TWI489014B - Surface treatment of copper foil and the use of its laminated board, copper laminated board, printed wiring board, and electronic equipment - Google Patents

Description

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

The present invention relates to a surface-treated copper foil and a laminated board using the same, and more particularly to a surface-treated copper foil and a laminated board using the same, which is suitable for the transparency of a resin which requires the remaining portion of the copper foil to be etched. Copper laminates, printed wiring boards, and electronic equipment.

In terms of the ease of wiring or the lightness, a small-sized electronic device such as a smart phone or a tablet PC uses a flexible printed wiring board (hereinafter referred to as FPC). In recent years, with the high functionality of these electronic devices, the speed of signal transmission has been increasing, and impedance matching has become an important factor in FPC. As a countermeasure against impedance matching in which the signal capacity is increased, thick layering of a resin insulating layer (for example, polyimide) which becomes an FPC substrate is progressing. Further, with the demand for higher density of wiring, the multi-layering of FPC has further developed. On the other hand, the FPC is subjected to processing such as bonding of a liquid crystal substrate or mounting of an IC wafer, and the alignment is performed by etching the copper foil in the laminate of the copper foil and the resin insulating layer. The positioning pattern recognized by the resin insulating layer is performed, and therefore, 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 plating on its 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 after hot rolling, the ingots are repeatedly subjected to cold rolling and Annealing is performed up to a predetermined thickness.

As such a technique, for example, Patent Document 1 discloses a copper-clad laminate in which a layer of a polyimide film and a low-roughness copper foil are laminated, and a film after copper foil etching is exposed 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 a flexible printed wiring board for COF (Chip on Flex) having an insulating layer in which a conductor layer formed of an electrolytic copper foil is laminated, and the conductor layer is laminated. When the circuit is formed by etching to form a circuit, the light transmittance of the insulating layer in the etching region is 50% or more, and the electrodeposited copper foil is provided with a rust-preventing layer using a nickel-zinc alloy on the surface adjacent to the insulating layer. The surface roughness (Rz) of the next surface is 0.05 to 1.5 μm, and the specular gloss at an incident angle of 60° is 250 or more.

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

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

[Patent Document 2] WO2003/096776

[Patent Document 3] Japanese Patent No. 2849059

In Patent Document 1, the low-roughness copper foil obtained by the adhesion improving treatment by the organic treatment agent after the blackening treatment or the plating treatment may be used for the purpose of requiring flexibility for the copper-clad laminate. Broken due to fatigue, and there is a case where the resin has poor transparency.

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

Further, in the treatment method described in Patent Document 3, the copper foil may be subjected to fine treatment using Cu-Co-Ni. However, the resin obtained by removing the copper foil and the resin and removing the copper foil by etching cannot achieve excellent transparency.

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 a laminated board, a copper-clad laminate, a printed wiring board, and an electronic apparatus using the same.

As a result of intensive studies, the present inventors have found that the following conditions are not affected by the type of the substrate resin film or the thickness of the substrate resin film, and the resin transparency after etching and removing the copper foil is affected: for the bonding and removal of the copper foil The polyimide substrate is placed under the printed matter with the mark, and the printed matter is photographed by a CCD camera through the polyimide substrate, and the observation point-brightness chart obtained by the image of the mark portion is obtained. The brightness curve is controlled by focusing on the brightness curve near the end of the marked mark.

The present invention, which has been completed on the basis of the above findings, is a surface-treated copper foil which is formed by roughening particles on at least one surface to form roughened particles, and the copper foil is bonded to the polyimide. After the two sides of the amine resin substrate, the copper foil on both sides is removed by etching, and the printed matter having the printed linear mark is laid under the exposed polyimide substrate, and the printed matter is applied to the printed matter via the polyimide substrate. When photographing is performed, the brightness of each observation point is measured in the direction perpendicular to the direction in which the linear mark is observed in the image obtained by the above-mentioned photographing, and an observation point-luminance chart is formed. The difference ΔB (ΔB = Bt - Bb) between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion to the portion without the above-described mark is 40 or more.

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

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

In still another embodiment of the surface-treated copper foil of the present invention, in the observation point-luminance chart, a value indicating a position closest to an intersection of the linear marks in the intersection of the brightness curve and Bt is t1, and The value from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt indicates that the value of the position closest to the intersection of the linear marks in the intersection of the brightness curve and 0.1 ΔB is set to t2, at this time, The Sv defined by the formula (1) is 3.5 or more, and Sv = (ΔB × 0.1) / (t1 - t2) (1).

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

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

In still another embodiment of the surface-treated copper foil of the present invention, the average roughness Rz of the TD of the roughened surface is 0.20 to 0.80 μm, and the 60 degree gloss of the MD of the roughened surface is 76 to 350%. The ratio A/B of the surface area A of the roughened particles and the area B obtained by looking down the roughened particles from the surface side of the copper foil is 1.90 to 2.40.

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 TD has an average roughness Rz of 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) / ( The 60 degree gloss of TD)) 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) / ( The 60 degree gloss of TD)) is 0.90~1.35.

Still another aspect of the present invention provides a laminated board comprising a surface-treated copper foil of the present invention and a resin substrate.

Still another aspect of the present invention is a printed wiring board using the surface treated copper foil of the present invention.

Still another aspect of the present invention is an electronic machine using the printed wiring board of the present invention.

Still another aspect of the present invention is a printed wiring board comprising: an insulating resin substrate; and a surface-treated copper foil formed by laminating a surface of the surface-treated surface and the insulating substrate to form a copper circuit; When the copper circuit is photographed by the CCD camera on the insulating resin substrate laminated on the surface side of the surface, the brightness of each observation point is measured in the direction perpendicular to the direction in which the copper circuit is observed in the image obtained by the photographing. And an observation point-brightness graph is produced, in which the difference between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion of the copper circuit to the portion without the copper circuit is ΔB (ΔB= Bt-Bb) is 40 or more.

According to still another aspect of the present invention, a copper-clad laminate is composed of an insulating resin substrate and a surface-treated copper foil laminated on the surface of the surface of the surface of the surface of the surface, and the copper-clad layer is laminated by etching. After the surface-treated copper foil of the board is formed into a linear surface-treated copper foil, the image obtained by the photographing is imaged by the CCD camera while the insulating resin substrate laminated on the surface side of the surface treatment is photographed by a CCD camera. Observing the brightness of each observation point in a direction perpendicular to the direction in which the linear surface-treated copper foil is observed to be observed to form an observation point-brightness graph, in which the end portion of the copper surface-treated copper foil is not The difference between the top average Bt of the brightness curve generated by the portion of the linear surface-treated copper foil and the bottom average value Bb ΔB (ΔB=Bt-Bb) is 40 or more.

Still another aspect of the invention is an electronic machine using the printed wiring board of the invention.

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

Still another aspect of the invention is an electronic machine using the copper clad laminate of the present invention.

According to still another aspect of the invention, there is provided a method of manufacturing a printed wiring board, wherein two or more printed wiring boards of the present invention are connected to each other to manufacture a printed wiring board to which two or more printed wiring boards are connected.

Still another aspect of the invention is a method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least one printed wiring board of the present invention, and another printed wiring board of the present invention or The step of connecting the printed wiring board of the printed wiring board of the present invention is not equivalent.

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 of the invention is connected, or a printed wiring board of the invention.

Still another aspect of the invention is a method of manufacturing a printed wiring board comprising at least a step of connecting a printed wiring board of at least one printed wiring board of the present invention or a printed wiring board of the present invention to a component.

According to still another aspect of the invention, a method of manufacturing a printed wiring board to which two or more printed wiring boards are connected includes at least one printed wiring board of the present invention and another printed wiring board of the present invention. Or the step of connecting the printed wiring board of the printed wiring board of the present invention, and the step of connecting the printed wiring board of the present invention or the printed wiring board to which two or more printed wiring boards of the present invention are connected, to the parts.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes: preparing a present The step of attaching the carrier copper foil and the insulating substrate; and the step of laminating the copper foil with the carrier and the insulating substrate; and laminating the carrier copper foil and the insulating substrate, and then removing the carrier of the copper foil with the carrier Forming a copper clad laminate, and thereafter, forming a circuit by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method includes the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; a step of forming a resin layer on the side surface of the ultra-thin copper layer of the carrier copper foil: a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and removing the carrier after peeling off the carrier The ultra-thin copper layer is formed by exposing the circuit buried in the resin layer on the side surface of the ultra-thin copper layer.

According to the present invention, it is possible to provide 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 a laminated board, a copper-clad laminate, a printed wiring board, and an electronic apparatus using the same.

Figure 1 is a schematic diagram defining Bt and Bb.

Figure 2 is a schematic diagram defining t1 and t2 and Sv.

Fig. 3 is a schematic view showing a method of measuring the configuration of the imaging device and the slope of the luminance curve when evaluating the slope of the luminance curve.

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

Fig. 4b is a SEM observation photograph of the surface of the copper foil of Comparative Example 3 in (b) at the time of Rz evaluation.

Fig. 4c is a SEM observation photograph of the surface of the copper foil of Comparative Example 5 in (c) at the time of Rz evaluation.

Fig. 4d is a SEM observation photograph of the surface of the copper foil of Comparative Example 6 in (d) when Rz was evaluated.

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

Fig. 4f is a SEM observation photograph of the surface of the copper foil of Example 2 in (f) at the time of Rz evaluation.

5A to 5C are schematic views showing a cross section of a wiring board in a step of removing a circuit plating layer and a resist from a specific example of a method for producing a printed wiring board with a copper foil with a carrier of the present invention.

6D to F are patterns of a cross section of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening in the specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention. Figure.

7G to 1 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 a specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention.

8J to K are schematic views showing a cross section of the wiring board in the step from the rapid etching to the step of forming the bumps and the copper pillars in the specific example of the method for manufacturing the printed wiring board with the carrier copper foil of the present invention.

[Formation and Manufacturing Method of Surface-treated Copper Foil]

The copper foil used in the present invention can be used as a copper foil which is produced by laminating a resin substrate and removing it by etching.

The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. In general, in order to increase the peeling strength of the copper foil after lamination of the copper foil to the surface of the resin substrate, that is, the roughened surface, the surface of the copper foil after degreasing may be subjected to roughening treatment by knob-shaped electrodeposition. The electrolytic copper foil has irregularities at the time of production, and the convex portion of the electrolytic copper foil can be reinforced by the roughening treatment to further increase the unevenness. In the present invention, the roughening treatment is 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 copper alloy plating. 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 it is more preferable to use copper and a material selected from the group consisting of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese, and Any one or more of the group consisting of molybdenum is used as a plating bath. Also, in the present invention, This roughening treatment increases the current density and shortens the roughening processing time as compared with the previous roughening treatment. There is a case where normal copper plating or the like is performed as a pre-roughing treatment, and in order to prevent the electrodeposited material from falling off, a normal copper plating or the like may be used as a refining treatment after roughening. Calendered copper foil and electrolytic copper foil are also slightly different in handling. The present invention also encompasses such pre-treatment and finishing treatments, and includes well-known treatments associated with copper foil roughening, as desired, collectively referred to as roughening treatment.

