 76 to 350%, the surface area A of the roughened particles, and the area B obtained when the roughened particles are viewed from the surface side of the copper foil. The ratio A/B is 1.90 to 2.40, and the surface of the roughening treatment contains an element selected from the group consisting of Ni and Co. When the surface of the roughened surface contains Ni, the adhesion amount of Ni is 1400 μg/ When dm ² or less, when Co is contained in the surface of the roughening treatment, the adhesion amount of Co is 2400 μg/dm ² or less, and the surface of the other copper foil may be surface-treated.

Regarding the surface treated copper foil of the present invention, the surface of the roughened copper foil and/or the surface of the copper foil which has not been roughened is measured by a laser microscope having a laser wavelength of 405 nm. The roughness Rz is preferably 0.35 μm or more. With such a configuration, the problem that the contact area between the copper foil and the protective film is further increased can be more satisfactorily prevented, and the protective film is attached to the copper foil at the step of laminating with the resin substrate. The surface roughness of the copper foil of the surface treated copper foil of the present invention and/or the surface roughness of the copper foil without the roughening is measured by a laser microscope having a laser wavelength of 405 nm. Rz is more preferably 0.40 μm or more, still more preferably 0.50 μm or more, still more preferably 0.60 μm or more, and still more preferably 0.80 μm or more. Furthermore, the surface of the roughened copper foil of the surface treated copper foil of the present invention and/or the surface of the copper foil which has not been roughened is measured by a laser microscope having a laser wavelength of 405 nm. The upper limit of the average roughness Rz is not particularly limited, and is typically 4.0 μm or less. More typically, it is 3.0 μm or less, typically 2.5 μm or less, and typically 2.0 μm or less.

Regarding the surface-treated copper foil of the present invention, the rough averaged copper foil surface and/or the surface of the copper foil which has not been roughened has an arithmetic mean roughness of TD measured by a laser microscope having a laser wavelength of 405 nm. The degree Ra is preferably 0.05 μm or more. With such a configuration, the problem that the contact area between the copper foil and the protective film is further increased can be more satisfactorily prevented, and the protective film is attached to the copper foil at the step of laminating with the resin substrate. The rough averaged copper foil surface of the surface treated copper foil of the present invention and/or the surface roughness of the copper foil without roughening is measured by a laser microscope having a laser wavelength of 405 nm. More preferably, it is 0.08 μm or more, further preferably 0.10 μm or more, further preferably 0.20 μm or more, and still more preferably 0.30 μm or more. Further, the rough averaged copper foil surface of the surface-treated copper foil of the present invention and/or the surface roughness of the copper foil without roughening is measured by a laser microscope having a laser wavelength of 405 nm. The upper limit of the degree Ra is not particularly limited, and is typically 0.80 μm or less, more typically 0.65 μm or less, more typically 0.50 μm or less, and more typically 0.40 μm or less.

Regarding the surface treated copper foil of the present invention, the surface of the roughened copper foil and/or the surface of the copper foil which has not been roughened is measured by a laser microscope having a laser wavelength of 405 nm and the root mean square of TD The height Rq is preferably 0.08 μm or more. With such a configuration, the problem that the contact area between the copper foil and the protective film is further increased can be more satisfactorily prevented, and the protective film is attached to the copper foil at the step of laminating with the resin substrate. The surface of the roughened copper foil of the surface treated copper foil of the present invention and/or the surface of the copper foil which has not been roughened is measured by a laser microscope having a laser wavelength of 405 nm, and the root mean square height Rq of the TD is measured. More preferably 0.10 μm or more, and further It is preferably 0.15 μm or more, more preferably 0.20 μm or more, and still more preferably 0.30 μm or more. Further, the surface of the roughened copper foil of the surface-treated copper foil of the present invention and/or the surface of the copper foil which has not been roughened is measured by a laser microscope having a laser wavelength of 405 nm and the root mean square of TD The upper limit of the height Rq is not particularly limited, and is typically 0.80 μm or less, more typically 0.60 μm or less, more typically 0.50 μm or less, and more typically 0.40 μm or less.

The surface of the copper foil which has not been subjected to the roughening treatment may be subjected to a treatment of plating (normal plating, plating which is not rough plating) and providing a heat-resistant layer or a rust-proof layer.

For the roughening treatment, for example, a plating solution containing copper sulfate and a sulfuric acid aqueous solution may be used for the roughening treatment, or a plating solution composed of a copper sulfate and a sulfuric acid aqueous solution may be used for the roughening treatment. Alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating or nickel-zinc alloy plating may be used. Further, it is preferably carried out by a copper plating alloy. As the copper alloy plating bath, for example, a plating bath containing copper and one or more elements other than copper is preferably used, and more preferably contains copper and is selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese, and Any one or more of the plating baths of the group consisting of molybdenum.

Further, a roughening treatment other than the above-described roughening treatment may be used, and when it is not a roughening treatment, a surface treatment other than the above-described plating treatment may be used.

As the surface treatment for forming irregularities on the surface, surface treatment by electrolytic polishing may also be performed. For example, in the solution composed of copper sulfate and an aqueous sulfuric acid solution, the other surface of the copper foil is subjected to electrolytic polishing, whereby irregularities can be formed on the other surface of the copper foil. In general, electrolytic polishing is aimed at smoothing. However, in the surface treatment of the other surface of the copper foil of the present invention, irregularities are formed by electrolytic polishing, which is contrary to the conventional idea. The method of forming irregularities by electrolytic polishing can also be carried out by a known technique. Examples of the known technique for electrolytic polishing for forming the above-mentioned irregularities include the methods described in JP-A-2005-240132, JP-A-2010-059547, and JP-A-2010-047842. Specific conditions of the treatment for forming irregularities by electrolytic polishing include, for example, a treatment solution: Cu: 20 g/L, H ₂ SO ₄ : 100 g/L, and temperature: 50 ° C.

‧ Electrolytic grinding current: 15A/dm ²

‧ Electrolytic grinding time: 15 seconds

Wait.

As the surface treatment for forming irregularities on the other surface, for example, irregularities may be formed by mechanically grinding the other surface. Mechanical polishing can also be carried out using well-known techniques.

Further, after the surface treatment of the surface-treated copper foil of the present invention, a heat-resistant layer or a rust-proof layer or a weather-resistant layer may be provided. The heat-resistant layer, the rust-preventive layer, and the weather-resistant layer can be formed by the methods described in the above description or experimental examples, or can be formed by a known technical method.

[Gloss]

The glossiness of the surface treated copper foil roughened surface at an incident angle of 60 degrees in the direction of the MD (Machine direction) has a large influence on the haze value of the resin and the transmission loss of the signal. In other words, the copper foil having a higher glossiness of the roughened surface has a smaller haze value of the resin and a smaller transmission loss of the signal. Therefore, the roughened surface of the surface-treated copper foil of the present invention has a gloss of 76 to 350%, preferably 80 to 350%, preferably 90 to 300%, more preferably 90 to 250%, still more preferably 100. ~250%.

Here, in order to obtain the effect of the visibility of the present invention and the effect of reducing the transmission loss, it is necessary to previously control the treated side surface of the copper foil before the surface treatment (in the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil) In order to form the middle of the carrier before the middle layer TD of the surface on the side of the layer (the direction perpendicular to the rolling direction (the width direction of the copper foil), which is the direction perpendicular to the advance direction of the copper foil in the electrolytic copper foil manufacturing apparatus when the copper foil is electrolytically) (Rz (referred to as ten point average roughness Rz (JIS B0601 1994); the same in the present specification) and gloss (refers to 60 degree gloss (measured according to JIS Z8741); the same in the present specification). Specifically, if the copper foil before surface treatment (in the case where the surface-treated copper foil is a very thin copper layer with a carrier copper foil, the carrier before forming the intermediate layer) has a surface roughness (Rz) of 0.30. ~0.80μm, preferably 0.30~0.50μm, and the gloss angle of the incident angle of 60 degrees in the rolling direction (MD, in the direction of advancement of the copper foil in the electrolytic copper foil manufacturing apparatus in the case of electrolytic copper foil) is 350-800 %, preferably 500 to 800%, and further use a copper alloy plating bath (a plating bath containing copper and one or more elements other than copper, more preferably containing copper and selected from cobalt, nickel, arsenic, tungsten, chromium, a plating bath of any one or more of the group consisting of zinc, phosphorus, manganese, and molybdenum) as a plating for roughening treatment, and the current density of the roughening treatment is higher than a current density of a conventional roughening treatment, When the roughening treatment time is shorter than the processing time of the conventional roughening treatment, the gloss of the surface-treated copper foil after the surface treatment in the rolling direction (MD) at an incident angle of 60 degrees is 76 to 350%, and The surface roughness Rz of the roughened surface and the surface area A of the roughened particles and the above-mentioned roughening from the surface side of the copper foil The ratio A/B of the area B obtained when the particles are obtained is controlled within the specific range of the present invention. Such a copper foil (in the case where the surface-treated copper foil is a carrier-attached copper foil, it means a carrier; the same applies hereinafter), can be produced by adjusting the oil film equivalent of the rolling oil and performing rolling (high gloss rolling), or borrowing It is produced by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Further, such a copper foil can be produced by producing an electrolytic copper foil by a specific electrolytic solution or a specific electrolytic condition.

Furthermore, the incident angle 60 in the rolling direction (MD) after the surface treatment is desired When the gloss of the degree becomes higher (for example, the gloss of the incident angle of 60 degrees in the rolling direction (MD) = 350%), the roughness of the TD of the treated side surface of the copper foil before the surface treatment (Rz) ) is set to 0.18 to 0.80 μm, preferably 0.25 to 0.50 μm, and the gloss at an incident angle of 60 degrees in the rolling direction (MD) is set to 350 to 800%, preferably 500 to 800%, and further a copper alloy is used. A plating bath (a plating bath containing copper and one or more elements other than copper, more preferably containing copper and a group selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese, and molybdenum) One or more plating baths are used as the plating for the roughening treatment, and the current density of the roughening treatment is higher than the current density of the conventional roughening treatment, and the roughening treatment time is shortened.

Further, the high gloss rolling can be carried out by setting the oil film equivalent of the following formula to 13,000 or more and 24,000 or less. In addition, when the glossiness of the incident angle of 60 degrees in the rolling direction (MD) after the surface treatment is to be made higher (for example, the glossiness of the incident angle of 60 degrees in the rolling direction (MD) is 350%) The high gloss rolling is performed by setting the oil film equivalent of the following formula to 12,000 or more and 24,000 or less.

Oil film equivalent = {(calendering oil viscosity [cSt]) × (passing speed [mpm] + roll peripheral speed [mpm])} / {(roller bite angle [rad]) × (material lodging stress [kg/mm ² ])}

The rolling oil viscosity [cSt] is the dynamic viscosity at 40 °C.

In order to set the oil film equivalent to 12,000 to 24,000, it is sufficient to use a known method such as using a low-viscosity rolling oil or slowing the passage speed.

