JP2018076601A - Electrolytic copper foil, production method thereof, copper clad laminate, printed wiring board and production method thereof, and production method of electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic copper foil having excellent circuit formability.SOLUTION: The electrolytic copper foil does not contain a roughening treatment layer at the side of a glossy surface, and the root mean square height of the glossy surface is below 0.315 μm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrolytic copper foil, a method for producing an electrolytic copper foil, a copper clad laminate, a printed wiring board, a method for producing a printed wiring board, and a method for producing an electronic device.

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  In order to realize the miniaturization of the conductor pattern as described above using the electrolytic copper foil, conventionally, an electrolytic copper having a smooth surface on the deposition surface side by adding a brightening agent to the electrolytic solution for producing the electrolytic copper foil. A foil was produced and a circuit was formed on the surface (Patent Document 1).

JP 2004-162172 A

  However, when a brightening agent is added to the electrolytic solution for producing an electrolytic copper foil as described above to produce an electrolytic copper foil with a smooth surface on the precipitation side, and a circuit is formed on the surface, Under the influence of the additive contained, wrinkles are likely to occur in the copper foil due to recrystallization at normal temperature and the accompanying shrinkage during the production of the electrolytic copper foil. And when the said wrinkle generate | occur | produces, there exists a problem which a wrinkle generate | occur | produces also when bonding subsequent electrolytic copper foil with a resin substrate. Thus, when wrinkles are generated in the electrolytic copper foil, it becomes difficult to make a fine pitch when forming a circuit on the electrolytic copper foil.

  Then, this invention makes it a subject to provide the electrolytic copper foil with favorable circuit formation property.

  In one aspect, the present invention is an electrolytic copper foil that does not have a roughening treatment layer on the glossy surface side, and the root mean square height Sq of the glossy surface is 0.315 μm or less.

  In one embodiment, the electrolytic copper foil of the present invention has a surface roughness Sa of the glossy surface of 0.150 μm or less.

  In another embodiment of the electrolytic copper foil of the present invention, the root mean square height Sq of the glossy surface is 0.200 μm or less.

  Another aspect of the present invention is an electrolytic copper foil that does not have a roughening layer on the glossy surface side and that has a root mean square height Sq of 0.200 μm or less.

  In another embodiment of the electrolytic copper foil of the present invention, the glossy surface has a surface roughness Sa of 0.133 μm or less, or 0.130 μm or less.

  In still another embodiment of the electrolytic copper foil of the present invention, the root mean square height Sq of the glossy surface is 0.180 μm or less.

  In still another embodiment of the electrolytic copper foil of the present invention, the root mean square height Sq of the glossy surface is 0.120 μm or less.

  According to another aspect of the present invention, there is provided an electrolytic copper foil having a roughened layer on the glossy surface side and having a root mean square height Sq of the glossy surface of 0.550 μm or less.

  In another embodiment of the electrolytic copper foil of the present invention, the glossy surface has a surface roughness Sa of 0.380 μm or less.

  In still another embodiment of the electrolytic copper foil of the present invention, the root mean square height Sq on the glossy surface side is 0.490 μm or less, or 0.450 μm or less, or 0.400 μm or less, or 0.330 μm or less. It is.

  In still another embodiment of the electrolytic copper foil of the present invention, the surface roughness Sa on the glossy surface side is 0.355 μm or less, or 0.300 μm or less, or 0.200 μm or less.

  In still another embodiment of the electrolytic copper foil of the present invention, the surface roughness Sa of the glossy surface before providing the roughening layer on the glossy surface side is 0.270 μm or less, or 0.150 μm or less, or 133 μm or less, or 0.130 μm or less.

  In yet another embodiment of the electrolytic copper foil of the present invention, the root mean square height Sq of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.315 μm or less, or 0.200 μm or less, Or it is 0.180 micrometer or less, or 0.120 micrometer or less.

In still another embodiment, the electrolytic copper foil of the present invention has a normal temperature tensile strength of 30 kg / mm ² or more.

  In yet another embodiment, the electrolytic copper foil of the present invention has a room temperature elongation of 3% or more.

In yet another embodiment, the electrolytic copper foil of the present invention has a high-temperature tensile strength of 10 kg / mm ² or more.

  In still another embodiment, the electrolytic copper foil of the present invention has a high temperature elongation of 2% or more.

  In yet another embodiment, the electrolytic copper foil of the present invention has a roughening treatment layer on the surface opposite to the glossy surface of the electrolytic copper foil.

  In another embodiment of the electrolytic copper foil of the present invention, the roughening layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is a layer made of any simple substance or an alloy containing any one or more kinds.

  In another embodiment of the electrolytic copper foil of the present invention, a heat-resistant layer on the surface of one or both of the glossy surface side of the electrolytic copper foil and the surface side opposite to the glossy surface, It has 1 or more types of layers selected from the group which consists of a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer.

  In yet another embodiment of the electrolytic copper foil of the present invention, one or both of the glossy surface side and the surface side opposite to the glossy surface of the electrolytic copper foil are a heat-resistant layer, a rust prevention layer, and a chromate treatment layer. And one or more layers selected from the group consisting of silane coupling treatment layers.

  In still another embodiment, the electrolytic copper foil of the present invention includes a resin layer on one or both of the glossy surface side and the surface side opposite to the glossy surface of the electrolytic copper foil.

  In still another embodiment, the electrolytic copper foil of the present invention includes a resin layer on the roughening treatment layer.

  In yet another embodiment, the electrolytic copper foil of the present invention has a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. Prepare.

  In still another aspect, the present invention is a method for producing an electrolytic copper foil, wherein an electrolytic copper foil is produced using an electrolytic drum having a surface root mean square height Sq of 0.315 μm or less.