Furthermore, the rolled copper foil of the present invention also includes one or more copper alloys containing elements of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B, and the like. Foil. When the concentration of the above elements is increased (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 total amount of the elements other than copper may be 0 mass% or more and 50 mass% or less, and may be 0.0001 mass% or more and 40 mass% or less, and may be 0.0005 mass% or more and 30 mass% or less, or may be 0.001 mass% or more. 20mass% or less.

Further, the copper foil used in the present invention may be a copper foil with a carrier which has 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 carrier-attached copper foil will be described below.

Further, one of the production conditions of the electrolytic copper foil which can be used in the invention of the present invention is as follows.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 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 those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

Further, as the electrolytic copper foil which can be used in the invention of the present invention, an HLP foil manufactured by JX Nippon Mining & Metal Co., Ltd. can be cited.

As the roughening treatment of copper - cobalt - nickel alloy may be plated by electrolytic plating to form as deposition amount of 15 ~ 40mg / dm ² of copper -100 ~ 3000μg / dm ² of cobalt -50 ~ 1500μg / dm ² of The ternary system of the nickel ternary alloy layer is preferably formed by forming a ternary system of nickel-100-3000 μg/dm ² of cobalt-100-1500 μg/dm ² of nickel as an adhesion amount of 15 to 40 mg/dm ² . The alloy layer is implemented in a manner. When the Co adhesion amount is less than 100 μg/dm ² , the heat resistance is deteriorated and the etching property is deteriorated. When the Co adhesion amount exceeds 3000 μg/dm ² , it is not preferable in the case where the influence of magnetism is necessary, and there is a case where an etching spot is generated and acid resistance and chemical resistance are deteriorated. If the Ni adhesion amount is less than 50 μg/dm ² , the heat resistance may be deteriorated. On the other hand, when the Ni adhesion amount exceeds 1500 μg/dm ² , there is a case where the etching residue increases. Preferably, the deposited mass of Co is 1000 ~ 2500μg / dm ^2, preferably of the deposited mass of nickel is 500 ~ 1200μg / 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 etching residue refers to a case where Ni is not dissolved and remains in the case of performing alkali etching with ammonium chloride.

The plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating layer are 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: 0.3~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil.

Further, the conditions for plating the copper-nickel-phosphorus alloy which is the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 10~50g/L, Ni 3~20g/L, P 1~10g/L

pH: 1~4

Temperature: 30~40°C

Current density D _k : 30~50A/dm ²

Plating time: 0.3~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. The roughening treatment is performed under the condition that the plating time is shortened and the current density is increased, so that the coarser particles are formed more finely than before. On the surface of the copper foil.

Further, the copper-nickel-cobalt-tungsten alloy plating conditions which are the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 5~20g/L, Ni 5~20g/L, Co 5~20g/L, W 1~10g/L

pH: 1~5

Temperature: 30~50°C

Current density D _k : 30~50A/dm ²

Plating time: 0.3~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil.

Further, the copper-nickel-molybdenum-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.

Composition of plating bath: Cu 5~20g/L, Ni 5~20g/L, Mo 1~10g/L, P 1~10g/L

pH: 1~5

Temperature: 30~50°C

Current density D _k : 30~50A/dm ²

Plating time: 0.3~3 seconds

Further, the surface-treated copper foil according to an embodiment of the present invention can be subjected to a roughening treatment under the conditions of shortening the plating time and increasing the current density. By roughening the film under the conditions of shortening the plating time and increasing the current density, the coarser particles which are finer than before are formed on the surface of the copper foil.

After the roughening treatment, a heat-resistant layer and a rust-proof layer may be disposed on the roughened surface. One or more layers of the group of the weather resistant layer. Further, each layer may be a plurality of layers such as two or three layers, and the order of the respective layers may be in any order, or the layers may be alternately laminated.

Here, as the heat-resistant layer, a known heat-resistant layer can be used. Further, 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 rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. The layer of one or more elements of the group of strontium may 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 a platinum group element, iron, and lanthanum. Moreover, 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. An oxide, a nitride or a telluride of one or more elements selected from the group consisting of iron and strontium. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50% 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 amount of zinc and nickel attached to the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the 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-containing zinc alloy 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-preventive layer is a layer containing a nickel-zinc alloy, when the inner wall portion of a through hole or a via hole is in contact with a desmear liquid, The interface between the copper foil and the resin substrate is not easily corroded by the degreasing liquid, 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 comprising 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, Form of sulfide, etc.). Specific examples of the chromate treatment layer include a pure chromate treatment layer, a zinc chromate treatment layer, and the like. 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, the chromate treatment layer treated with the treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

For example, the heat-resistant layer and/or the rust-preventive layer may be a layer of nickel or a 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 attached. The nickel alloy layer may be any one of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt, in an amount of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² . A composition. Further, the heat-resistant layer and/or the rust-preventive layer preferably have a total adhesion amount of nickel or a nickel alloy to tin of 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 deposited in the nickel or 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, the chemical-resistant deterioration rate of the peeling strength, etc. are favorable.

Further, as the heat-resistant layer and / or rust proof layer, may be formed in a deposition amount of 200 ~ 2000μg / dm ² of cobalt -50 ~ 700μg / dm ² of nickel, cobalt - nickel alloy plated layer. This treatment can be regarded as a rust-proof treatment in a broad sense. The cobalt-nickel alloy plating layer must be formed 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 oxidation resistance and chemical resistance are deteriorated. Further, as another reason, if the amount of cobalt is small, the treated surface is easily reddish, which is not preferable.

After the roughening treatment, the roughened surface may be formed in a deposition amount of 200 ~ 3000μg / dm ² of cobalt -100 ~ 700μg / dm ² of nickel, cobalt - nickel alloy plated layer. This treatment can be regarded as a rust-proof treatment in a broad sense. The cobalt-nickel alloy plating layer must be formed 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 oxidation resistance and chemical resistance are deteriorated. Further, as another reason, if the amount of cobalt is small, the treated surface is easily reddish, which is not preferable. When the cobalt adhesion amount exceeds 3000 μg/dm ² , it is not preferable in the case where the influence of magnetism must be considered, and there is a case where an etching spot is generated, and acid resistance and chemical resistance are deteriorated. A preferred amount of cobalt adhesion is 500 to 2500 μg/dm ² . On the other hand, when the nickel adhesion amount is less than 100 μg/dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance are deteriorated. If the nickel exceeds 1300 μg/dm ² , the alkali etching property is deteriorated. A preferred nickel adhesion amount is 200 to 1200 μg/dm ² .

Further, one of the conditions for cobalt-nickel alloy plating is as follows: plating bath composition: Co 1 to 20 g/L, Ni 1 to 20 g/L.

pH: 1.5~3.5

Temperature: 30~80°C

Current density D _k : 1.0~20.0A/dm ²

Plating time: 0.5~4 seconds

According to the present invention, a zinc plating layer having an adhesion amount of 30 to 250 μg/dm ² is further formed on the cobalt-nickel alloy plating layer. When the amount of zinc adhesion is less than 30 μg/dm ² , the effect of improving the heat-resistant deterioration rate may be lost. On the other hand, when the amount of zinc adhesion exceeds 250 μg/dm ² , the rate of deterioration of hydrochloric acid resistance may be extremely poor. 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 conditions of the above zinc plating 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, a zinc alloy plating layer such as a zinc-nickel alloy plating layer may be formed instead of the zinc plating layer. Further, a rustproof layer or a weather resistant layer may be formed on the outermost surface by chromate treatment or decane coupling agent coating or the like.

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

As the decane coupling agent used for the decane coupling treatment, a known decane coupling agent may be used, and for example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent may be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropane can also be used. Propyltrimethoxydecane, 4-epoxypropylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyl Trimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer can 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, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amino decane coupling agent herein may be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-amine Ethylethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyl Trimethoxydecane, N-methylaminopropyltrimethoxydecane, 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-(aminohexylaminopropyl)trimethoxynonane, Aminophenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyltris(methoxy B) Oxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N- Benzylaminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-amino Propyl)trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyl Trimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(amine Benzyl)-γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane Among the group of people.

The decane coupling treatment layer is preferably set to 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. The range of m ² . In the case of 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 preferably forms roughened particles on the surface of the copper foil by roughening treatment, and the average roughness Rz of the TD of the roughened surface is 0.20 to 0.80 μm. According to this configuration, the peeling strength is improved, and the resin is satisfactorily adhered to, and the transparency of the resin after the copper foil is removed by etching is improved. As a result, it is easier to position the IC wafer during mounting by the positioning pattern recognized by the resin. If the average roughness Rz of the TD is less than 0.20 μm, there is a fear of manufacturing cost for producing an ultra-smooth surface. On the other hand, when the average roughness Rz of the TD exceeds 0.80 μm, the unevenness of the surface of the resin after the removal of the copper foil by etching is increased, and as a result, there is a problem that the transparency of the resin is deteriorated. Roughing the surface of the TD The average roughness Rz is more preferably from 0.30 to 0.70 μm, still more preferably from 0.35 to 0.60 μm, still more preferably from 0.35 to 0.55 μm, still more preferably from 0.35 to 0.50 μm.

Further, in the case where the surface-treated copper foil of the present invention is used in the use of the Rz, the average roughness Rz of the TD of the roughened surface of the surface-treated copper foil of the present invention is preferably 0.20 to 0.70 μm. The ratio is preferably 0.25 to 0.60 μm, more preferably 0.30 to 0.60 μm, still more preferably 0.30 to 0.55 μm, and still more preferably 0.30 to 0.50 μm.

In the case of the surface-treated copper foil of the present invention, the "roughening treatment surface" refers to a case where a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like 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" 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.

[Gloss]

The gloss of the incident angle of 60 degrees in the rolling direction (MD) of the roughened surface of the surface-treated copper foil greatly affects the transparency of the above resin. That is, the more the copper foil having a higher glossiness of the roughened surface, the better the transparency of the above resin. Therefore, the surface-treated copper foil of the present invention preferably has a roughened surface having a gloss of 76 to 350%, preferably 80 to 350%, more preferably 90 to 300%, and still more preferably 90 to 250%. More preferably 100~250%.