The chemical polishing system uses an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system to make the concentration lower than the normal concentration and takes a long time.

Further, the production conditions and the like of the electrolytic copper foil which can be used in the present invention are as follows.

‧ electrolyte composition

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

Leveling agent 1 (bis(3 sulfopropyl) sulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are a group 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).

In addition, the remainder of the treatment liquid used for the desmear treatment, electrolysis, surface treatment, plating, and the like used in the present invention is water unless otherwise specified.

‧Manufacture conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

Further, as the electrolytic copper foil which can be used in the present invention, an electrolytic copper foil HLP foil manufactured by JX Nippon Steel Co., Ltd. can be used.

The ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of TD (C = (60 degree gloss of MD) / (60 degree gloss of TD)) is preferably 0.80 to 1.40. If the ratio C of the 60-degree gloss of the MD of the roughened surface to the 60-degree gloss of TD is less than 0.80, the haze value becomes higher than the case where the ratio C is 0.80 or more. Further, when the ratio C exceeds 1.40, the haze value becomes higher than the case where the ratio C is 1.40 or less. The ratio C is preferably from 0.90 to 1.35, and more preferably from 1.00 to 1.30.

[Haze value]

In the surface-treated copper foil of the present invention, since the average roughness Rz and the glossiness of the roughened surface of the surface-treated copper foil are controlled as described above, the portion of the copper foil is removed after the copper foil is bonded to the resin substrate. The haze value of the resin substrate becomes small. Here, the haze value (%) is a value calculated from (diffusion transmittance) / (total light transmittance) × 100. Specifically, when the surface-treated copper foil of the present invention is bonded to both sides of the resin substrate having a thickness of 50 μm from the roughened surface side, and the copper foil is removed by etching, the haze value of the resin substrate is preferably 20 ~70%, more preferably 30~55%.

[surface area of particles]

The ratio A/B of the surface area A of the roughened particles to the area B obtained when the roughened particles are viewed from the surface side of the copper foil has a large influence on the haze value of the above resin. In other words, when the surface roughness Rz is the same, the haze value of the resin becomes smaller as the copper foil having a smaller A/B ratio. Therefore, the ratio A/B of the surface-treated copper foil of the present invention is 1.90 to 2.40, preferably 2.00 to 2.20.

By controlling the current density and the plating time at the time of particle formation, the morphology or formation density of the particles is fixed, and the surface roughness Rz, the glossiness, and the area ratio A/B of the particles can be controlled.

In the surface-treated copper foil of the present invention, as described above, the ratio A/B of the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed from the surface side of the copper foil is controlled to 1.90 to 2.40, and the surface is made. There is a certain degree of unevenness. Further, since the ten-point average roughness Rz of the TD of the roughened surface is controlled to 0.20 to 0.80 μm, there is no extremely rough portion on the surface. On the other hand, the gloss of the roughened surface is as high as 76 to 350%. It is understood that, in consideration of such a case, in the surface-treated copper foil of the present invention, the particle diameter of the roughened particles of the roughened surface is controlled to be small. The particle size of the roughened particles affects the transparency of the resin after the copper foil is removed. However, in the surface-treated copper foil of the present invention, the surface average roughness Rz on the side following the resin substrate is as described above. The ratio of the glossiness and the surface area of the roughened particles to the area obtained when the roughened particles are viewed from the surface side of the copper foil is controlled within the scope of the present invention, meaning that the particle diameter of the roughened particles becomes smaller within an appropriate range, and Therefore, the transparency of the resin after the copper foil is removed by etching is improved, and the peel strength is also good. Since the particle size of the roughened particles is small in an appropriate range, although there is a certain degree of unevenness on the surface, there is no large unevenness, and therefore the length of the surface of the surface-treated copper foil corresponding to the length through which the electrons flow is shortened. The transmission loss becomes small.

[etching factor]

When the value of the etching factor when the copper foil is used to form the circuit is large, the skirt bottom portion at the bottom of the circuit which is generated during etching becomes small, so that the space between the circuits can be narrowed. Therefore, a larger value of the etching factor is preferable because it is formed by a circuit of a fine pattern. The surface-treated copper foil of the present invention has a value of, for example, an etching factor of preferably 1.8 or more, preferably 2.0 or more, preferably 2.2 or more, preferably 2.3 or more, and more preferably 2.4 or more.

Further, in the printed wiring board or the copper clad laminate, the resin is dissolved and removed, whereby the surface roughness (Rz), the area ratio (A/B) of the particles, and the surface area of the copper circuit or the copper foil can be measured. Gloss.

[transmission loss]

In the case where the transmission loss is small, the attenuation of the signal when the signal is transmitted at a high frequency is suppressed, so that stable signal transmission can be performed in the circuit for transmitting signals at a high frequency. Therefore, a copper foil having a small value of transmission loss is suitable for use in a circuit for transmitting signals at a high frequency, and thus is preferable. After the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), a microstrip transmission line was formed by etching to have a characteristic impedance of 50 Ω, and HP was used. The manufactured network analyzer HP8720C measures the penetration coefficient, and when the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is obtained, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB/10 cm, more preferably less than 4.1 dB. /10cm, and more preferably less than 3.7dB/10cm.

[heat resistance]

In the case where the heat resistance is high, the adhesion between the surface-treated copper foil and the resin is hardly deteriorated even in a high-temperature environment, and it can be used in a high-temperature environment, which is preferable.

In the present application, the heat resistance was evaluated by the peel strength retention ratio. The surface area of the surface-treated side of the surface-treated copper foil was applied to a polyimide film (thickness: 50 μm, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination, and heated at 150 ° C for 168 hours. Thereafter, according to IPC-TM-650, the tensile strength of the normal peel strength and the peel strength after heating at 150 ° C for 168 hours were measured using a tensile tester Autograph 100.

Then, the peel strength retention ratio represented by the following formula was calculated.

Peel strength retention ratio (%) = peel strength (kg/cm) after normal heating at 150 ° C for 168 hours / normal peel strength (kg / cm) × 100

Further, the peel strength retention ratio is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more.

[with carrier copper foil]

A copper foil with a carrier according to another embodiment of the present invention includes a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer. Further, the ultra-thin copper layer is a surface-treated copper foil according to an embodiment of the present invention described above. In addition, the carrier copper foil may be provided with a carrier, an intermediate layer and an extremely thin copper layer in this order. The copper foil with a carrier may have a surface treatment layer such as a roughening treatment layer on either or both sides of the carrier side surface and the ultra-thin copper layer side surface.

When the roughened layer is provided on the side surface of the carrier-attached copper foil, the carrier copper foil is laminated on the surface side of the carrier side to a support such as a resin substrate, and the carrier and the resin substrate are provided. The support becomes difficult to peel off.

<carrier>

The carrier usable in the present invention is typically a metal foil or a resin film such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin film. (Available, for example, in the form of a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like).

As the carrier which can be used in the present invention, copper foil is preferably used. The reason for this is that the copper foil has a high electrical conductivity, so that it is easy to form an intermediate layer and an extremely thin copper layer thereafter. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, an electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath on a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, copper to which Sn is added, copper to which Ag is added, Cr added, or A copper alloy such as Zr or Mg, or a copper alloy such as a Cason copper alloy such as Ni or Si.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a thickness suitable for functioning as a carrier, and may be, for example, 12 μm or more. However, if it is too thick, the production cost becomes high, and therefore it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

Further, the carrier used in the present invention must control the surface roughness Rz and the glossiness of the intermediate layer side as described above. The purpose is to control the glossiness, surface roughness Rz, and surface area ratio A/B of the roughened surface of the ultra-thin copper layer after the surface treatment.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is difficult to be peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and the insulating layer is insulated. After the step of laminating the substrate, the extremely thin copper layer becomes peelable from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or two or more of the group consisting of such oxides and organic substances. In addition, the intermediate layer may also be a plurality of layers.

Further, for example, the intermediate layer may be configured by forming one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. The single metal layer formed or an alloy composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn a layer on which a hydrate or oxidation of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cn, Al, and Zn is formed. The layer formed by the object.

Further, as the intermediate layer, a known organic substance can be used as the organic substance, and it is preferable to use at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. For example, as a specific nitrogen-containing organic compound, it is preferred to use 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzo) as a triazole compound having a substituent. Triazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

The sulfur-containing organic compound preferably uses mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiophenol, and the like.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid or the like is preferably used.

Further, for example, the intermediate layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy on the carrier, and chromium. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, it peels off at the interface between the ultra-thin copper layer and chromium. Further, for the nickel of the intermediate layer, it is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer. Adhesion amount of the intermediate layer of nickel, preferably 100μg / dm ² or more 40000μg / dm ² or less, more preferably 100μg / dm ² or more 4000μg / dm ² or less, more preferably 100μg / dm ² or more 2500μg / dm ² or less, More preferably, it is 100 μg/dm ² or more and less than 1000 μg/dm ² , and the adhesion amount of chromium in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof 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 affects the gloss of the roughened surface of the ultra-thin copper layer after the surface treatment and the size and number of the roughened particles, so that the thickness is extremely thin. The thickness of the intermediate layer of the roughened surface of the layer is preferably from 1 to 1,000 nm, preferably from 1 to 500 nm, preferably from 2 to 200 nm, more preferably from 2 to 100 nm, still more preferably from 3 to 60 nm. In addition, An intermediate layer may also be provided on both sides of the carrier.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. In addition, an extremely thin copper layer may be provided on both sides of the carrier. An extremely thin copper layer having the carrier is a surface-treated copper foil according to an embodiment of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 1.5 to 5 μm. Further, before the ultra-thin copper layer is provided on the intermediate layer, pre-plating using a copper-phosphorus alloy may be performed in order to reduce pinholes of the ultra-thin copper layer. In the pre-plating, a copper pyrophosphate plating solution or the like can be mentioned.

Further, the ultra-thin copper layer of the present application is formed under the following conditions. The purpose is to control the size and number of the roughened particles and the gloss after the roughening treatment by forming a smooth ultra-thin copper layer.

‧ electrolyte composition

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

Leveling agent 1 (bis(3 sulfopropyl) sulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are a group 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).

‧Manufacture conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5 to 10 minutes (adjusted according to copper thickness and current density)

[Refining the resin layer on the surface]

Further, a resin layer may be provided on the roughened surface of the surface-treated copper foil of the present invention. The above resin layer may also be an insulating resin layer. In the surface-treated copper foil of the present invention, the "roughening treatment surface" refers to a case where a surface treatment for providing a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like is performed after the roughening treatment. The surface of the surface treated copper foil after surface treatment. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the term "roughened surface" refers to a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after the roughening treatment. In the case of surface treatment, the surface of the ultra-thin copper layer after the surface treatment is performed.