  In one embodiment, the present invention is a method for producing an electrolytic copper foil in which an electrolytic copper foil is produced using an electrolytic drum having a surface roughness Sa of 0.150 μm or less.

  In one embodiment, the present invention is a method for producing an electrolytic copper foil, which uses an electrolytic drum having a surface root mean square height Sq of 0.200 μm or less.

  In yet another aspect, the present invention is a copper clad laminate having the electrolytic copper foil of the present invention.

  In yet another aspect, the present invention is a printed wiring board having the electrolytic copper foil of the present invention.

  In still another aspect, the present invention is a printed wiring board manufacturing method for manufacturing a printed wiring board using the electrolytic copper foil of the present invention.

  In yet another aspect of the present invention, a copper-clad laminate is formed by laminating the electrolytic copper foil of the present invention and an insulating substrate, and then a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. A method of manufacturing a printed wiring board including a step of forming a circuit by any one of the methods.

  In still another aspect of the present invention, there is provided an electronic device manufacturing method for manufacturing an electronic device using the printed wiring board manufactured by the method of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the electrolytic copper foil with favorable circuit formation property can be provided.

(A) is the SEM image of the glossy surface of the electrolytic copper foil of Example 2. FIG. (B) is the SEM image of the glossy surface of the electrolytic copper foil of Example 10.

  Hereinafter, embodiments of the electrolytic copper foil of the present invention will be described. In this specification, “surface roughness Sa of glossy surface” and “root mean square height Sq of glossy surface” are a roughened layer, a heat-resistant layer, and a rust-proof layer on the glossy surface of electrolytic copper foil, respectively. When a surface treatment layer such as a chromate treatment layer or a silane coupling treatment layer is provided, the surface roughness Sa of the surface (outermost layer surface) after the surface treatment layer is provided, and the root mean square The height Sq is indicated. Further, “the surface roughness Sa of the glossy surface before providing the roughening treatment layer on the glossy surface side” and “the root mean square height Sq of the glossy surface before providing the roughening treatment layer on the glossy surface side” are: Each surface treatment layer other than the roughening treatment layer such as a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer is provided on the glossy surface before providing the roughening treatment layer on the glossy surface side. In the case, the surface roughness Sa and the root mean square height Sq of the surface (surface of the outermost layer) after the surface treatment layer is provided are shown.

<Electrolytic copper foil without roughening layer on the glossy surface>
In one aspect, the electrolytic copper foil of the present invention does not have a roughening treatment layer on the glossy surface side, and the surface roughness Sa of the glossy surface is 0.270 μm or less, preferably 0.150 μm or less. In the present invention, the glossy surface of the electrolytic copper foil refers to the surface (shiny surface: S surface) on the drum side when the electrolytic copper foil is produced. In the electrolytic copper foil of the present invention, the surface opposite to the glossy surface is the surface (mat surface: M surface) on the opposite side (deposition surface) from the drum when the electrolytic copper foil is produced. Show.
With such a configuration, a fine pitch of L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less is possible for the pitch of the circuit formed using the electrolytic copper foil. The surface roughness Sa of the glossy surface is preferably 0.230 μm or less, preferably 0.180 μm or less, preferably 0.150 μm or less, preferably 0.133 μm or less, 0 More preferably, it is 130 μm or less, and more preferably 0.120 μm or less. Although the minimum of surface roughness Sa of the glossy surface of an electrolytic copper foil is not specifically limited, For example, it is 0.001 micrometer or more, 0.010 micrometer or more, 0.050 micrometer or more, or 0.100 micrometer or more.

In another aspect, the electrolytic copper foil of the present invention does not have a roughening treatment layer on the glossy surface side, and the root mean square height Sq of the glossy surface is 0.315 μm or less, preferably 0.8. 200 μm or less.
With such a configuration, a fine pitch of L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less is possible for the pitch of the circuit formed using the electrolytic copper foil. The root mean square height Sq of the glossy surface is preferably 0.292 μm or less, preferably 0.230 μm or less, preferably 0.200 μm or less, and 0.180 μm or less. Preferably, it is 0.120 μm or less, and more preferably 0.115 μm or less. The lower limit of the root mean square height Sq of the glossy surface of the electrolytic copper foil is not particularly limited, but is, for example, 0.001 μm or more, or 0.010 μm or more, or 0.050 μm or more, or 0.100 μm or more.

<Electrolytic copper foil having a roughened layer on the glossy surface>
In another aspect, the electrolytic copper foil of the present invention has a roughening treatment layer on the glossy surface side, and the surface roughness Sa of the glossy surface is 0.470 μm or less, preferably 0.380 μm or less. Electrolytic copper foil.
With such a configuration, a fine pitch of L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less is possible for the pitch of the circuit formed using the electrolytic copper foil. The surface roughness Sa of the glossy surface is preferably 0.385 μm or less, preferably 0.380 μm or less, preferably 0.355 μm or less, and preferably 0.340 μm or less. It is preferably 0.300 μm or less, preferably 0.295 μm or less, preferably 0.230 μm or less, and more preferably 0.200 μm or less. Although the minimum of surface roughness Sa of the glossy surface of an electrolytic copper foil is not specifically limited, For example, it is 0.001 micrometer or more, 0.010 micrometer or more, 0.050 micrometer or more, or 0.100 micrometer or more.

