KR20150040235A - Surface-treated rolled copper foil, laminate, printed wiring board, electronic device, and method of manufacturing printed wiring board - Google Patents

Abstract

The present invention provides a surface-treated rolled copper foil that attaches well to resin with excellent etching capacity and flexibility and a superior transparency of resin after the cooper foil is removed by etching. The surface-treated rolled copper foil has the surface of at least one side and/or the surface of both sides that satisfies 2.5 <= I{110}/I{112} <= 6.0, and the surface treatment is done on the surface of at least one side and/or the surface on both sides. Also, in the surface-treated rolled copper foil and a copper clad laminate made by laminating a polyimide with the below ΔB (PI) before attaching to the copper foil of 50 or higher and 65 or lower, the chrominance (ΔE*ab) based on JIS Z 8730 on the surface beyond the polyimide becomes 50 or higher. The Sv defined by the below Formula (1) of the surface-treated rolled copper foil becomes 3.0 or higher when, after it is bound to both sides of polyimide resin substrate from the surface side where surface treatment is done, the rolled copper foil on both sides is removed by etching, a printed matter is placed at the bottom of the polyimide substrate, and a photo is taken by a CCD camera beyond the polyimide substrate. Formula (1): Sv = (ΔB × 0.1)/(t1 - t2).

Description

TECHNICAL FIELD [0001] The present invention relates to a surface-treated rolled copper foil, a surface-treated rolled copper foil, a laminated board, a printed wiring board, an electronic apparatus and a manufacturing method of a printed wiring board.

The present invention relates to a surface-treated rolled copper foil, a laminated board, a printed wiring board, an electronic apparatus and a method for producing a printed wiring board.

As the FPC (Flexible Printed Substrate), a copper foil composite formed by laminating a copper foil and a resin layer is used, and this copper foil is required to have etching property in forming a circuit and flexibility in consideration of the use of an FPC.

The FPC is generally used in a state in which the copper foil is recrystallized. It is known that when the copper foil is rolled, the crystal rotates to form the rolled aggregate structure, and the rolling aggregate structure of the pure copper becomes the {112} < 111 > Then, the rolled copper foil is annealed after rolling or recrystallized when heat is applied in the process until the final product is processed, in other words, until the FPC is obtained. The recrystallized structure after being rolled copper foil is referred to simply as &quot; recrystallized structure &quot; hereinafter, and the rolled structure before heat is applied is simply referred to as &quot; rolled structure &quot;. Further, the recrystallized structure is largely influenced by the rolled structure, and the recrystallized structure can be controlled by controlling the rolled structure.

In this respect, a technique has been proposed in which the orientation of the {001} < 100 > Cube after the recrystallization of the rolled copper foil is developed to improve the bendability (for example, Patent Documents 1 and 2).

In addition, as the miniaturization of electronic devices such as smart phones and tablet PCs is becoming more sophisticated, signal transmission speeds have been increasing, and impedance matching has become an important factor in FPCs. As a measure for impedance matching with an increase in the signal capacity, a post-layering (thickening) of a resin insulating layer (for example, polyimide) as a base of the FPC is progressing. In accordance with the demand for higher density of wirings, the FPC has been further layered. On the other hand, the FPC is subjected to processing such as bonding to a liquid crystal substrate or mounting of an IC chip. In this case, alignment is performed by passing the resin insulating layer remaining after etching the copper foil on the laminate of the copper foil and the resin insulating layer, The visibility of the resin insulating layer becomes important.

As such a technique, for example, in Patent Document 3, a polyimide film and a low-roughness copper foil are laminated, and the light transmittance at a wavelength of 600 nm of the film after the copper foil etching is 40% or more, ) Is 30% or less, and the adhesive strength is 500 N / m or more.

Patent Document 4 discloses a chip on film having an insulating layer in which a conductor layer is laminated by an electrolytic copper foil and having a light transmittance of an insulating layer in an etching region when a circuit is formed by etching the conductor layer, (COF), wherein the electrolytic copper foil is provided with a rust-preventive treatment layer made of a nickel-zinc alloy on a bonding surface to be bonded to an insulating layer, and a surface roughness Rz of the bonding surface is 0.05 to 1.5 탆 And a mirror polish degree at an incident angle of 60 DEG of not less than 250. The present invention relates to a flexible printed wiring board for COF.

Patent Document 5 discloses a method of treating a copper foil for a printed circuit, which comprises the steps of forming a cobalt-nickel alloy plating layer on the surface of a copper foil after roughening by copper-cobalt-nickel alloy plating, An alloy plating layer is formed on the surface of the copper foil.

Japanese Patent Publication No. 3856616 Japanese Patent Publication No. 4716520 Japanese Patent Application Laid-Open No. 2004-98659 WO2003 / 096776 Japanese Patent Publication No. 2849059

However, in the case of developing the Cube orientation of the copper foil as in Patent Documents 1 and 2, if the degree is too large, there is a problem that the etching property is lowered. This is considered to be because, even if the Cube set texture is developed, not the single crystal but the mixed crystal where the other crystal is present in the crystal grain having a large Cube orientation is present, and the etching rate varies in each orientation grain. In particular, as the L / S (line / space) width of the circuit becomes narrower (the finer the pitch), the etching property becomes a problem. In addition, if the orientation of the cube is excessively developed, the copper foil becomes excessively flexible, and the handling property may be inferior.

In addition, there is a method to control the rolling structure after recrystallization in the final rolling to adjust the development degree of the Cube bearing. However, there is a possibility that the Cube bearing is not developed or excessively developed and the development degree of the Cube bearing can not be sufficiently adjusted there is a problem.

Further, in Patent Document 3, the low-illuminance copper foil obtained by an improved treatment of the adhesiveness by an organic treatment after the blackening treatment or the plating treatment may be broken due to fatigue in applications where the copper-clad laminate is required to have flexibility, Sometimes the transparency is inferior.

In Patent Document 4, the roughening treatment is not carried out, and the adhesion strength between the copper foil and the resin is low in applications other than the COF flexible printed wiring board, which is insufficient.

Further, in the treatment method described in Patent Document 5, the copper foil can be finely treated with Cu-Co-Ni, but excellent transparency can not be realized with respect to the resin after the copper foil is bonded to the resin and removed by etching.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a surface-treated rolled copper foil excellent in both etching and bending properties, good adhesion to a resin, and excellent transparency of a resin after removal of the copper foil by etching do.

The inventors of the present invention have found that as the ratio of {110} planes to the {112} planes existing on the rolling surface in the rolled structure increases, the rolled aggregate structure of the copper foil develops and the Cube orientation develops during the recrystallization annealing I found out. Thus, in order to appropriately adjust the degree of development of the cube orientation which improves the bendability but deteriorates the etching property, the ratio of development of the {112} plane and the {110} plane on the rolled surface of the copper foil is controlled, In the same way. Further, a printed copper foil whose surface chromaticity is controlled to a predetermined range by surface treatment is placed on a polyimide substrate from which the printed copper foil has been bonded (adhered) from the treated surface side, and a printed material to which the mark is affixed is placed under the polyimide It is preferable to control the inclination of the lightness curve by focusing on the slope of the lightness curve near the mark end portion drawn in the observation point-lightness graph obtained from the image of the mark portion photographed by the CCD camera over the substrate, It has been found that the resin transparency after the removal of the copper foil is affected by the kind of the substrate resin film and the thickness of the substrate resin film.

In one aspect of the present invention, which is completed on the basis of the above findings, the surface of the one copper foil and / or the copper foil on both sides is the surface treatment surface (S), and one or both of the surface treatment surface When the calculated X-ray diffraction intensity from the {112} plane and the calculated X-ray diffraction intensity from the {110} plane of the surface other than the surface-treated surface S are I {110} ,

2.5? I {110} / I {112}? 6.0

Lt; / RTI &gt;

Treated copper foil and a polyimide having a? B (PI) of not less than 50 and not more than 65 before being adhered to the copper foil are laminated from the surface-treated surface (S) side of the surface-treated rolled copper foil, A surface-treated rolled copper foil having a color difference (? E * ab) based on JIS Z 8730 on the surface of polyimide exceeding 50,

The surface-treated, rolled copper foil is applied to both surfaces of the polyimide resin substrate from the surface-treated surface (S) side, and then the rolled copper foil on both sides is removed by etching,

When a printed matter on which a mark on a line is printed is laid under the exposed polyimide substrate and the printed matter is photographed with a CCD camera beyond the polyimide substrate,

In an observation point-brightness graph produced by measuring the brightness of each observation point along a direction perpendicular to the direction in which the mark on the line is observed, with respect to the image obtained by the photographing,

The difference between the top average value Bt and the bottom average value Bb of the brightness curve occurring from the end of the mark to the portion where the mark is not drawn is defined as? B (? B = Bt - Bb) A value indicating the position of an intersection closest to the mark on the line among the intersections of the brightness curve and Bt is t1 and the brightness curve is 0.1 And a value indicating a position of an intersection point closest to the mark on the line among the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections.

Sv = (DELTA Bx0.1) / (t1 - t2) (1)

In the surface-treated rolled copper foil of the present invention, the surface of the one copper foil is the surface-treated surface (S), and the surface of the other copper foil is surface-treated.

In another embodiment of the surface treated rolled copper foil of the present invention, the rolled copper foil is formed of at least 99.9% by mass of copper.

In the surface treated rolled copper foil of the present invention, the total amount of one or more selected from the group consisting of Ag, Sn, Mg, In, B, Ti, Zr and Au is 10 to 300 mass ppm And the balance Cu and inevitable impurities.

In another embodiment of the surface treated rolled copper foil of the present invention, the rolled copper foil contains 2 to 50 mass ppm of oxygen.

In the surface treated rolled copper foil of the present invention, I {112} / I {100}? 1.0 is satisfied on at least one surface after heating at 200 占 폚 for 30 minutes in another embodiment.

In the surface treated rolled copper foil of the present invention, the X-ray diffraction intensity at the {200} plane of the rolled copper foil of the rolled copper foil is I {200} after heating at 350 DEG C for 1 second, When the X-ray diffraction intensity of the {200} plane of the sample is I ₀ {200}

5.0? I {200} / I ₀ {200}? 27.0.