The above resin layer may be an adhesive or a semi-hardened state for subsequent use (B-stage) State) insulating resin layer. The semi-hardened state (B-stage state) includes a state in which there is no adhesive feeling even if the surface is in contact with a finger, and the insulating resin layer can be stacked and stored, and if subjected to heat treatment, a hardening reaction occurs.

The resin layer may be a resin, that is, an adhesive, or an insulating resin layer which is used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no adhesive feeling even if the surface is in contact with a finger, and the insulating resin layer can be stacked and stored, and if subjected to heat treatment, a hardening reaction occurs.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. In addition, the above-mentioned resin layer may be, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. 11-5828, Japanese Patent Laid-Open No. Hei 11-140281, Japanese Patent No. No. 3,184,485, International Publication No. WO97/02728, 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 -304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060 No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153 , Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815 No., International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japan Special Open 2013- Substance (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton, etc.) and/or method for forming resin layer described in No. 19056 Formed by forming a device.

Further, the type of the resin layer is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polymaleimide compound. , Malayan amide resin, aromatic maleic amide resin, polyvinyl acetal resin, amine ester resin, polyether oxime (also known as polyethersulfone, polyethersulphone), polyether oxime (also known as polyethersulfone, polyethersulphone Resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamidamine resin, rubber modified epoxy resin, phenoxy resin , carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide III Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional groups, polyphenylene ether resin, 2,2-bis(4-cyanide) Acid ester phenyl) propane, phosphorus phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin, oxime modification Polyamidamine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, One or more resins selected from the group consisting of a polymer epoxy resin, an aromatic polyamine, a fluororesin, a bisphenol, a block copolymerized polyimide resin, and a cyanoester resin are preferred types of the resin layer.

Further, the epoxy resin having two or more epoxy groups in the epoxy resin may be used as long as it is an epoxy resin which can be used for electrical and electronic materials, and there is no particular problem. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. In addition, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AD type epoxy resin, a novolak type epoxy resin, and a cresol novolac type may be used. Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolak epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac Type epoxy resin, rubber modified bisphenol A epoxy resin, epoxy propylamine epoxy resin, triepoxypropyl isocyanurate, N, N-diepoxypropyl aniline and other glycidyl compounds , a glycidyl ester compound such as diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenol novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin One type of the tetraphenylethane type epoxy resin or a mixture of two or more types may be used, or a hydride or a halide of the above epoxy resin may be used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin is preferably, for example, an epoxy resin derived from 9,10-dihydro-9-oxa-10-phosphine having two or more epoxy groups in the molecule. A form of a derivative of phenanthrene-10-oxide is obtained.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl stilbene, N-methyl-2-pyrrolidine Ketone, N,N-dimethylacetamide, A resin liquid (resin varnish) is prepared in a solvent such as N,N-dimethylformamide, and the resin liquid is applied to the roughened surface of the surface-treated copper foil by, for example, a roll coating method. Then, it is heated and dried as needed, and the solvent is removed to form a B-stage state. In the drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The solvent may be used to dissolve the composition of the above resin layer to form a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, more preferably 10 wt% to 40 wt%, still more preferably 25 wt%. %~40wt% resin solution. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone to dissolve at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Further, the resin layer is preferably a semi-hardened resin film having a resin flow rate in the range of 5% to 35% in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the resin flow rate is based on the following number 1. According to MIL-P-13949G in the MIL standard, four 10 cm square samples are taken from the surface-treated copper foil with a resin having a resin thickness of 55 μm. The film was laminated under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf/cm ² , and a pressing time of 10 minutes in a state in which the four samples were stacked (layered body), and the resin outflow weight at this time was measured, and The value calculated from the result of the measurement.

The surface-treated copper foil (surface-treated copper foil with resin) provided with the above resin layer is used in such a manner that after the resin layer is superposed on the substrate, the entire resin layer is thermocompression-bonded to thermally harden the resin layer. Then the surface treated copper foil is a very thin copper layer with a carrier copper foil When the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface of the intermediate layer side of the ultra-thin copper layer is exposed), and the surface of the surface-treated copper foil opposite to the roughened side is formed. Specific wiring pattern.

When the surface-treated copper foil with the resin is used, the number of sheets of the prepreg used when manufacturing the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be such that the thickness of the interlayer insulation can be ensured, or the copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

Furthermore, when the prepreg is not used, the following advantages are obtained: saving the pre In addition, the material cost of the immersion material is also simple, so that it is economically advantageous, and the thickness of the multilayer printed wiring board manufactured by only the thickness of the prepreg is thinned, and the layer 1 can be manufactured. An extremely thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 120 μm.

When the thickness of the resin layer is thinner than 0.1 μm, there is a case where the adhesion is lowered, and when the surface-treated copper foil with the resin is laminated on the substrate having the inner layer without interposing the prepreg material, It becomes difficult to ensure interlayer insulation between the inner layer and the circuit. On the other hand, when the thickness of the resin layer is made thicker than 120 μm, it becomes difficult to form a resin layer of a desired thickness by one coating step, and it takes an extra material cost and a number of steps, so that it is economical. It became unfavorable.

Further, when the surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, in order to reduce the thickness of the multilayer printed wiring board, it is preferable to set the thickness of the above resin layer to 0.1 μm. ~5 μm, more preferably 0.5 μm to 5 μm, still more preferably 1 μm to 5 μm.

Further, in the case where the resin layer contains a dielectric, the thickness of the resin layer is preferably from 0.1 to 50. The μm is preferably 0.5 μm to 25 μm, more preferably 1.0 μm to 15 μm.

Further, the total thickness of the resin layer and the resin layer of the cured resin layer and the semi-hardened resin layer is preferably from 0.1 μm to 120 μm, preferably from 5 μm to 120 μm, preferably from 10 μm to 120 μm, more preferably from 10 μm to 60 μm. Further, the thickness of the cured resin layer is preferably from 2 μm to 30 μm, preferably from 3 μm to 30 μm, more preferably from 5 to 20 μm. Further, the thickness of the semi-hardened resin layer is preferably from 3 μm to 55 μm, preferably from 7 μm to 55 μm, more preferably from 15 to 115 μm. The reason for this is that when the total thickness of the resin layer exceeds 120 μm, it becomes difficult to manufacture a thin multilayer printed wiring board. If the total thickness of the resin layer is less than 5 μm, the following tendency tends to occur: In the case of a thin multilayer printed wiring board, the resin layer as an insulating layer between the circuits of the inner layer becomes too thin, and the insulation between the circuits of the inner layer becomes unstable. Further, when the thickness of the cured resin layer is less than 2 μm, it is necessary to consider the surface roughness of the roughened surface of the surface-treated copper foil. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect of the resin layer formed by hardening is not particularly improved, and the total thickness of the insulating layer is increased.

In the case where the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the surface-treated copper foil, it is preferable to provide a roughened surface of the surface-treated copper foil. After the heat-resistant layer and/or the rust-preventive layer and/or the weather-resistant layer, a resin layer is formed on the heat-resistant layer or the rust-preventive layer or the weather-resistant layer.

Further, the thickness of the above resin layer means an average value of the thickness measured by a cross-sectional observation at any 10 points.

Further, as another form of the product in which the surface-treated copper foil with the resin is an extremely thin copper layer with a carrier copper foil, the roughening of the ultra-thin copper layer (surface-treated copper foil) may be used. A resin layer is provided on the surface of the treatment to make the resin layer semi-hardened, and then the carrier is peeled off, and the carrier is produced in the form of an ultra-thin copper layer (surface-treated copper foil) to which a resin is not present.

Examples of the manufacturing steps of a plurality of printed wiring boards using the copper foil with a carrier of the present invention are disclosed below.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and The copper foil with a carrier and the insulating substrate are laminated such that the ultra-thin copper layer side faces the insulating substrate, and then the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and thereafter, by a half-addition. The steps of forming a circuit by any of the methods, the modified semi-additive method, the partial addition method, and the subtractive method. The insulating substrate may also be an insulating substrate on which an inner layer circuit is mounted.

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, and a pattern is formed, and a conductor pattern is formed by plating and etching.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention having a semi-additive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and using the copper foil with the carrier a step of laminating an insulating substrate; and laminating the carrier-attached copper foil and the insulating substrate, and then peeling off the carrier of the carrier-attached copper foil; and peeling off the carrier by etching or plasma etching using an acid or the like a step of removing all of the extremely thin copper layers exposed; a step of providing a through hole or/and a blind hole in the resin exposed by removing the ultra-thin copper layer by etching; performing a desmear treatment step on the region including the through hole or/and the blind hole; And the step of providing an electroless plating layer in the region including the through hole or/and the blind hole; the step of providing a plating resist on the electroless plating layer; exposing the anti-plating agent, and then forming the circuit for forming a step of removing the plating resist in the region; a step of providing an electrolytic plating layer in the region for forming the circuit to remove the plating resist; a step of removing the plating resist; and, by rapid etching, etc. The step of removing the electroless plating layer existing in the region other than the region where the circuit is formed.

In another embodiment of the method for manufacturing a printed wiring board of the present invention having a semi-additive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and insulating the copper foil with the carrier a step of laminating the substrate; and laminating the carrier-attached copper foil and the insulating substrate, and then peeling off the carrier of the carrier-attached copper foil; and peeling off the carrier by etching or plasma etching using an acid or the like a step of completely removing the ultra-thin copper layer; and providing an electroless plating layer for the surface of the resin exposed by removing the ultra-thin copper layer by etching; a step of providing a plating resist on the electroless plating layer; exposing the anti-plating agent, and thereafter removing a plating resist for forming a region of the circuit; removing the anti-plating agent The step of forming an electrolytic plating layer in the region for forming the circuit; the step of removing the plating resist; and the electroless plating layer and the ultra-thin copper layer existing in the region outside the region for forming the circuit by rapid etching or the like The steps to remove.

In the present invention, the modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening the copper in the circuit forming portion by electrolytic plating to remove the anti-circuit. The etching agent is a method of forming a circuit on the insulating layer by (fast) etching to remove the metal foil other than the above-described circuit forming portion.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprising the steps of: preparing the copper foil with a carrier of the present invention and the insulating substrate; and the copper foil with the carrier a step of laminating the insulating substrate; and laminating the carrier-attached copper foil and the insulating substrate; and removing the carrier of the carrier-attached copper foil; and providing a through-hole or an insulating substrate with the through-hole formed by peeling the carrier And a step of blinding holes; a step of removing the slag treatment for the above-mentioned area containing the through holes or/and the blind holes; and a step of providing an electroless plating layer for the above-mentioned area containing the through holes or/and the blind holes; a step of providing a plating resist on the surface of the ultra-thin copper layer exposed by peeling the carrier; a step of forming a circuit by electrolytic plating after the plating resist is provided; and a step of removing the plating resist; and The step of removing the extremely thin copper layer exposed by removing the above-mentioned anti-plating agent by rapid etching.