  The electrolytic copper foil preferably has a glossy surface roughness Sa of 0.270 μm or less, preferably 0.230 μm or less, before the roughening layer is provided on the glossy surface side. It is preferably 180 μm or less, preferably 0.150 μm or less, more preferably 0.133 μm or less, still more preferably 0.130 μm or less, and even more preferably 0.120 μm or less. According to such a configuration, the surface roughness Sa of the glossy surface of the electrolytic copper foil after providing the roughening treatment layer and / or the glossy surface 2 of the electrolytic copper foil after providing the roughening treatment layer. The root mean square height Sq can be controlled to an appropriate value, and the pitch of the circuit formed using the electrolytic copper foil is L / S (line / space) = 22 μm or less / 22 μm or less, more preferably 20 μm. Fine pitches of 20 μm or less are possible. The lower limit of the surface roughness Sa of the glossy surface before the roughening treatment layer is provided on the glossy surface side of the electrolytic copper foil is not particularly limited. For example, 0.001 μm or more, or 0.010 μm or more, or 0.050 μm or more, or It is 0.100 μm or more.

In another aspect, the electrolytic copper foil of the present invention has a roughened layer on the glossy surface side, and the root mean square height Sq of the glossy surface is 0.550 μm or less, preferably 0.490 μm. It is as follows.
With such a configuration, a fine pitch of L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less is possible for the pitch of the circuit formed using the electrolytic copper foil. The root mean square height Sq of the glossy surface is preferably 0.490 μm or less, preferably 0.450 μm or less, preferably 0.435 μm or less, and 0.400 μm or less. Preferably, it is 0.395 μm or less, more preferably 0.330 μm or less, and more preferably 0.290 μm or less. The lower limit of the root mean square height Sq of the glossy surface of the electrolytic copper foil is not particularly limited, but is, for example, 0.001 μm or more, or 0.010 μm or more, or 0.050 μm or more, or 0.100 μm or more.

  The electrolytic copper foil preferably has a root mean square height Sq of 0.35 μm or less, preferably 0.292 μm or less, of the glossy surface before the roughening layer is provided on the glossy surface side. 0.230 μm or less, preferably 0.200 μm or less, preferably 0.180 μm or less, more preferably 0.120 μm or less, and more preferably 0.115 μm or less. According to such a configuration, the surface roughness Sa of the glossy surface of the electrolytic copper foil after providing the roughening treatment layer and / or the glossy surface 2 of the electrolytic copper foil after providing the roughening treatment layer. The root mean square height Sq can be controlled to an appropriate value, and the pitch of the circuit formed using the electrolytic copper foil is L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less. A fine pitch of / 20 μm or less is possible. The lower limit of the root mean square height Sq of the glossy surface before the roughening layer is provided on the glossy surface side of the electrolytic copper foil is not particularly limited. For example, 0.001 μm or more, or 0.010 μm or more, or 0.050 μm. Or 0.100 μm or more.

The electrolytic copper foil of the present invention preferably has a normal temperature tensile strength of 30 kg / mm ² or more. “Room temperature tensile strength” indicates the tensile strength at room temperature and is measured according to IPC-TM-650. When the normal temperature tensile strength is 30 kg / mm ² or more, there is an effect that wrinkles are hardly generated during handling. More preferably, it is 35 kg / mm ² or more.

  The electrolytic copper foil of the present invention preferably has a room temperature elongation of 3% or more. “Normal temperature elongation” indicates elongation at room temperature and is measured according to IPC-TM-650. When the room temperature elongation is 3% or more, there is an effect that it is difficult to break. The room temperature elongation is more preferably 4% or more.

The electrolytic copper foil of the present invention preferably has a high temperature tensile strength of 10 kg / mm ² or more. “High temperature tensile strength” refers to tensile strength at 180 ° C., and is measured according to IPC-TM-650. When the high temperature tensile strength is 10 kg / mm ² or more, there is an effect that wrinkles are hardly generated when sticking to the resin. More preferably, it is 15 kg / mm ² or more.

  The electrolytic copper foil of the present invention preferably has a high temperature elongation of 2% or more. “High temperature elongation” refers to elongation at 180 ° C. and is measured according to IPC-TM-650. When the high temperature elongation is 2% or more, there is an effect in preventing the occurrence of cracks in the circuit. The high temperature elongation is preferably 3% or more, more preferably 6% or more, and more preferably 15% or more.

  The electrolytic copper foil of the present invention has, in addition to pure copper, for example, Sn-containing copper, Ag-containing copper, Ti, W, Mo, Cr, in addition to pure copper, when a later-described surface treatment layer is provided. Copper alloys added with Zr, Mg, Ni, Sn, Ag, Co, Fe, As, P, etc. can also be used. In this specification, when the term “copper foil” is used alone, it also includes a copper alloy foil. These copper alloy foils are composed of alloying elements (for example, Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Co, Fe, As, and P) in an electrolytic solution used for producing an electrolytic copper foil. It can be manufactured by adding electrolytic copper foil by adding one or more elements selected from the group. The thickness of the electrolytic copper foil is not particularly limited, but is typically 0.5 to 3000 μm, preferably 1.0 to 1000 μm, preferably 1.0 to 300 μm, preferably 1.0 to 100 μm. The thickness is preferably 3.0 to 75 μm, preferably 4 to 40 μm, preferably 5 to 37 μm, preferably 6 to 28 μm, preferably 7 to 25 μm, preferably 8 to 19 μm.

<Method for producing electrolytic copper foil>
The electrolytic copper foil of the present invention is produced by electrolytically depositing copper from a copper sulfate plating bath onto a titanium or stainless steel drum. The electrolysis conditions are shown below.
<Electrolysis conditions>
Electrolyte composition: Cu 50-150 g / L, H ₂ SO ₄ 60-150 g / L,
Current density: 30 to 120 A / dm ²
Electrolyte temperature: 50 to 60 degrees Additive: Chlorine ion 20 to 80 ppm, Nika 0.01 to 10.0 ppm
In addition, the balance of the processing liquid (etching liquid, electrolytic solution, etc.) used for electrolysis, etching, surface treatment or plating described in this specification is water unless otherwise specified.