Here, in order to obtain the effect of the identification of the present invention, it is necessary to control the surface of the treated side of the copper foil before the surface treatment (when the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, before the formation of the intermediate layer) The TD of the surface of the carrier on the side of the intermediate layer or the surface of the ultra-thin copper layer (the direction perpendicular to the rolling direction (the width direction of the copper foil) is the copper foil manufacturing device for the electrolytic copper foil. The roughness (Rz) and gloss of the direction perpendicular to the foil direction. Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is preferably 0.20 to 0.80 μm, more preferably 0.30 to 0.80 μm, still more preferably 0.30 to 0.50 μm, in the rolling direction (MD). Incident The gloss of 60 degrees is 350-800%, more preferably 500-800%. Further, if the current density is increased and the roughening time is shortened compared with the previous roughening treatment, the surface-treated copper foil after surface treatment is performed. The gloss at an incident angle of 60 degrees in the rolling direction (MD) is 90 to 350%. Such a copper foil can be produced by calendering (high gloss rolling) by adjusting the oil film equivalent of the rolling oil or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. By setting the surface roughness (Rz) and the gloss of the TD of the copper foil before the treatment to the above range, the surface roughness (Rz) and the surface area of the treated copper foil can be easily controlled.

Further, in order to further reduce the surface roughness (Rz) of the surface-treated copper foil (for example, Rz = 0.20 μm), the roughness (Rz) of the TD of the treated side surface of the copper foil before the surface treatment is obtained. It 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 350 to 800%, preferably 500 to 800%, and further, compared with the previous one. The roughening treatment increases the current density and shortens the roughening processing time.

Further, the copper foil before the roughening treatment is preferably a 60-degree gloss of MD of 500 to 800%, more preferably 501 to 800%, and still more preferably 510 to 750%. If the 60-degree gloss of the MD of the copper foil before the roughening treatment is less than 500%, the transparency of the above-mentioned resin becomes poor as compared with the case of 500% or more, and if it exceeds 800%, it may be produced. It is difficult to carry out the problem of manufacturing.

Further, the high gloss rolling can be carried out by setting the oil film equivalent of the following formula to 13,000 to 24,000 or less. In the case where the surface roughness (Rz) (for example, Rz = 0.20 μm) of the copper foil after the surface treatment is to be further reduced, the oil film equivalent of the following formula is set to be 12,000 or more and 24,000 or less. High gloss calendering.

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

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

Since the oil film equivalent is set to 12,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing the passage speed can be used.

The chemical polishing system uses an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system, and the concentration is lowered as usual, and the etching is carried out for a long period of time.

The ratio C 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 transparency of the resin is lowered as compared with the case of 0.80 or more. Further, when the ratio C exceeds 1.40, the transparency of the resin is lowered as compared with the case of 1.40 or less. The ratio C is preferably from 0.90 to 1.35, and more preferably from 1.00 to 1.30.

[Brightness curve]

The surface-treated copper foil of the present invention is attached to the both sides of the polyimide substrate, and the copper foil on both sides is removed by etching, and the printed printed mark is laid under the exposed polyimide substrate. When the printed matter is photographed by the CCD camera through the polyimide substrate, the brightness of each observation point is measured in the direction perpendicular to the direction in which the linear mark is observed, and the image obtained by the photographing is observed. Location-brightness graph, in which the difference ΔB (ΔB=Bt-Bb) between the top average Bt and the bottom average Bb of the luminance curve generated from the end of the mark to the portion without the mark is 40 or more .

Further, in the surface-treated copper foil of the present invention, in the observation point-luminance chart, a value indicating a position of the intersection of the brightness curve and the point closest to the linear mark in the intersection of Bt is set to t1, and the self-luminance curve is The value of the intersection of Bt and the depth of 0.1 ΔB based on Bt indicates that the value of the position closest to the intersection of the linear marks in the intersection of the luminance curve and 0.1 ΔB is t2, and in this case, the following is preferable. The Sv defined by the formula (1) is 3.5 or more.

Sv=(△B×0.1)/(t1-t2) (1)

Further, in the above-described observation position-luminance graph, the horizontal axis represents position information (pixel × 0.1), and the vertical axis represents the value of luminance (gray scale).

Here, use the graph to "top average Bt of the brightness curve" and "bottom average of the brightness curve" The value Bb" and the following "t1", "t2", and "Sv" will be described.

FIGS. 1(a) and 1(b) are schematic diagrams showing the definition of Bt and Bb when the width of the mark is set to about 0.3 mm. When the width of the mark is set to about 0.3 mm, there is a case where the V-shaped luminance curve is as shown in Fig. 1(a) and the bottom luminance curve is obtained as shown in Fig. 1(b). In either case, the "top average value Bt of the brightness curve" indicates the brightness at the time of measuring five places (the total of 10 parts on both sides) at intervals of 30 μm from the position of the end position on both sides of the mark. average value. On the other hand, the "base value Bb of the brightness curve" indicates the lowest value of the brightness of the front portion of the V-shaped concave portion when the brightness curve is V-shaped as shown in Fig. 1(a). (b) In the case of having a bottom, it means a value of a center portion of about 0.3 mm.

Fig. 2 is a schematic diagram showing definitions of t1, t2, and Sv. "t1 (pixel × 0.1)" indicates the value of the intersection of the brightness curve and Bt closest to the above-mentioned linear mark and the position of the intersection (the above-mentioned observation point - the value of the horizontal axis of the brightness chart). "t2 (pixel × 0.1)" is the intersection point from the intersection of the luminance curve and Bt to the depth of 0.1 ΔB based on Bt, and represents the intersection of the luminance curve and the 0.1 ΔB closest to the above-mentioned linear marker and the intersection. The value of the position (the above observation point - the value of the horizontal axis of the brightness chart). At this time, the slope of the luminance curve indicated by the line connecting t1 and t2 is defined by Sv (gray scale/pixel × 0.1) calculated by the y-axis direction being 0.1 ΔB and the x-axis direction being (t1-t2). Furthermore, one pixel on the horizontal axis corresponds to a length of 10 μm. Further, regarding Sv, both sides of the mark are measured and a small value is used. Further, when the shape of the luminance curve is unstable and there are a plurality of the above-mentioned "intersection points of the luminance curve and Bt", the intersection point of the closest mark is adopted.

In the above image taken by the CCD camera, the portion not marked with a high brightness is high, but the brightness is lowered just after reaching the end portion of the mark. When the visibility of the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the recognition property of the polyimide substrate is poor, the brightness does not suddenly decrease from "high" to "low" in the vicinity of the mark end portion, but the state of the reduction is gentle, and the state of the brightness is not lowered. clear.

The present invention is based on the insight that a polyimide substrate with a surface-treated copper foil of the present invention is attached and removed, and a printed matter with a mark is placed under it, and a CCD camera is used according to the polyimide substrate. The image of the above-mentioned marked portion obtains an observation point-brightness graph, and controls the luminance curve near the marked end portion depicted in the graph. More specifically, the difference ΔB (ΔB = Bt - Bb) between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion of the mark to the portion without the mark is 40 or more. According to this configuration, the recognition power of the mark of the CCD camera via the polyimide film is improved without being affected by the type or thickness of the substrate resin. Therefore, it is possible to produce a polyimide substrate having excellent visibility, and when the polyimide substrate is subjected to a predetermined treatment in an electronic substrate production step or the like, the positioning accuracy of the mark is improved, thereby obtaining an effect of improving yield and the like.

The above ΔB (ΔB = Bt - Bb) is preferably 50 or more, and more preferably 60 or more. The Sv is more preferably 3.9 or more, more preferably 4.5 or more, still more preferably 5.0 or more. The upper limit of ΔB is not particularly limited, and is, for example, 100 or less, or 80 or less, or 70 or less. Further, the upper limit of Sv is not particularly limited, and is, for example, 15 or less and 10 or less. According to this configuration, the boundary between the mark and the portion other than the mark is more clear, the positioning accuracy is improved, the error caused by the mark image recognition is reduced, and the positional alignment can be performed more accurately.

[surface area of particles]

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 greatly affects the transparency of the above resin. That is, when the surface roughness Rz is the same, the more the copper foil is smaller than A/B, the better the transparency of the resin. Therefore, the surface-treated copper foil of the present invention preferably has a ratio A/B of 1.90 to 2.40, more preferably 2.00 to 2.20.

By controlling the current density and plating time at the time of particle formation, the morphology or formation density of the particles can be determined, and the top average Bt and the bottom average value of the brightness curve generated from the end of the mark to the portion where the mark is not drawn can be controlled. The difference ΔB of Bb (ΔB=Bt-Bb), Sv, surface roughness Rz, glossiness, and area ratio A/B of the particles.

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 unevenness of the surface is increased, and the TD of the roughened surface is increased. The average roughness Rz is controlled to be 0.20 to 0.80 μm to remove the extremely thick portion, and on the other hand, the gloss of the roughened surface can be increased to 76 to 350%. By performing such control, the particle size of the roughened particles of the roughened surface in the surface-treated copper foil of the present invention can be reduced. The particle size of the roughened particles affects the transparency of the resin after etching and removing the copper foil, but such control means that the particle diameter of the roughened particles is reduced within an appropriate range, and therefore, the resin transparency after etching and removing the copper foil It becomes better and the peel strength becomes better.

[etching factor]

When the value of the etching factor when the copper foil is used to form the circuit is large, the curl at the bottom of the circuit which is generated during etching is reduced, so that the space between the circuits can be narrowed. Therefore, a larger value of the etching factor is suitable for forming a circuit using a fine pattern, which is preferable. In the surface-treated copper foil of the present invention, for example, the value of the etching factor is 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, the printed wiring board or the copper clad laminate can be measured by measuring the area ratio (A/B), the glossiness, and the surface roughness Rz of the particles on the surface of the copper circuit or the copper foil by melting and removing the resin.

[transmission loss]

In the case of a small transmission loss, the attenuation of the signal at the time of signal transmission at a high frequency can be suppressed, so that the circuit for transmitting the signal at a high frequency can perform stable signal transmission. Therefore, the smaller value of the transmission loss is suitable for circuit use for transmitting signals at high frequencies, 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 line was formed by etching to have a characteristic impedance of 50 Ω, and was manufactured by HP. The network analyzer HP8720C measures the transmission coefficient and determines the transmission loss at a frequency of 20 GHz. In this case, the transmission loss at a frequency of 20 GHz is higher. The ratio is less than 5.0 dB/10 cm, more preferably less than 4.1 d/10 cm, and even more preferably less than 3.7 dB/10 cm.

[with carrier copper foil]

The copper foil with a carrier according to another embodiment of the present invention is provided with a carrier, an intermediate layer, and an extremely thin copper layer in this order. Further, the ultra-thin copper layer is a surface-treated copper foil in the form of one of the above-described embodiments of the present invention.

<carrier>

The carrier which can be used 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. A film (for example, 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) is provided.

As the carrier which can be used in the present invention, copper foil is preferably used. Since the copper foil has a high electrical conductivity, it is easy to form an intermediate layer and an extremely thin copper layer. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electroplating 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 the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, or Mg is added, or Ni, Si, or the like may be used. A copper alloy such as a copper alloy.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a suitable thickness in addition to the function as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost will increase, 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, as described above, the carrier used in the present invention must control the surface roughness Rz and the glossiness on the side of the intermediate layer. Therefore, the glossiness of the roughened surface of the extremely thin copper layer after the surface treatment and the size and number of the roughened particles are controlled.