In another embodiment of the method for producing a printed wiring board of the present invention having a modified semi-additive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and using the copper foil with the carrier a step of laminating an insulating substrate; a step of laminating the carrier-attached copper foil and the insulating substrate; and removing the carrier of the carrier-attached copper foil; and providing a plating resist on the ultra-thin copper layer exposed by peeling the carrier a step of exposing the above-mentioned anti-plating agent, and then removing the anti-plating agent for forming a region of the circuit; and removing the step of forming the electroplated layer in the region for forming the circuit of the anti-plating agent; The step of removing the plating resist; and removing the electroless plating layer and the ultra-thin copper layer existing in the region other than the region where the circuit is formed by rapid etching or the like.

In the present invention, the partial addition method refers to a method in which a catalyst core is provided on a substrate on which a conductor layer is provided, and a via hole or a via hole is formed, and a conductor circuit is formed by etching. After the solder resist or anti-plating agent is set as needed, it is treated by electroless plating. On the above conductor circuit, a method of manufacturing a printed wiring board by thickening a via hole or a via hole or the like.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a partial addition method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and using the copper foil with the carrier a step of laminating an insulating substrate; and laminating the carrier-attached copper foil and the insulating substrate, and then peeling off the carrier of the carrier-attached copper foil; and providing a through-hole or/or an insulating layer in the ultra-thin copper layer and/or the insulating substrate a step of blinding holes; a step of removing desmear for the above-mentioned region containing through holes or/and blind holes; a step of imparting a catalyst core to the above-mentioned region containing through holes or/and blind holes; and exposing the carrier a step of providing an etching resist on the surface of the extremely thin copper layer; a step of exposing the etching resist to form a circuit pattern; and using the etching or plasma etching method of an acid or the like to form the ultra-thin copper layer and a step of forming a circuit by removing the catalyst core; a step of removing the etching resist; and etching the ultra-thin copper layer by etching or plasma etching using an acid or the like The insulating substrate is removed from the catalyst nucleus exposed surface of the solder resist or plating resist agent of step plating; and is not provided to the above-described solder resist or an anti-plating agent of the plating zone setting step of electroless plating.

In the present invention, the subtractive method refers to laminating a copper clad laminate by etching or the like. A method of forming a conductor pattern by unnecessary removal of a portion of the copper foil.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with the carrier of the present invention and the insulating substrate; and insulating the copper foil with the carrier a step of laminating the substrate; laminating the carrier with the carrier copper foil and laminating the carrier with the carrier copper foil; and providing a through hole or/and a blind hole for the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier a step of performing a desmear treatment on the region containing the through hole and/or the blind hole; a step of providing an electroless plating layer on the region including the through hole or/and the blind hole; on the surface of the electroless plating layer a step of providing an electrolytic plating layer; a step of providing an etching resist on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; a step of exposing the etching resist to form a circuit pattern; and etching the solution by using an acid or the like Etching or plasma etching, removing the ultra-thin copper layer and the electroless plating layer and the electrolytic plating layer to form a circuit; and removing the etching resist step.

In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and the copper foil and the insulating substrate with the carrier a step of laminating; after laminating the copper foil with the carrier and the insulating substrate, the step of peeling off the carrier with the carrier copper foil; a step of providing a through hole or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; performing a desmear treatment step on the region including the through hole or/and the blind hole; and the through hole for the above Or a step of providing an electroless plating layer in the region of the blind hole; a step of forming a mask on the surface of the electroless plating layer; a step of providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; and the electrolytic plating layer or And a step of providing an etching resist on the surface of the ultra-thin copper layer; a step of exposing the etching resist to form a circuit pattern; and using the etching or plasma etching method of an acid or the like a step of removing the copper layer and the above electroless plating layer to form a circuit; and removing the etching resist.

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

Further, the method for producing a printed wiring board according to the present invention may be a method for producing a printed wiring board, comprising: forming a circuit on the surface of the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention; a step of forming a resin layer on the side surface of the ultra-thin copper layer or the side surface of the carrier on the carrier-attached copper foil by burying the above-mentioned circuit; forming a circuit on the resin layer; and forming the circuit on the resin layer After forming the circuit, the step of stripping the carrier or the ultra-thin copper layer; and after peeling off the carrier or the ultra-thin copper layer, removing the ultra-thin copper layer or the carrier In addition, a step of exposing the circuit formed on the surface of the ultra-thin copper layer or the side surface of the carrier to the resin layer is exposed.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail using a drawing. Further, here, a copper foil with a carrier having an extremely thin copper layer on which a roughened layer is formed will be described as an example, but the invention is not limited thereto, and a carrier having an extremely thin copper layer in which a roughened layer is not formed is used. In the copper foil, the following method for producing a printed wiring board can be similarly performed.

First, as shown in FIG. 2-A, a copper foil with a carrier (first layer) having an extremely thin copper layer having a roughened layer formed on its surface is prepared.

Next, as shown in FIG. 2-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape.

Next, as shown in Fig. 2-C, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Next, as shown in FIG. 3-D, a resin layer is laminated on the ultra-thin copper layer to cover the circuit plating layer (the method of burying the circuit plating layer), and then the other layer is provided with the carrier copper foil (the second layer). Adjacent to the very thin copper layer.

Next, as shown in Fig. 3-E, the carrier is peeled off from the carrier copper foil of the second layer.

Next, as shown in Fig. 3-F, a laser opening is formed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Next, as shown in FIG. 4-G, copper is buried in the blind via hole to form a via fill.

Next, as shown in FIG. 4-H, on the via fill, a circuit plating is formed as in the above-described FIGS. 1-B and 1-C.

Next, as shown in Fig. 4-I, the carrier was peeled off from the carrier-attached copper foil of the first layer.

Next, as shown in Fig. 5-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Next, as shown in Fig. 5-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in the above manner.

The other copper foil with a carrier (the second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil may be used, and a conventional copper foil may be used. Alternatively, a circuit of one or more layers may be formed on the circuit of the second layer shown in FIG. 4-H, and may also be a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either of these methods performs such circuit formation.

The copper foil with a carrier of the present invention preferably controls the chromatic aberration of the surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer, or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably controls the chromatic aberration of the roughened surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the surface-treated copper foil of the present invention, the term "roughening surface" refers to a case where a surface treatment such as a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like is performed after the roughening treatment. The surface of the surface treated copper foil after the surface treatment. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the term "roughened surface" refers to a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after the roughening treatment. In the case of surface treatment, the surface of the ultra-thin copper layer after the surface treatment is performed.

(1) The color difference of the surface of the ultra-thin copper layer is 45 or more based on the color difference ΔE*ab of JISZ8730.

Here, the color differences ΔL, Δa, and Δb are measured by a color difference meter, respectively, and Add black/white/red/green/yellow/blue, and use the L*a*b color system based on JIS Z8730 to display the comprehensive index to △L: white black, △a: red green, △b : Yellow and blue form representation. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration described above can be adjusted by increasing the current density when forming an extremely thin copper layer, lowering the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the above-described chromatic aberration can be adjusted by providing a roughening treatment layer by roughening the surface of the ultra-thin copper layer. In the case where the roughening layer is provided, an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum can be used, and the current density is higher than a conventional current. The density (for example, 40 to 60 A/dm ² ) is adjusted so that the processing time is shorter than the conventional processing time (for example, 0.1 to 1.3 seconds). In the case where the roughened layer is not provided on the surface of the ultra-thin copper layer, the above-described color difference adjustment can be realized by using a plating bath in which the Ni concentration is twice or more of other elements, and is lower than Know the current density (0.1 ~ 1.3A / dm ² ), and set the processing time (20 seconds ~ 40 seconds), and in the very thin copper layer or heat-resistant layer or rust-proof layer or chromate treatment layer or decane coupling The surface of the treatment layer is subjected to Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating).

When the color difference ΔE*ab based on JISZ8730 is 45 or more, the contrast of the ultra-thin copper layer and the circuit becomes sharp when the circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil. As a result, the visibility is improved, and the positional alignment of the circuit can be performed with high precision. The color difference ΔE*ab based on JISZ8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the color difference of the surface of the ultra-thin copper layer is controlled as described above, the contrast with the circuit plating layer becomes clear, and the visibility becomes good. Therefore, in the manufacturing steps as shown in FIG. 2-C of the printed wiring board as described above, the circuit plating layer can be formed accurately at a specific position. Further, according to the method for manufacturing a printed wiring board as described above, the circuit plating layer is embedded in the resin layer. Therefore, for example, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 5-J, the circuit plating layer is subjected to resin. The layer is protected and its shape is maintained, whereby it becomes easy to form a fine circuit. Further, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the wiring of the circuit is well suppressed. Therefore, it becomes easy to form a fine circuit. In addition, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 5-J and FIG. 5-K, the exposed surface of the circuit plating layer is recessed from the resin layer, so that bumps are easily formed on the circuit plating layer. Further, copper pillars are easily formed thereon, and manufacturing efficiency is improved.

Further, as the resin (RESIN), a known resin or prepreg can be used. For example, BT (Bismaleimide III) can be used. Resin or prepreg as a glass cloth impregnated with BT resin, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, as the above-mentioned embedded resin (RESIN), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

Further, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil with the carrier. By having the substrate or the resin layer, the carrier-attached copper foil used for the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, the substrate or the resin layer may be any substrate or resin layer as long as it exhibits the effect of supporting the copper foil with a carrier used for the first layer. For example, a carrier, a prepreg, a resin layer or a known carrier, prepreg as described in the specification of the present application can be used. A body, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, and a foil of an organic compound are used as the substrate or the resin layer.

The surface-treated copper foil of the present invention can be bonded to the resin substrate from the side of the roughened surface to produce a laminate. The resin substrate is not particularly limited as long as it has a property applicable to a printed wiring board or the like. For example, for rigid PWB, a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth can be used. Base material epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin, glass cloth substrate epoxy resin, etc., for FPC, polyester film or Polyimine film, liquid crystal polymer (LCP) film, fluororesin film, and the like. Further, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peeling strength of the film and the surface-treated copper foil tends to be smaller than in the case of using a polyimide film. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, by forming a copper circuit and covering the copper circuit with a cover layer, the film and the copper circuit become difficult to be peeled off, and peeling strength can be prevented from being lowered. The film is peeled off from the copper circuit.

Further, since the liquid crystal polymer (LCP) film or the fluororesin film has a small dielectric loss tangent, a liquid crystal polymer (LCP) film or a fluororesin film and a copper-clad laminate of the surface-treated copper foil of the present invention are used. Boards, printed wiring boards, and printed circuit boards are suitable for high-frequency circuits (circuits that transmit signals at high frequencies). Further, the surface-treated copper foil of the invention of the present application has a small surface roughness Rz and a high gloss, so that the surface is smooth and suitable for high-frequency circuit applications.