The electrolytic drum used at this time has a surface roughness Sa of the drum surface of 0.270 μm or less, preferably 0.15 μm or less. Further, the root mean square height Sq of the drum surface is 0.315 μm or less, preferably 0.20 μm or less. In the electrolytic drum having the surface roughness Sa or the root mean square height Sq on the surface, first, the surface of a titanium or stainless steel drum is polished by a polishing belt having a count of 300 (P300) to 500 (P500). . At this time, the polishing belt is wound by a predetermined width in the drum width direction, and polishing is performed by rotating the drum while moving the polishing belt in the drum width direction at a predetermined speed. The rotation speed of the drum surface during the polishing is 130 to 190 m / min. The polishing time is the product of the time required to pass one point (position in the width direction) on the drum surface and the number of passes in one pass of the polishing belt. The time for passing one point on the drum surface in one pass described above was a value obtained by dividing the width of the polishing belt by the moving speed of the polishing belt in the width direction of the drum. The single pass of the polishing belt means that the surface of the drum in the circumferential direction is polished once from one end in the drum axis (width) direction (width direction of the electrolytic copper foil) to the other end. It means polishing with a belt. That is, the polishing time is expressed by the following formula.
Polishing time (minutes) = width of polishing belt per pass (cm / time) / moving speed of polishing belt (cm / minute) × number of passes (times)
So far, in the production of electrolytic copper foil, the polishing time has been 1.6 to 3 minutes, but in the present invention it is 3.5 to 10 minutes, and in the present invention, 6 to 6 when the drum surface is wet with water during polishing. 10 minutes. As an example of calculation of the polishing time, for example, when a moving speed is set to 20 cm / min with a polishing belt having a width of 10 cm, the polishing time for one pass at one point on the drum surface is 0.5 minutes. This is calculated by multiplying the total number of passes (for example, 0.5 minutes × 10 passes = 5 minutes). Drum by increasing the count of the polishing belt and / or increasing the rotational speed of the drum surface and / or increasing the polishing time and / or wetting the drum surface with water during polishing The surface roughness Sa of the surface and the root mean square height Sq of the drum surface can be reduced. Also, by reducing the count of the polishing belt and / or decreasing the rotation speed of the drum surface and / or shortening the polishing time and / or drying the drum surface during polishing The surface roughness Sa of the drum surface and the root mean square height Sq of the drum surface can be increased. Note that by increasing the polishing time, the surface roughness Sa can be reduced, and the root mean square height Sq can be reduced to a greater extent than Sa can be reduced. Further, by shortening the polishing time, the surface roughness Sa can be increased, and the root mean square height Sq can be increased to a greater extent than the extent that the surface roughness Sa is increased. The count of the above-described abrasive belt means the particle size of the abrasive used in the abrasive belt. And the particle size of the said abrasives is based on FEPA (Federation of European Producers of Abbreviations) -standard 43-1: 2006, 43-2: 2006.

In addition, when the surface of the drum is wetted with water, the root mean square height Sq can be reduced, and the surface roughness Sa can be reduced to a greater extent than the extent that the root mean square height Sq is reduced. I can do it. Further, by drying the drum surface during polishing, the root mean square height Sq can be increased, and the surface roughness Sa can be increased to a greater extent than the extent that the root mean square height Sq is increased. .
In this way, electrolysis in which the surface roughness Sa of the glossy surface is 0.270 μm or less, preferably 0.150 μm or less, and / or the root mean square height Sq is 0.315 μm or less, preferably 0.200 μm or less. Copper foil can be produced.
Moreover, the surface roughness Sa of the glossy surface is 0.270 μm or less, preferably 0.150 μm or less, and / or the root mean square height Sq is 0.315 μm or less, preferably 0.200 μm or less. By carrying out the roughening treatment or surface treatment described later on the glossy surface side, the glossy surface side has a roughening treatment layer, and the surface roughness Sa of the glossy surface is 0.470 μm or less, preferably 0.380 μm or less, and Or, an electrolytic copper foil having a root mean square height Sq of the glossy surface of 0.550 μm or less, preferably 0.490 μm or less can be produced.

The surface roughness Sa and the root mean square height Sq of the electrolytic drum surface can be measured as follows.
-A resin film (polyvinyl chloride) is swollen by immersing it in a solvent (acetone).
-The swollen resin film is brought into contact with the surface of the electrolytic drum. After the acetone is volatilized from the resin film, the resin film is peeled off, and a replica of the electrolytic drum surface is collected.
The replica is measured with a laser microscope, and the surface roughness Sa and the root mean square height Sq are measured.
Then, the surface roughness Sa and the root mean square height Sq of the obtained replica were set as the surface roughness Sa and the root mean square height Sq of the surface of the electrolytic drum.

<Roughening treatment and other surface treatment>
One or both of the glossy surface of the electrolytic copper foil and the surface opposite to the glossy surface is subjected to a roughening treatment, for example, to improve the adhesion to the insulating substrate, etc. May be provided. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment may be fine, or may be performed by forming needle-like, rod-like or particle-like roughened particles. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing at least one of them. It may be. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. Further, one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

  The roughening treatment layer can be formed by using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one kind of a material selected from alkyl sulfate salts, tungsten ions, and arsenic ions. The roughened layer is preferably plated with an electrolytic bath made of sulfuric acid / copper sulfate to prevent powder falling and improve peel strength.