<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 required to be peeled off from the carrier before the step of laminating the insulating substrate to the copper foil with a carrier, and the ultra-thin copper layer may be formed after the laminating step to the insulating substrate. The composition from the carrier peeling is not particularly limited. For example, the intermediate layer of the copper foil with carrier of the present invention may comprise a metal hydrate selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, the like, and the like. One or more of a group consisting of oxides and organic substances. Also, the intermediate layer may be a plurality of layers.

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

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 the specific nitrogen-containing organic compound, it is preferred to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzo Triazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiol or the like is preferably used.

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, a nickel-cobalt alloy, and chromium on a carrier. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer. Adhesion amount of the intermediate layer of nickel, preferably 100μg / dm ² or more and 40000μg / dm ² or less, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² or less, more preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where only the intermediate layer is provided as a single surface, it is preferable to provide a rustproof layer such as a Ni plating layer on the surface opposite to the carrier.

If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer affects the glossiness of the roughened surface of the ultra-thin copper layer after the surface treatment and the size and number of the roughened particles, and thus is extremely thin. The thickness of the intermediate layer of the roughened surface of the copper 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.

<very thin copper layer>

An extremely thin copper layer is placed on top of the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer having the carrier is a surface-treated copper foil in the form of one embodiment of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1.5 to 5 μm. Further, before the ultra-thin copper layer is provided on the intermediate layer, in order to reduce pinholes of the ultra-thin copper layer, strike plating using a copper-phosphorus alloy can be performed. For the plating of the base, a copper pyrophosphate plating solution or the like can be cited.

Further, the ultra-thin copper layer of the present application was formed under the following conditions. The reason for this is that the size and number of the roughened particles and the gloss after the roughening treatment are controlled 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) disulfide): 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 those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

. Manufacturing conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5~10 minutes (by copper thickness and current density adjustment)

[Refining the resin layer on the surface]

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. The above resin layer may be provided in part or all of the roughened surface of the surface-treated copper foil of the present invention. In the case of the surface-treated copper foil of the present invention, the "roughening treatment surface" refers to a case where a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like after the roughening treatment. The surface of the surface treated copper foil after the surface treatment. Moreover, when the surface-treated copper foil is a very thin copper layer with a carrier copper foil, the so-called "roughening treatment" The surface refers to the surface of the ultra-thin copper layer after the surface treatment in the case where the surface treatment is performed in order to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like after the roughening treatment.

The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in an overlapping manner even if the surface is in contact with a finger, and the insulating resin layer can be stored in a superposed manner.

The resin layer may be an adhesive which is followed by a resin, or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in an overlapping manner even if the surface is in contact with a finger, and the insulating resin layer can be stored in a superposed manner.

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 include 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 material, and the like. Further, as the resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei 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 Japanese Patent Laid-Open 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. 5,046,927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815 , 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, Japanese Patent Publication No. 2013-19056 A material (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) and/or a method of forming a resin layer, Formed by forming a device.

In addition, the type of the resin layer is not particularly limited, and examples thereof include a resin containing at least one selected from the group consisting of an epoxy resin, a polyimide resin, and a polyfunctional cyanide. Acid ester compound, maleic acid amide compound, polymaleimide compound, maleic amide resin, aromatic maleic amide resin, polyvinyl acetal resin, urethane resin, acrylic acid Resin, polyether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine , aromatic polyamine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide III Resin, thermosetting polyphenylene ether resin, cyanate ester resin, acid anhydride, acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2- Bis(4-cyanooxyphenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin, Alkoxysilane modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, Phenoxy group, polymer epoxy resin, aromatic polyamine, fluororesin, bisphenol, block copolymer polyimine resin and cyanoester resin.

Further, the epoxy resin has two or more epoxy groups in the molecule, and It can be used for electrical and electronic materials, especially for problem-free use. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. Further, it can be used in combination: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac Varnish type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol Novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, epoxy propyl amine type epoxy resin, triglycidyl isocyanurate, N, N-diepoxypropyl aniline and the like a propylamine compound, a glycidyl ester compound such as diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenyl novolac type epoxy resin, or a trihydroxyphenyl group One or two or more of a group of a methane type epoxy resin and a tetraphenylethane type epoxy resin, or a hydrogenated body or a halogenated body 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 derived from a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derived from, for example, two or more epoxy groups in the molecule. Epoxy resin obtained in the form of a substance.

(In the case where the resin layer contains a dielectric (dielectric filler))

The above resin layer may contain a dielectric (dielectric filler).

In the case where a dielectric (dielectric filler) is contained in any of the above resin layers or resin compositions, it can be used for the purpose of forming a capacitor layer, and the capacitance of the capacitor circuit is increased. The dielectric (dielectric filler) is BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), PbLaTiO ₃ -PbLaZrO (commonly known as PLZT), and SrBi ₂ Ta ₂ O ₉ (commonly known as SBT). A dielectric powder having a composite oxide having a perovskite structure.

The dielectric (dielectric filler) can be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder property of the dielectric (dielectric filler) is preferably from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0. The range of μm. Furthermore, the following length is set as the dielectric The diameter of the bulk particle, which is the length of the dielectric particle when the dielectric is imaged by a scanning electron microscope (SEM) and the line is drawn on the dielectric particles on the photo. The length of the dielectric particles of the longest part. Further, the average value of the diameters of the dielectric particles in the measurement field of view is defined as the particle diameter of the dielectric.

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 methyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl stilbene, N-methyl-2-pyrrolidine A resin liquid (resin varnish) is prepared in a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and is applied to the resin liquid (resin varnish) by, for example, a roll coating method. The surface of the surface-treated copper foil is subjected to a roughening treatment surface, and then heated and dried as necessary to remove the solvent to be in a B-stage state. The drying system may be, for example, a hot air drying oven, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The solvent is used to dissolve the composition of the above resin layer to obtain a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Resin solution. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution 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-cured resin film having a resin flow rate of 5% to 35% in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the amount of resin flow refers to four 10 cm square samples taken from a resin-coated surface-treated copper foil having a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard. In the state in which the sheet samples were stacked (layered body), the bonding was carried out under the conditions of a pressurization temperature of 171 ° C, a pressurization pressure of 14 kgf/cm ² , and a pressurization time of 10 minutes, and the result of measuring the resin outflow weight at this time was obtained. , the value calculated based on the number 1.

[Number 1]

The surface-treated copper foil (resin-treated copper foil with resin) provided with the above resin layer is used in such a manner that the resin layer is superposed on the substrate and then thermally bonded to the entire resin layer, and then the resin layer is thermally cured. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the carrier is peeled off to expose an extremely thin copper layer (of course, the surface of the intermediate layer side of the extremely thin copper layer is exposed), and the surface treatment is performed. The surface of the copper foil on the side opposite to the roughened side forms a predetermined wiring pattern.

When the surface-treated copper foil with a resin is used, the number of sheets of the prepreg used in the production of the multilayer printed wiring board can be reduced. Further, a copper clad laminate can be produced by making the thickness of the resin layer such that the thickness of the interlayer insulation can be ensured or that the prepreg material is not used at all. Further, at this time, the insulating resin is applied to the surface of the substrate, and the smoothness of the surface can be further improved.

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: only the prepreg material is manufactured. The thickness of the multilayer printed wiring board of the thickness is reduced, and it is possible to manufacture a very 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, the resin-treated surface-treated copper foil is laminated on the substrate having the inner layer material without inserting the prepreg material without lowering the adhesion. At this time, it is difficult to ensure interlayer insulation between the circuits of the inner layer material. On the other hand, when the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one coating step, and an unnecessary material cost and number of steps are required, which is economically disadvantageous. .

Further, when the surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm. 5 μm, more preferably 1 μm to 5 μm, is preferable because the thickness of the multilayer printed wiring board can be reduced.

Hereinafter, an example of a manufacturing procedure of a plurality of printed wiring boards using the copper foil with a carrier of the present invention will be described.

An embodiment of the method for producing a printed wiring board of the present invention comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate; After the side of the insulating substrate is opposed to the insulating substrate, the copper foil and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then the semi-additive method is modified. The step of forming a circuit by any of the semi-additive method, the partial addition method, and the subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

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, an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and peeling off the carrier by etching or plasma using an etching solution such as acid; a step of completely removing the thin copper layer; a step of providing a perforation or/and a blind via on the resin exposed by removing the ultra-thin copper layer by etching; and removing the region including the perforation or/and the blind via a step of treating the resin; and the step of providing an electroless plating layer on the resin and the region including the perforation or/and the blind hole; and providing a plating resist on the electroless plating layer; and performing the plating resist Exposure, followed by the step of removing the plating resist in the region where the circuit is formed; and the step of providing the electrolytic plating layer in the region where the above-mentioned circuit is formed by removing the plating resist Removing the plating resist of step; and removing the formed quickly by the steps of etching the electroless plated layer area other than the area of the circuit.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method 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 After laminating the copper foil with the carrier and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the carrier is peeled off by etching or plasma using an etching solution such as acid. a step of completely removing the copper layer; a step of providing an electroless plating layer on 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; a step of exposing the resist, and then removing the plating resist in the region where the circuit is formed; removing the plating resist to form an electrolytic plating layer in the region where the circuit is formed; and removing the plating resist And a step of removing the electroless plating layer and the ultra-thin copper layer in a region other than the region in which the circuit is formed by rapid etching or the like.

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 of the circuit forming portion by electrolytic plating to remove the resistance. A method of forming a circuit on an insulating layer by using a (flash) etching to remove a metal foil other than the above-described circuit forming portion.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a modified semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil and laminating the carrier with the carrier copper foil; a step of performing desmear treatment on the region including the perforation or/and the blind hole; a step of providing an electroless plating layer on the region including the perforation or/and the blind hole; and exposing the carrier a step of plating a resist on the surface of the thin copper layer; a step of forming a circuit by electrolytic plating after the plating resist is disposed; a step of removing the plating resist; and removing the plating by using rapid etching removal A step of exposing a very thin copper layer exposed by a resist.

Further, in the step of forming a circuit on the resin layer, another carrier copper foil may be attached to the resin layer from the side of the ultra-thin copper layer, and the circuit may be formed by using a copper foil with a carrier attached to the resin layer. step. Further, another copper foil with a carrier adhered to the above resin layer may be the copper foil with a carrier of the present invention. Further, the step of forming a circuit on the resin layer may be carried out by any one of a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Further, the copper foil with a carrier on which the circuit is formed on the surface may have a substrate or a resin layer on the surface of the carrier of the copper foil with the carrier.