In the case of the rigid PWB, the method of bonding is prepared by impregnating a resin with a substrate such as a glass cloth to cure the resin to a semi-hardened state. This is carried out by superposing the surface of the copper foil from the side subjected to the roughening treatment on the prepreg and heating and pressurizing the surface. In the case of FPC, the substrate of a polyimide film or the like is deposited under high temperature and high pressure via an adhesive or without an adhesive. The layer is then coated on a copper foil, or the polyimide precursor is coated, dried, hardened, etc., whereby a laminate can be produced.

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, it can be applied to a single-sided PWB, a double-sided PWB, or a multilayer PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be applied to rigid PWB, soft PWB (FPC), and rigid-elastic PWB.

[Layering board and positioning method of printed wiring board using the same]

A method of positioning a 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. Specific examples of the laminated sheet of the surface-treated copper foil and the resin substrate of the present invention include at least one of a main substrate and an attached circuit board, and a resin for electrically connecting the same to a polyimide or the like. In an electronic device including a flexible printed circuit board having a copper wiring formed thereon, the flexible printed circuit board is accurately positioned and pressed against the wiring end portion of the main substrate and the attached circuit substrate to form a laminated body. In other words, in this case, the laminated board is a laminated body in which the wiring end portions of the flexible printed circuit board and the main substrate are bonded by pressure bonding, or the wiring ends of the flexible printed circuit board and the circuit board are bonded by pressure bonding. Laminated laminate. The laminate has indicia formed from a portion of the copper wiring or other material. The position of the mark is not particularly limited as long as it can be photographed by a filming means such as a CCD camera through a resin constituting the laminate. Here, the mark refers to a mark (mark) used to detect the position of the laminate, the printed wiring board, or the like, or to perform positioning or alignment. Further, in the case where the surface-treated copper foil of the present invention is an extremely thin copper layer (having an extremely thin copper layer with a carrier) with a carrier copper foil, the carrier is removed from the laminate of the surface-treated copper foil and the resin substrate as needed.

In the laminated board prepared as described above, the position of the mark can be satisfactorily detected by photographing the mark with a resin by a photographing means. Then, the position of the mark is detected as described above, and the position of the laminated sheet of the surface-treated copper foil and the resin substrate can be satisfactorily performed based on the position of the mark to be detected. Further, in the case where a printed wiring board is used as the laminated board, the positioning means can well detect the position of the mark by the positioning method, and the positioning of the printed wiring board can be performed more accurately.

Therefore, it is considered that when a printed wiring board is connected to another printed wiring board, connection failure is reduced and the yield is improved. Further, as a method of connecting one printed wiring board to another printed wiring board, connection via solder or anisotropic conductive film (ACF), via anisotropic conductive paste (Anisotropic Conductive Paste) can be used. A known connection method such as connection of ACP) or connection via a conductive adhesive. Further, in the present invention, the "printed wiring board" also includes a printed wiring board on which components are mounted, a printed circuit board, and a printed circuit board. Further, two or more printed wiring boards of the present invention may be connected to each other to manufacture a printed wiring board to which two or more printed wiring boards are connected, and at least one of the printed wiring boards of the present invention may be connected to another invention. The printed wiring board or the printed wiring board not belonging to the printed wiring board of the present invention is connected, and an electronic device can be manufactured using such a printed wiring board. Further, in the present invention, the "copper circuit" also includes copper wiring. Further, the printed wiring board of the present invention can be connected to a component to manufacture a printed wiring board. Further, at least one of the printed wiring boards of the present invention is connected to another printed wiring board of the present invention or a printed wiring board not belonging to the printed wiring board of the present invention, and two or more printings of the present invention are connected. The printed wiring board of the wiring board is connected to the component, whereby a printed wiring board to which two or more printed wiring boards are connected can be manufactured. Here, as the "parts", a connector or an LCD (Liquid Crystal Display) can be cited and used for Electronic components such as glass substrates for LCDs, and electronic components including semiconductor integrated circuits such as IC (Integrated Circuit), LSI (Large Scale Integrated Circuit), VLSI (Very Large Scale Integrated Circuit), and ULSI (Ultra-Large Scale Integration) (for example) An IC chip, an LSI wafer, a VLSI wafer, a ULSI wafer, a component for shielding an electronic circuit, and a component required for fixing a cover or the like to a printed wiring board.

Furthermore, the positioning method according to the embodiment of the present invention may include a step of moving a laminate (including a laminate of a copper foil and a resin substrate or a printed wiring board). In the moving step, for example, the laminated plate can be moved by a conveyor such as a belt conveyor or a chain conveyor, or the laminated plate can be moved by a moving device having an arm mechanism, and the laminated layer can be utilized by using a gas. A moving device or a moving means for moving the plate to move the laminated plate, or a moving device or a moving means (including a roller or a bearing) for moving the laminated plate by rotating a substantially cylindrical shape or the like, and oil a mobile device or a moving means that is pressed as a power source, a moving device or a moving means that uses air pressure as a power source, a moving device or a moving means that uses a motor as a power source, a bracket-moving linear guide rail table, a bracket moving air rail table, The laminated plate is moved by a moving device or a moving means such as a stacked linear guide table or a linear motor swing table. Alternatively, a moving step using a known moving means can be performed. In the step of moving the laminated plate as described above, the laminated plate can be moved to be aligned. Further, it is considered that when a printed wiring board is connected to another printed wiring board or component by performing alignment, the connection failure is reduced and the yield is improved.

Furthermore, the positioning method of the embodiment of the present invention can also be applied to a surface mounter or a mounter.

Further, in the present invention, the laminated board of the surface-treated copper foil and the resin substrate to be positioned may be a printed wiring board having a resin board and a circuit provided on the resin board. Further, in this case, the above-mentioned mark may be the above circuit.

In the present invention, "positioning" includes "detecting the position of a mark or object." Further, in the present invention, the "positional alignment" includes "moving the marker or object to a specific position based on the detected position after detecting the position of the marker or the object".

[Examples]

As Examples 1 to 24, 29 to 36, and Comparative Examples 1 to 13, various copper foils described in Table 9 were prepared, and one surface was subjected to a plating treatment as a roughening treatment by the conditions described in Tables 1 to 8. .

Further, in Examples 25 to 28, various carriers described in Table 9 were prepared, and an intermediate layer was formed on the surface of the carrier under the following conditions, and an extremely thin copper layer was formed on the surface of the intermediate layer. Then, under the conditions described in Tables 1 and 2, the surface of the ultra-thin copper layer was plated as a roughening treatment.

‧Example 25

<intermediate layer>

(1) Ni layer (Ni plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Ni layer having an adhesion amount of 1000 μg/dm ² . The specific plating conditions are described below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) was subjected to water washing and pickling, and then subjected to electrolytic chromate treatment on a continuous roll line of a roll-to-roll type under the following conditions to obtain 11 μg/dm ² The adhesion amount of the Cr layer adheres to the Ni layer.

Potassium dichromate 1~10g/L, zinc 0g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

<very thin copper layer>

Next, after the surface of the Cr layer formed in (2) is washed with water and pickled, then a plate having a thickness of 1.5 μm is formed on the Cr layer by electroplating on a continuous roll line of a roll-to-roll type under the following conditions. A thin copper layer is formed, and an extremely thin copper foil with a carrier is produced.

Copper concentration: 90~110g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

Leveling agent 1 (bis(3 sulfopropyl) sulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

Further, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are a group 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: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

‧Example 26

<intermediate layer>

(1) Ni-Mo layer (nickel-molybdenum alloy plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Ni-Mo layer having an adhesion amount of 3000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Ni hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 25 except that the thickness of the ultra-thin copper layer was set to 3 μm.

‧Example 27

<intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 25.

(2) Organic layer (organic layer formation treatment)

Next, after washing the surface of the Ni layer formed in (1) with water and pickling, the liquid temperature of the carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L is then 40 ° C under the following conditions. The aqueous solution of pH 5 was spray-washed to the surface of the Ni layer for 20 to 120 seconds, thereby forming an organic layer.

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 25 except that the thickness of the ultra-thin copper layer was set to 2 μm.

‧Example 28

<intermediate layer>

(1) Co-Mo layer (cobalt-molybdenum alloy plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Co-Mo layer of an adhesion amount of 4000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Co: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 25 except that the thickness of the ultra-thin copper layer was set to 5 μm.

After performing the plating treatment as described above (described in Tables 1 to 8), Examples 1 to 13, 15 to 20, 22 to 24, 26 to 28, 31 to 36, and Comparative Examples 2, 4, and 7 were carried out. ~10, the next plating treatment for forming the heat-resistant layer and the rust-proof layer. In addition, "Ni-Co", "Ni-Co(2)", "Ni-Co(3)", "Ni-P", "Ni-Zn", and "Ni-Zn" described in Table 10 2)", "Ni-Zn(3)", "Ni-W", "chromate", and "decane coupling treatment" refer to the following surface treatment.

The formation conditions of the heat-resistant layer 1 are shown below.

‧Heat resistant layer 1

[Ni-Co]: Nickel-cobalt alloy plating

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

[Ni-Co(2)]: Nickel-cobalt alloy plating

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 35~50As/dm ²

[Ni-Co(3)]: Nickel-cobalt alloy plating

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 25~35As/dm ²

[Ni-P]: Nickel-phosphorus alloy plating

Liquid composition: nickel 5~20g/L, phosphorus 2~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

‧Heat resistant layer 2

[Ni-Zn]: Nickel-zinc alloy plating

The heat-resistant layer 2 is formed on the copper foil provided with the above heat-resistant layer 1. With respect to Comparative Examples 3, 5, and 6, the heat-resistant layer 2 was directly formed on the prepared copper foil without performing a rough plating treatment. The formation conditions of the heat-resistant layer 2 are shown below.

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

[Ni-Zn(2)]: Nickel-zinc alloy plating

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 3~4As/dm ²

[Ni-Zn(3)]: Nickel-zinc alloy plating

Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 2~3As/dm ²

[Ni-W]: Nickel-tungsten alloy plating

Liquid composition: nickel 2~30g/L, tungsten 0.5~20g/L

pH: 3~4

Liquid temperature: 30~50°C

Current density: 1~2A/dm ²

Coulomb amount: 1~2As/dm ²

‧Anti-rust layer

[chromate]: chromate treatment

A rustproof layer is further formed on the copper foil provided with the heat-resistant layers 1 and 2 described above. Shape of the rustproof layer The conditions are shown below.

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (for impregnation chromate treatment)

Coulomb amount: 0~2As/dm ² (for impregnation chromate treatment)

A weather-resistant layer is further formed on the copper foil on which the heat-resistant layers 1 and 2 and the rust-preventing layer are provided or on the copper foil on which the heat-resistant layers 1 and 2 and the rust-preventing layer are not provided. The formation conditions are shown below.