The surface-treated rolled copper foil of the present invention has a thickness of 4 to 100 mu m in another embodiment.

In the surface-treated rolled copper foil of the present invention, it is preferable that the surface-treated rolled copper foil of the present invention further comprises a copper foil having a surface of the copper foil other than the surface-treated surface S and / The 10-point average roughness (Rz) of TD is 0.35 탆 or more.

In the surface-treated rolled copper foil of the present invention, it is preferable that the surface-treated rolled copper foil of the present invention further comprises a copper foil having a surface of the copper foil other than the surface-treated surface S and / The arithmetic average roughness (Ra) of TD is 0.05 탆 or more.

In the surface-treated rolled copper foil of the present invention, it is preferable that the surface-treated rolled copper foil of the present invention further comprises a copper foil having a surface of the copper foil other than the surface-treated surface S and / Square root mean square height (Rq) of TD is 0.08 탆 or more.

In another aspect, the present invention is a laminated board produced by laminating a surface treated rolled copper foil of the present invention and a resin substrate.

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

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

According to another aspect of the present invention, there is provided a method for manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards of the present invention.

According to another aspect of the present invention, there is provided a printed wiring board comprising at least one printed wiring board of the present invention, and a step of connecting a printed wiring board of the present invention or a printed wiring board not corresponding to the other one of the present invention, Thereby manufacturing two or more connected printed wiring boards.

According to another aspect of the present invention, there is provided an electronic device using at least one printed wiring board to which at least one printed wiring board of the present invention is connected.

According to still another aspect of the present invention, there is provided a method for manufacturing a printed wiring board including at least a printed wiring board manufactured by the method of the present invention and a step of connecting the components.

According to still another aspect of the present invention, there is provided a process for producing a printed wiring board A by connecting at least one printed wiring board of the present invention and another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, And

A step of connecting the printed wiring board A to the component, and a step of connecting the printed wiring board A to the component.

According to another aspect of the present invention, there is provided a printed wiring board,

A printed wiring board manufactured by the method of the present invention, and

One or more printed wiring boards selected from the group consisting of a printed wiring board according to the present invention or a printed wiring board manufactured according to the method of the present invention,

A printed wiring board manufactured by the method of the present invention is connected to a printed wiring board in which two or more printed wiring boards are connected.

According to the present invention, it is possible to provide a surface treated rolled copper foil which is excellent in both etching and bending properties, is well adhered to a resin, and has excellent transparency of the resin after the copper foil is removed by etching.

Fig. 1 is a diagram schematically showing the relationship between the tensile force applied to the copper foil in the final recrystallization annealing and the amount of the added element in the copper foil for increasing the {112} plane on the rolled surface of the copper foil.
2 is an optical microscope image of the etched surface of Example 5 and Comparative Example 1, respectively.
3 is a diagram showing the correspondence between the reference image and the etching property evaluation.
4 is a schematic view for defining Bt and Bb when the mark width is about 0.3 mm.
5 is a schematic view for defining Bt and Bb when the mark width is set to about 1.3 mm.
6 is a schematic diagram defining t1 and t2 and Sv.
7 is a schematic diagram showing a configuration of a photographing apparatus and a method of measuring a tilt of a lightness curve at the time of evaluating the tilt of the lightness curve.
8 is a photograph of the appearance of the impurities used in the examples.
Fig. 9 is a photograph of the appearance of the impurities used in the embodiment. Fig.
10 is a photograph of the appearance of the impurities used in the examples.

<Composition of rolled copper foil>

The surface-treated rolled copper foil of the present invention is preferably formed of copper in an amount of 99.9 mass% or more. Examples of such a composition include oxygen-free copper specified in JIS-H 3510 (C1011) or JIS-H 3100 (C1020), or tough pitch copper specified in JIS-H 3100 (C1100). The oxygen content of the surface-treated rolled copper foil is preferably 2 to 50 mass ppm. When the oxygen content in the surface treated rolled copper foil is as small as 2 to 50 mass ppm, there is almost no copper oxide in the rolled copper foil. Therefore, when the rolled copper foil is bent, there is almost no accumulation of deformation caused by the copper oxide, so that cracks are not easily generated and the flexibility is improved. The upper limit of the oxygen content in the copper is not particularly limited, but is generally not more than 500 mass ppm, more usually not more than 320 mass ppm.

The surface treated rolled copper foil contains 10 to 300 mass ppm in total of one or more selected from the group consisting of Ag, Sn, Mg, In, B, Ti, Zr and Au in total, and the remainder Cu and inevitable impurities . When the elements of Ag, Sn, Mg, In, B, Ti, Zr and Au are added, the surface of the rolled copper foil (hereinafter also referred to as "rolled surface" , The {110} plane tends to increase in the direction of the surface of the substrate, so that the value of I {110} / I {112} described later can be easily adjusted. If the total amount of the elements is less than 10 mass ppm, the effect of developing the {110} plane on the rolled surface is small, and if it exceeds 300 mass ppm, the conductivity is lowered and the recrystallization temperature rises, It may be difficult to recrystallize while inhibiting oxidation.

<Thickness>

The thickness of the copper foil is preferably 4 to 100 占 퐉, more preferably 4 to 70 占 퐉, and still more preferably 5 to 70 占 퐉. If the thickness is less than 4 mu m, the handling property of the copper foil may be inferior. When the thickness exceeds 100 mu m, the copper foil may have inferior flexibility.

<Surface {112} and {110} of the surface of the rolled copper foil>

The presence intensity of each surface on the rolled copper foil surface calculated from the X-ray diffraction intensity of the {200}, {220}, and {111} planes is defined as the calculated X-ray diffraction intensity. When the calculated X-ray diffraction intensity of the {112} plane is I {112} and the calculated X-ray diffraction intensity from the {110} plane is I {110}, the surface- I {110} / I {112}? 6.0 on one or both sides of the surface S, or on the surface other than the surface-treated surface S. A more preferable range is 4.0? I {110} / I {112}? 5.6.

The larger the ratio of the {110} plane than the {112} planes on the rolling surface in the rolled structure, the more the rolling aggregate structure of the copper foil is developed and the Cube orientation develops during the recrystallization annealing. As a result, the degree of development of the Cube orientation which improves the bendability but deteriorates the etching property is appropriately adjusted to control the rate at which the {112} plane and the {110} plane are developed on the rolled surface of the copper foil, The flexibility can be improved together. That is, when I {110} / I {112} is less than 2.5, the bending property of the rolled copper foil is deteriorated, and when I {110} / I {112} exceeds 6.0, the etched property of the rolled copper foil is deteriorated.

In the surface-treated copper foil of the present invention, the surface of the one copper foil may be the surface-treated surface S and the surface of the other copper foil may be surface-treated.

Since the X-ray diffraction has a long wavelength, the diffraction intensity of the {200}, {220}, and {111} planes of the copper foil can be measured but diffraction peaks of {422} planes Do not. Therefore, the calculated X-ray diffraction of the {110} plane and the {112} plane is obtained by using the geometrical relationship of the crystal orientation from the X-ray diffraction results of {200}, {220}, and {111} Find the strength. The diffraction intensity of the {110} plane can be measured directly in the same manner as the diffraction intensity of the {220} plane. In the present invention, the calculated X-ray diffraction intensity calculated from the diffraction intensity of {200}, {220} Strength is applied.

Specifically, the values of the calculated X-ray diffraction intensity of the {110} and {112} planes are obtained as follows.

First, the positive electrode viscosity measurement is performed on the {200}, {220}, and {111} faces of the copper foil. In the positive electrode viscosity measurement method, a two-axis (?,?) Rotation mechanism is attached to a goniometer for setting a sample, and X-ray diffraction is measured while changing these angles. Then, the degree of aggregation of the {110} plane and the {112} plane is calculated by using the geometrical relationship from the X-ray diffraction positive point measurement result (the positive electrode viscosity of {200}, {220}, and {111} . This calculation can be carried out by converting to an inverse polynomial representation using commercially available software (for example, Standard ODF (manufactured by NORMS Engineering Co., Ltd.).

The aggregation diagrams of the {110} and {112} planes are obtained by first measuring the positive electrode points of the {200}, {220}, and {111} planes, 220}, and the {111} plane of the film is measured. Then, the aggregates of {200}, {220}, and {111} planes are normalized to a set of {200}, {220}, and {111} planes of the pure powdered standard sample, respectively. Then, by converting the positive electrode viscosity of the thus-standardized {200}, {220}, and {111} planes to the inverse poles by the software, the degree of aggregation (calculated X-ray diffraction intensity) of {110} .

The rolled copper foil of the present invention is usually produced by repeating several times (usually about twice) of cold rolling and annealing after hot rolling and after machining, followed by final recrystallization annealing, followed by final cold rolling. Here, the term &quot; final recrystallization annealing &quot; refers to the last annealing before final cold rolling. The recrystallized structure after the final recrystallization annealing is referred to as &quot; intermediate recrystallized structure &quot; in order to distinguish it from the above-mentioned &quot; recrystallized structure &quot; (recrystallized structure after being rolled copper foil). First, a simple method of adjusting the intermediate recrystallized structure is to change the annealing temperature. However, when the final recrystallization annealing temperature is simply increased, recrystallized grains having a random orientation are grown, and when recrystallized grains become coarse grains (width of grain size distribution of grains becomes large), the cause of surface defects such as streaks after final rolling And therefore it is difficult to appropriately control the value of I {110} / I {112}.

On the other hand, if the tensile force applied to the copper foil in the final recrystallization annealing is increased, the tensile force becomes a driving force, and the crystal grain diameter in the intermediate recrystallized structure becomes large, and the {112} If the tensile strength becomes too high, the {110} plane decreases on the rolled surface after the final rolling, so that the range of the tension may be adjusted so that the value of I {110} / I {112} is within the above range. Further, the value of the tensile force also varies depending on the temperature of the final recrystallization annealing and the amount of the above-described additive element, so that the value of the tensile force can be adjusted according to them. The term "tensile force" refers to the tensile force between the rolls at the entrance side and the exit side of the final recrystallization annealing atmosphere when the copper strip is charged into the atmosphere for performing the final recrystallization annealing. It is desirable to manage a non-dimensional value of the tension divided by the proof stress of the material at the annealing temperature, in that an appropriate value (absolute value) of the tension varies depending on the annealing temperature and the composition of the copper strip. In addition, conventionally, for the purpose of preventing deterioration of the conveying roll, etc., the value of the tension in the continuous annealing furnace is usually set in the range of 0.1 to 0.15.