Another embodiment of the method for producing a printed wiring board of the present invention using a modified semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and a step of providing a plating resist on the ultra-thin copper layer exposed by peeling the carrier; a step of exposing the plating resist, and then removing the plating resist in the region where the circuit is formed; removing the plating resist to form an electrolytic plating layer in the region where the circuit is formed; removing the plating resistance The step of removing the electroless plating layer and the ultra-thin copper layer in the region other than the region in which the above-mentioned circuit is formed by rapid etching or the like.

In the present invention, the partial addition method refers to providing a catalyst core on a substrate provided with a conductor layer and passing through a hole for a through hole or a via hole as needed, and etching to form a conductor circuit, as needed. After the solder resist or the plating resist is provided, a method of manufacturing a printed wiring board by thickening a via hole or a via hole by electroless plating treatment on the above conductor circuit.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a partial addition method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and providing a step of perforating or/and blinding holes on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier ; pairs containing the above perforations or / And a step of removing the slag treatment in the region of the blind hole; a step of applying a catalyst core to the region including the above-mentioned perforation or/and the blind hole; and a step of providing an etch resist on the surface of the extremely thin copper layer exposed by peeling the carrier a step of exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the catalyst core by etching or plasma using an etching solution such as an acid to form a circuit; removing the etching a step of providing a solder resist or a plating resist by removing the surface of the insulating substrate by exposing the ultra-thin copper layer and the catalyst core by etching or plasma using an etching solution such as an acid or the like And a step of providing an electroless plating layer in a region where the above-mentioned solder resist or plating resist is not provided.

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

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using the subtractive method 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 After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer exposed on the carrier is peeled off and the insulating substrate is provided with a perforation or/and a blind hole. a step of performing desmear treatment on the region including the perforation or/and the blind hole; a step of providing an electroless plating layer on the region including the perforation or/and the blind hole; and disposing electrolysis on the surface of the electroless plating layer a step of plating; 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 by using an etching solution having an acid or the like a step of removing the above-mentioned ultra-thin copper layer and the electroless plating layer and the electrolytic plating layer by a plasma or the like to form a circuit; and removing the etching resist.

Another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method 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 carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the carrier is peeled off to be extremely thin a step of providing a pair of perforations or/and blind holes on the copper layer and the insulating substrate; and performing a desmear treatment on the region including the perforation or/and the blind holes; and setting the region including the perforation or/and the blind holes a step of forming an electroless plating layer; a step of forming a mask on the surface of the electroless plating layer; a step of providing an electrolytic plating layer on a surface of the electroless plating layer not having a mask; and the electroplating layer or/and the ultrathin copper layer a step of providing an etch resist on the surface; a step of exposing the etch resist to form a circuit pattern; and removing the ultra-thin copper layer and the electroless plating layer by etching or plasma using an etching solution such as acid a step of the circuit; and a step of removing the above etch resist.

The step of arranging the perforations or/and blind holes, and the subsequent desmearing step may also be omitted.

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 with reference to the drawings. Here, the copper foil with a carrier having an ultra-thin copper layer in which a roughened layer is formed is exemplified, but the invention is not limited thereto, and an ultrathin copper layer having a roughened layer is not used. The carrier copper foil can also be similarly produced in the following method for producing a printed wiring board.

First, as shown in Fig. 5-A, a carrier-attached copper foil (first layer) having a very thin copper layer on which a roughened layer is formed is prepared.

Next, as shown in FIG. 5-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a predetermined shape.

Then, as shown in FIG. 5-C, after the plating for forming the circuit, the resist is removed, thereby forming a circuit coating of a predetermined shape.

Then, as shown in FIG. 6-D, a resin layer is embedded on the ultra-thin copper layer by coating the circuit layer (in the form of a buried circuit plating layer), and then the resin layer is laminated on the side of the ultra-thin copper layer. Carrier copper foil (layer 2).

Then, as shown in Fig. 6-E, the carrier was peeled off from the second layer of the carrier-attached copper foil.

Then, as shown in FIG. 6-F, a laser opening is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind hole.

Then, as shown in FIG. 7-G, a via fill of buried copper is formed in the blind via.

Then, as shown in FIG. 7-H, a circuit plating layer is formed on the via fill in the manner of FIGS. 5-B and 5-C described above.

Then, as shown in Fig. 7-I, the carrier was peeled off from the first layer of the carrier-attached copper foil.

Then, as shown in FIG. 8-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.

Then, as shown in FIG. 8-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier copper foil (second layer) may be a copper foil with a carrier of the present invention, and a conventional copper foil with a carrier may be used, and a usual copper foil may be used. Further, a layer 1 or a plurality of layers may be further formed on the second layer circuit shown in FIG. 7-H, and may be a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. A method forms the circuits.

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 case of the surface-treated copper foil of the present invention, the "roughening treatment surface" refers to a case where a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like after the roughening treatment. The surface of the surface treated copper foil (very thin copper layer) 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 "roughening treatment surface" means to provide 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. (1) The color difference of the surface of the ultra-thin copper layer is based on the color difference △E of JISZ8730 * ab is 45 or more.

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is used, and a comprehensive index expressed by the L*a*b color system based on JISZ8730 is used. And expressed as ΔL: white black, Δa: red green, △ b: yellow blue. Further, ΔE* ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, lowering the concentration of copper in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by performing a roughening treatment on the surface of the ultra-thin copper layer and providing a roughened layer. When the roughening treatment layer is provided, the current density (for example, 40 to 60 A) can be further increased by using an electrolyte containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. /dm ² ), shorten the processing time (for example, 0.1 to 1.3 seconds) and adjust. When the roughened layer is not provided on the surface of the ultra-thin copper layer, it can be used in a very thin copper layer or a heat-resistant layer or a rust-proof layer or chromium by using a plating bath in which the concentration of Ni is twice or more of other elements. The surface of the acid salt treatment layer or the decane coupling treatment layer is set to be lower than the previous one for Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating). This is achieved by processing the current density (0.1 to 1.3 A/dm ² ) and increasing the processing time (20 seconds to 40 seconds).

If the color difference of the surface of the ultra-thin copper layer is based on JISZ8730, the color difference ΔE* ab is 45 or more, the contrast between the ultra-thin copper layer and the circuit is clear when the circuit is formed on the surface of the extremely thin copper layer with the carrier copper foil, and the result is recognized. The performance is good, and the positional alignment of the circuit can be performed with high precision. The color difference ΔE* ab based on JIS Z8730 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, the printed wiring board as described above For example, in the manufacturing steps shown in FIG. 5-C, the circuit plating layer can be formed accurately at a predetermined position. Further, according to the method for manufacturing a printed wiring board as described above, the circuit layer is embedded in the resin layer. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in, for example, FIG. 8-J, the resin layer is protected. The circuit is plated and maintained in shape, whereby it is easy to form a fine circuit. Moreover, in order to protect the circuit plating layer by the resin layer, the electron mobility resistance is improved, and the wiring of the circuit is favorably suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIGS. 8-J and 8-K, the exposed surface of the circuit plating layer is formed into a shape recessed from the resin layer, so that it is easy to form a convex on the circuit plating layer, respectively. The block, which in turn forms a copper pillar thereon, improves manufacturing efficiency.

Further, a well-known resin or prepreg can be used as the resin (Resin). For example, BT (Bismaleimide III) can be used. A resin or a glass cloth impregnated with BT resin, that is, a prepreg, ABF film or ABF manufactured by Ajinomoto Fine-Techno. 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 in the first layer may have a substrate or a resin layer on the surface of the copper foil with the carrier. The copper foil with a carrier used in the first layer of the substrate or the resin layer is supported, and wrinkles are less likely to be formed, so that productivity is improved. Further, the substrate or the resin layer may use all of the substrate or the resin layer as long as it exhibits the effect of supporting the copper foil with a carrier used in the first layer. As the substrate or the resin layer, for example, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, an inorganic compound foil, or an organic compound described in the present specification can be used. Compound plate, organic compound foil.

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 characteristics applicable to a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber cloth substrate epoxy resin can be used for the rigid PWB. , glass cloth-paper composite substrate epoxy resin, glass cloth - Glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc. For FPC, polyester film or polyimide film, liquid crystal polymer (LCP) film, Teflon (registered trademark) film, fluororesin can be used. Membrane and the like. Further, in the case of using a liquid crystal polymer (LCP) film or a fluororesin film, 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, after the surface-treated copper foil is etched to form a copper circuit, the copper circuit is covered with a cover layer, whereby the film and the copper circuit are not easily used. Peeling prevents the film from peeling off from the copper circuit due to a decrease in peel strength.

Further, a resin having good dielectric characteristics (the dielectric loss tangent is small (for example, the dielectric loss tangent is 0.008 or less) and/or the dielectric constant is small (for example, when the signal frequency is 25 GHz, it is 3 or less) The resin) or the low dielectric resin (the resin having a smaller dielectric constant (for example, 3 or less in the case where the signal frequency is 25 GHz) has a small dielectric loss. Therefore, a copper-clad laminate, a printed wiring board, and a printed circuit board using the surface-treated copper foil of the present invention having a resin or a low dielectric resin or a low dielectric loss resin having good dielectric properties are suitable for high-frequency circuits ( The circuit for transmitting signals at high frequencies. Here, the term "low dielectric loss resin" means a resin having a dielectric loss smaller than that of the polyimine which has been conventionally used for a copper clad laminate. Further, the surface-treated copper foil of the present invention has a small surface roughness Rz and a high gloss, so that the surface is smooth and suitable for high-frequency circuit applications. Examples of the resin having a good dielectric property or a low dielectric resin or a low dielectric loss resin include a liquid crystal polymer (LCP) film or a fluororesin film.

Further, the surface-treated copper foil of the present invention can be preferably used for all purposes. For example, it can be used for a printed wiring board or a printed circuit board, a printed wiring board or a printed circuit board for a high-frequency circuit, a semiconductor package substrate, an electrode of a secondary battery or a capacitor, or the like.

In the case of the rigid PWB application, the method of bonding the resin to a substrate such as a glass cloth to harden the resin to a semi-hardened prepreg is prepared. The copper foil can be superposed on the side opposite to the coating layer and superposed on the prepreg, and heated and pressurized. In the case of FPC, the base of the polyimide film can be obtained under high temperature and high pressure by means of an adhesive or without an adhesive. The laminate is then applied to a copper foil, or the polyimide precursor is coated, dried, hardened, or the like to produce a laminate.

The thickness of the polyimide substrate resin is not particularly limited, and is usually 25 μm or 50 μm.

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 one-sided PWB, two-sided PWB, and multi-layer PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and soft and hard composite PWB. The electronic device of the present invention can be produced using such a printed wiring board.