Using N-2-(aminoethyl)-3-aminopropyltrimethoxydecane as an amine-based decane coupling agent (Example 17), N-2-(aminoethyl)-3- Aminopropyltriethoxydecane (Examples 1 to 13, 15, 16, 24, 26 to 33; Comparative Examples 2 to 10), N-2-(aminoethyl)-3-aminopropyl Methyldimethoxydecane (Example 18), 3-aminopropyltrimethoxydecane (Example 19), 3-aminopropyltriethoxydecane (Examples 20, 34-36), 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine (Example 22), N-phenyl-3-aminopropyltrimethoxydecane (Examples) 23) Coating and drying to form a weather resistant layer. These decane coupling agents may be used in combination of two or more kinds.

Further, with respect to the surface-treated copper foils obtained in Examples 1 to 23 and Comparative Example 4, a surface-treated copper foil having the surface treatment described in Table 12 on the other surface was also produced. Here, the "Example No. - Number" of Table 12 means that the surface of the surface-treated copper foil obtained in the Example was subjected to the surface treatment described in Table 12. For example, in Table 12, "Example 2-1", "Example 2-2", and "Example 2-3" were respectively subjected to the other surface of the surface-treated copper foil obtained in Example 2. The surface-treated copper foil of the surface treatment described in Table 12, "Example 3-1" and "Example 3-2" are respectively The surface-treated copper foil subjected to the surface treatment described in Table 12 was subjected to the other surface of the surface-treated copper foil obtained in Example 3.

Further, the rolled copper foil was produced in the following manner. A copper ingot having the composition shown in Table 9 was produced, and after hot rolling, annealing and cold rolling of a continuous annealing line of 300 to 800 ° C were repeatedly performed to obtain a rolled plate having a thickness of 1 to 2 mm. The rolled sheet was annealed on a continuous annealing line of 300 to 800 ° C, recrystallized, and finally cold rolled until the thickness of Table 9 to obtain a copper foil. The "fine copper" in the "type" column of Table 9 indicates fine copper based on JIS H3100 C1100, and the "oxygen-free copper" indicates oxygen-free copper based on JIS H3100 C1020. In addition, "fine copper + Ag: 100 ppm" means that 100 mass ppm of Ag is added to the refined copper.

The electrolytic copper foil was an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metal Co., Ltd. Further, in Example 21, Example 25, and Comparative Example 10, a specific surface treatment or an intermediate layer was formed on the deposition surface (the surface on the side opposite to the surface on the side opposite to the electrolytic drum when the electrolytic copper foil was produced), Very thin copper layer. In the case of electrolytic polishing, the thickness of the plate after electrolytic polishing is described.

Further, in Table 9, the main points of the copper foil production step before the surface treatment are described. "High gloss rolling" means final cold rolling (cold rolling after final recrystallization annealing) at the value of the oil film equivalent described. "Normally calendering" means the final cold rolling (cold rolling after final recrystallization annealing) at the value of the oil film equivalent described. "Chemical polishing" and "electrolytic polishing" are carried out under the following conditions.

The "chemical polishing" is an etching solution in which H ₂ SO ₄ is 1 to 3% by mass, H ₂ O ₂ is 0.05 to 0.15% by mass, and the remainder is water, and the polishing time is 1 hour.

"Electrolytic polishing" is based on a voltage of 10 V/cm ² and a time as described in Table 9 under the conditions of phosphoric acid 67% + sulfuric acid 10% + water 23% (if electrolytic polishing is performed for 10 seconds, the polishing amount becomes 1~) 2 μm).

Each of the samples of the examples and the comparative examples produced in the above manner was subjected to various evaluations as follows.

(1-1) Measurement of surface roughness (Rz) (measurement of surface roughness (Rz) measured by contact type roughness meter):

The ten-point average roughness Rz was measured for the roughened surface in accordance with JIS B0601-1994 using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Research Institute Co., Ltd. It is perpendicular to the rolling direction under conditions of a measurement reference length of 0.8 mm, an evaluation length of 4 mm, a cutoff value of 0.25 mm, and a conveying speed of 0.1 mm/sec (TD, in the case of electrolytic copper foil, perpendicular to the advance direction of the copper foil (ie, In the width direction)), the measurement position was changed and 10 measurements were performed, and the value obtained by 10 measurements was obtained. In addition, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, the heat-resistant layer is provided for the surface. The surface of the surface-treated copper foil after surface treatment such as a rust preventive layer or a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

Further, the surface roughness (Rz) was also determined in the same manner for the copper foil before the surface treatment.

(1-2) Determination of surface roughness after surface treatment of another surface:

For the other surface after the surface treatment of each of the examples and the comparative examples, it is preferred to measure the roughness of the surface by a non-contact method. Specifically, the state of the other surface after the surface treatment of each of the examples and the comparative examples was evaluated by the value of the roughness measured by a laser microscope. The reason for this is that the state of the surface can be evaluated in more detail.

‧ Determination of surface roughness (Rz):

The surface roughness (ten-point average roughness) Rz was measured in accordance with JIS B0601 1994 using a laser microscope OLS4000 manufactured by Olympus Corporation for the other surface of the surface-treated copper foil. The surface of the copper foil was observed 50 times using an objective lens, and the rolled copper foil was measured in a direction perpendicular to the rolling direction (TD) under the condition of an evaluation length of 258 μm and a cutoff value of zero, or electrolysis was performed on the electrolytic copper foil. In the copper foil manufacturing apparatus, the electrodeposited copper foil is measured in the direction perpendicular to the direction (TD), and the respective values are obtained. Further, the measurement ambient temperature of the surface roughness Rz of the laser microscope was set to 23 to 25 °C. Rz was measured at 10 points, and the average value of 10 Rz was set to the value of surface roughness (ten-point average roughness) Rz. Further, the wavelength of the laser of the laser microscope used for the measurement was set to 405 nm.

‧ Determination of the root mean square height Rq of the surface:

For the other surface of the surface-treated copper foil after the surface treatment of each of the examples, the root mean square height Rq of the surface of the copper foil was measured in accordance with JIS B0601 2001 using a laser microscope OLS4000 manufactured by Olympus. The surface of the copper foil was observed 50 times using an objective lens, and the rolled copper foil was measured in a direction perpendicular to the rolling direction (TD) under the condition of an evaluation length of 258 μm and a cutoff value of zero, or electrolysis was performed on the electrolytic copper foil. In the copper foil manufacturing apparatus, the electrodeposited copper foil is measured in the direction perpendicular to the direction (TD), and the respective values are obtained. Further, the measurement ambient temperature of the surface root height Rq of the surface of the laser microscope was set to 23 to 25 °C. Rq was measured at any 10 places, and the average value of 10 Rqs was set to the value of the root mean square height Rq. Further, the wavelength of the laser of the laser microscope used for the measurement was set to 405 nm.

‧ Determination of the arithmetic mean roughness Ra of the surface:

The surface roughness Ra of the other surface of the copper foil after the surface treatment of each experimental example was measured by the laser microscope OLS4000 manufactured by Olympus Corporation in accordance with JIS B0601-1994. The surface of the copper foil was observed 50 times using an objective lens, and the rolled copper foil was measured in a direction perpendicular to the rolling direction (TD) under the condition of an evaluation length of 258 μm and a cutoff value of zero, or electrolysis was performed on the electrolytic copper foil. In the copper foil manufacturing apparatus, the electrodeposited copper foil is measured in the direction perpendicular to the direction (TD), and the respective values are obtained. Further, the measurement ambient temperature of the arithmetic mean roughness Ra of the surface of the laser microscope was set to 23 to 25 °C. Ra was measured at 10 arbitrary places, and the average value of 10 Ra was set to the value of arithmetic mean roughness Ra. Further, the wavelength of the laser of the laser microscope used for the measurement was set to 405 nm.

(2) Area ratio of particles (A/B):

The surface area of the roughened particles is obtained using an assay using a laser microscope. Using a laser microscope VK8500 manufactured by KEYENCE Co., Ltd., the three-dimensional surface area A in the area B of the 100 × 100 μm area (9982.52 μm ² in the actual data) of the roughened surface was measured by a magnification of 2000 times. The method is set for a three-dimensional surface area A ÷ two-dimensional surface area B = area ratio (A / B). Further, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, heat resistance is set for the heat-treated layer. The surface of the surface-treated copper foil after surface treatment such as a layer, a rustproof layer, and a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(3) Gloss:

A gloss meter Handy gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z8741 is used, and the rolling direction (MD, in the case of electrolytic copper foil, the forward direction of the copper foil) and the direction perpendicular to the rolling direction are used. The roughened surface was measured by the respective incident angles of 60 degrees in the direction (TD, in the direction perpendicular to the advance direction of the copper foil in the case of electrolytic copper foil). another In the case where the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like without being subjected to the roughening treatment, the heat-resistant layer is provided for the surface. The surface of the surface-treated copper foil after surface treatment such as a rust preventive layer or a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

Further, the surface of the surface of the copper foil before the surface treatment and the surface of the carrier on the side where the intermediate layer is provided are also obtained in the same manner in advance.

(4) Haze value:

The roughened surface of the surface-treated copper foil is bonded to a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Upilex (Uptradex)-VT, BPDA (biphenyl) manufactured by Ube Industries On both sides of the tetracarboxylic acid dianhydride (BPDA-PDA (p-phenylenediamine)-based polyimine resin substrate)), the copper foil was removed by etching (aqueous solution of ferric chloride) to prepare a sample film. The haze value of the sample film was measured using HAZE METER HM-150 manufactured by Murakami Color Research Institute, JIS K7136 (2000).

(5) Visibility (resin transparency):

The surface of the surface-treated copper foil on the surface-treated side was bonded to both sides of a polyimide film (thickness 50 μm, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination, by etching (trichlorination) A molten iron solution) The surface-treated copper foil was removed to prepare a sample film. A printed matter (a black circle having a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed matter was judged from the opposite surface via a resin layer. The outline of the black circle of the printed matter is clearly defined as "◎" in the length of 90% or more of the circumference, and the outline of the black circle is more than 80% of the circumference and less than 90% of the circumference. ○" (above qualified), the outline of the black circle is 0 to the circumference of the circle The clearer and contour deformer of 80% of the length were evaluated as "x" (failed). In addition, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, the heat-resistant layer is provided for the surface. The surface of the surface-treated copper foil after surface treatment such as a rust preventive layer or a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(6) Peel strength (follow strength):

The surface layer of the surface-treated copper foil on the surface of the surface-treated side is laminated with a polyimide film (thickness of 50 μm, Upilex manufactured by Ube Industries, Inc.) with a thermosetting adhesive for lamination, and is used in accordance with IPC-TM-650. The tensile tester Autograph 100 measures the normal peel strength. Further, the surface-treated copper foil having the above-described normal peel strength of 0.7 N/mm or more is used as a surface-treated copper foil which can be used for a laminated substrate.