Fig. 1 shows an example of adjusting the tension applied to the copper foil in the final recrystallization annealing for increasing the {112} plane on the rolled surface of the copper foil. As described above, when the tension is increased, {112} planes are increased in the rolled surface, but when the amount of the added element (Ag or the like) is increased, the {110} The ratio of the {112} plane on the rolled surface is not increased. Therefore, the area enclosed by the two lines in Fig. 1 is a preferable range.

It is preferable that the rolled copper foil is heated at 200 占 폚 for 30 minutes and then at least one surface satisfies I {112} / I {100}? 1.0. Heating at 200 占 폚 for 30 minutes simulates the heating conditions of the copper foil when the FPC is produced by the so-called casting method. If the heating-induced copper foil is completely recrystallized and the non-recrystallized region does not remain, I {112} / I {100}? 1.0 is obtained. In the case of I {112} / I {100} &gt; 1.0, the non-recrystallization remains and the bending property of the FPC may be inferior.

After the rolled copper foil was heated at 350 占 폚 for 1 second, the X-ray diffraction intensity at the {200} plane of the rolled copper foil was taken as I {200} and the X-ray diffraction intensity at the {200} I ₀ {200}? 27.0 when I ₀ {200} is satisfied. When {001} &lt; 100 &gt; orientation (cube orientation) develops after recrystallization, excellent bendability is obtained, so that the higher I {200} / I ₀ {200} is preferable. 5.0 &gt; I {200} / I ₀ {200}, the flexibility may be lowered. In particular, if the 13.0 ≤ I {200} / I 0 {200} ≤ 27.0 is more preferable. In addition, since it is industrially difficult to realize I {200} / I ₀ {200}> 27.0 in balance with other characteristics, the upper limit is set to 27.0.

<Surface treated rolled copper foil>

The copper foil used in the present invention is useful for a copper foil to be used by forming a laminate by laminating it on a resin substrate and forming a circuit by etching.

Conventionally, in order to improve the peel strength of the copper foil after lamination, the surface of the copper foil to be adhered to the resin substrate, that is, the surface of the surface treatment side, is subjected to a roughening treatment for electrodepositing the surface of the copper foil after degreasing . In the present invention, this roughening treatment can be carried out by alloy plating, particularly copper-containing alloy plating such as copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating. In the present invention, the roughening treatment can be preferably carried out by copper alloy plating. The copper alloy plating bath includes, for example, a plating bath containing at least one element other than copper and copper, more preferably a group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum Is preferably used as the plating bath. In the present invention, the coarsening treatment is an example of a surface treatment for forming the surface treatment surface S, and the coarsening treatment is made to have a higher current density than the conventional coarsening treatment, thereby shortening the coarsening treatment time. Conventional copper plating or the like may be applied as a pretreatment before conditioning, and in order to prevent electrodeposition from coming off as a post-conditioning finishing treatment, conventional copper plating may be performed.

The copper foil to be used in the present invention may be formed with a heat-resistant plating layer or a rust-preventive plating layer on the surface after the roughening treatment or the roughening treatment is omitted.

Cobalt-copper as a roughening treatment to form a surface-treated surface (S) is a nickel alloy plating, electrolytic plating coating weight by 15 ~ 40 ㎎ / dm ² of copper -100 to 3000 ㎍ / dm ² of cobalt -100 to 1500 Mu] g / dm &lt; ² &gt;. When the Co deposition amount is less than 100 / / dm ² , the heat resistance is deteriorated and the etching property is sometimes deteriorated. When Co coating weight exceeds 3000 ㎍ / dm ^2, if you take into account the influence of the magnetic, the undesirable, uneven etching occurs, there is also when the acid resistance and chemical resistance are deteriorated. If the Ni coating weight is 100 ㎍ / dm ² under a case, heat resistance is poor. On the other hand, if the Ni deposition amount exceeds 1500 / / dm ² , the etching residue may increase. Co preferred coating weight is 1000 ~ 2500 ㎍ / dm ^2, a preferred nickel coating weight is 500 ~ 1200 ㎍ / dm ^2. Here, the term "etching unevenness" means that Co remains unmelted when etching with copper chloride, and that the etching residue means that Ni remains unmelted when subjected to alkali etching with ammonium chloride.

The plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating are as follows:

Plating bath composition: Cu 10 to 20 g / l, Co 1 to 10 g / l, Ni 1 to 10 g / l

PH: 1 to 4

· Temperature: 30 ~ 50 ℃

Current density (D _k ): 30 to 45 A / dm ²

· Plating time: 0.2 ~ 1.5 seconds

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

In order to form the surface-treated surface S, a heat-resistant plating layer or a rust-preventive plating layer may be formed on the surface by omitting the roughening treatment. As such treatment, a Ni alloy plating bath such as Ni- Is an alloy plating bath containing Ni and at least one element selected from the group consisting of Zn, W, P, Co, Mo, In, Sn and Cu, , Mo, In, Sn, and Cu can be used as the plating bath. In other words, the surface-treated surface S may have a Ni alloy plating layer when omitting the roughening treatment, or may include at least one selected from the group consisting of Ni and Zn, W, P, Co, Mo, In, Sn and Cu It is more preferable to have an alloy plating layer containing at least one element selected from the group consisting of Ni, W, P, Co, Mo, In, Sn and Cu . In addition, it is necessary to lower the current density and increase the plating time in the process of forming the heat resistant plating layer and the anti-corrosive plating layer on the surface by omitting the roughening treatment.

Plating bath composition: Ni 10 to 30 g / l, W 5 to 50 mg / l

PH: 3-5

· Bath temperature: 40 ~ 50 ℃

Current density (D _k ): 0.5 to 3 A / dm ²

· Plating time: 10 ~ 30 seconds

Further, a plating treatment using a Ni plating bath can be used. In addition, it is necessary to lower the current density and increase the plating time in the process of forming the heat resistant plating layer and the anti-corrosive plating layer on the surface by omitting the roughening treatment.

· Plating bath composition: Ni 10 ~ 40 g / ℓ

PH: 1 to 4

· Bath temperature: 35 ~ 50 ℃

Current density (D _k ): 0.2 to 3 A / dm ²

· Plating time: 5 ~ 20 seconds

Further, after the roughening treatment, the adhesion amount of the cobalt is 200 ~ 3000 ㎍ / dm ² of cobalt -100 ~ 700 ㎍ / dm ² of nickel on the roughened surface - it is possible to form a nickel alloy plating layer. This treatment can be regarded as a kind of rust treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be carried out to such an extent that the bonding strength between the copper foil and the substrate is not substantially lowered. In the cobalt coating weight is less than 200 ㎍ / dm ² is heat-resistant peel strength is decreased, there is a case where the oxidation resistance and chemical resistance are deteriorated. In addition, as another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable. When the amount of cobalt adhering exceeds 3000 占 퐂 / dm ² , it is not preferable when the influence of magnetic property should be considered, etching unevenness may occur, and acid resistance and chemical resistance may be deteriorated. The preferred cobalt deposition amount is 500 to 2500 [mu] g / dm &lt; ^{2 &} gt ;. On the other hand, in the Ni coating weight is less than 100 ㎍ / dm ² is heat-resistant peel strength is reduced, there is a case where the oxidation resistance and chemical resistance deteriorates. When the nickel exceeds 1300 / / dm ² , the alkali etching property deteriorates. The preferred nickel coating weight is 200 ~ 1200 ㎍ / dm ^2.

The conditions of the cobalt-nickel alloy plating are as follows:

Plating bath composition: Co 1 to 20 g / l, Ni 1 to 20 g / l

PH: 1.5 to 3.5

· Temperature: 30 ~ 80 ℃

Current density (D _k ): 1.0 to 20.0 A / dm ²

· Plating time: 0.5 to 4 seconds

According to the invention, the cobalt-adhesion amount, in addition to the nickel alloy plating 30-2 250 ㎍ / dm ² zinc plated layer is formed. When the zinc adhesion amount is less than 30 占 퐂 / dm ² , the effect of improving the thermal deterioration rate may be lost. On the other hand, there is a case the coating weight of zinc when it is more than 250 ㎍ / dm ² in hydrochloric acid degradation rate is extremely deteriorated by. Preferably, the zinc coating weight is 30 ~ 240 ㎍ / dm ^2, and more preferably 80 ~ 220 ㎍ / dm ^2.

The conditions of the zinc plating are as follows:

· Plating bath composition: Zn 100 ~ 300 g / ℓ

PH: 3 to 4

· Temperature: 50 ~ 60 ℃

Current density (D _k ): 0.1 to 0.5 A / dm ²

· Plating time: 1 ~ 3 seconds

Alternatively, a zinc alloy plating layer such as a zinc-nickel alloy plating layer may be formed instead of the zinc plating layer, or a rust-preventive layer may be formed on the outermost surface by chromate treatment, application of a silane coupling agent or the like.

Conventionally, when the roughening treatment is applied to the surface of the copper foil, the copper foil in the aqueous solution of copper sulfate is the prior art, but copper-cobalt-nickel alloy plating or copper-nickel-phosphorus alloy plating (PI) of not less than 50 and not more than 65 before adhering to the copper foil by means of alloy plating of a color difference (JIS Z 8730) based on JIS Z 8730 on the surface of the polyimide over the copper clad laminate ? E * ab) is 50 or more.