Further, the printed wiring board of the present invention comprises an insulating resin substrate and a surface-treated copper foil which is formed by laminating a surface of the surface-treated surface and an insulating substrate and having a copper circuit, and is laminated on the surface side of the surface-treated surface. When an insulating resin substrate is photographed by a CCD camera, the brightness of each observation point is measured in an image perpendicular to the direction in which the observed copper circuit extends in an image obtained by photographing, thereby forming an observation point-luminance chart. In the graph, the difference ΔB (ΔB = Bt - Bb) between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion of the copper circuit to the portion without the copper circuit is 40 or more. When such a printed wiring board is used, the positioning of the printed wiring board can be performed more accurately. Therefore, when a printed wiring board is connected to another printed wiring board, it is considered that the connection failure is reduced and the yield is improved. Further, as a method of connecting one printed wiring board to another printed wiring board, soldering or connection via an anisotropic conductive film (ACF), via anisotropic conductive paste (Anisotropic Conductive Paste) may be used. A connection of ACP) or a known connection method via connection of a conductive adhesive.

Further, the copper clad laminate of the present invention is composed of an insulating resin substrate, a surface-treated copper foil laminated on the surface side treated with the surface of the insulating substrate, and a surface-treated copper foil of a copper clad laminate by etching. After the copper foil is treated with a linear surface, the image obtained by photographing is imaged by the CCD camera when the insulating resin substrate laminated on the surface side of the surface treatment is photographed. Observing the brightness of each observation point in the direction perpendicular to the direction in which the linear surface-treated copper foil is extended to obtain an observation point-brightness chart, in which the end portion of the copper foil is treated from the end of the linear surface to the absence of the above-mentioned line shape The difference ΔB (ΔB = Bt - Bb) between the top average value Bt and the bottom average value Bb of the luminance curve generated by the surface-treated copper foil is 40 or more. When a printed wiring board is manufactured using such a copper clad laminate, the positioning of the printed wiring board can be performed more accurately. Therefore, when a printed wiring board is connected to another printed wiring board, it is considered that the connection failure is lowered and the yield is improved. Further, as a method of connecting one printed wiring board to another printed wiring board, soldering or connection via an anisotropic conductive film (ACF) may be used, via an anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection of ACP) or connection via a conductive adhesive.

Furthermore, in the present invention, the "printed wiring board" also includes a printed wiring board on which components are mounted and a printed circuit board.

[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, an attached circuit substrate, and a resin substrate such as a polyimide which is electrically connected thereto. In an electronic device including a flexible printed circuit board having a copper wiring formed thereon, a flexible printed circuit board is accurately positioned and pressure-bonded to the wiring board of the main board and the attached circuit board. In other words, in this case, the laminated board is a laminated body which is bonded by crimping the flexible printed circuit board to the wiring end portion of the main substrate, or by using the flexible printed circuit board and the circuit board. The laminated board in which the wiring end portions are crimped and bonded to each other. 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 is a position at which the resin constituting the laminate can be imaged by a photographing means such as a CCD camera. Here, the mark refers to a mark for detecting the position or positioning or positional alignment of a laminate or a printed wiring board or the like.

In the laminate thus prepared, when the mark is imaged by a photographing means via a resin, the position of the mark can be satisfactorily detected. Further, by detecting the position of the mark as described above, 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 detected. Moreover, when a printed wiring board is used as a laminated board, the positioning means can be similarly detected by the positioning method, and the positioning of the printed wiring board can be performed more accurately.

Therefore, when a printed wiring board is connected to another printed wiring board, it is considered that the connection failure is reduced and the yield is improved. Further, as a method of connecting one printed wiring board to another printed wiring board, soldering or connection via an anisotropic conductive film (ACF) may be used, via an anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection of ACP) or connection via a conductive adhesive. Furthermore, 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 can 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 printed wiring board of the present invention can be printed with another of the present invention. The wiring board or the printed wiring board which does not correspond to the printed wiring board of this invention is connected, and the electronic device can also be manufactured using such a printed wiring board. Furthermore, 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, it is also possible to connect at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board which is not equivalent to the printed wiring board of the present invention, and further connect two The printed wiring board of the printed wiring board of the present invention is connected to a component, and a printed wiring board in which two or more printed wiring boards are connected is manufactured. Here, examples of the "parts" include electronic components such as a connector, an LCD (Liquid Cristal Display), and a glass substrate used in an LCD, and include an IC (Integrated Circuit) and an LSI (Large scale). Integrated circuit, large integrated circuit, VLSI (Very Large scale integrated circuit), ULSI (Ultra-Large Scale Integrated circuit) An electronic component (for example, an IC chip, an LSI chip, a VLSI chip, or a ULSI wafer) of a semiconductor integrated circuit, such as an integrated circuit, is used to shield components of an electronic circuit, and to fix a cover or the like to a necessary component on 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). The moving step can be moved by, for example, a conveyor such as a belt conveyor or a chain conveyor, and can be moved by a moving device having an arm mechanism, and can be moved by floating the laminated plate by using a gas. A moving device or a moving means (including a roller or a bearing) or a moving device using a hydraulic pressure as a power source by moving a device or a moving means, or moving a laminated plate by rotating a substantially cylindrical shape or the like Or moving means, moving device or moving means using air pressure as power source, moving device or moving means using motor as power source, gantry mobile linear guide stage, bracket moving air guiding The mobile device or the moving means of the platform such as the air guide stage, the stacked linear guide platform, and the linear motor drive platform are moved. Further, the moving step can be performed by a known moving means. The step of moving the laminated plate described above allows the laminated plate to be moved for alignment. Further, it is considered that when a printed wiring board is connected to another printed wiring board or component by positional alignment, 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, the laminated board of the surface-treated copper foil and the resin substrate positioned in the present invention may be a printed wiring board having a resin board and a circuit provided on the resin board. Moreover, 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, "positioning" includes "moving the marker or object to a predetermined position based on the detected position after detecting the position of the marker or the object".

[Examples]

Examples 1 to 35 and Comparative Examples 1 to 14 are prepared for various coppers described in Table 2. For the foil, one surface was subjected to a plating treatment as a roughening treatment under the conditions described in Table 1.

Further, in Examples 31 to 35, various carriers described in Table 2 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. Further, the surface of the ultra-thin copper layer was plated as a roughening treatment under the conditions described in Table 1.

. Example 31

<intermediate layer>

(1) Ni layer (Ni plating)

The carrier was plated by a roll to roll type continuous plating line under the following conditions, thereby forming a Ni layer of 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, butyl diol, 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 by (1) was washed with water and pickled, and then, on a roll-to-roll type continuous plating line, an adhesion amount of 11 μg/dm ^{2 was} treated by electrolytic chromate treatment under the following conditions. The Cr layer is attached 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, the surface of the Cr layer formed by (2) is washed with water and pickled, and then, on a roll-to-roll type continuous plating line, an extremely thin copper layer having a thickness of 1.5 μm is formed on the Cr layer by electroplating under the following conditions. On top of it, a very 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) disulfide): 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 those 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

The surface roughness of the TD of the ultra-thin copper layer surface was 0.55 μm, and the 60-degree gloss of MD was 519%.

. Example 32

<intermediate layer>

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

The carrier was plated by a roll-to-roll type continuous plating line 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) Nickel sulfate hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed using (1). An extremely thin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultra-thin copper layer was changed to 3 μm. The surface roughness of the TD of the ultra-thin copper layer surface was 0.26 μm, and the 60-degree gloss of MD was 770%.

. Examples 33, 34

<intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 31.

(2) Organic layer (organic layer formation treatment)

Next, after washing and pickling the surface of the Ni layer formed by (1), the liquid temperature of the carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L is sprayed on the surface of the Ni layer under the following conditions. The aqueous solution was dried at 40 ° C and pH 5 for 20 to 120 seconds to form an organic layer.

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed using (2). An extremely thin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultra-thin copper layer was set to 2 μm. Very thin copper layer The surface roughness of the surface TD was 0.40 μm, and the 60 degree gloss of MD was 528%.

. Example 35

<intermediate layer>

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

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

(Liquid composition) Cobalt sulfate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed using (1). An extremely thin copper layer was formed under the same conditions as in Example 31 except that the thickness of the ultra-thin copper layer was set to 8 μm. The surface roughness of the TD of the ultra-thin copper layer surface was 0.75 μm, and the 60-degree gloss of MD was 453%.

After performing the above roughening plating treatment, Examples 1 to 10, 12 to 27, 32 to 35, and Comparative Examples 3, 4, 6, and 9 to 14 were subjected to plating for forming a heat-resistant layer and a rust-proof layer. Apply treatment.

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

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

The heat-resistant layer 2 is formed on the copper foil to which the above heat-resistant layer 1 is applied. Comparative Examples 5, 7, and 8 are not advanced. The heat-resistant layer 2 is directly formed on the prepared copper foil by a roughening 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

Further, a rustproof layer is formed on the copper foil to which the heat-resistant layers 1 and 2 are applied. The formation conditions of the rustproof layer 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 to which the heat-resistant layers 1 and 2 and the rust-preventing layer are applied. The formation conditions are expressed as follows.

N-2-(aminoethyl)-3-aminopropyltrimethoxydecane as an amine-based decane coupling agent (Examples 17, 24 to 27), N-2-(aminoethyl) 3-aminopropyltriethoxydecane (Examples 1 to 16, 32 to 35), N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane (implementation) Examples 18, 28, 29, 30), 3-aminopropyltrimethoxydecane (Example 19), 3-aminopropyltriethoxydecane (Examples 20, 21), 3-triethoxy Coating based on alkyl-N-(1,3-dimethyl-butylene)propylamine (Example 22), N-phenyl-3-aminopropyltrimethoxydecane (Example 23) Drying to form a weatherable layer. Two or more of these decane coupling agents may be used in combination. Similarly, Comparative Examples 1 to 14 were coated and dried with N-2-(aminoethyl)-3-aminopropyltrimethoxydecane to form a weather resistant layer.

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

In addition to Example 35, an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metal Co., Ltd. was used for the electrolytic copper foil. In Example 35, an electrolytic copper foil JTC foil manufactured by JX Nippon Mining & Metal Co., Ltd. was used as an electrolytic copper foil. In the case of electrolytic polishing or chemical polishing, the thickness of the plate after electrolytic polishing or chemical polishing is described.

In addition, Table 2 describes the points of the steps of producing the copper foil or the carrier before the surface treatment. "High gloss rolling" means final cold rolling (cold rolling after final recrystallization annealing) at the value of the oil film equivalent described. "Normal calendering" means that the final cold rolling is performed at the value of the oil film equivalent described (the cold rolling after the final recrystallization annealing). "Chemical polishing" and "electrolytic polishing" are carried out under the following conditions.

In the "chemical polishing", H ₂ SO ₄ is 1 to 3% by mass, and H ₂ O ₂ is 0.05 to 0.15% by mass. The polishing time of the remaining portion of water is used to set the polishing time to 1 hour.

