WO2013168646A1

WO2013168646A1 - Surface-treated copper foil and laminate using same, copper foil, printed wiring board, electronic device, and process for producing printed wiring board

Info

Publication number: WO2013168646A1
Application number: PCT/JP2013/062658
Authority: WO
Inventors: 新井　英太; 敦史三木
Original assignee: Jx日鉱日石金属株式会社
Priority date: 2012-05-11
Filing date: 2013-04-30
Publication date: 2013-11-14
Also published as: TW201402840A; KR101822325B1; MY194478A; KR101704892B1; CN104271813A; JP2014148691A; JP5475897B1; MY171074A; KR20150008482A; KR20160128467A; PH12014502509A1; CN107022774A; PH12014502509B1; TWI479036B; CN104271813B

Abstract

Provided are: a surface-treated copper foil which can adhere satisfactorily to a resin and which has an advantage in that, when the foil has been removed by etching, the resulting resin exhibits high transparency; and a laminate using the foil. This surface-treated copper foil has roughening particles on the surface, said particles being formed by roughening treatment. In the surface-treated copper foil, the surface which has undergone roughening treatment exhibits a TD average roughness (Rz) of 0.20 to 0.80μm and an MD glossiness at 60°of 76 to 350%, and the A/B ratio is 1.90 to 2.40 [wherein A is the surface area of the roughening particles and B is the area of the roughening particles as observed in the planar view from the surface side of the copper foil.]

Description

Surface-treated copper foil and laminate using the same, copper foil, printed wiring board, electronic device, and method for manufacturing printed wiring board

The present invention relates to a surface-treated copper foil and a laminate using the same, a copper foil, a printed wiring board, an electronic device, and a method for producing a printed wiring board, and in particular, the remaining resin transparent after etching the copper foil. The present invention relates to a surface-treated copper foil suitable for a field where properties are required, a laminated board using the copper foil, a copper foil, a printed wiring board, an electronic device, and a method for manufacturing a printed wiring board.

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

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

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

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

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

As a result of intensive research, the present inventors have found that the copper foil in which the roughened particles are formed on the surface by the roughening treatment, the surface average roughness Rz on the side adhered to the resin substrate, the glossiness, and the roughness. It has been found that the ratio of the surface area of the roughened particles and the area obtained when the roughened particles are planarly viewed from the copper foil surface side affects the resin transparency after the copper foil is removed by etching.

In one aspect of the present invention completed based on the above knowledge, roughened particles are formed on the surface of the copper foil by the roughening treatment, and the average roughness Rz of the TD on the roughened treatment surface is 0.20 to 0.80 μm. The surface roughness A of the roughened particles and the area obtained when the roughened particles are viewed in plan from the copper foil surface side, the 60 degree glossiness of MD on the roughened surface is 76 to 350%. A surface-treated copper foil having a ratio A / B to B of 1.90 to 2.40.

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

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

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

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

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

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

In another aspect of the present invention, roughened particles are formed on the surface of the copper foil by a roughening treatment, and the copper foil is bonded to both surfaces of a 50 μm thick resin substrate from the roughening treatment surface side, and then etched. When the copper foil on both sides is removed, the surface-treated copper foil has a haze value of 20 to 70% when the resin substrate is removed.

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

In yet another aspect, the present invention is a copper foil before roughening used for the surface-treated copper foil of the present invention.

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

In yet another aspect, the present invention is a copper foil having an MD 60 degree gloss of 501 to 800%.

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

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

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

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

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

In yet another aspect, the present invention is a method for manufacturing a printed wiring board, including at least a step of connecting the printed wiring board of the present invention and a component.

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

According to the present invention, it is possible to provide a surface-treated copper foil that adheres well to a resin and is excellent in the transparency of a resin after the copper foil is removed by etching, and a laminate using the same.

It is a SEM observation photograph of the copper foil surface of (a) comparative example 1 in the case of Rz evaluation. It is a SEM observation photograph of the copper foil surface of (b) comparative example 2 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (c) comparative example 3 in the case of Rz evaluation. It is a SEM observation photograph on the surface of copper foil of (d) comparative example 4 in the case of Rz evaluation. (E) It is a SEM observation photograph of the copper foil surface of Example 1 in the case of Rz evaluation. (F) It is a SEM observation photograph of the copper foil surface of Example 2 in the case of Rz evaluation.