[Surface color difference (? E * ab)]

The surface-treated, rolled copper foil of the present invention is a copper foil laminate obtained by laminating a polyimide having a? B (PI) of 50 or more and 65 or less before adhering to a copper foil from the surface- The color difference (DELTA E * ab) based on JIS Z 8730 of the surface beyond the polyimide is controlled to 50 or more. With this structure, the contrast with the back surface becomes clear, and the visibility when the copper foil is observed over the polyimide substrate is enhanced. As a result, in the case of using the copper foil for circuit formation or the like, it becomes easy to align the IC chip when mounting the IC chip through a positioning pattern which is visible through the polyimide substrate. If the color difference (DELTA E * ab) is less than 50, there is a possibility that the contrast with the back surface may not become clear. The color difference (? E * ab) is more preferably 53 or more, 55 or more, and more preferably 60 or more. The upper limit of the color difference (ΔE * ab) is not particularly limited, but is, for example, 90 or less, 88 or less, or 87 or less, or 85 or less, or 75 or less, or 70 or less.

Here, the color difference DELTA E * ab is an aggregate index measured by a colorimeter and represented by using an L * a * b colorimetric system based on JIS Z 8730 with black / white / red / green / : Monochrome,? A: redox, and? B: sulfur, represented by the following formula:

In order to improve the effect of visibility, the roughness of the TD (the direction perpendicular to the rolling direction (the width direction of the copper foil)) measured by the contact type roughness meter on the processing side surface of the copper foil before the surface treatment for forming the surface treatment surface S (10-point average roughness (Rz)) and gloss. Specifically, the surface roughness (10-point average roughness (Rz)) of TD measured by a contact type roughness meter on the surface of the treated side of the copper foil before the surface treatment is 0.20 to 0.55 μm, preferably 0.20 to 0.42 μm. Such a copper foil may be rolled by adjusting the surface roughness (arithmetic mean roughness (Ra) (JIS B 0601 1994) of the rolling roll or rolling by adjusting the oil film equivalent of the rolling oil, (10-point average roughness (Rz)) and gloss of the TD measured by a contact type roughness meter on the surface of the treated side of the copper foil before the treatment are measured by a chemical polishing such as etching or electrolytic polishing in a phosphoric acid solution. By setting the above range, the surface roughness (10-point average roughness (Rz)) and surface area of the surface-treated surface S of the copper foil after the treatment can be easily controlled.

Further, the copper foil before surface treatment to form the surface-treated surface S preferably has a 60 degree glossiness of TD of 300 to 910%, more preferably 500 to 810%, and further preferably 500 to 710% . If the 60 degree glossiness of the TD of the copper foil before the surface treatment is less than 300%, the transparency of the above-mentioned resin may become worse than that of 300% or more, and if it exceeds 910% have.

The high gloss rolling can be carried out by setting the oil film equivalent defined by the following formula to 13000 to 24000 or less.

(Yielding stress [kg / mm &lt; 2 &gt;]) of the material = {(rolling oil viscosity [cSt]) x (passing speed [mpm] + roll main speed [mpm])} }

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

In order to make the oil film equivalent to 13000 to 24000, it is possible to use a known method such as using low-viscosity rolling oil or slowing the passing speed.

The surface roughness of the rolled roll can be, for example, from 0.01 to 0.25 탆 in terms of arithmetic mean roughness (Ra) (JIS B 0601 1994). When the value of the arithmetic mean roughness Ra of the rolling roll is large, the roughness Rz of the TD of the surface of the copper foil before the surface treatment to form the surface S becomes large, The gloss tends to be lowered. When the value of the arithmetic average roughness Ra of the rolling roll is small, the roughness Rz of the TD on the surface of the copper foil before the surface treatment tends to be small and the 60 degree glossiness of the TD on the surface of the copper foil before the surface treatment tends to be high .

The chemical polishing is carried out over a long period of time by lowering the concentration by an etching solution such as sulfuric acid-hydrogen peroxide-aqueous or ammonia-hydrogen peroxide-aqueous system.

[Brightness Curve]

The surface treated rolled copper foil of the present invention is characterized in that the surface treated copper foil is adhered to both surfaces of a polyimide resin substrate from the side of the surface treatment surface (S), then the copper foils on both sides are removed by etching, When the printed material is laid under the exposed polyimide substrate and the printed matter is photographed by the CCD camera over the polyimide substrate, the mark on the line observed with respect to the image obtained by the photographing is observed along the direction perpendicular to the extending direction of the mark The difference between the top average value Bt and the bottom average value Bb of the brightness curve that occurs from the end portion of the mark to the portion where the mark is not drawn in the observation point-brightness graph produced by measuring the brightness of the mark is? B (? B = Bt - Bb), and a value indicating the position of an intersection closest to the mark on the line among the intersections of the brightness curve and Bt in the observation point-brightness graph t1 and a value indicating the position of an intersection nearest to the mark on the line among the intersection of the brightness curve and 0.1 x? B in the depth range from the intersection of the brightness curve and Bt to 0.1 x? B with respect to Bt as t2 , The Sv defined by the above formula (1) becomes 3.0 or more.

Here, the top average value Bt of the luminosity curve, the bottom average value Bb of the luminosity curve, and t1, t2, and Sv described later will be described with reference to the drawings.

Figs. 4 (a) and 4 (b) are schematic views for defining Bt and Bb when the width of the mark is about 0.3 mm. When the width of the mark is about 0.3 mm, there is a case where the lightness curve is a V-type lightness curve as shown in Fig. 4A and a lightness curve having a bottom as shown in Fig. 4B have. In any case, the "top average value (Bt) of the brightness curve" represents an average value of brightness measured at five points (10 points on both sides) at intervals of 30 μm from a position spaced by 50 μm from the end positions on both sides of the mark . On the other hand, the "bottom average value Bb of brightness curve" indicates the minimum brightness value at the tip of the V-shaped valley when the brightness curve becomes V-shape as shown in FIG. 4 (a) , And the bottom portion of Fig. 4 (b), the value of the central portion of about 0.3 mm is shown.

The width of the mark may be about 1.3 mm, 0.2 mm, 0.16 mm, and 0.1 mm. The top average value (Bt) of the lightness curve was obtained by dividing a total of 10 points from both ends by a distance of 100 占 퐉 from the end positions of both sides of the mark, 300 占 퐉 apart or 500 占 퐉 apart at intervals of 30 占 퐉 ) May be an average value of brightness when measured. Bt and Bb in the case where the width of the mark is approximately 1.3 mm are defined in Fig. 5 (a): "when the brightness curve is V-shaped" and Fig. 5 Fig. 5A and 5B, an average value of brightness when measured at five points (10 points on both sides in total) at a distance of 500 mu m from the end position on both sides of the mark at intervals of 30 mu m is defined as &quot; (Bt) &quot;

Fig. 6 shows a schematic diagram defining t1 and t2 and Sv. &Quot; t1 (pixel x 0.1) &quot; indicates an intersection closest to the line mark among intersections of the brightness curve and Bt. "T2 (pixel x 0.1)" represents an intersection closest to the line-shaped mark among the intersections of the brightness curve and 0.1 × ΔB in the depth range of 0.1 × ΔB with respect to Bt from the intersection of the brightness curve and Bt. At this time, the slope of the brightness curve represented by the line connecting t1 and t2 is defined as Sv (grayscale / pixel x 0.1) calculated by 0.1 x? B in the y axis direction and (t1 - t2) in the x axis direction . Further, one pixel on the horizontal axis corresponds to a length of 10 mu m. Sv measures both sides of the mark and employs a small value. Further, when the shape of the brightness curve is unstable and a plurality of "intersection points of the brightness curve and Bt" exist, an intersection nearest to the mark is adopted.

In the image photographed by the CCD camera, a high brightness is obtained in a portion not marked, but the brightness is reduced as soon as it reaches the end of the mark. When the visibility of the polyimide substrate is good, such a state of decrease in brightness is clearly observed. On the other hand, if the visibility of the polyimide substrate is poor, the brightness does not suddenly drop from "high" to "low" at once in the vicinity of the mark end, and the state of degradation becomes gentle and the state of decrease in brightness becomes unclear.

On the basis of this finding, the present invention is based on such a finding that, with respect to the polyimide substrate on which the surface-treated rolled copper foil of the present invention is removed by coalescence, the printed material with the mark is placed under the polyimide substrate, The inclination of the brightness curve near the mark end portion drawn in the observation point-brightness graph obtained from the image is controlled. More specifically, assuming that the difference between the top average value Bt of the brightness curve and the bottom average value Bb is DELTA B (DELTA B = Bt - Bb), in the observation point- A value indicating the position of the intersection closest to the image mark is t1 and a value indicating the position of the intersection of the brightness curve and 0.1 x? B from the intersection of the brightness curve and Bt to the depth of 0.1 x? And the value indicating the position of the intersection closest to the center of gravity is t2, the Sv defined by the above formula (1) becomes 3.0 or more. According to this structure, the discrimination power of the mark beyond the polyimide by the CCD camera can be improved without being influenced by the type and thickness of the substrate resin. Therefore, it is possible to manufacture a polyimide substrate having excellent visibility, and it is possible to improve positioning accuracy by marking when a predetermined process is performed on a polyimide substrate in an electronic substrate manufacturing process or the like, thereby improving the yield Effect is obtained. Sv is preferably not less than 3.5, preferably not less than 4.0. The upper limit of Sv is not particularly limited, but is, for example, 15 or less and 10 or less. According to such a configuration, the boundary between the mark and the non-mark portion becomes more clear, the positioning accuracy is improved, the error caused by the mark image recognition is reduced, and more precise alignment is possible.

Therefore, when the copper foil according to the embodiment of the present invention is used for a printed wiring board, it is considered that the connection defect is reduced and yield is improved when one printed wiring board is connected to another printed wiring board.

By controlling the current density and the plating time at the time of surface treatment such as formation of particles, the surface state of the surface treated surface S of the surface-treated copper foil, such as the shape and density of the particles and the surface irregularities of the surface, , Surface roughness (Rz), color difference (? E * ab) based on JIS Z 8730 of the surface beyond the polyimide, and glossiness can be controlled.