"Electrolytic polishing" is based on the conditions of 67% phosphoric acid + 10% sulfuric acid + 23% water, and the voltage is 10 V/cm ² and the time shown in Table 2 (if the electrolytic polishing is performed for 10 seconds, the polishing amount is 1 to 2 μm) get on.

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

(1) Determination of surface roughness (Rz):

Contact roughness meter Surfcorder SE-3C manufactured by Kosaka Research Institute Co., Ltd. The ten point average roughness was measured for the roughened surface in accordance with JIS B0601-1994. The measurement was carried out under the 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 conveyance speed of 0.1 mm/sec, which were perpendicular to the rolling direction (TD, perpendicular to the direction of the foil in the case of electrolytic copper foil). The position was determined 10 times and the value of 10 measurements was obtained.

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

Further, the surface roughness (Rz) of the surface of the carrier on the side of the intermediate layer and the surface of the ultra-thin copper layer was also determined in the same manner.

In addition, after 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, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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.

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

The surface area of the roughened particles is measured using a laser microscope. Using a laser microscope VK8500 manufactured by Ens Co., Ltd., the three-dimensional surface area A corresponding to an area B of 100 × 100 μm (actual data of 9982.52 μm ² ) in a magnification of 2000 times of the roughened surface was measured by the three-dimensional surface area A. The method of setting the two-dimensional surface area B = area ratio (A/B) is set.

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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 was used in the rolling direction (MD, in the case of electrolytic copper foil) The direction of the direction and the direction perpendicular to the rolling direction (TD, in the case of electrolytic copper foil, the direction perpendicular to the direction of the foil) were 60 degrees, and the roughened surface was measured.

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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 copper foil before the surface treatment was also subjected to the gloss in the same manner.

Further, the surface of the copper foil before the surface treatment on the surface to be treated, the surface on which the carrier was provided on the intermediate layer side, and the surface of the ultra-thin copper layer were also obtained in the same manner.

(4) slope of the brightness curve

The surface-treated copper foil is bonded to the surface of the roughened surface of the surface-treated copper foil to a polyimide film (the thickness of 25 μm or 50 μm manufactured by Chung Ching Co., Ltd., or 50 μm by Toray DuPont Co., Ltd.). On both sides, a copper foil was removed by etching (aqueous solution of ferric chloride) to prepare a sample film. Further, in the roughened copper foil, the roughened surface of the copper foil was bonded to the polyimide film to prepare the sample film. In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer and the rust preventive layer are subjected to the rust prevention. The surface-treated copper foil after the surface treatment such as the layer and the weather-resistant layer is bonded to both sides of the polyimide film from the surface side subjected to the surface treatment, and the surface-treated copper foil is removed by etching (aqueous solution of ferric chloride). The sample film is made. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the copper foil with a carrier is attached to both sides of the polyimide film from the roughened surface side of the ultra-thin copper layer, and thereafter the carrier After peeling, thereafter, the ultrathin copper layer was removed by etching (aqueous solution of ferric chloride) to prepare a sample film. Then, the print with the printed black mark is laid under the sample film, and the printed matter is photographed by the CCD camera through the sample film, and the image obtained by the photographing is extended along the direction of the observed linear mark. The brightness of each observation point was measured in the vertical direction to prepare an observation point-luminance chart. In the graph, ΔB and t1, t2, and Sv were measured based on the brightness curve. A schematic diagram showing a configuration of a photographing apparatus used at this time and a method of measuring a luminance curve is shown in Fig. 3 .

Further, ΔB and t1, t2, and Sv were measured by the following imaging apparatus as shown in Fig. 2 .

The photographing apparatus includes a CCD camera, a platform (white) on which a polyimide substrate having a marked paper is placed, and a lighting power source for illuminating the photographing unit of the polyimide substrate, and a lower side is attached thereto. The evaluation of the mark paper of the photographic subject was carried out by a conveyor (not shown) on the platform by the polyimide substrate. The main specifications of the photographic device are expressed as follows:

. Photographic device: sheet inspection device manufactured by Nireco Co., Ltd. Mujiken

. CCD camera: 8192 pixels (160MHz), 1024 grayscale digits (10 bits)

. Lighting power supply: high-frequency lighting power supply (power supply unit × 2)

. Lighting: Fluorescent (30W)

Furthermore, regarding the brightness shown in FIG. 3, 0 means "black", brightness 255 means "white", and the degree of gray between black and white (white and black, grayscale) is divided into 256 Displayed in grayscale.

(5) Identification (resin transparency):

The surface of the surface-treated copper foil on the surface of the surface-treated side is bonded to both sides of a polyimide film (25 μm or 50 μm thick manufactured by Chung-Chung Co., Ltd., or 50 μm thick manufactured by Toray DuPont Co., Ltd.) by etching ( The copper foil was removed to form a sample film. Further, in the roughened copper foil, the roughened surface of the copper foil was bonded to the polyimide film to prepare the sample film. In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer and the rust preventive layer are subjected to the rust prevention. The surface-treated copper foil after the surface treatment such as the layer and the weather-resistant layer is bonded to both sides of the polyimide film from the surface side subjected to the surface treatment, and the surface-treated copper foil is removed by etching (aqueous solution of ferric chloride). The sample film is made. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the copper foil with the carrier is roughened from the ultra-thin copper layer. The side was bonded to both sides of the polyimide film, and then the carrier was peeled off, and thereafter, the ultrathin copper layer was removed by etching (aqueous solution of ferric chloride) to prepare a sample film. A printed matter (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 the resin layer. When the length of the black circle of the printed matter is more than 90% of the circumference, it is judged as "◎", and the outline of the black circle is 80% or more of the circumference and the length of less than 90% is clearly defined as "○". (The above is acceptable), and the black circle contour is evaluated as "X" (failed) in the case where the length of the circle is 0 or more and the length is less than 80%.

(6) Peel strength (follow strength):

After the surface layer of the surface-treated copper foil surface-treated side is coated with a polyimide film (25 μm or 50 μm thick manufactured by Chung Ching Co., Ltd., or 50 μm thick manufactured by Toray DuPont Co., Ltd.), according to IPC-TM -650, the normal peeling strength is measured by the tensile tester autostereoscopic plotter 100, and the normal peeling strength of 0.7 N/mm or more is used as a laminated substrate. Further, in Examples 31 to 35, the surface-treated layer of the surface-treated copper foil on the surface-treated side was coated with a polyimide film (a thickness of 25 μm or 50 μm manufactured by Zhonghua Co., Ltd., or manufactured by Toray DuPont Co., Ltd.). After the thickness was 50 μm, the carrier was peeled off, and copper plating was performed so that the thickness of the ultra-thin copper layer laminated with the polyimide film was 12 μm thick, and the peel strength was measured. In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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) Solder heat resistance evaluation:

The surface of the surface-treated copper foil on the surface-treated side was bonded to both sides of a polyimide film (25 μm or 50 μm thick manufactured by Chung Ching Co., Ltd., or 50 μm thick manufactured by Toray DuPont Co., Ltd.). Furthermore, the roughened copper foil is bonded to the roughened surface of the copper foil. The above polyimine film. The obtained two-area laminate was made into an attached test piece in accordance with JIS C6471. The prepared test piece was exposed to high temperature and high humidity of 85 ° C and 85% RH for 48 hours, and then floated in a solder bath of 300 ° C to evaluate the heat resistance of the solder. After the solder heat resistance test, in the interface between the copper foil roughening surface and the polyimide back surface of the polyimide film, the area of 5% or more of the area of the copper foil in the attached test piece was expanded to cause the interface discoloration to be evaluated as × (Failed), the case where the expansion discoloration area was less than 5% was evaluated as ○, and the case where the expansion discoloration did not occur at all was evaluated as ◎.

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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) Yield

The surface of the surface-treated copper foil on the surface of the surface-treated side is bonded to both sides of a polyimide film (25 μm or 50 μm thick manufactured by Chung Ching Co., Ltd., or 50 μm thick manufactured by Toray DuPont Co., Ltd.), and copper foil Etching (aqueous solution of ferric chloride) was carried out to prepare an FPC having a circuit width of L/S of 30 μm / 30 μm. Further, the roughened copper foil is bonded to the above-mentioned polyimide film by the roughened surface of the copper foil. Thereafter, it was attempted to detect a mark of 20 μm × 20 μm square by a CCD camera via polyimide. The case where 9 or more times can be detected in 10 times is set to "◎", the case where 7 to 8 times can be detected is set to "○", and the case where 6 times can be detected is set to "△", and The case where 5 or less times is detected is set to "X".

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was subjected to the above evaluation. 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 using etching (fine pattern characteristics)

The surface of the surface-treated copper foil on the surface of the surface-treated side is bonded to a polyimide film with a thermosetting adhesive for lamination (a thickness of 25 μm or 50 μm manufactured by Chung Ching Co., Ltd., or manufactured by Toray DuPont Co., Ltd.) Both sides of the thickness of 50 μm). In order to evaluate the fine pattern circuit formability, it is necessary to make the thickness of the copper foil the same, here based on the thickness of the 12 μm copper foil. That is, when the thickness is thicker than 12 μm, the thickness is reduced to 12 μm by electrolytic polishing. On the other hand, when the thickness is thinner than 12 μm, it is thickened to a thickness of 12 μm by a copper plating treatment. The single-sided side of the two-layered laminate obtained is printed on the shiny side of the copper foil of the laminated board by a photosensitive resist coating and exposure step, and the unnecessary portion of the copper foil is etched by the following conditions. A fine pattern circuit such as L/S = 20/20 μm is formed. Here, the circuit width is such that the bottom width of the circuit section becomes 20 μm.

(etching conditions)

Device: spray type small etching device

Spray 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, the photosensitive resist film was peeled off by immersing in an aqueous NaOH solution at 45 ° C for 1 minute.

(10) Calculation of etching factor (Ef)

Using the scanning electron microscope photograph S4700 manufactured by Hitachi High-Technologies Co., Ltd., the fine pattern circuit sample obtained above was observed 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 of the bottom of the circuit were measured. Width (Wb). The copper foil thickness (T) was set to 12 μm. The etching factor (Ef) was calculated by the following formula.

Etch factor (Ef)=(2×T)/(Wb-Wa)

Furthermore, after roughening the surface of the copper foil or not performing roughening treatment, When the surface treatment is performed by providing a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the surface of the surface-treated copper foil subjected to surface treatment such as the heat-resistant layer, the rust-preventing layer, and the weather-resistant layer is subjected to the above measurement. In the case where the surface-treated copper foil is a carrier-attached copper foil, the above-described measurement is performed on the roughened surface of the ultra-thin copper layer.

