WO2018207786A1 - Electrolytic copper foil, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor - Google Patents

Abstract

An electrolytic copper foil having a glossy surface and a deposition surface. This electrolytic copper foil has a roughened layer on the glossy surface side thereof. The root mean square height Sq of the glossy surface is no more than 0.550 µm. The deposition surface side fulfills at least one condition among the following: (a) the surface roughness Sa is at least 0.115 µm; (b) the root mean square height Sq is at least 0.120 µm; (c) the maximum peak height Sp is at least 0.900 µm; (d) the maximum valley depth Sv is at least 0.600 µm; the maximum height Sz is at least 1.500 µm; (f) the kurtosis Sku is 2.75–4.00; and (g) the skewness Ssk is 0.00–0.35.

Description

Electrolytic copper foil, copper clad laminate, printed wiring board and method for producing the same, and electronic device and method for producing the same

The present disclosure relates to an electrolytic copper foil, a copper-clad laminate, a printed wiring board, a manufacturing method thereof, an electronic device, and a manufacturing method thereof.

A printed wiring board is generally manufactured through a process in which an insulating substrate (for example, a resin substrate) is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern (circuit) is formed on the copper foil by etching. The
In recent years, with increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and the miniaturization of conductor patterns on printed wiring boards ( Fine pitch) and high frequency response are required.

Therefore, in order to realize the miniaturization of the conductor pattern using the electrolytic copper foil, Patent Document 1 adds an additive such as a sulfur-containing compound that acts as a brightening agent to the electrolytic solution so that the surface on the deposition surface side is reduced. It has been proposed to form a circuit on an electrolytic copper foil after producing a smooth electrolytic copper foil.

JP 2004-162172 A

However, in the method of Patent Document 1, due to the influence of the additive contained in the electrolytic solution, 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 such a wrinkle generate | occur | produces, a wrinkle will also generate | occur | produce when adhering subsequent electrolytic copper foil with an insulated substrate (resin board | substrate). If wrinkles are generated in the electrolytic copper foil in this way, it is difficult to make a fine pitch when forming a conductor pattern on the electrolytic copper foil, and thus it cannot be said that the circuit formability is sufficient. Moreover, the electrolytic copper foil of patent document 1 also has the problem that mechanical characteristics (for example, a tensile strength, high temperature elongation, etc.) are easy to change under the influence of the additive added to electrolyte solution.

On the other hand, since a solder resist is applied to the conductor pattern in order to ensure insulation and prevent short-circuiting, the surface of the electrolytic copper foil serving as the conductor pattern may have good adhesion to the solder resist. Required. However, when the surface of the electrolytic copper foil serving as the conductor pattern is smooth, there is a problem that the adhesion with the solder resist is lowered. Therefore, the surface of the electrolytic copper foil used as the conductor pattern needs to have a certain degree of roughness.
In this way, the electrolytic copper foil requires smoothness on the surface to be bonded to the insulating substrate in order to increase the adhesion to the insulating substrate and achieve a fine pitch, while ensuring the adhesion of the solder resist. Therefore, a certain degree of roughness is required for the surface to be a conductor pattern.

Some embodiments of the present invention have been made in order to solve the above-described problems, and an object of the present invention is to provide an electrolytic copper foil excellent in circuit formability and solder resist adhesion.
In addition, some embodiments of the present invention provide a copper-clad laminate, a printed wiring board, a manufacturing method thereof, an electronic device, and a manufacturing method thereof using an electrolytic copper foil excellent in circuit formability and solder resist adhesion. It is an issue to provide.

As a result of earnest research to solve the above problems, the present inventors have controlled the surface roughness Sa and / or the root mean square height Sq on the glossy surface side of the electrolytic copper foil to a predetermined range, At least one of the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk on the deposition surface side of the copper foil is within a predetermined range. By controlling, the glossy surface is excellent in adhesion to the insulating substrate and the deposited surface is in a surface state excellent in adhesion of the solder resist. As a result, both circuit formability and solder resist adhesion can be achieved. We have found that we have completed several embodiments of the present invention.

That is, the electrolytic copper foil according to the embodiment of the present invention has a glossy surface and a precipitation surface,
The glossy surface has a roughening layer, the root mean square height Sq of the glossy surface is 0.550 μm or less, and the precipitation surface side has the following conditions:
(A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more Satisfy at least one of 0.35 or less.