The surface-treated copper foil of the present invention is characterized in that the ten-point average roughness (Rz) of TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface S and / ) Is 0.35 탆 or more. The surface of the copper foil other than the surface-treated surface S of the surface-treated copper foil of the present invention is more preferably surface-treated. With this configuration, it is possible to further suppress the problem that the protective film is stuck to the copper foil in the lamination step with the resin substrate by further increasing the contact area between the copper foil and the protective film. The surface-treated copper foil of the present invention is characterized in that the ten-point average roughness (Rz) of TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface S and / More preferably 0.40 mu m or more, still more preferably 0.50 mu m or more, still more preferably 0.60 mu m or more, and still more preferably 0.80 mu m or more. Further, the 10-point average roughness (TD) of the surface treated surface S of the surface-treated copper foil of the present invention and / or TD measured by a laser microscope having a laser beam wavelength of 405 nm on the surface of the copper surface other than the surface- Rz) is not particularly limited, but is typically 4.0 μm or less, more typically 3.0 μm or less, more typically 2.5 μm or less, and more typically 2.0 μm or less.

The surface-treated copper foil of the present invention has an arithmetic average roughness (Ra) of TD measured by a laser microscope having a wavelength of laser light of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface (S) Is preferably 0.05 m or more. The surface of the copper foil other than the surface-treated surface S of the surface-treated copper foil of the present invention is more preferably surface-treated. With this configuration, it is possible to further suppress the problem that the protective film is attached to the copper foil in the lamination step with the resin substrate by further increasing the contact area between the copper foil and the protective film. The surface-treated copper foil of the present invention has an arithmetic average roughness (Ra) of TD measured by a laser microscope having a wavelength of laser light of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface (S) More preferably 0.08 mu m or more, still more preferably 0.10 mu m or more, still more preferably 0.20 mu m or more, still more preferably 0.30 mu m or more. The arithmetic average roughness (Ra) of the TD measured by a laser microscope with a wavelength of 405 nm of the laser light of the surface of the copper foil other than the surface-treated surface S and / or the surface-treated surface S of the surface- ) Is not particularly limited, but is typically 0.80 mu m or less, more typically 0.65 mu m or less, more typically 0.50 mu m or less, and more typically 0.40 mu m or less.

The surface-treated copper foil of the present invention is characterized in that the square root mean square height (Rq) of TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface S and / ) Is preferably 0.08 mu m or more. The surface of the copper foil other than the surface-treated surface S of the surface-treated copper foil of the present invention is more preferably surface-treated. With this configuration, it is possible to further suppress the problem that the protective film is attached to the copper foil in the lamination step with the resin substrate by further increasing the contact area between the copper foil and the protective film. The surface-treated copper foil of the present invention is characterized in that the square root mean square height (Rq) of TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface of the surface of the copper foil other than the surface-treated surface S and / ) Is more preferably 0.10 占 퐉 or more, more preferably 0.15 占 퐉 or more, still more preferably 0.20 占 퐉 or more, and still more preferably 0.30 占 퐉 or more. The square root mean square root height of TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface-treated surface S of the surface-treated copper foil of the present invention and / or the surface of the copper foil other than the surface- Rq) is not particularly limited, but is typically 0.80 mu m or less, more typically 0.60 mu m or less, more typically 0.50 mu m or less, and more typically 0.40 mu m or less.

The surface of the copper foil other than the surface-treated surface S may be subjected to a treatment for forming a heat-resistant layer or rust-preventive layer by plating (normal plating, plating instead of plating) as a surface treatment. The surface of the copper foil other than the surface-treated surface S may be roughened as a surface treatment.

For the roughening treatment, for example, a roughening treatment may be performed using a plating solution containing copper sulfate and an aqueous sulfuric acid solution, or the roughening treatment may be performed using a plating solution comprising an aqueous solution of copper sulfate and an aqueous solution of sulfuric acid. It may be an alloy plating such as a copper-cobalt-nickel alloy plating, a copper-nickel-phosphorus alloy plating or a nickel-zinc alloy plating. It is also preferable to conduct the plating by copper alloy plating. The copper alloy plating bath includes, for example, a plating bath containing at least one element other than copper and copper, more preferably a group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum Is used as the plating bath.

The roughening treatment other than the roughening treatment may be used for the surface of the copper foil other than the surface treatment surface S, or the surface treatment other than the plating treatment may be used even when the roughening treatment is not performed.

The surface of the copper foil other than the surface treated surface S may be subjected to a surface treatment for forming irregularities on the surface.

As the surface treatment for forming the irregularities on the surface, surface treatment by electrolytic polishing may be performed. For example, irregularities can be formed on the surface of the copper foil other than the surface-treated surface S by electrolytically polishing the surface of the copper foil other than the surface-treated surface S in a solution composed of copper sulfate and an aqueous solution of sulfuric acid. Generally, electrolytic polishing is aimed at smoothing, but in the surface treatment of the surface of the copper foil other than the surface treatment surface S of the present invention, irregularities are formed by electrolytic polishing, which is contrary to the usual practice. The method of forming the irregularities by electrolytic polishing may be carried out by a known technique. Examples of known techniques of electrolytic polishing for forming the irregularities include the methods described in JP-A-2005-240132, JP-A-2010-059547, and JP-A-2010-047842. Specific conditions for the process of forming the concavities and convexities by electrolytic polishing include, for example,

Treatment solution: Cu: 5 to 40 g / l, H ₂ SO ₄ : 50 to 150 g / l, Temperature: 30 to 70 ° C

Electrolytic polishing current: 10 to 50 A / dm ²

Electrolytic polishing time: 5 to 20 seconds

Etc. More specifically, for example,

Treatment solution: Cu: 20 g / l, H ₂ SO ₄ : 100 g / l, temperature: 50 ° C

Electrolytic polishing current: 15 A / dm ²

Electrolytic polishing time: 15 seconds

And the like.

As the surface treatment for forming the irregularities on the surface of the copper foil other than the surface treatment surface S, for example, the surface of the copper foil other than the surface treatment surface S may be mechanically polished to form irregularities. The mechanical polishing may be performed by a known technique.

Further, after the surface treatment of the surface of the copper foil other than the surface treatment surface S of the surface-treated copper foil of the present invention, a heat-resistant layer, rust-preventive layer or weather-resistant layer may be formed. The heat-resistant layer, the rust-preventive layer, and the weather-resistant layer may be the methods described in the above description of the base material or the experimental example, but may be a known technique.

Treated copper foil of the present invention can be bonded to a resin substrate from the surface-treated surface (S) side to produce a laminated board. The resin substrate is not particularly limited as long as it has properties that can be applied to a printed wiring board and the like. For example, for a rigid PWB, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber base epoxy resin, A polyester film, a polyimide film, a liquid crystal polymer (LCP) film, a Teflon (registered trademark) film, or the like can be used for an FPC using a resin, glass / glass nonwoven composite substrate epoxy resin, have.

In the case of a rigid PWB, prepregs prepared by impregnating a base material such as a glass foil with a resin and hardening the resin to a semi-hardened state are prepared. The copper foil is superimposed on the prepreg from the opposite surface side of the coating layer and is heated and pressed. In the case of FPC, a laminated board can be produced by laminating a laminate to a base material such as a polyimide film with an adhesive or without using an adhesive under high temperature and high pressure, or by applying a polyimide precursor, drying and curing have.

The thickness of the polyimide base resin is not particularly limited, but it is generally 25 占 퐉 or 50 占 퐉.

The laminate of the present invention can be applied to various printed wiring boards (PWB), and is not particularly limited. For example, it is applicable to single-sided PWB, double-sided PWB, multilayer PWB (three or more layers) The present invention is applicable to Rigid PWB, Flexible PWB (FPC) and Rigid Flex PWB from the viewpoint of kinds of insulating substrate materials.

(Method of positioning a laminated board and a printed wiring board using the same)

A method of positioning the surface-treated rolled copper foil of the present invention and the laminated board of the resin substrate will be described. First, a laminate of a surface-treated rolled copper foil and a resin substrate is prepared. Specific examples of the laminate of the surface-treated rolled copper foil and the resin substrate of the present invention include a laminate of a copper substrate and at least one resin substrate such as polyimide, In which the flexible printed board is precisely positioned and pressed onto the end of the circuit board of the main board and the circuit board to which the flexible printed board is attached. That is, in this case, the laminated board is a laminated board in which the wiring end portions of the flexible printed board and the main board are bonded by compression bonding, or a laminated board in which the wiring end portions of the flexible printed board and the circuit board are bonded by press bonding. The laminated board has a mark formed of a part of the copper wiring or a separate material. The position of the mark is not particularly limited as far as it can be photographed by a photographing means such as a CCD camera or the like beyond the resin substrate constituting the laminated plate.

In the thus prepared laminate, when the mark described above is photographed by the photographing means over the resin substrate, the position of the mark can be detected satisfactorily. Then, the position of the mark is detected in this way, and the positioning of the laminate of the surface treated rolled copper foil and the resin substrate can be favorably performed based on the detected position of the mark. Also in the case where a printed wiring board is used as the laminated board, the position of the mark is well detected by the photographing means by such a positioning method, and the positioning of the printed wiring board can be performed more accurately.

Therefore, it is considered that when one printed wiring board is connected to another printed wiring board, defective connection is reduced and the yield is improved. As a method for connecting one printed wiring board to another printed wiring board, a method of connecting via anisotropic conductive film (ACF), anisotropic conductive paste (ACP) A known connection method such as connection through an adhesive having conductivity can be used. In the present invention, the &quot; printed wiring board &quot; includes a printed wiring board on which components are mounted, a printed circuit board, and a printed board. It is also possible to manufacture a printed wiring board to which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention and also to at least one printed wiring board of the present invention and another printed wiring board of the present invention A printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured by using such a printed wiring board. The method for manufacturing a printed wiring board of the present invention may include at least a step of connecting a printed wiring board manufactured by the method of the present invention to a component. The method for manufacturing a printed wiring board of the present invention is a method for manufacturing a printed wiring board A by connecting at least one printed wiring board of the present invention and another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention And a step of connecting the printed wiring board A to the component. The method for producing a printed wiring board of the present invention is not limited to any of the printed wiring board of the present invention, the printed wiring board produced by the method of the present invention, and the printed wiring board of the present invention or the printed wiring board manufactured by the method of the present invention A printed wiring board selected from the group consisting of non-printed wiring boards, and a printed wiring board produced by the method of the present invention may be connected to each other to manufacture a printed wiring board in which two or more printed wiring boards are connected. In the present invention, the "copper circuit" is also assumed to include a copper wiring.