Further, the lamination conditions of the surface-treated copper foil and the polyimide film are set as recommended by the above-mentioned polyimide film manufacturer. In addition, in the examples 25 to 28, the surface layer of the surface-treated copper foil on the surface of the surface-treated copper layer was laminated on a polyimide film (thickness: 50 μm, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination. The carrier was peeled off, and copper plating was performed so that the thickness of the ultra-thin copper layer laminated with the above polyimide film was 12 μm, and thereafter the peel strength was measured. In addition, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, the heat-resistant layer is provided for the surface. The surface of the surface-treated copper foil after surface treatment such as a rust preventive layer or a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(7) Heat resistance:

The surface area of the surface-treated copper foil on the surface of the surface-treated copper layer was laminated on a polyimide film (thickness: 50 μm, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination, and heated at 150 ° C for 168 hours. According to IPC-TM-650, the tensile strength of the normal peel strength and the peel strength after heating at 150 ° C for 168 hours were measured using a tensile tester Autograph 100.

Then, the peel strength retention ratio represented by the following formula was calculated.

Peel strength retention ratio (%) = peel strength (kg/cm) after normal heating at 150 ° C for 168 hours / normal peel strength (kg / cm) × 100

In the case where 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 "○". When the peel strength retention ratio is 50% or more and less than 60%, the heat resistance is "Δ", and when the peel strength retention rate is less than 50%, the heat resistance is "x". In addition, in the examples 25 to 28, the surface layer of the surface-treated copper foil on the surface of the surface-treated side was laminated with a polyimide film of a thermosetting adhesive for lamination (thickness: 50 μm, Upilex manufactured by Ube Industries) The carrier was peeled off, and copper plating was performed so that the thickness of the ultra-thin copper layer laminated with the above polyimide film was 12 μm, and thereafter the peel strength was measured. In addition, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, the heat-resistant layer is provided for the surface. The surface of the surface-treated copper foil after surface treatment such as a rust preventive layer or a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(8) Solder heat resistance evaluation:

Bonding the surface of the surface-treated copper foil to the surface of the surface-treated side to the thermal hardening property of the laminate The two sides of the polyimide film (thickness 50 μm, Upilex manufactured by Ube Industries). For the two-area laminate obtained, a test coupon according to JIS C6471 was prepared. The prepared test piece was exposed to high temperature and high humidity of 85 ° C and 85% RH for 48 hours, floated in a solder bath of 300 ° C, and evaluated for solder heat resistance. After the solder heat resistance test, in the interface between the roughened surface of the copper foil and the surface of the polyimide film, the area of the copper foil in the attached test piece is 5% or more, and the interface is discolored due to expansion. In the case of × (failed), the case where the expansion discoloration of the area of less than 5% was evaluated as ○, and the case where the discoloration did not occur at all was evaluated as ◎.

Further, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, heat resistance is set for the heat-treated layer. The surface of the surface-treated copper foil after surface treatment such as a layer, a rustproof layer, and a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(9) Circuit shape formed by etching (fine pattern characteristics)

The surface of the surface-treated copper foil on the surface of the surface-treated side was bonded to both sides of a polyimide film (thickness: 50 μm, Upilex manufactured by Ube Industries, Ltd.) with a thermosetting adhesive for lamination. In order to form a fine pattern circuit, it is necessary to make the thickness of the copper foil the same, and here, the thickness of the 12 μm copper foil is used as a reference. That is, when the thickness is thicker than 12 μm, the thickness is reduced to 12 μm by electrolytic polishing. On the other hand, in the case where the thickness is thinner than 12 μm, it is thickened to a thickness of 12 μm by a copper plating treatment. On the single-sided side of the obtained two-area laminate, a fine pattern circuit is printed on the shiny side of the copper foil of the laminated board by the coating and exposure steps of the photosensitive resist, and the copper foil is used under the following conditions. It is not necessary to partially perform an etching process to form a fine pattern circuit such as L/S = 20/20 μm. Here, the circuit width is set so that the bottom width of the circuit section becomes 20 μm.

(etching conditions)

Device: Jet small etching device

Injection pressure: 0.2MPa

Etching solution: aqueous solution of ferric chloride (specific gravity 40 Baume)

Liquid temperature: 50 ° C

After the fine pattern circuit was formed, it was immersed in an aqueous NaOH solution at 45 ° C for 1 minute to peel off the photosensitive resist film.

(10) Calculation of etching factor (Ef)

For the fine pattern circuit sample obtained above, a scanning electron microscope photograph S4700 manufactured by Hitachi High-Technologies Co., Ltd. was used to observe from the upper portion of the circuit at a magnification of 2000 times, and the top width (Wa) of the upper portion of the circuit and the bottom width of the bottom of the circuit were measured. (Wb). The copper foil thickness (T) was set to 12 μm. The etching factor (Ef) is calculated by the following formula.

Etch factor (Ef)=(2×T)/(Wb-Wa)

Further, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, heat resistance is set for the heat-treated layer. The surface of the surface-treated copper foil after surface treatment such as a layer, a rustproof layer, and a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(11) Determination of transmission loss

For each sample, the surface-treated side of the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), and the characteristic impedance was 50 Ω by etching. Way to form a microstrip transmission line, using a network made by HP The analyzer HP8720C measured the transmission coefficient and found the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz. As an evaluation of the transmission loss at a frequency of 20 GHz, it is set to ◎ 3.7 dB/10 cm, 3.7 dB/10 cm or more, and less than 4.0 dB/10 cm is set to ○○, which is 4.0 dB/10 cm or more and is not reached. 4.1 dB/10 cm is set to ○, and is 4.1 dB/10 cm or more and less than 5.0 dB/10 cm is set to Δ, and 5.0 dB/10 cm or more is set to ×.

Further, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, heat resistance is set for the heat-treated layer. The surface of the surface-treated copper foil after surface treatment such as a layer, a rustproof layer, and a weather resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(12) Adhesion of nickel and cobalt on the roughened surface

The nickel adhesion amount and the cobalt adhesion amount were measured by dissolving the sample with a concentration of 20% by mass of nitric acid, and using an atomic absorption spectrophotometer (Model: AA240FS) manufactured by VARIAN Co., Ltd., and performing quantitative analysis by atomic absorption method. . The measurement samples of the nickel and cobalt adhesion amounts of the examples and the comparative examples were set to 50 mm × 50 mm. Further, the measurement of the adhesion amount of the above nickel and cobalt was carried out in the following manner. After the prepreg (FR4) was pressure-bonded to the surface of the surface-treated copper foil which was not surface-treated, and laminated, the surface of the surface-treated copper foil was melted to a thickness of 2 μm, and the surface-treated copper was applied. The amount of adhesion of nickel and cobalt adhering to the surface of the foil on the surface of the surface was measured. Then, the adhesion amounts of nickel and cobalt obtained were respectively set to the adhesion amounts of nickel and cobalt on the roughened surface. Further, the surface-treated copper foil may not have an effective thickness of 2 μm on the surface-treated side, and may be dissolved and measured by a thickness (for example, 1.5 to 2.5 μm) in which the surface-treated surface portion is completely dissolved. In addition, the surface treatment of copper foil is attached In the case of the ultra-thin copper layer of the body copper foil, first, the prepreg (FR4) is heat-bonded to the surface of the carrier side to be laminated, and only the vicinity of the surface of the ultra-thin copper layer on the surface-treated side is dissolved ( When the thickness of the ultra-thin copper layer is 1.4 μm or more, the surface of the ultra-thin copper layer on the surface-treated side is only dissolved to a thickness of 0.5 μm; when the thickness of the ultra-thin copper layer is less than 1.4 μm, The surface of the ultra-thin copper layer on the surface-treated side dissolves only 20% of the thickness of the extremely thin copper layer, and the adhesion of nickel to cobalt on the surface of the ultra-thin copper layer on the surface-treated side is measured. Then, the adhesion amounts of nickel and cobalt obtained were respectively set to the adhesion amounts of nickel and cobalt on the roughened surface.

Further, the adhesion amount of the above nickel and cobalt means the adhesion amount (mass) of nickel and cobalt per unit area (1 dm ² ) of the sample.

(13) Evaluation of copper foil wrinkles due to lamination processing, etc.:

The surface-treated copper foils of the examples and the comparative examples were laminated on both surfaces of a polyimide film having a thickness of 25 μm from one surface side, and further coated with a protective film of 125 μm on the other surface side of each surface-treated copper foil. In the state of the protective film/surface-treated copper foil/polyimine resin/surface-treated copper foil/protective film, a laminating roll is used, and the outer side of the two protective films is used. The surface-treated copper foil was bonded to both sides of the polyimide resin by applying heat and pressure and performing lamination processing (lamination processing). Next, after peeling off the protective film of both surfaces, the other surface of the surface-treated copper foil was visually observed, and the presence or absence of wrinkles or streaks was confirmed, and when wrinkles or stripes were not produced at all, it was evaluated as ◎, and the copper foil length was observed only every 5 m. When it was one wrinkle or streak, it was evaluated as ○, and when the copper foil was observed at two or more wrinkles or streaks per 5 m, it was evaluated as ×.

Further, when the surface of the copper foil is roughened or the surface is treated to provide a heat-resistant layer, a rustproof layer, a weather resistant layer, or the like without being subjected to the roughening treatment, heat resistance is set for the heat-treated layer. Surface treated copper foil after surface treatment such as layer, rustproof layer, weather resistant layer, etc. On the surface, the above measurement was carried out. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

The conditions and evaluation results of the above tests are shown in Tables 1 to 12.

In addition, "-" in the column of the heat-resistant layer 1, the heat-resistant layer 2, the rust-proof layer, and the weather-resistant layer in Table 10 indicates that the heat-resistant layer 1, the heat-resistant layer 2, the rust-preventing layer, and the weather-resistant layer were not formed. .

[Evaluation results]

In Examples 1 to 36, the haze value, visibility, and peel strength were good. In addition, the solder heat resistance evaluation was also good. In addition, the transmission loss is also small and good.

The haze values of Comparative Examples 1 to 2, 4, 7 to 11, and 13 were significantly higher, and the surface roughness was also larger, so that the visibility was poor.

Comparative Examples 3, 5, 6, and 12 were excellent in visibility, but the peel strength was insufficient, and the substrate adhesion was poor. Further, the solders of Comparative Examples 1 to 13 were poor in heat resistance evaluation.

Further, in Example 5, the 60-degree gloss and the surface area ratio A/B of Rz and MD were substantially the same as those of Example 15, but the MD of the roughened surface of Example 5 was 60 degree gloss and TD. The ratio of the 60 degree gloss ratio C is 0.84, which is in the range of 0.80 to 1.40. Therefore, the haze value of Example 5 is smaller than the embodiment 15 except that the C value is 0.75 and the range is 0.80 to 1.40.

The haze value of Example 16 was less than the haze value of Example 17 for the same reason.