[Form and manufacturing method of surface-treated copper foil]
The copper foil used in the present invention is useful for a copper foil used by making a laminate by bonding to a resin substrate and removing it by etching.
The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Usually, the surface of the copper foil that adheres to the resin substrate, that is, the roughened surface, has a fist-like electric surface on the surface of the copper foil after degreasing in order to improve the peel strength of the copper foil after lamination. A roughening process is carried out to wear. Although the electrolytic copper foil has irregularities at the time of manufacture, the irregularities are further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. In the present invention, this roughening treatment can be performed by copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or the like. Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off. The content of treatment may be somewhat different between the rolled copper foil and the electrolytic copper foil. In the present invention, including such pretreatment and finishing treatment, known treatments related to copper foil roughening are included as necessary, and are collectively referred to as roughening treatment.
The rolled copper foil according to the present invention includes a copper alloy foil containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. It is. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more.

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

An example of a general bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1 to 4
Temperature: 30-50 ° C
Current density D _k : 20 to 30 A / dm ²
Plating time: 1-5 seconds

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

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

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

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

A zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer may be formed on the outermost surface by chromate treatment or application of a silane coupling agent. Good.

[Surface roughness Rz]
In the surface-treated copper foil of the present invention, roughened particles are formed by a roughening treatment on the surface of the copper foil, and the average roughness Rz of the TD on the roughened surface is 0.20 to 0.80 μm. With such a configuration, the peel strength becomes high and the resin adheres well to the resin, and the degree of haze (haze value) of the resin after the copper foil is removed by etching is reduced and the transparency is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin are facilitated. If the average roughness Rz of TD is less than 0.20 μm, there is a concern about manufacturing costs for manufacturing an ultra-smooth copper foil. On the other hand, if the average roughness Rz of TD is more than 0.80 μm, the unevenness of the resin surface after the copper foil is removed by etching increases, and as a result, the haze value of the resin increases. The TD average roughness Rz of the roughened surface is preferably 0.30 to 0.70 μm, more preferably 0.35 to 0.60 μm, still more preferably 0.35 to 0.55 μm, and more preferably 0.35 to Even more preferred is 0.50 μm.
When the surface-treated copper foil of the present invention is used for an application that requires a small Rz, the TD average roughness Rz of the roughened surface is preferably 0.20 to 0.70 μm, 0 More preferred is .25 to 0.60 μm, even more preferred is 0.30 to 0.55 μm, and even more preferred is 0.30 to 0.50 μm.

[Glossiness]
The glossiness at an incident angle of 60 degrees in the rolling direction (MD) of the roughened surface of the surface-treated copper foil greatly affects the haze value of the resin. That is, the haze value of the above-mentioned resin becomes smaller as the copper foil has a higher glossiness on the roughened surface. For this reason, the surface-treated copper foil of the present invention has a glossiness of the roughened surface of 76 to 350%, preferably 80 to 350%, preferably 90 to 300%, and 90 to 250%. Is more preferable, and 100 to 250% is more preferable.

Here, in order to further improve the visibility effect of the present invention, it is also important to control the TD roughness (Rz) and the glossiness of the surface of the copper foil before the surface treatment on the treatment side. Specifically, the TD surface roughness (Rz) of the copper foil before the surface treatment is 0.30 to 0.80 μm, preferably 0.30 to 0.50 μm, and the incident angle 60 in the rolling direction (MD) is 60. After the surface treatment, if the glossiness at 350 degrees is 350 to 800%, preferably 500 to 800%, the current density is higher than the conventional roughening treatment and the roughening treatment time is shortened. The glossiness of the surface-treated copper foil is 76 to 350% at an incident angle of 60 degrees in the rolling direction (MD). Such a copper foil can be produced by adjusting the oil film equivalent of rolling oil (high gloss rolling), or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, it is easy to control the surface roughness (Rz) and the surface area of the copper foil after the treatment by setting the TD surface roughness (Rz) and the glossiness of the copper foil before the treatment within the above range. Can do.
If the surface roughness (Rz) after the surface treatment is desired to be smaller (for example, Rz = 0.20 μm), the TD roughness (Rz) of the treated surface of the copper foil before the surface treatment is 0.18. 0.80 μm, preferably 0.25 to 0.50 μm, and the glossiness at an incident angle of 60 degrees in the rolling direction (MD) is 350 to 800%, preferably 500 to 800%. The current density is made higher than the roughening treatment, and the roughening treatment time is shortened.
Further, the copper foil before the roughening treatment preferably has a 60 degree gloss of MD of 500 to 800%, more preferably 501 to 800%, and still more preferably 510 to 750%. . If the 60-degree glossiness of MD of the copper foil before the roughening treatment is less than 500%, the haze value may be higher than the case of 500% or more, and if it exceeds 800%, it is difficult to produce. Problems may arise.
The high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000. When the surface roughness (Rz) after the surface treatment is desired to be smaller (for example, Rz = 0.20 μm), high gloss rolling should have an oil film equivalent defined by the following formula of 12000 to 24000. To do.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to make the oil film equivalent 12000 to 24000, a known method such as using a low viscosity rolling oil or slowing a sheet passing speed may be used.
Chemical polishing is performed with an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a lower concentration than usual and for a long time.