Moreover, the electrolytic copper foil according to another embodiment of the present invention has a glossy surface and a precipitation surface,
It has a roughening treatment layer on the glossy surface side, the surface roughness Sa on the glossy surface side is 0.470 μm or less, and the precipitation surface side has the following conditions:
(A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more Satisfy at least one of 0.35 or less.

Moreover, the electrolytic copper foil according to another embodiment of the present invention has a glossy surface and a precipitation surface,
There is no roughening layer on the glossy surface side, the surface roughness Sa on the glossy surface side is 0.270 μm or less, and the precipitation surface side has the following conditions:
(A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more Satisfy at least one of 0.35 or less.

Moreover, the electrolytic copper foil according to another embodiment of the present invention has a glossy surface and a precipitation surface,
The glossy surface side does not have a roughening treatment layer, the root mean square height Sq on the glossy surface side is 0.315 μm or less, and the precipitation surface side has the following conditions:
(A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more Satisfy at least one of 0.35 or less.

Moreover, the copper clad laminated board which concerns on embodiment of this invention has the said electrolytic copper foil.
Moreover, the printed wiring board which concerns on embodiment of this invention has the said electrolytic copper foil.
Moreover, the manufacturing method of the printed wiring board which concerns on embodiment of this invention uses the said electrolytic copper foil.
In addition, a method for manufacturing a printed wiring board according to another embodiment of the present invention includes: producing a copper-clad laminate by laminating the electrolytic copper foil and an insulating substrate; then, a semi-additive method, a subtractive method, and a partial additive method. Forming a circuit by either a method or a modified semi-additive method.
Moreover, the electronic device which concerns on embodiment of this invention has the said printed wiring board.
Furthermore, the method for manufacturing an electronic device according to an embodiment of the present invention uses the printed wiring board.

According to some embodiments of the present invention, an electrolytic copper foil excellent in circuit formability and solder resist adhesion can be provided. In addition, according to some embodiments of the present invention, a copper-clad laminate using an electrolytic copper foil excellent in circuit formability and solder resist adhesion, a printed wiring board, a manufacturing method thereof, and an electronic device and A manufacturing method can be provided.

(A) is the SEM image of the glossy surface of the electrolytic copper foil of Example 2 before forming a roughening process layer and a surface treatment layer, (b) forms a roughening process layer and a surface treatment layer. It is a SEM image of the glossy surface of the electrolytic copper foil of the previous Example 10.

Hereinafter, embodiments of the electrolytic copper foil of the present invention will be described.
The electrolytic copper foil according to the embodiment of the present invention has a glossy surface and a precipitation surface.
Here, “electrolytic copper foil” in the present specification means copper foil and copper alloy foil produced by using an electrolysis drum using the principle of electroplating.
In addition, in this specification, the “glossy surface of the electrolytic copper foil” means a surface on the drum side (shiny surface: S surface) when the electrolytic copper foil is produced. "Means the surface (mat surface: M surface) opposite to the drum when the electrolytic copper foil is produced.

In the present specification, “surface roughness Sa on the glossy surface side” and “root mean square height Sq on the glossy surface side” are the roughened layer and / or the glossy surface of the electrolytic copper foil (raw foil). Or when providing a surface treatment layer, the surface roughness Sa and the root mean square height Sq of the surface (surface of the outermost layer) after providing the said layer are each meant. The “surface roughness Sa of the glossy surface” and the “root mean square height Sq of the glossy surface” are the surface of the glossy surface before the roughening treatment layer and / or the surface treatment layer is provided on the glossy surface side ( It means the surface roughness Sa and the root mean square height Sq of the outermost surface.

Further, in this specification, “the surface roughness Sa on the precipitation surface side”, “the root mean square height Sq on the precipitation surface side”, “the maximum peak height Sp on the precipitation surface side”, “the maximum valley depth on the precipitation surface side” "Sv", "Maximum height Sz on the precipitation surface side", "Cultosis Sku on the precipitation surface side" and "Skness Ssk on the precipitation surface side" In the case where a surface treatment layer is provided, the surface roughness (surface of the outermost layer) after the layer is provided (surface roughness Sa, root mean square height Sq, maximum peak height Sp, maximum valley depth Sv) , Mean maximum height Sz, kurtosis Sku and skewness Ssk.