Specific processing conditions are as follows.
(Liquid composition 1)
CuSO ₄ .5H ₂ O: 39.3 to 118 g / L
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
Na ₂ WO ₄ .2H ₂ O: 0 to 90 mg / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0-50mg
H ₃ AsO ₃ (60% aqueous solution): 0-6315 mg / L
As: 0 to 2000 mg / L

(Electroplating condition 1)
Temperature: 30-70 ° C
(Current condition 1)
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds (Liquid composition 2)
CuSO ₄ .5H ₂ O: 78 to 314 g / L
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
(Current condition 2)
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds

Also, copper as a roughened layer - cobalt - nickel alloy plated layer by electrolytic plating, deposition amount of 15~40mg / dm ² of copper -100~3000μg / dm ² of cobalt -100~1500μg / dm ² A ternary alloy layer such as nickel can be formed. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. If the amount of Co adhesion 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 plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density: 20-30 A / dm ²
Plating time: 1 to 5 seconds Another example of the plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density: 30 to 45 A / dm ²
Plating time: 0.1-2.0 seconds In addition, in the process which forms the above-mentioned roughening process layer, the said gloss of the electrolytic copper foil which has a roughening process layer in a glossy surface side by shortening plating time. The surface roughness Sa of the surface and / or the root mean square height Sq of the glossy surface can be reduced. Further, in the treatment for forming the roughening treatment layer, by increasing the plating time, the surface roughness Sa of the glossy surface of the electrolytic copper foil having the roughening treatment layer on the glossy surface side, and / or The root mean square height Sq of the glossy surface can be increased.
Further, in the treatment for forming the roughened layer, the surface roughness of the glossy surface of the electrolytic copper foil having the roughened layer on the glossy surface side can be increased by increasing the current density and significantly shortening the plating time. Sa and / or the root mean square height Sq of the glossy surface can be further reduced. Further, in the treatment for forming the roughening treatment layer described above, the surface roughness Sa of the glossy surface of the electrolytic copper foil having the roughening treatment layer on the glossy surface side by increasing the current density and increasing the plating time. And / or the root mean square height Sq of the glossy surface can be further increased.

  The electrolytic copper foil of the present invention may be provided with a roughening treatment layer on one or both of the glossy surface and the surface opposite to the glossy surface. One or more layers selected from the group consisting of a layer, a chromate treatment layer, and a silane coupling treatment layer may be provided. In addition, a roughened layer may be provided on the electrolytic copper foil, a heat-resistant layer and a rust-proof layer may be provided on the roughened layer, and a chromate-treated layer may be provided on the heat-resistant layer and the rust-proof layer. Alternatively, a silane coupling treatment layer may be provided on the chromate treatment layer.

  The electrolytic copper foil of the present invention has a glossy surface and / or a surface opposite to the glossy surface, or a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, or a silane coupling treatment. A resin layer may be provided on the layer. The resin layer may be an insulating resin layer.

Moreover, a well-known heat resistant layer and a rust preventive layer can be used as a heat resistant layer and a rust preventive layer. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a copper-zinc alloy layer, a zinc-nickel alloy layer, a nickel-cobalt alloy layer, a copper-nickel alloy layer, or a chromium-zinc alloy layer. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred.

  The chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

  As the silane coupling agent used for the silane coupling treatment, a known silane coupling agent may be used. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-Aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane Good.

The silane coupling treatment layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the resin base material and the metal foil can be further improved.

  The resin layer may be an adhesive, or an insulating resin layer in a semi-cured state (B stage state) for bonding. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, and the like can be preferably used. .

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO2006 / 028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  These resins are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin solution, which is used on the electrolytic copper foil, the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane coupling. On the agent layer, it is applied by, for example, a roll coater method or the like, and then heated and dried as necessary to remove the solvent to obtain a B-stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

  The electrolytic copper foil provided with the resin layer is used in such a manner that a predetermined wiring pattern is formed after the resin layer is superposed on a substrate and the whole is thermocompression bonded to thermally cure the resin layer. The

  When this electrolytic copper foil with resin is used, the number of prepreg materials used at the time of manufacturing a multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

  In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.

  The thickness of this resin layer is preferably 0.1 to 80 μm. When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when this copper foil with a carrier with a resin is laminated on a base material provided with an inner layer material without interposing a prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.

  On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

  Further, as another product form of the resin-coated electrolytic copper foil, a resin layer is coated on the glossy surface, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. And after making it into a semi-hardened state, it is also possible to manufacture in the form of electrolytic copper foil with resin.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, a printed board, a flexible printed wiring board, and a rigid printed wiring board on which electronic components are mounted in this manner.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the electrolytic copper foil which concerns on this invention are shown.

  In one embodiment of a method for producing a printed wiring board according to the present invention, a copper-clad laminate is formed by laminating an electrolytic copper foil and an insulating substrate according to the present invention, and then a semi-additive method, a modified semi-additive method, A step of forming a circuit by any one of a partly additive method and a subtractive method is included. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, the step of laminating the electrolytic copper foil and the insulating substrate according to the present invention,
Removing all of the electrolytic copper foil by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the electrolytic copper foil by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

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

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

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of laminating the electrolytic copper foil according to the present invention and an insulating substrate,
Providing a through hole or / and a blind via in the electrolytic copper foil and the insulating substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the electrolytic copper foil,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the electrolytic copper foil exposed by removing the plating resist by flash etching;
including.