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

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

[Particle surface area]
The ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side greatly affects the haze value of the resin. That is, if the surface roughness Rz is the same, the haze value of the above-described resin decreases as the copper foil having a smaller ratio A / B. Therefore, in the surface-treated copper foil of the present invention, the ratio A / B is 1.90 to 2.40, and preferably 2.00 to 2.20.

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

As described above, the surface-treated copper foil of the present invention has a ratio A / B of 1.90 between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side. It is controlled to ˜2.40, and the surface unevenness is large. Further, since the average TD roughness Rz of the roughened surface is controlled to 0.20 to 0.80 μm, there is no extremely rough portion on the surface. On the other hand, the glossiness of the roughened surface is as high as 76 to 350%. Considering these, it can be seen that in the surface-treated copper foil of the present invention, the particle size of the roughened particles on the roughened surface is controlled to be small. The particle size of the roughened particles affects the transparency of the resin after the copper foil is etched away, but the surface-treated copper foil of the present invention has a surface average roughness on the side bonded to the resin substrate in this way. Controlling the ratio of the surface roughness Rz, the glossiness, and the surface area of the roughened particles to the area obtained when the roughened particles are planarly viewed from the copper foil surface side is within the scope of the present invention. This means that the diameter is reduced within an appropriate range. For this reason, the resin transparency after removing the copper foil by etching becomes good, and the peel strength also becomes good.

[Etching factor]
When the value of the etching factor when forming a circuit using copper foil is large, the bottom of the circuit that occurs during etching is reduced, so that the space between the circuits can be narrowed. Therefore, a larger etching factor is preferable because it is suitable for forming a circuit with a fine pattern. In the surface-treated copper foil of the present invention, for example, the etching factor is preferably 1.8 or more, preferably 2.0 or more, preferably 2.2 or more, and 2.3 or more. Preferably, it is 2.4 or more.
In the printed wiring board or copper-clad laminate, the surface roughness (Rz), particle area ratio (A / B), and gloss of the copper circuit or copper foil surface can be obtained by dissolving and removing the resin. The degree can be measured.
[Transmission loss]
When the transmission loss is small, attenuation of the signal when performing signal transmission at a high frequency is suppressed, so that a stable signal transmission can be performed in a circuit that transmits the signal at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency. After bonding the surface-treated copper foil to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), a microstrip line is formed by etching so that the characteristic impedance is 50Ω, and the network manufactured by HP When the transmission coefficient is measured using the analyzer HP8720C and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is determined, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm, and more preferably less than 4.1 dB / 10 cm. Preferably, less than 3.7 dB / 10 cm is even more preferable.

The surface-treated copper foil of the present invention can be bonded to a resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film, fluorine for FPC Resin etc. can be used. In addition, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the copper circuit is covered with a coverlay after the copper circuit is formed, so that the film and the copper circuit are not easily peeled off, and the peel strength is reduced. The film can be prevented from peeling off from the copper circuit.
In addition, since a liquid crystal polymer (LCP) film or a fluororesin film has a small dielectric loss tangent, a copper-clad laminate using a liquid crystal polymer (LCP) film or a fluororesin film and the surface-treated copper foil according to the present invention, printed wiring Boards and printed circuit boards are suitable for high-frequency circuits (circuits that transmit signals at high frequencies). Further, the surface-treated copper foil according to the present invention has a small surface roughness Rz and a high glossiness, so that the surface is smooth and suitable for high-frequency circuit applications.

For the bonding method, in the case of rigid PWB, a prepreg in which a base material such as glass cloth is impregnated with a resin and the resin is cured to a semi-cured state is prepared. It can be carried out by superposing a copper foil on the prepreg from the opposite surface of the coating layer and heating and pressing. In the case of FPC, it is laminated on a copper foil under high temperature and high pressure without using an adhesive on a substrate such as a polyimide film, or a polyimide precursor is applied, dried, cured, etc. A laminated board can be manufactured by performing.