Further, the positioning method according to the embodiment of the present invention may include a step of moving the laminate (including a laminate of a copper foil and a resin substrate or a printed wiring board). In the transferring process, for example, it may be moved by a conveyor such as a belt conveyor or a chain conveyor, or may be moved by a moving device having an arm mechanism, or may be moved by a moving device or a moving device (Including rollers, bearings, and the like) for moving the laminate by rotating a substantially cylindrical or the like, a moving device or a moving device using hydraulic pressure as a power source, a moving device using air pressure as a power source, A moving device or a moving device having a stage such as a moving device or a moving device using a motor as a power source, a linear guide stage for moving a gantry, a gantry moving air guide stage, a stacked linear guide stage, a linear motor driving stage, do. Also, a moving process by a known moving means may be carried out.

The positioning method according to the embodiment of the present invention may be used in a surface mount machine or a chip mounter.

The laminate of the surface-treated rolled copper foil and the resin substrate positioned in the present invention may be a printed wiring board having a resin plate and a circuit formed on the resin plate. In this case, the mark may be the above circuit.

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

Further, in the printed wiring board, the circuit on the printed wiring board may be used as a mark instead of the mark of the printed material, and the circuit may be photographed with a CCD camera over the resin substrate to measure the value of Sv. Copper clad laminate was prepared by etching copper to form a line, then, instead of the mark of the printed material, the copper in the form of the line was used as a mark, and copper on the line above the resin substrate was photographed with a CCD camera The value of Sv can be measured.

[Example]

<Production of rolled copper foil>

An ingot having a thickness of 100 mm was cast using tough pitch copper or anoxic copper added with an element of the composition shown in Table 1 as a raw material and subjected to hot rolling to a thickness of 10 mm at 800 ° C or higher to finish the oxide scale of the surface . Thereafter, cold rolling and annealing were repeated to obtain a rolled sheet coil having a thickness of 0.5 mm. After the last cold rolling, the copper strips were passed through a continuous annealing furnace at 700 ° C and under the tension shown in Table 1 to carry out the final recrystallization annealing. Further, the value of the tensile force was normalized by dividing it by the proof stress under the recrystallization annealing temperature of the sample ({tensile force (N / mm2) / proof stress (N / mm2) under annealing temperature of recrystallization)}. The heating time of the copper strip in the recrystallization annealing was 100 to 200 seconds. Finally, final cold rolling was performed to the thickness shown in Table 1. The rolling degree in the final cold rolling was set to 86 to 99%.

Table 1 shows the points of the copper foil manufacturing process before the surface treatment. &Quot; High gloss rolling &quot; means that the final cold rolling (cold rolling after final recrystallization annealing) is carried out at the value of the film equivalent described. Each of the copper foils was prepared as an example and a comparative example, and plating treatment was carried out on the surface of one of the surfaces with the condition (plating bath 1 or 2) listed in Table 2 as the coarsening treatment. In addition, it was also prepared under the condition described in Table 2 (plating bath 3) that the roughening treatment was not performed.

Further, "Ag 190 ppm + OFC" in the composition column of Table 1 was added to oxygen-free copper (OFC) of JIS-H 3510 (C1011) (Example 10) or JIS-H 3100 (C1020) Of Ag added. "Ag190 ppm + TPC" means that 190 mass ppm of Ag was added to tough pitch copper (TPC) of JIS-H 3100 (C1100). The same is true for other addition amounts.

The surface-treated copper foils obtained in Examples 1 to 5, 9, 19 to 21, 25 and 26 were also subjected to the surface treatment described in Table 3 on the other surface. Here, &quot; Example No.-number &quot; in Table 3 means that the surface of the other surface of the surface-treated copper foil obtained in Examples was subjected to the surface treatment described in Table 3. [ For example, in Table 3, &quot; Example 1-1 &quot; is obtained by subjecting the other surface of Example 1 to the surface treatment described in Table 3, &quot; Example 2-1 & And the surface treatment described in Table 3 was carried out.

&Lt; Crystal orientation &gt;

The surface (rolled surface) of the copper foil after the final cold rolling was measured for positive electrode points (X (X)) of {200}, {220}, and {111} faces using an X-ray diffractometer (RINT- Line reflection average strength). The obtained measurement results were converted into an inverse pole position using a standard ODF (manufactured by NORUMON Co., Ltd.), and the calculated X-ray diffraction intensity of {110} plane and {112} plane was calculated.

X-ray diffraction measurement conditions were: incident X-ray source: Cu, acceleration voltage: 30 kV, tube current: 100 mA, divergence slit: 0.5 degree, scattering slit: 4 mm, light receiving slit: 4 mm, . The degree of aggregation of the {200}, {220}, and {111} planes was standardized using the value of the pure powder (X-ray reflection average intensity) subjected to X-ray diffraction for each surface under the same conditions, Respectively. Powdered fine copper powder (325 mesh) was used.

&Lt; Crystal grain size &

The grain size of the copper foil immediately after the final recrystallization annealing (before the final cold rolling) was measured on the rolled surface according to the JIS-H 0501 cutting method.

&Lt; I {200} / I ₀ {200} &gt;

After the final cold-rolled copper foil was annealed at 200 DEG C for 0.5 hour and annealed at 350 DEG C for 1 second, the X-ray diffraction intensity (integrated intensity) of the {200} plane was measured on the surface. Then, the value (I ₀ {200}: X-ray reflection average intensity (integral intensity), i.e., X-ray diffraction intensity (integral intensity) of the {200} plane of the pure powder) of the pure powder subjected to X- .

X-ray diffraction measurement conditions were: incident X-ray source: Cu, acceleration voltage: 25 kV, tube current: 20 mA, divergence slit: 1 degree, scattering slit: 1 degree, light receiving slit: 0.3 mm, , And a monochrome light receiving slit of 0.8 mm. Powdered fine copper powder (325 mesh) was used.

<Flexibility>

First, a thermosetting polyimide film having a thickness of 12.5 占 퐉 was coated with a thermoplastic polyimide adhesive and dried. Next, after the final cold-rolled copper foil was laminated on both sides of the film, the film was hot-pressed to produce a double-side CCL. A circuit pattern having a line / space width of 100 占 퐉 / 100 占 퐉 was formed by etching on both surfaces of this double-sided CCL, and then covered with a coverlay film having a thickness of 25 占 퐉 and processed into an FPC.

The FPC was subjected to a slide bending test to evaluate its bending property. Specifically, a sliding tester (type TK-107 manufactured by Applied Technology Research Co., Ltd.) was used, and the slide radius r (mm) was r = 4 mm for Example 9, , R = 0.72 mm, and in any case, the FPC was bent at a slide speed of 120 times / minute.

The number of bending times when the electric resistance of the copper foil circuit was increased by 10% was evaluated as less than 150,000 times as compared with that before the test, and the evaluation was evaluated as being 100,000 times to less than 150,000 times. The evaluation was made as 150,000 to 300,000 times , And when it exceeded 300,000 times, it was evaluated as ◎. If the bending property is ⊚ to △, it can be said that the bending property is good.

<Etching Properties>

The above-mentioned both-side CCL was immersed in an etching solution (product name: TAK-CL-8 made by Adeka Co., Ltd., 20% by mass solution) having a solution temperature of 30 캜 for 1 minute and etched, and the etched surface was photographed with an optical microscope.

Since the dark portion of the image indicates an area where the etching is uniform, the etched property was evaluated by comparing the photographed image with the reference image. Fig. 3 shows the correspondence between the reference image and the etching property evaluation. The higher the area ratio of the dark portion, the better the etching property, and the &amp; cir &amp; indicates the highest etching property. It can be said that the etching property is good if the etching property is ⊚ to △.

&Lt; Color difference (? E * ab) beyond polyimide>

A surface-treated rolled copper foil and a polyimide film having a? B (PI) of 50 or more and 65 or less before adhering to the copper foil (25 mu m or 50 mu m in thickness produced by Kaneka) (? E * ab) based on JIS Z 8730 on the surface of the substrate was measured. The color difference (? E * ab) was measured in accordance with JIS Z 8730 using a color difference system MiniScan XE Plus manufactured by HunterLab. In the above-mentioned color difference meter, the measured value of the white plate is covered with a black envelope of? E * ab = 0, and the measured value at the time of measurement in the dark is? E * ab = 90 to correct the color difference. ? E * ab was measured based on the following formula using L * a * b color system,? L: black and white,? A: red color, and? B: Here, the color difference (DELTA E * ab) is defined as zero for white and 90 for black;

The color difference (DELTA E * ab) based on JIS Z 8730 on the surface of the copper circuit can be measured by using, for example, a fine-particle spectral colorimeter (model: VSS400, etc.) manufactured by Nippon Denshoku Kogyo Co., And a colorimeter (model: SC-50 占 or the like).

<Brightness Curve>

The surface-treated copper foil was laminated on a polyimide film (PIXEO (polyimide type: FRS), a polyimide film with an adhesive layer for a copper clad laminate, a polyimide film with a thickness of 50 占 퐉 and a PMDA (pyromellitic anhydride) PMDA-ODA (4,4'-diaminodiphenyl ether) -based polyimide film)), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. Subsequently, printed matter printed with black mark on the line was laid under the sample film, the printed matter was photographed with a CCD camera (line CCD camera of 8192 pixels) beyond the sample film, and the line image In the observation point-brightness graph prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the mark extends, ΔB and t1 and t2 are calculated from the brightness curve that occurs from the end of the mark to the portion where the mark is not drawn , And Sv were measured. Fig. 7 shows a configuration of the photographing apparatus used at this time and a schematic diagram showing a method of measuring the lightness curve. Further, Sv measures both sides of the mark and adopts a small value.

As shown in Fig. 7,? B and t1, t2, and Sv were measured by the following photographing apparatus. Further, one pixel on the horizontal axis corresponds to a length of 10 mu m. As another method of obtaining the slope Sv of the brightness curve, it is preferable that the ratio of the length of one pixel to the length of one grayscale in the graph of the brightness curve is set to 3.5: 6 (the length of one pixel in the brightness curve: The value of t1, t2, and Sv in a graph of a brightness curve can be calculated with the length of one gray level in the curve of the curve = 3.5 (mm): 6 (mm).