Further, using the same copper foil as each of the above examples and comparative examples, the both surfaces of the copper foil were subjected to surface treatment under the same conditions, and the same carrier as each of the above examples was used, and formed on both sides of the carrier under the same conditions. After the intermediate layer and the ultra-thin copper layer were subjected to the same surface treatment, and the surface-treated copper foil was produced and evaluated, the same evaluation results as in the above Examples and Comparative Examples were obtained on both sides. Further, in the case of electrolytic polishing or chemical polishing of the copper foil or the carrier, the both surfaces are subjected to electrolytic polishing or chemical polishing, followed by surface treatment. Further, in Example 21, Example 25, and Comparative Example 10, the shiny surface of the copper foil (the surface on the side in contact with the drum when the electrolytic copper foil was produced) was subjected to electrolytic polishing and/or chemical polishing to thereby make TD The roughness Rz and the glossiness are the same as those of the precipitation surface, and then a specific surface treatment or an intermediate layer or the like is formed.

In the case of surface treatment such as roughening treatment on both sides of the copper foil, both surfaces may be subjected to surface treatment at the same time, or both surfaces may be separately treated. Further, in the case where the both surfaces are simultaneously subjected to surface treatment, a surface treatment apparatus (plating apparatus) provided with an anode on both sides of the copper foil may be subjected to surface treatment. Furthermore, in the present embodiment, the surfaces of both sides are simultaneously Reason.

Further, the ten-point average roughness Rz of the TD measured by a laser microscope having a laser wavelength of 405 nm on the surface of the roughened copper foil of each of the examples was 0.35 μm or more. Further, the arithmetic mean roughness Ra of TD measured by a laser microscope having a laser wavelength of 405 nm on the surface of the roughened copper foil of each of the examples was 0.05 μm or more. Further, the root mean square height Rq of the TD measured by a laser microscope having a laser wavelength of 405 nm on the surface of the roughened copper foil of each of the examples was 0.08 μm or more.

Fig. 1 shows (a) comparative example 1, (b) comparative example 2, (c) comparative example 3, (d) comparative example 4, (e) example 1, (f) in the case of the above Rz evaluation. SEM observation photograph of the surface of the copper foil of Example 2.

Claims (47)

A surface-treated copper foil which is roughened to form roughened particles on a copper foil surface and/or two copper foil surfaces, and the tenth point of the TD measured by a contact roughness meter for roughening the surface The average roughness Rz is 0.20 to 0.80 μm, and the 60 degree gloss of the MD of the roughened surface is 76 to 350%, and the surface area A of the roughened particles is obtained when the roughened particles are viewed from the surface side of the copper foil. The ratio A of the area B is 1.90 to 2.40, and the surface of the roughened surface contains an element selected from the group consisting of Ni and Co, and the amount of Ni is attached when the surface of the roughened surface contains Ni. When it is 1400 μg/dm ² or less and Co is contained in the surface of the roughening treatment, the adhesion amount of Co is 2400 μg/dm ² or less. The surface-treated copper foil of claim 1, wherein the roughened particles are formed on the surface of a copper foil by roughening, and the tenth point of the TD measured by the contact roughness meter is used for roughening the surface The average roughness Rz is 0.20 to 0.80 μm, and the 60 degree gloss of the MD of the roughened surface is 76 to 350%, and the surface area A of the roughened particles is obtained when the roughened particles are viewed from the surface side of the copper foil. The ratio A of the area B is 1.90 to 2.40, and the surface of the roughened surface contains an element selected from the group consisting of Ni and Co, and the amount of Ni is attached when the surface of the roughened surface contains Ni. When it is 1400 μg/dm ² or less and Co is contained in the surface of the roughening treatment, the adhesion amount of Co is 2400 μg/dm ² or less, and the surface of the other copper foil is surface-treated. The surface-treated copper foil according to the first aspect of the invention, wherein when the roughening treatment surface contains Ni, the adhesion amount of Ni is 1000 μg/dm ² or less. The surface-treated copper foil according to the second aspect of the invention, wherein when the roughening treatment surface contains Ni, the adhesion amount of Ni is 1000 μg/dm ² or less. The surface-treated copper foil according to the first aspect of the invention, wherein when the roughening treatment 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 the second aspect of the invention, wherein when the roughening treatment 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 the first aspect of the invention, wherein when the surface of the roughening treatment contains Co, the adhesion amount of Co is 2000 μg/dm ² or less. The surface-treated copper foil according to the second aspect of the invention, wherein when the roughening treatment surface contains Co, the adhesion amount of Co is 2000 μg/dm ² or less. The surface-treated copper foil according to the first aspect of the invention, wherein when the roughening treatment surface contains Co, the adhesion amount of Co is 300 μg/dm ² or more and 2000 μg/dm ² or less. The surface-treated copper foil according to the second aspect of the invention, wherein when the roughening treatment surface contains Co, the adhesion amount of Co is 300 μg/dm ² or more and 2000 μg/dm ² or less. The surface treated copper foil of claim 1, wherein the MD has a 60 degree gloss of 90 to 250%. The surface treated copper foil of claim 2, wherein the MD has a 60 degree gloss of 90 to 250%. The surface-treated copper foil according to claim 1, wherein the ten-point average roughness Rz of the TD measured by the contact type roughness meter is 0.30 to 0.60 μm. The surface-treated copper foil according to claim 2, wherein the ten-point average roughness Rz of the TD measured by the contact type roughness meter is 0.30 to 0.60 μm. The surface treated copper foil of claim 1, wherein the A/B is 2.00 to 2.20. For example, the surface treated copper foil of claim 2, wherein the A/B is 2.00 to 2.20. The surface-treated copper foil according to claim 1, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm. The ten-point average roughness Rz of the obtained TD is 0.35 μm or more. The surface-treated copper foil of claim 2, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm The ten-point average roughness Rz of the obtained TD is 0.35 μm or more. The surface-treated copper foil according to claim 1, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm. The arithmetic mean roughness Ra of the obtained TD is 0.05 μm or more. The surface-treated copper foil of claim 2, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm The arithmetic mean roughness Ra of the obtained TD is 0.05 μm or more. The surface-treated copper foil according to claim 1, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm. The radix height Rq of the obtained TD is 0.08 μm or more. The surface-treated copper foil of claim 2, wherein the surface of the roughened copper foil and/or the surface of the copper foil not subjected to the roughening treatment are measured by a laser microscope having a laser wavelength of 405 nm The radix height Rq of the obtained TD is 0.08 μm or more. The surface treated copper foil of claim 1, wherein the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of the TD is C (C=(60 degree gloss of MD)) / (60 degree gloss of TD)) is 0.80~1.40. The surface treated copper foil of claim 23, wherein the ratio of the 60 degree gloss of the MD of the roughened surface to the 60 degree gloss of the TD is C (C = (60 degree gloss of MD) / (TD) The 60 degree gloss)) is 0.90~1.35. The surface-treated copper foil according to the first aspect of the invention, wherein the copper foil is bonded to both sides of a resin substrate having a thickness of 50 μm from the roughened surface side, and then the copper foil on both sides is removed by etching. The haze value of the resin substrate is 20 to 70%. The surface-treated copper foil according to the second aspect of the invention, wherein the copper foil is bonded to both sides of the resin substrate having a thickness of 50 μm from the roughened surface side, and then the copper foil on both sides is removed by etching. The haze value of the resin substrate is 20 to 70%. The surface-treated copper foil according to claim 1, wherein the roughened surface contains at least one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A surface-treated copper foil according to the first aspect of the invention, comprising a resin layer on the roughened surface. The surface-treated copper foil of claim 28, wherein the resin layer contains a dielectric. A copper foil with a carrier, which is provided with a copper foil with a carrier, an intermediate layer, and an ultra-thin copper layer, and the ultra-thin copper layer is a surface-treated copper foil according to any one of claims 1 to 29. . The carrier-attached copper foil according to claim 30, wherein the copper foil with the carrier is bonded to both sides of the resin substrate having a thickness of 50 μm from the roughened surface side of the ultra-thin copper layer of the copper foil with the carrier. The carrier with the carrier copper foil is removed, and then bonded to the tree by etching When the extremely thin copper layer on both sides of the grease substrate is removed, the haze value of the resin substrate is 20 to 70%. The carrier copper foil of claim 30, which has the ultra-thin copper layer on both sides of the carrier. The copper foil with a carrier of claim 30, which has a roughened layer on the side of the carrier opposite to the ultra-thin copper layer. A laminated board produced by laminating a surface-treated copper foil according to any one of claims 1 to 29 or a carrier-attached copper foil according to any one of claims 30 to 33 and a resin substrate. A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 29 or the carrier-attached copper foil of any one of claims 30 to 33. An electronic machine using the printed wiring board of claim 35. A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected, wherein two or more printed wiring boards of claim 35 are connected. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising the steps of: at least one printed wiring board of claim 35, and a printed wiring board of another application patent item 35 Or a printed wiring board that does not belong to the printed wiring board of claim 35. An electronic device using one or more printed wiring boards to which at least one printed wiring board manufactured by the method of claim 37 or 38 is connected. A method of manufacturing a printed wiring board comprising at least the step of connecting a printed wiring board manufactured by the method of claim 37 or 38 to a component. A method for manufacturing a printed wiring board to which two or more printed wiring boards are connected, at least The method comprises the steps of: at least one printed wiring board of claim 35, and a printed wiring board of another patent application scope 35 or a printed wiring board not belonging to the printed wiring board of claim 35 And a step of connecting the printed wiring board of claim 35 or the printed wiring board to which two or more printed wiring boards are connected, which are manufactured by the method of claim 37, to the parts. A manufacturing method of a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating substrate according to any one of claims 30 to 33; and laminating the carrier copper foil and the insulating substrate And laminating the copper foil with the carrier and the insulating substrate, and then forming a copper-clad laminate by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition The method of forming a circuit by either one of a method or a modified semi-additive method. A method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier of any one of claims 30 to 33 or the side surface of the carrier; a step of burying the circuit in a manner of forming a resin layer on the side surface of the ultra-thin copper layer of the carrier copper foil or the side surface of the carrier; forming a circuit on the resin layer; after forming a circuit on the resin layer, a step of stripping the carrier or the ultra-thin copper layer; After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer is removed, whereby the circuit formed on the side surface of the ultra-thin copper layer or the side surface of the carrier is exposed to the circuit of the resin layer. The method of manufacturing a printed wiring board according to claim 43 wherein the step of forming a circuit on the resin layer is the step of attaching another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer. The circuit is formed using a copper foil with a carrier attached to the resin layer. The method of manufacturing a printed wiring board according to claim 44, wherein the other carrier-attached copper foil bonded to the resin layer is the carrier-attached copper foil according to any one of claims 30 to 33. The method of manufacturing a printed wiring board according to any one of claims 43 to 45, wherein the step of forming a circuit on the resin layer is by a semi-additive method, a subtractive method, a partial addition method or an improvement It is carried out by any one of the semi-additive methods. The method of manufacturing a printed wiring board according to any one of claims 43 to 45, wherein the carrier-attached copper foil on the surface of the circuit is on the carrier side surface of the carrier copper foil or the ultra-thin copper layer side surface. There is a substrate or a resin layer.