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

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

In the thus prepared laminated plate, when the above-mentioned mark is photographed by the photographing means through the resin, the position of the mark can be detected well. And the position of the said mark can be detected in this way, and based on the position of the said detected mark, the positioning of the laminated board of surface-treated copper foil and a resin substrate can be performed favorably. Similarly, when a printed wiring board is used as the laminated board, the photographing means can detect the position of the mark well by such a positioning method, and the printed wiring board can be positioned more accurately.

Therefore, it is considered that when one printed wiring board and another printed wiring board are connected, the connection failure is reduced and the yield is improved. In addition, as a method of connecting one printed wiring board and another printed wiring board, soldering, connection through an anisotropic conductive film (Anisotropic Conductive Film, ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. Also, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring. Furthermore, the printed wiring board of the present invention may be connected to a component to produce a printed wiring board. Further, at least one printed wiring board of the present invention is connected to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention. A printed wiring board in which two or more printed wiring boards are connected may be manufactured by connecting two or more printed wiring boards and components. Here, “components” include connectors, LCDs (Liquid Crystal Display), electronic components such as glass substrates used in LCDs, ICs (Integrated Circuits), LSIs (Large Scale Integrated Circuits), VLSIs (Very Large Circuits). ), Electronic components including semiconductor integrated circuits such as ULSI (Ultra-Large Scale Integration) (for example, IC chips, LSI chips, VLSI chips, ULSI chips), components for shielding electronic circuits and covers on printed wiring boards Examples include parts necessary for fixing.

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

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

As Examples 1 to 24 and Comparative Examples 1 to 13, various copper foils were prepared, and plating treatment was performed on one surface under the conditions described in Tables 1 to 8 as a roughening treatment.
After performing the above-described rough plating treatment, the following plating treatment for forming the heat-resistant layer and the rust-preventing layer was carried out for Examples 1 to 13, 15 to 20, 22 to 24 and Comparative Examples 2, 4, and 7 to 10. went.
The conditions for forming the heat-resistant layer 1 are shown below.
Liquid composition: Nickel 5-20 g / L, Cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
A heat-resistant layer 2 was formed on the copper foil provided with the heat-resistant layer 1. In Comparative Examples 3, 5, and 6, the rough plating treatment was not performed, and the heat-resistant layer 2 was directly formed on the prepared copper foil. The conditions for forming the heat-resistant layer 2 are shown below.
Liquid composition: Nickel 2-30 g / L, Zinc 2-30 g / L
pH: 3-4
Liquid temperature: 30-50 ° C
Current density: 1 to 2 A / dm ²
Coulomb amount: 1 to ^{2 As} / dm ²
On the copper foil which gave the said heat-resistant layers 1 and 2, the antirust layer was further formed. The conditions for forming the rust preventive layer are shown below.
Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 ° C
Current density: 0-2A / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)
On the copper foil which gave the said heat-resistant layers 1 and 2 and a rust prevention layer, the weathering layer was further formed. The formation conditions are shown below.
As a silane coupling agent having an amino group, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Example 17), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (Example) Examples 1 to 13, 15, 16, 24), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (Example 18), 3-aminopropyltrimethoxysilane (Example 19), 3-amino Propyltriethoxysilane (Example 20), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Example 22), N-phenyl-3-aminopropyltrimethoxysilane (Example 23) ) Was applied and dried to form a weather resistant layer. These silane coupling agents can be used in combination of two or more.

In addition, the rolled copper foil was manufactured as follows. A copper ingot having the composition shown in Table 9 was manufactured and hot-rolled, and then the annealing and cold rolling of a continuous annealing line at 300 to 800 ° C. were repeated to obtain a rolled plate having a thickness of 1 to 2 mm. This rolled sheet was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thickness shown in Table 9 to obtain a copper foil. “Tough pitch copper” in the “Type” column of Table 9 indicates tough pitch copper standardized in JIS H3100 C1100, and “Oxygen-free copper” indicates oxygen-free copper standardized in JIS H3100 C1020. “Tough pitch copper + Ag: 100 ppm” means that 100 mass ppm of Ag is added to tough pitch copper.
The electrolytic copper foil used was an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metals. When electrolytic polishing was performed, the plate thickness after electrolytic polishing was described.
Table 9 shows the points of the copper foil preparation process before the surface treatment. “High gloss rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the value of the oil film equivalent. “Normal rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the oil film equivalent value described. “Chemical polishing” and “electropolishing” mean the following conditions.
“Chemical polishing” was performed using an etching solution of 1 to 3% by mass of H ₂ SO ₄ , 0.05 to 0.15% by mass of H ₂ O ₂ , and the remaining water, and the polishing time was 1 hour.
“Electropolishing” is a condition of phosphoric acid 67% + sulfuric acid 10% + water 23%, voltage 10 V / cm ² , and the time shown in Table 9 (when electropolishing for 10 seconds, the polishing amount is 1 to 2 μm. ).

Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
(1) Measurement of surface roughness (Rz);
Ten-point average roughness was measured on the roughened surface in accordance with JIS B0601-1994, using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory. Measurement standard length 0.8mm, evaluation length 4mm, cut-off value 0.25mm, feed rate 0.1mm / sec. Perpendicular to rolling direction (in TD, in case of electrolytic copper foil, in foil passing direction) The measurement position was changed 10 times (perpendicularly), and the values for 10 measurements were obtained.
In addition, the surface roughness (Rz) was calculated | required similarly about the copper foil before surface treatment.

(2) Particle area ratio (A / B);
The surface area of the roughened particles was measured by a laser microscope. Using a laser microscope VK8500 manufactured by Keyence Co., Ltd., measuring the three-dimensional surface area A in an area B equivalent to 100 × 100 μm at a magnification of 2000 times the roughened surface (actual data: 9982.52 μm ² ) Setting was performed by a method of setting a two-dimensional surface area B = area ratio (A / B).

(3) Glossiness;
Using a gloss meter PG-1 made by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741, the rolling direction (MD, foil direction in the case of electrolytic copper foil) and the direction perpendicular to the rolling direction (TD, In the case of an electrolytic copper foil, the roughened surface was measured at an incident angle of 60 degrees in a direction perpendicular to the direction of threading.
In addition, the glossiness was calculated | required similarly about the copper foil before surface treatment.

(4) haze value;
The copper foil was laminated on both sides of a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. The haze value of the sample film was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory based on JIS K7136 (2000).

(5) Visibility (resin transparency);
The copper foil was laminated on both sides of a polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex), and the copper foil was removed by etching (ferric chloride aqueous solution) to prepare a sample film. A printed material (black circle with a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer. “◎” indicates that the outline of the black circle of the printed material is clear when the length is 90% or more of the circumference, and “Clear” indicates that the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. “O” (passed above), a black circle with a clear outline of 0 to less than 80% of the circumference and a broken outline were evaluated as “x” (failed).

(6) Peel strength (adhesive strength);
In accordance with PC-TM-650, the normal peel strength was measured with a tensile tester Autograph 100, and the normal peel strength of 0.7 N / mm or more could be used for laminated substrates.

(7) Solder heat resistance evaluation;
The copper foil was bonded to both surfaces of a polyimide film with a thermosetting adhesive for laminating (thickness 50 μm, Upilex manufactured by Ube Industries). About the obtained double-sided laminated board, the test coupon based on JISC6471 was created. The prepared test coupon was exposed to high temperature and high humidity of 85 ° C. and 85% RH for 48 hours, and then floated in a solder bath at 300 ° C. to evaluate solder heat resistance. After the solder heat resistance test, at the interface between the copper foil roughening surface and the polyimide resin adhesion surface, the area where the interface discolored due to blistering in an area of 5% or more of the copper foil area in the test coupon is x (failed), area When the color change was less than 5%, the case was evaluated as ◯, and the case where no color change occurred was evaluated as ◎.

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

(9) Calculation of etching factor (Ef) The fine pattern circuit sample obtained above was observed from the top of the circuit at a magnification of 2000 using a scanning electron micrograph S4700 manufactured by Hitachi High-Technologies Corporation. The top width (Wa) at the top and the bottom width (Wb) at the bottom of the circuit were measured. The copper foil thickness (T) was 12 μm. The etching factor (Ef) was calculated by the following formula.
Etching factor (Ef) = (2 × T) / (Wb−Wa)
(10) Measurement of transmission loss For each sample with a thickness of 18 μm, after bonding with a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), a microstrip line is formed so that the characteristic impedance becomes 50Ω by etching. The transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. As an evaluation of transmission loss at a frequency of 20 GHz, 未満 less than 3.7 dB / 10 cm, ◎ 3.7 dB / 10 cm or more and less than 4.1 dB / 10 cm, 、４ 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm, △, 5.0 dB / 10 cm or more was defined as x.
The conditions and evaluation of each test are shown in Tables 1-10.