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

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the partly additive method, a step of laminating the electrolytic copper foil and the insulating substrate according to the present invention,
Providing a through hole or / and a blind via in the electrolytic copper foil and the insulating substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the electrolytic copper foil,
Exposing the etching resist to form a circuit pattern;
Removing the electrolytic copper foil and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the electrolytic copper foil and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

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

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

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

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

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

1. Preparation of electrolytic copper foil (Examples 1-14, Comparative Example 1)
A rotating drum (electrolytic drum) made of titanium was prepared. Next, polishing was performed under the electrolytic drum surface control conditions shown in Table 1 to obtain an electrolytic drum having a predetermined surface roughness Sa and root mean square height Sq. Specifically, the surface of the electrolytic drum was polished by a count polishing belt described in Table 1. At this time, the polishing belt was wound by a predetermined width in the drum width direction, and was polished by rotating the drum while moving the polishing belt in the drum width direction. Table 1 shows the rotational speed of the drum surface during the polishing. The polishing time was the product of the time required to pass one point on the drum surface in one pass and the number of passes based on the width of the polishing belt and the moving speed of the polishing belt. Here, a single pass of the polishing belt means that the circumferential surface of the rotating drum is polished by one polishing belt from one end in the axial direction (width direction of the electrolytic copper foil) to the other end. It means to do.
That is, the polishing time is expressed by the following formula.
Polishing time (minutes) = width of polishing belt per pass (cm / time) / moving speed of polishing belt (cm / minute) × number of passes (times)

Next, an electrode was placed in the electrolytic cell with the electrolytic drum and a predetermined inter-electrode distance around the drum. Next, electrolysis was performed in the electrolytic bath under the following conditions, and copper was deposited on the surface of the electrolytic drum until the thickness became 18 μm while rotating the electrolytic drum.
<Electrolysis conditions>
Electrolyte composition: Cu 50-150 g / L, H ₂ SO ₄ 60-150 g / L,
Current density: 30 to 120 A / dm ²
Electrolyte temperature: 50-60 degrees Additive: Chlorine ion 20-80 mass ppm, Nika 0.01-5.0 mass ppm
In Examples 1, 2, 5, 6, 10 to 12, and Comparative Example 1, the glue concentration was low within the above range.
In Examples 3, 4, 7, 8, 9, 13, and 14, the glue concentration was set high within the aforementioned range.

  Next, the copper deposited on the surface of the rotating electrolytic drum was peeled off to continuously produce an electrolytic copper foil having a thickness of 18 μm.

  For Examples 1 to 4, 10 and Comparative Example 1, the surfaces shown in the following (1) to (4) are further added to the surface (glossy surface) on the electrolytic drum side of the electrolytic copper foil produced as described above. Processing was performed in this order.

(1) Roughening treatment Roughened particles were formed using a copper roughening plating bath described below, consisting of Cu, H ₂ SO ₄ , As, and W.
(Liquid composition 1)
CuSO ₄ .5H ₂ O: 39.3 to 118 g / L
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
Na ₂ WO ₄ .2H ₂ O: 0 to 90 mg / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0-50mg
H ₃ AsO ₃ (60% aqueous solution): 0-6315 mg / L
As: 0 to 2000 mg / L

(Electroplating condition 1)
Temperature: 30-70 ° C
(Current condition 1)
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds (Liquid composition 2)
CuSO ₄ .5H ₂ O: 78 to 314 g / L
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
(Current condition 2)
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds

(2) Barrier treatment (heat-resistant treatment)
Nickel zinc alloy plating (liquid composition)
Ni 13g / L
Zn 5g / L
pH 2
(Electroplating conditions)
Temperature 40 ℃
Current density 8A / dm ²

(3) Chromate treatment Zinc chromate treatment (liquid composition)
CrO ₃ 2.5g / L
Zn 0.7g / L
Na ₂ SO ₄ 10 g / L
pH 4.8
(Zinc chromate condition)
Temperature 54 ° C
Current density 0.7 As / dm ²

(4) Silane coupling treatment (liquid composition)
Tetraethoxysilane content 0.4 vol%
pH 7.5
Application method Spraying solution

  For Examples 5 to 8 and 14, the surface treatment shown in the following (1) to (5) is further applied to the surface (glossy surface) on the electrolytic drum side of the electrolytic copper foil produced as described above. Conducted in order.

(1) Roughening treatment Roughening treatment was performed in the following plating bath and plating conditions in order to form roughening particles of ternary copper-cobalt-nickel alloy plating.
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density: 20-30 A / dm ²
Plating time: 1-5 seconds

(2) Heat-resistant Co—Ni alloy plating was performed. Co-Ni alloy plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²
Plating time: 0.1 to 5 seconds

(3) Rust-proof zinc-nickel alloy plating (liquid composition)
Ni 1-15g / L
Zn 10-40g / L
pH 3-4
(Electroplating conditions)
Temperature 40-55 ° C
Current density 2-5A / dm ²

(4) Chromate treatment Zinc chromate treatment (liquid composition)
CrO ₃ 2.5g / L
Zn 0.7g / L
Na ₂ SO ₄ 10 g / L
pH 4.8
(Zinc chromate condition)
Temperature 54 ° C
Current density 0.7 As / dm ²

(5) Silane coupling treatment (liquid composition)
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane content 0.4 vol%
pH 7.5
Application method Spraying solution

  About Example 9, the surface treatment shown in the following (1) to (3) was further performed in this order on the surface (glossy surface) on the electrolytic drum side of the electrolytic copper foil produced as described above. .

(1) Barrier treatment (heat-resistant treatment)
Nickel-zinc alloy plating (liquid composition)
Ni 13g / L
Zn 5g / L
pH 2
(Electroplating conditions)
Temperature 40 ℃
Current density 8A / dm ²

(2) Chromate treatment Zinc chromate treatment (liquid composition)
CrO ₃ 2.5g / L
Zn 0.7g / L
Na ₂ SO ₄ 10 g / L
pH 4.8
(Zinc chromate condition)
Temperature 54 ° C
Current density 0.7 As / dm ²

(3) Silane coupling treatment (liquid composition)
Tetraethoxysilane content 0.4%
pH 7.5
Application method Spraying solution

After the surface treatment described above, a resin layer was formed on the surface of the copper foil surface treatment layer under the following conditions.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap equipped with a nitrogen inlet tube and a stopcock, and a reflux condenser equipped with a ball cooling tube, 3,4, 3 ', 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, then 3, 4, 3 ′, 4′- Add 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 200 g of NMP, and 40 g of toluene. After 1 hour mixing at room temperature, and heated for 3 hours at 180 ° C., to obtain a 38% solids polyimide block copolymer. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