In the polyimide film used for the measurement of the brightness curve, any polyimide film may be used provided that the value of? B (PI) before adhesion to the copper foil is 50 or more and 65 or less.

The printed matter on which the black mark on the line is printed has a gloss value of 43.0 ± 2 on a white glossy paper in accordance with JIS P 8208 (1998) (copy of the contamination measurement chart of Figure 1) and JIS P 8145 (2011) ) Observation method Foreign matter comparison chart JA 1-copy of visual inspection method foreign substance comparison chart) The transparent film shown in Fig. 8, which is adopted in all, Full-size version "part number: JQA160-20151-1 (manufactured by National Printing Bureau, independent administrative agency)) was used.

The glossiness of the glossy paper was measured at an incident angle of 60 degrees using a gloss meter Handy Gloss Meter PG-1 manufactured by Denso Corporation of Japan according to JIS Z 8741.

The photographing apparatus includes a stage (white) on which a polyimide substrate on which a CCD camera, a mark-affixed paper (glossy paper of white color with a contour over it) is placed, a power source for illuminating the photographing section of the polyimide substrate, And a conveyor (not shown) for conveying a polyimide substrate for evaluation on a stage, on which a paper sheet with an adhesive layer thereon is placed. The main specifications of the photographing apparatus are as follows:

· Photographing apparatus: sheet inspection apparatus of NIKEO CO., LTD. Mujiken

CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits)

· Lighting power supply: High frequency lighting power supply (power supply unit × 2)

· Lighting: fluorescent lamp (30 W, model name: FPL27EX-D, twin fluorescent lamp)

The Sv measuring line used was a line indicated by an arrow drawn in the obscuration of Fig. 8 of 0.7 mm &lt; 2 &gt;. The width of the line is 0.3 mm. The line CCD camera field of view was arranged by the dotted line in Fig.

In photographing with a line CCD camera, a signal is checked at a full-scale 256 gradation. In a state in which a polyimide film (polyimide substrate) to be measured is not laid, a white mark on the white glossy paper The above-mentioned transparent film was placed on the transparent film side, and a point other than the mark printed on the impure substance was measured with a CCD camera from the side of the transparent film) was adjusted to 230 ± 5. The camera scan time (the time when the camera shutter was opened and the time when the light was received) was fixed at 250 占 sec, and the lens iris was adjusted so as to be within the above-mentioned gradation.

7, "0" means "black", brightness 255 means "white", and the degree of gray from "black" to "white" (grayscale in black and white) is 256 Are displayed in a gradation.

&Lt; Visibility (Resin transparency) &gt;

The copper foil was coated with a polyimide film (PIXEO (polyimide type: FRS), a polyimide film having an adhesive layer for a copper clad laminate formed thereon, a polyimide film of PMDA (pyromellitic anhydride) 4,4'-diaminodiphenyl ether) -based polyimide film)), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A printed matter (a black circle having a diameter of 6 cm) was pasted on one side of the obtained resin layer, and the visibility of the printed matter was judged from the reverse side to the resin layer. A "indicates that the outline of the black circle of the printed matter is at least 90% of the circumference," ⊚ "indicates that the outline of the circle is at least 80% It was evaluated that the outline of the black circle was clear when the length was less than 0 to 80% of the circumference, and that the outline was broken as &quot; x &quot; (rejection).

<Yield>

The copper foil was coated with a polyimide film (PIXEO (polyimide type: FRS), a polyimide film having an adhesive layer for a copper clad laminate formed thereon, a polyimide film of PMDA (pyromellitic anhydride) (4,4'-diaminodiphenyl ether) -based polyimide film)), and the copper foil was etched (ferric chloride aqueous solution) to prepare an FPC having a circuit width of L / S of 30 μm / 30 μm . After that, an attempt was made to detect a mark having a size of 20 mu m x 20 mu m on a polyimide with a CCD camera. Quot ;, &quot;? &Quot;, &quot;? &Quot;, &quot;? &Quot;, and &quot; x &quot;, respectively.

&Lt; Peel strength (adhesive strength) &gt;

According to IPC-TM-650, state (normal) fill strength was measured with a tensile tester Autograph 100, and the state fill strength was 0.7 N / mm or more so that it could be used for laminated board applications. The peel strength was measured with a copper foil thickness of 18 占 퐉. The copper foil having a thickness of less than 18 占 퐉 was plated with copper to give a copper foil thickness of 18 占 퐉. When the thickness is larger than 18 占 퐉, etching is performed to make the thickness of the copper foil 18 占 퐉. The peel strength was measured using a polyimide film (PIXEO (polyimide type FRS): an adhesive layer for a copper clad laminate formed with a thickness of 50 占 퐉, manufactured by Kaneka, a polyimide film based on PMDA (pyromellitic anhydride) (PMDA-ODA (4,4'-diaminodiphenyl ether) -based polyimide film)) and the surface treated surface of the surface treated rolled copper foil according to the examples and comparative examples of the present invention were used. In the measurement, the polyimide film was fixed by affixing the polyimide film to a hard substrate (a plate of stainless steel or a plate of synthetic resin (which should not be deformed during peel strength measurement)) with a double-sided tape.

Further, in the case of a printed wiring board or a copper clad laminate, the aforementioned evaluation items can be measured on the surface of a copper circuit or a copper foil by melting and removing the resin.

&Lt; Measurement of surface roughness after surface treatment of the other surface (surface of copper foil other than surface treatment surface S)

It is preferable to measure the surface roughness of the other surface of each of the Examples and Comparative Examples using a non-contact method. Specifically, the state of the other surface after the surface treatment of each of the examples and the comparative examples is evaluated by the value of the roughness measured by a laser microscope. This is because the state of the surface can be evaluated in more detail.

Measurement of surface roughness (Rz);

The surface roughness (10 points) was measured with a laser microscope LEXT OLS4000 manufactured by Olympus, Inc., on the other surface of the surface treated copper foil of each of the examples and comparative examples (when the other surface was subjected to surface treatment, the other surface after the surface treatment) Average roughness) (Rz) was measured according to JIS B0601 1994. Using an objective lens of 50 times, an evaluation length of 258 占 퐉 in the observation of the surface of the copper foil and a measurement of a direction (TD) perpendicular to the rolling direction for the rolled copper foil on the condition of a cutoff value of zero, And the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the production apparatus of the present invention. The measurement environment temperature of the surface roughness (Rz) by the laser microscope was 23 to 25 占 폚. Rz was arbitrarily measured at 10 points, and the average value of 10 points of Rz was taken as the value of surface roughness (10 point average roughness) (Rz). The wavelength of the laser light of the laser microscope used for the measurement was 405 nm. In addition, the same measurement was performed on the surface-treated surface S as well.

Measuring the root mean square height (Rq) of the surface;

The surface of the other surface of the copper foil of each of the examples and comparative examples (the other surface after the surface treatment when the other surface was subjected to the surface treatment) was measured with a laser microscope LEXT OLS4000 manufactured by Olympus Co., The height (Rq) was measured according to JIS B 0601 2001. Using an objective lens of 50 times, an evaluation length of 258 占 퐉 in the observation of the surface of the copper foil and a measurement of a direction (TD) perpendicular to the rolling direction for the rolled copper foil on the condition of a cutoff value of zero, And the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the production apparatus of the present invention. Also, the measurement environment temperature of the root-mean-square root height (Rq) of the surface by the laser microscope was 23 to 25 占 폚. Rq was arbitrarily measured at 10 points, and the average value of 10 points of the Rq was taken as the value of the root-mean-square root height (Rq). The wavelength of the laser light of the laser microscope used for the measurement was 405 nm. In addition, the same measurement was performed on the surface-treated surface S as well.

Measurement of arithmetic average roughness (Ra) of the surface:

The surface roughness (Ra) of the other surface of the surface-treated copper foil of each of the examples and comparative examples (the other surface after the surface treatment when the other surface was subjected to the surface treatment) was measured according to JIS B 0601-1994, Was measured with a laser microscope LEXT OLS4000 manufactured by Olympus Corporation. Using an objective lens of 50 times, an evaluation length of 258 占 퐉 and a cutoff value of zero for observation of the surface of the copper foil were measured by measuring the direction (TD) perpendicular to the rolling direction of the rolled copper foil, And the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the production apparatus of the present invention. In addition, the measurement environmental temperature of the arithmetic average roughness (Ra) of the surface by the laser microscope was 23 to 25 占 폚. The Ra was arbitrarily measured at 10 points, and the average value of 10 points of the Ra was taken as the value of the arithmetic average roughness (Ra). The wavelength of the laser light of the laser microscope used for the measurement was 405 nm. In addition, the same measurement was performed on the surface-treated surface S as well.

&Lt; Evaluation of copper foil wrinkles by laminate processing &gt;

Treated copper foils of Examples and Comparative Examples were laminated on both surfaces of a polyimide resin having a thickness of 25 占 퐉 from one surface (surface-treated surface (S)) side and the other surface of each surface-treated copper foil (Protective film / surface-treated copper foil / polyimide resin / surface-treated copper foil / protective film) having a thickness of 125 mu m laminated on the side of the protective film (Laminate processing) was performed while applying heat and pressure using a laminate roll from the outside of both protective films, and a surface-treated copper foil was bonded to both surfaces of the polyimide resin. Subsequently, the protective film on both surfaces was peeled off, and the other surface of the surface-treated copper foil was observed with naked eyes to confirm whether wrinkles or streaks were present. When no wrinkles or streaks occurred, When the wrinkles or streaks per m were observed at only one point, it was evaluated as?, when the wrinkles or streaks per 5 m of the copper foil were observed at two or more points.

The obtained results are shown in Tables 1 to 3.

As apparent from Tables 1 to 3, in each of the examples satisfying 2.5? I {110} / I {112}? 6.0, both the etching property and the bendability of the rolled copper foil were excellent.

In comparison between Examples 1 and 2 in which the thickness and the final recrystallization annealing condition are the same, the (110) orientation increases in Example 1 with a large amount of Ag added, and the value of I {110} / I {112} . In the case of Examples 20 to 23 in which 13.0> I {200} / I ₀ {200}, the flexural properties were slightly lower than those of the other Examples, but there was no practical problem.