〔Evaluation results〕
Examples 1 to 24 all had good haze values, visibility and peel strength. The solder heat resistance evaluation was also good.
Comparative Examples 1 to 2, 4, 7 to 11 and 13 had a very high haze value and a large surface roughness, so that the visibility was poor.
In Comparative Examples 3, 5, 6, and 12, the visibility was excellent, but the peel strength was insufficient and the substrate adhesion was poor. In Comparative Examples 1 to 13, the solder heat resistance evaluation was poor.
Further, in Example 5, the 60 degree glossiness of Rz and MD and the surface area ratio A / B are substantially the same values as in Example 15, but the 60 degree glossiness of MD and TD of the roughened surface of Example 5 are the same. Since the value of the ratio C to 60 degree glossiness was within the range of 0.84 and 0.80 to 1.40, the C value was outside the range of 0.75 and 0.80 to 1.40. The haze value was smaller than in Example 15.
For the same reason, the haze value of Example 16 was smaller than that of Example 17.
FIG. 1 shows (a) Comparative Example 1, (b) Comparative Example 2, (c) Comparative Example 3, (d) Comparative Example 4, (e) Example 1, and (f) in the Rz evaluation. The SEM observation photograph of the copper foil surface of Example 2 is shown, respectively.

Claims

Roughening particles are formed on the surface of the copper foil by the roughening treatment, the average roughness Rz of the TD on the roughening treatment surface is 0.20 to 0.80 μm, and the 60 degree glossiness of MD on the roughening treatment surface is 76. ~ 350%,
A surface-treated copper foil having a ratio A / B of 1.90 to 2.40 of a surface area A of the roughened particles and an area B obtained when the roughened particles are viewed in plan from the copper foil surface side.
The surface-treated copper foil according to claim 1, wherein the MD has a 60-degree glossiness of 90 to 250%.
The surface-treated copper foil according to claim 1 or 2, wherein the average roughness Rz of the TD is 0.30 to 0.60 µm.
The surface-treated copper foil according to any one of claims 1 to 3, wherein the A / B is 2.00 to 2.20.
The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of the 60 degree gloss of MD and the 60 degree gloss of TD on the roughened surface is 0.80 to 1. The surface-treated copper foil according to any one of claims 1 to 4, which is 40.
The ratio C (C = (60 degree gloss of MD) / (60 degree gloss of TD)) of 0.90 to 1.60 of the 60 degree gloss of MD and 60 degree gloss of TD on the roughened surface. The surface-treated copper foil according to claim 5, which is 35.
When the copper foil is bonded to both surfaces of a 50 μm thick resin substrate from the roughened surface side and then the copper foil on both surfaces is removed by etching, the haze value of the resin substrate becomes 20 to 70%. The surface-treated copper foil according to any one of claims 1 to 6.
Roughening particles are formed by roughening treatment on the surface of the copper foil, and the copper foil is bonded to both surfaces of a 50 μm thick resin substrate from the roughening treatment surface side, and then the copper foils on both sides are removed by etching. When the surface-treated copper foil has a haze value of 20 to 70%.
A laminate comprising a laminate of the surface-treated copper foil according to any one of claims 1 to 8 and a resin substrate.
A copper foil before the roughening treatment used for the surface-treated copper foil according to any one of claims 1 to 8.
The copper foil before roughening according to claim 10, wherein the 60 ° gloss of MD is 500 to 800%.
A copper foil with a 60 degree gloss of MD of 501 to 800%.
A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 8.
An electronic device using the printed wiring board according to claim 13.
A method for manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to claim 13.
Connecting at least one printed wiring board according to claim 13 to another printed wiring board according to claim 13 or a printed wiring board not corresponding to the printed wiring board according to claim 13; A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected.
An electronic device using one or more printed wiring boards to which at least one printed wiring board according to claim 15 or 16 is connected.
A method for manufacturing a printed wiring board, comprising at least a step of connecting the printed wiring board according to claim 13 and a component.
Connecting at least one printed wiring board according to claim 13 to another printed wiring board according to claim 13 or a printed wiring board not corresponding to the printed wiring board according to claim 13, and
A printed wiring board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board according to claim 13 or two or more printed wiring boards according to claim 16 and a component. A method of manufacturing a wiring board.