  The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%. In this block copolymerized polyimide solution, bis (4-maleimidophenyl) methane (BMI-H, Silica Chemical) is contained in a solid content weight ratio of 35 and a solid content weight ratio of block copolymer polyimide of 65 (that is, included in the resin solution). Bis (4-maleimidophenyl) methane solid content weight: block copolymerized polyimide solid content weight contained in resin solution = 35: 65) A resin solution was prepared by dissolving and mixing at 60 ° C. for 20 minutes. Thereafter, in Example 9, the surface of the copper foil surface treatment layer was coated with the resin solution using a reverse roll coater, and dried at 120 ° C. for 3 minutes and at 160 ° C. for 3 minutes in a nitrogen atmosphere. Then, finally, heat treatment was performed at 300 ° C. for 2 minutes to produce a copper foil provided with a resin layer. The thickness of the resin layer was 2 μm.

  About Examples 11-13, after performing the roughening process shown to the following (1) with respect to the surface (glossy surface) of the electrolytic drum side of the electrolytic copper foil produced as mentioned above, Example 5 (2) to (5) were surface treated in this order.

(1) Roughening treatment Roughening treatment was performed in the following plating bath and plating conditions in order to form roughening particles of ternary copper-cobalt-nickel alloy plating.
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density: 30 to 45 A / dm ²
Plating time: 0.1 to 1.5 seconds

2. Evaluation of electrolytic copper foil <Glossy surface roughness Sa and root mean square height Sq>
For the glossy surface of the electrolytic copper foil before the surface treatment (that is, having no roughened layer) and the glossy surface of the electrolytic copper foil after the surface treatment, manufactured by Olympus Corporation in accordance with ISO-25178-2: 2012 Surface roughness Sa and root mean square height were measured with a laser microscope OLS4100 (LEXT OLS 4100). At this time, measurement of 200 μm × 1000 μm area (specifically 200,000 μm ² ) was performed at three locations using an objective lens 50 times in a laser microscope, and surface roughness Sa and root mean square height Sq were calculated. The arithmetic average values of the surface roughness Sa and the root mean square height Sq obtained at three locations were taken as the values of the surface roughness Sa and the root mean square height Sq, respectively. In the laser microscope measurement, when the measurement surface of the measurement result is not a flat surface but a curved surface, the surface roughness Sa and the root mean square height Sq were calculated after performing plane correction. In addition, the measurement environmental temperature of surface roughness Sa by a laser microscope was 23-25 degreeC.

<Normal temperature tensile strength, high temperature tensile strength>
The normal temperature tensile strength and high temperature tensile strength of the electrolytic copper foil were measured according to IPC-TM-650.

<Normal temperature elongation, high temperature elongation>
The normal temperature elongation and high temperature elongation of the electrolytic copper foil were measured according to IPC-TM-650. As described above, “high temperature tensile strength” refers to tensile strength at 180 ° C. “High temperature elongation” indicates elongation at 180 ° C.

<Circuit formability>
The surface-treated electrolytic copper foil was bonded to a bismaleimide triazine resin prepreg by thermocompression bonding from the glossy surface side. Thereafter, the electrolytic copper foil bonded to the prepreg was etched from the side opposite to the side bonded to the prepreg until the thickness became 9 μm. Then, after an etching resist is provided on the surface of the electrolytic copper foil after etching, exposure and development are performed to form a resist pattern, and then etching is performed with ferric chloride. L / S = 25 μm / 25 μm, L / S Twenty wires each having a length of 1 mm were formed with S = 22 μm / 22 μm, L / S = 20 μm / 20 μm, and L / S = 15 μm / 15 μm. Subsequently, the difference (μm) between the maximum value and the minimum value of the circuit lower end width viewed from the circuit upper surface was measured, and the average value was measured at five locations. If the difference between the maximum value and the minimum value was 2 μm or less, it was judged that the circuit had good circuit linearity, and it was marked ◎. In addition, when the difference between the maximum value and the minimum value is more than 2 μm and not more than 4 μm, it is marked as ◯. Moreover, when the difference between the maximum value and the minimum value exceeded 4 μm, it was marked as x.
Test conditions and test results are shown in Table 2. 1A is an SEM image of the glossy surface of the electrolytic copper foil of Example 2. FIG. FIG. 1B is an SEM image of the glossy surface of the electrolytic copper foil of Example 10.

<Evaluation results>
In Examples 1 to 14, the glossy surface roughness Sa of the electrolytic copper foil having no roughening treatment layer is 0.270 μm or less and the root mean square height Sq is 0.315 μm or less. The surface roughness Sa of the glossy surface of the electrolytic copper foil having the roughened layer was 0.470 μm or less, and the root mean square height Sq was 0.550 μm or less, and the circuit formation was good.
In Comparative Example 1, the surface roughness Sa of the glossy surface of the electrolytic copper foil having no roughening treatment layer exceeds 0.270 μm, and the root mean square height Sq exceeds 0.315 μm. Further, the surface roughness Sa of the glossy surface of the electrolytic copper foil having the roughened layer exceeds 0.470 μm, and the root mean square height Sq exceeds 0.550 μm. It was bad.