On the other hand, in the case of Comparative Examples 1 and 4 in which the tension at the final recrystallization annealing was made lower than that in Example 6 having the same composition of the copper foil, the (112) orientation decreased and the value of I {110} / I {112} Exceeding 6.0, and the etching property was deteriorated.

In the case of Comparative Example 2 in which the tension at the final recrystallization annealing was made higher than that in Example 5 in which the composition of the copper foil was the same and in the case of Comparative Example 3 in which the tension at the final recrystallization annealing was higher than that of Example 7 in which the composition of the copper foil was the same , All the (110) orientations decreased, and the value of I {110} / I {112} was less than 2.5, and the bendability deteriorated.

In Examples 1 and 6 in which the production method is the same, Example 1 having a low oxygen concentration of the copper foil is excellent in flexibility.

2 (a) and 2 (b) are optical microscope images of the etching surfaces of Example 5 and Comparative Example 1, respectively. It can be seen that the ratio of the dark portions is large in the case of Example 5 having excellent etching properties.

In all of Examples 1 to 26, the color difference (DELTA E * ab) beyond polyimide was 50 or more, Sv was 3.0 or more, and visibility was good.

In Comparative Examples 1 to 4, the color difference (DELTA E * ab) over the polyimide was less than 50, or Sv was less than 3.0, and the visibility was poor.

In the first to the twenty-sixth embodiments, the width of the mark is changed from 0.3 mm to 0.16 mm (the third mark (the mark indicated by the arrow in Fig. 9) from the side closer to the base of 0.5 of the sheet area of 0.5 mm2) And the same Sv was measured. However, all Sv values were the same as those obtained when the width of the mark was 0.3 mm.

In the first to the twenty-sixth embodiments, the width of the mark was changed from 0.3 mm to 1.3 mm (the sixth mark (the mark indicated by the arrow in Fig. 10) from the side closer to the substrate of 3.0 with the area of the sheet of the impurity 3.0 mm2) And the same Sv was measured. However, all Sv values were the same as those obtained when the width of the mark was 0.3 mm.

In the above Examples 1 to 26, the position of 50 占 퐉 apart from the end position on both sides of the mark was set at a position 100 占 퐉 apart, 300 占 퐉 apart, and 500 占 퐉 apart from the top average value Bt of the lightness curve , And the same Sv was measured by changing to the average value of the lightness measured at five points (10 points on both sides) at intervals of 30 占 퐉 from the position, but all Sv were located at positions spaced 50 占 퐉 from the end positions on both sides of the mark (Bt) of the lightness curve, the average value of the lightness when measured at five points (total of 10 points on both sides) at intervals of 30 占 퐉 was the same value as the Sv value.

The surface-treated copper foil was subjected to surface treatment on the both surfaces of the copper foil under the same conditions using the same copper foils as in each of the examples and the comparative examples. As a result, both surfaces were evaluated in the same manner as in the above- .

When the surface treatment such as roughening treatment is applied to both surfaces of the copper foil, surface treatment may be performed on both surfaces at the same time, or surface treatment may be separately performed on one surface and the other surface. When both surfaces are subjected to the surface treatment at the same time, the surface treatment may be performed using a surface treatment apparatus (plating apparatus) having an anode formed on both sides of the copper foil. In this embodiment, both surfaces were simultaneously subjected to surface treatment at the same time.

The 10-point average roughness (Rz) of TD measured by a laser microscope with a laser beam wavelength of 405 nm of the surface-treated copper foil surface (surface-treated surface S) of Examples 1 to 26 was all 0.35 탆 or more . The arithmetic mean roughness (Ra) of TD measured by a laser microscope with a laser beam wavelength of 405 nm of the surface-treated copper foil surface (surface-treated surface (S)) of Examples 1 to 26 was 0.05 mu m or more. The square root mean square height (Rq) of TD measured by a laser microscope with a laser beam wavelength of 405 nm of the surface-treated copper foil surface (surface-treated surface S) of Examples 1 to 26 was all 0.08 탆 or more .

Claims (24)

The surface of the copper foil on one side and / or the surface of the copper foil on both sides is the surface treatment surface S and the surface of the {112} surface (S) on one or both surfaces of the surface treatment surface S, Ray diffraction intensity is I {112}, and the calculated X-ray diffraction intensity from the {110} plane is I {110}
2.5? I {110} / I {112}? 6.0
Lt; / RTI &gt;
Treated copper foil and a polyimide having a? B (PI) of not less than 50 and not more than 65 before being adhered to the copper foil are laminated from the surface-treated surface (S) side of the surface-treated rolled copper foil , A color difference (DELTA E * ab) based on JIS Z 8730 of the surface of the polyimide is 50 or more,
The surface-treated, rolled copper foil is applied to both surfaces of the polyimide resin substrate from the surface-treated surface (S) side, and then the rolled copper foil on both sides is removed by etching,
When a printed matter on which a mark on a line is printed is laid under the exposed polyimide substrate and the printed matter is photographed with a CCD camera beyond the polyimide substrate,
In an observation point-brightness graph produced by measuring the brightness of each observation point along a direction perpendicular to the direction in which the mark on the line is observed, with respect to the image obtained by the photographing,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve occurring from the end of the mark to the portion where the mark is not drawn is defined as? B (? B = Bt - Bb) A value indicating the position of an intersection closest to the mark on the line among the intersections of the brightness curve and Bt is t1 and the brightness curve is 0.1 And a value indicating a position of an intersection point closest to the mark on the line among the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the intersections of the points A,
Sv = (DELTA Bx0.1) / (t1 - t2) (1) The method according to claim 1,
Wherein the one surface of the copper foil is a surface-treated surface (S), and the surface of the other copper foil is surface-treated. The method according to claim 1,
Wherein the rolled copper foil is formed of at least 99.9% by mass of copper. The method according to claim 1,
Wherein the total amount of one or more elements selected from the group consisting of Ag, Sn, Mg, In, B, Ti, Zr and Au is 10 to 300 mass ppm in total, and the balance Cu and inevitable impurities. The method according to claim 1,
Wherein the rolled copper foil contains 2 to 50 mass ppm of oxygen. The method according to claim 1,
Wherein I {112} / I {100}? 1.0 is satisfied on at least one surface after heating at 200 占 폚 for 30 minutes. The method according to claim 1,
The X-ray diffraction intensity at the {200} plane of the rolled copper foil was I {200}, and the X-ray diffraction intensity at the {200} plane of the copper powder sample was I ₀ { 200}.
5.0? I {200} / I ₀ {200}? 27.0. The method according to claim 1,
A surface treated rolled copper foil having a thickness of 4 to 100 탆. The method according to claim 1,
Wherein the surface treated surface S and / or the surface treated surface S, which is not the surface treated surface S, has a 10-point average roughness (Rz) of TD of 0.35 탆 or more as measured by a laser microscope with a laser beam wavelength of 405 nm Copper foil. The method according to claim 1,
Wherein the arithmetic mean roughness (Ra) of the TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface-treated surface (S) and / or the surface of the copper foil other than the surface-treated surface (S) . The method according to claim 1,
Wherein the surface-treated surface (S) and / or the surface-treated surface (S) are surface-treated with a square root mean square height (Rq) of TD of 0.08 탆 or more as measured by a laser microscope having a laser beam wavelength of 405 nm Copper foil. 3. The method of claim 2,
Wherein the surface treated surface S and / or the surface treated surface S, which is not the surface treated surface S, has a 10-point average roughness (Rz) of TD of 0.35 탆 or more as measured by a laser microscope with a laser beam wavelength of 405 nm Copper foil. 3. The method of claim 2,
Wherein the arithmetic mean roughness (Ra) of the TD measured by a laser microscope with a laser beam wavelength of 405 nm on the surface-treated surface (S) and / or the surface of the copper foil other than the surface-treated surface (S) . 3. The method of claim 2,
Wherein the surface-treated surface (S) and / or the surface-treated surface (S) are surface-treated with a square root mean square height (Rq) of TD of 0.08 탆 or more as measured by a laser microscope having a laser beam wavelength of 405 nm Copper foil. A laminate produced by laminating a surface-treated rolled copper foil according to any one of claims 1 to 14 and a resin substrate. A printed wiring board using the surface treated rolled copper foil according to any one of claims 1 to 14. An electronic device using the printed wiring board according to claim 16. A method for producing a printed wiring board in which two or more printed wiring boards according to claim 16 are connected and two or more printed wiring boards are connected. A printed wiring board comprising at least one printed wiring board according to claim 16 and at least one other printed wiring board according to claim 16 or a printed wiring board not corresponding to the printed wiring board according to claim 16, Or more. An electronic device using at least one printed wiring board manufactured by the method according to claim 18 or 19. A printed wiring board comprising at least a printed wiring board according to claim 16, or a printed wiring board manufactured by the method according to claim 18 or 19, and a step of connecting components. A step of connecting at least one printed wiring board according to claim 16 and another printed wiring board according to claim 16 or a printed wiring board not corresponding to the printed wiring board according to claim 16 to manufacture a printed wiring board A;
And connecting the printed wiring board (A) to the component. A printed wiring board according to claim 16,
A printed wiring board manufactured by the method according to claim 18 or 19, and
At least one printed wiring board selected from the group consisting of the printed wiring board according to claim 16 or the printed wiring board made according to the method according to claim 18 or 19,
A printed wiring board manufactured by the method for manufacturing a printed wiring board including at least a printed wiring board according to claim 16 or a printed wiring board manufactured by the method according to claim 18 or 19 and a process for connecting components is connected , And a printed wiring board to which at least two printed wiring boards are connected. A printed wiring board manufactured by a method for manufacturing a printed wiring board including at least a printed wiring board according to claim 16 or a printed wiring board manufactured by the method according to claim 18 or 19 and a step for connecting components,
A printed wiring board manufactured by the method for manufacturing a printed wiring board including at least a printed wiring board according to claim 16 or a printed wiring board manufactured by the method according to claim 18 or 19 and a process for connecting components is connected , And a printed wiring board to which at least two printed wiring boards are connected.

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