(11) Determination of transmission loss

In each sample, the surface of the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), and the characteristic impedance was changed to 50 Ω by etching. The microstrip line was formed, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. Further, in order to make the evaluation conditions as uniform as possible, after the surface-treated copper foil and the liquid crystal polymer resin were bonded together, the thickness of the copper foil was set to 18 μm. That is, when the thickness of the copper foil was thicker than 18 μm, the thickness was reduced to 18 μm by electrolytic polishing. On the other hand, in the case where the thickness is thinner than 18 μm, the thickness is increased to 18 μm by a copper plating treatment. As an evaluation of the transmission loss at a frequency of 20 GHz, 3.7 dB/10 cm is not set to ◎, 3.7 dB/10 cm or more and less than 4.1 dB/10 cm is set to ○, and 4.1 dB/10 cm or more and less than 5.0 dB/10 cm are used. Let △ be set to 5.0 dB/10 cm or more.

Further, the surface-treated copper foil having a printed wiring board or a copper clad laminate or a resin layer can be subjected to the above (1) surface roughness (Rz), on the surface of the copper circuit or the copper foil by melting and removing the resin. 2) The area ratio of the particles (A/B), (3) gloss, and (4) the slope of the brightness curve (ΔB and t1, t2, Sv) were measured.

In addition, when the surface of the copper foil is subjected to a roughening treatment or a roughening treatment, and a surface treatment is performed in order to provide a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like, the heat-resistant layer is prevented. The surface of the surface-treated copper foil after surface treatment such as a rust layer or a weather-resistant layer was 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.

The conditions and evaluations of the above tests are shown in Tables 1 to 5.

(Evaluation results)

In Examples 1 to 35, the visibility, the peel strength, the solder heat resistance evaluation, and the yield were good. Further, in Examples 1 to 35, the etching factor was large and the transmission loss was small, and both were good.

In Comparative Examples 1 to 4, 6, and 9 to 14, the value of ΔB was less than 40, and thus the recognition property was poor.

In Comparative Examples 5, 7, and 8, the visibility was excellent, but the substrate adhesion was poor. Further, in Comparative Examples 1 to 14, the solder heat resistance evaluation was poor.

Further, the surface-treated copper foils of Examples 10 to 12, 14, 32, and 35 were subjected to the above evaluation by applying an acrylic resin having a thickness of 1 μm to the roughened surface. As a result, the evaluation results were the same as those of the surface-treated copper foils of Examples 10 to 12, 14, 32, and 35.

4 shows (a) Comparative Example 1, (b) Comparative Example 3, (c) Comparative Example 5, (d) Comparative Example 6, (e) Example 1, and (f) Example 2 in the above Rz evaluation. SEM observation of the surface of the copper foil.

Claims (37)

A surface-treated copper foil obtained by roughening treatment on at least one surface thereof, and bonding the copper foil to both sides of a polyimide resin substrate, and then removing the copper foil on both sides by etching, The print having the printed linear mark is laid under the exposed polyimide substrate, and when the printed matter is photographed by the CCD camera through the polyimide substrate, the image obtained by the photograph is observed and observed. The brightness of each observation point is measured by the direction in which the linear mark extends in the direction perpendicular to the observation point-brightness chart. In the chart, the top value of the brightness curve generated from the end of the mark to the portion without the mark The difference ΔB (ΔB = Bt - Bb) between Bt and the bottom average value Bb is 40 or more. The surface-treated copper foil according to claim 1, wherein a difference between the top average Bt and the bottom average Bb of the luminance curve generated from the end portion of the mark to the portion without the mark is ΔB (ΔB=Bt -Bb) is 50 or more. The surface-treated copper foil of claim 2, wherein a difference ΔB between the top average Bt and the bottom average Bb of the brightness curve generated from the end of the mark to the portion without the mark (ΔB=Bt -Bb) is 60 or more. The surface-treated copper foil according to claim 1, wherein in the observation point-brightness chart, a value indicating a position closest to the intersection of the linear mark in the intersection of the brightness curve and Bt is set to t1, The value from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt indicates that the value of the position closest to the intersection of the linear mark in the intersection of the brightness curve and 0.1 ΔB is set to t2, at this time, The Sv defined by the formula (1) is 3.5 or more, and Sv = (ΔB × 0.1) / (t1 - t2) (1). The surface treated copper foil of claim 2 or 3, wherein in the observation point-brightness graph, the intersection point of the brightness curve and Bt is closest to the intersection of the linear marks. The value of the position is set to t1, and the value from the intersection of the brightness curve and Bt to the depth of 0.1 ΔB based on Bt represents the value of the position of the intersection of the brightness curve and 0.1 ΔB closest to the intersection of the linear marks. In the case of t2, the Sv defined by the following formula (1) is 3.5 or more, and Sv = (ΔB × 0.1) / (t1 - t2) (1). The surface-treated copper foil according to claim 4, wherein the Sv defined by the formula (1) in the luminance curve is 3.9 or more. The surface-treated copper foil according to claim 5, wherein the Sv defined by the formula (1) in the luminance curve is 3.9 or more. The surface-treated copper foil according to claim 6, wherein the Sv defined by the formula (1) in the luminance curve is 5.0 or more. The surface-treated copper foil according to claim 7, wherein the Sv defined by the formula (1) in the luminance curve is 5.0 or more. The surface-treated copper foil according to any one of claims 1 to 4, wherein the MD of the roughened surface has a gloss of 60 to 350%, and the surface area of the roughened particle is A. The ratio A/B of the area B obtained when the roughened particles are viewed from the surface side of the copper foil is 1.90 to 2.40. The surface treated copper foil of claim 10, wherein the MD has a 60 degree gloss of 90 to 250%. The surface treated copper foil of claim 10, wherein the A/B is 2.00 to 2.20. The surface treated copper foil of claim 10, 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 0.80~1.40. The surface treated copper foil of claim 13 wherein 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)) / (60 degree gloss of TD)) is 0.90~1.35. 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 15, wherein the resin layer comprises a dielectric. A copper foil with a carrier, which has a carrier, an intermediate layer, and an ultra-thin copper layer in this order, and the ultra-thin copper layer is the surface-treated copper foil according to any one of claims 1 to 16. A laminated board comprising a surface-treated copper foil according to any one of claims 1 to 16 and a resin substrate. A laminated board comprising a carrier copper foil of the 17th article of the patent application and a resin substrate. A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 16. A printed wiring board using the carrier copper foil of claim 17 of the patent application. A printed wiring board comprising an insulating resin substrate and a surface-treated copper foil laminated on the surface of the surface-treated surface and having a copper circuit formed thereon, the insulating layer being laminated on the surface side of the surface-treated surface When the copper substrate is photographed by a CCD camera on a resin substrate, the brightness of each observation point is measured in an image perpendicular to the direction in which the copper circuit is observed in the image obtained by the photographing, thereby forming an observation point-luminance chart. In the graph, the difference ΔB (ΔB = Bt - Bb) between the top average value Bt and the bottom average value Bb of the luminance curve generated from the end portion of the copper circuit to the portion without the copper circuit is 40 or more. A copper-clad laminate comprising an insulating resin substrate and a surface-treated copper foil laminated on the surface of the surface of the surface of the surface-treated copper substrate, and the surface-treated copper foil of the copper-clad laminate is formed into a wire by etching Surface treated copper foil Thereafter, when the insulating resin substrate laminated on the surface side of the surface treatment is photographed by a CCD camera, the image obtained by the photographing is perpendicular to the direction in which the linear surface-treated copper foil is observed to be observed. The direction is measured for the brightness of each observation point to form an observation point-brightness chart, in which the top of the brightness curve generated from the end of the linear surface-treated copper foil to the portion without the linear surface-treated copper foil is averaged The difference ΔB (ΔB = Bt - Bb) between the value Bt and the bottom average value Bb is 40 or more. A printed wiring board using the copper clad laminate of claim 23 of the patent application. A method of manufacturing a printed wiring board, which is manufactured by connecting two or more printed wiring boards of claim 20, 21, 22 or 24 to a printed wiring board of claim 20, 21, 22 or 24. A printed wiring board with two or more printed wiring boards connected. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least one printed wiring board of claim 20, 21, 22 or 24, and another patent application section 20, 21 The printed wiring board of item 22 or 24 or the step of connecting the printed wiring board of the printed wiring board of claim 20, 21, 22 or 24. An electronic device using one or more printed wiring boards to which at least one printed wiring board manufactured by the method of claim 25, or printing of the patent application No. 20, 21, 22 or 24 Wiring board. A method of manufacturing a printed wiring board comprising at least a step of connecting a printed wiring board having at least one printed wiring board produced by the method of claim 25 to a component. A method of manufacturing a printed wiring board comprising at least the step of connecting a printed wiring board of claim 20, 21, 22 or 24 to a component. A method of manufacturing a printed wiring board, which at least includes connecting at least one application The procedure for connecting the printed wiring board of the printed wiring board manufactured by the method of the twenty-fifth patent, and connecting the parts. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least: a printed wiring board of at least one of claims 20, 21, 22 or 24, and another patent application scope The step of manufacturing the printed wiring board (P1) by the printed wiring board of item 20, 21, 22 or 24 or the printed wiring board of the printed wiring board of claim 20, 21, 22 or 24, And a step of connecting the printed wiring board (P1) to the component. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least: connecting a printed wiring board of claim 20, 21, 22 or 24 to a component to manufacture a printed wiring board (P2) And the printed wiring board (P2), and the printed wiring board of claim 20, 21, 22 or 24 or the printed wiring board which is not equivalent to the scope of claim 20, 21, 22 or 24. The step of connecting the printed wiring board. A method of manufacturing a printed wiring board to which two or more printed wiring boards are connected, comprising at least a printed wiring board which is not equivalent to a printed wiring board of claim 20, 21, 22 or 24; A step of manufacturing a printed wiring board (P3), and a step of connecting the printed wiring board (P3) to a printed wiring board of claim 20, 21, 22 or 24. A method of manufacturing a printed wiring board comprising at least a step of connecting a printed wiring board having a printed wiring board of claim 20, 21, 22 or 24 to a component. A method of manufacturing a printed wiring board, comprising at least: A printed wiring board having a printed wiring board of claim 20, 21, 22 or 24, and a printed wiring board having a printed wiring board of claim 20, 21, 22 or 24 or not patented The step of connecting the printed wiring boards of the printed wiring board of the 20th, 21st, 22nd or 24th. A method for manufacturing a printed wiring board, comprising: preparing a step of attaching a carrier copper foil and an insulating substrate according to claim 17 of the patent application, stacking the copper foil with the insulating substrate, and insulating the copper foil with the carrier After the substrate is laminated, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and thereafter, by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method A method of forming a circuit. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the carrier copper foil of claim 17 in the patent application, in which the circuit is buried in the copper foil of the carrier a step of forming a resin layer on the side surface of the ultra-thin copper layer, a step of forming a circuit on the resin layer, a step of peeling off the carrier after forming a circuit on the resin layer, and removing the ultra-thin copper layer after peeling off the carrier, Thereby, the step of burying the circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.