Claims (44)

  The electrolytic copper foil which does not have a roughening process layer in a glossy surface side, and whose root mean square height Sq of the said glossy surface is 0.315 micrometer or less.   The electrolytic copper foil according to claim 1, wherein the glossy surface has a surface roughness Sa of 0.150 μm or less.   The electrolytic copper foil according to claim 1 or 2, wherein a root mean square height Sq of the glossy surface is 0.200 µm or less.   The electrolytic copper foil which does not have a roughening process layer in a glossy surface side, and whose root mean square height Sq of the said glossy surface is 0.200 micrometer or less.   The electrolytic copper foil according to any one of claims 1 to 4, wherein a surface roughness Sa of the glossy surface is 0.133 µm or less.   The electrolytic copper foil according to claim 5, wherein the glossy surface has a surface roughness Sa of 0.130 μm or less.   The root mean square height Sq of the glossy surface is 0.180 µm or less. The electrolytic copper foil according to any one of claims 1 to 6.   The electrolytic copper foil according to any one of claims 1 to 7, wherein a root mean square height Sq of the glossy surface is 0.120 µm or less.   The electrolytic copper foil which has a roughening process layer in a glossy surface side, and the root mean square height Sq of the said glossy surface is 0.550 micrometer or less.   The electrolytic copper foil according to claim 9, wherein the glossy surface has a surface roughness Sa of 0.380 μm or less.   The electrolytic copper foil according to claim 9 or 10, wherein a root mean square height Sq of the glossy surface is 0.490 µm or less.   The electrolytic copper foil according to any one of claims 9 to 11, wherein the glossiness side surface roughness Sa is 0.355 µm or less.   The electrolytic copper foil according to any one of claims 9 to 12, wherein a surface roughness Sa on the glossy surface side is 0.300 µm or less.   The electrolytic copper foil according to any one of claims 9 to 13, wherein a surface roughness Sa on the glossy side is 0.200 µm or less.   The electrolytic copper foil as described in any one of Claims 9-14 whose root mean square height Sq by the side of the said glossy surface is 0.450 micrometer or less.   The electrolytic copper foil as described in any one of Claims 9-15 whose root mean square height Sq by the side of the said glossy surface is 0.400 micrometer or less.   The electrolytic copper foil according to any one of claims 9 to 16, wherein a root mean square height Sq on the glossy surface side is 0.330 µm or less.   The electrolytic copper foil according to any one of claims 9 to 17, wherein a surface roughness Sa of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.270 µm or less.   The electrolytic copper foil according to any one of claims 9 to 18, wherein a surface roughness Sa of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.150 µm or less.   The electrolytic copper foil according to claim 19, wherein a surface roughness Sa of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.133 μm or less.   The electrolytic copper foil according to claim 20, wherein a surface roughness Sa of the glossy surface before providing the roughening layer on the glossy surface side is 0.130 µm or less.   The electrolytic copper foil as described in any one of Claims 9-21 whose root mean square height Sq of the glossy surface before providing a roughening process layer in the said glossy surface side is 0.315 micrometer or less.   The electrolytic copper foil according to any one of claims 9 to 22, wherein a root mean square height Sq of the glossy surface before the roughening layer is provided on the glossy surface side is 0.200 µm or less.   24. The electrolytic copper foil according to claim 23, wherein the root mean square height Sq of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.180 [mu] m or less.   The electrolytic copper foil according to claim 24, wherein a root mean square height Sq of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.120 µm or less. The electrolytic copper foil according to any one of claims 1 to 25, wherein the normal temperature tensile strength is 30 kg / mm ² or more.   The electrolytic copper foil according to any one of claims 1 to 26, wherein the room temperature elongation is 3% or more. The high temperature tensile strength is 10 kg / mm ² or more, The electrolytic copper foil according to any one of claims 1 to 27.   The high temperature elongation is 2% or more. The electrolytic copper foil according to any one of claims 1 to 28.   The electrolytic copper foil as described in any one of Claims 1-29 which has a roughening process layer in the surface on the opposite side to the glossy surface of the said electrolytic copper foil.   The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. It is a layer, The electrolytic copper foil as described in any one of Claims 9-30.   The surface of one or both of the glossy surface side and the surface side opposite to the glossy surface of the electrolytic copper foil is composed of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The electrolytic copper foil as described in any one of Claims 9-31 which has 1 or more types of layers selected from the group.   One type selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer on one or both of the glossy surface side and the surface side opposite to the glossy surface of the electrolytic copper foil The electrolytic copper foil as described in any one of Claims 1-8 and 26-29 which has the above layer.   The electrolytic copper foil as described in any one of Claims 1-8 and 26-29 provided with the resin layer in the glossy surface side of the said electrolytic copper foil, and one or both of the surface side on the opposite side to a glossy surface.   The electrolytic copper foil as described in any one of Claims 9-31 provided with a resin layer on the said roughening process layer.   The electrolytic copper foil according to claim 32 or 33, further comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.   The manufacturing method of the electrolytic copper foil which produces electrolytic copper foil using the electrolytic drum whose surface root mean square height Sq is 0.315 micrometer or less.   The method for producing an electrolytic copper foil according to claim 37, wherein the electrolytic copper foil is produced using an electrolytic drum having a surface roughness Sa of 0.150 μm or less.   The method for producing an electrolytic copper foil according to claim 37 or 38, wherein the electrolytic copper foil is produced using an electrolytic drum having a root mean square height Sq of 0.200 µm or less.   The copper clad laminated board which has the electrolytic copper foil as described in any one of Claims 1-36.   The printed wiring board which has the electrolytic copper foil as described in any one of Claims 1-36.   The manufacturing method of the printed wiring board which manufactures a printed wiring board using the electrolytic copper foil as described in any one of Claims 1-36.   A copper-clad laminate is formed by laminating the electrolytic copper foil according to any one of claims 1 to 36 and an insulating substrate, and then a semi-additive method, a subtractive method, a partial additive method or a modified semi-additive method. A method for producing a printed wiring board, comprising a step of forming a circuit by any one of the methods.   The manufacturing method of the electronic device which manufactures an electronic device using the printed wiring board manufactured by the method of Claim 42 or 43.