<Electrolytic copper foil without roughening layer on the glossy surface>
In one aspect, the electrolytic copper foil according to the embodiment of the present invention has no roughening treatment layer on the glossy surface side, and the surface roughness Sa on the glossy surface side is 0.270 μm or less and / or 2 on the glossy surface side. The root mean square height Sq is 0.315 μm or less.
Here, in this specification, “surface roughness Sa” is a roughness parameter obtained by extending Ra three-dimensionally, and the average of the absolute values of the height difference of each point with respect to the average surface of the surface. To express. The “root mean square height Sq” is a roughness parameter obtained by expanding Rq in three dimensions, and represents a standard deviation of the distance from the average surface of the surface.
By controlling the surface roughness Sa on the glossy surface side and / or the root mean square height Sq on the glossy surface side to the above range, the adhesiveness with the insulating substrate is improved and formed using electrolytic copper foil. With respect to the pitch of the circuit to be performed, a fine pitch can be achieved such that L / S (line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less.

The surface roughness Sa on the glossy surface side of the electrolytic copper foil is preferably 0.230 μm or less, more preferably 0.180 μm or less, further preferably 0.150 μm or less, and most preferably from the viewpoint of enhancing the effect of fine pitch. It is 0.133 μm or less. The lower limit of the surface roughness Sa on the glossy surface side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.8. 100 μm or more.
Further, the root mean square height Sq on the glossy surface side of the electrolytic copper foil is preferably 0.200 μm or less, more preferably 0.180 μm or less, from the viewpoint of enhancing the effect of fine pitch. The lower limit of the root mean square height Sq on the glossy surface side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and further preferably Is 0.100 μm or more.

<Electrolytic copper foil having a roughened layer on the glossy surface>
In another aspect of the electrolytic copper foil according to the embodiment of the present invention, the roughened layer is provided on the glossy surface side, and the surface roughness Sa on the glossy surface side is 0.470 μm or less and / or on the glossy surface side. The root mean square height Sq is 0.550 μm or less.
In general, in an electrolytic copper foil having a roughened layer on the glossy surface side, fine pitch may be reduced, but the surface roughness on the glossy surface side and / or the root mean square height on the glossy surface side By controlling Sq within the above range, the adhesion to the insulating substrate is improved 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, a fine pitch of 20 μm or less / 20 μm or less can be achieved.

The surface roughness Sa on the glossy surface side of the electrolytic copper foil is preferably 0.385 μm or less, more preferably 0.380 μm or less, more preferably 0.355 μm or less, more preferably from the viewpoint of enhancing the effect of fine pitch. It is 0.340 μm or less, more preferably 0.300 μm or less, still more preferably 0.295 μm or less, still more preferably 0.230 μm or less, and most preferably 0.200 μm or less. The lower limit of the surface roughness Sa on the glossy surface side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.8. 100 μm or more.

Further, the root mean square height Sq on the glossy surface side of the electrolytic copper foil is preferably 0.490 μm or less, more preferably 0.450 μm or less, more preferably 0.435 μm from the viewpoint of enhancing the effect of fine pitch. Hereinafter, it is more preferably 0.400 μm or less, further preferably 0.395 μm or less, still more preferably 0.330 μm or less, and most preferably 0.290 μm or less. The lower limit of the root mean square height Sq on the glossy surface side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and further preferably Is 0.100 μm or more.

The electrolytic copper foil according to the embodiment of the present invention having the glossy surface side roughness Sa and / or the root mean square height Sq as described above has a roughened layer and / or a surface-treated layer on the glossy side. Can be obtained by controlling the surface roughness Sa and / or the root mean square height Sq of the glossy surface.

That is, in order to obtain the electrolytic copper foil according to the embodiment of the present invention, the surface roughness Sa of the glossy surface before providing the roughening treatment layer and / or the surface treatment layer on the glossy surface side is preferably 0.270 μm. Or less, more preferably 0.230 μm or less, more preferably 0.180 μm or less, further preferably 0.150 μm or less, further preferably 0.133 μm or less, still more preferably 0.130 μm or less, and most preferably 0.120 μm or less. It may be controlled to. In addition, the lower limit of the surface roughness Sa of the glossy surface before providing the roughening treatment layer and / or the surface treatment layer on the glossy surface side is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, More preferably, it is 0.050 micrometer or more, More preferably, it is 0.100 micrometer or more.
By controlling the surface roughness Sa of the glossy surface before providing the roughening treatment layer and / or the surface treatment layer on the glossy surface side within the above range, the roughening treatment layer and / or the surface treatment layer is provided. Since the surface roughness Sa and / or the root mean square height Sq on the glossy surface side can be controlled within the above range, the pitch of the circuit formed using the electrolytic copper foil is expressed by L / S (line / Space) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less.

In order to obtain the electrolytic copper foil according to the embodiment of the present invention, the root mean square height Sq of the glossy surface before providing the roughening treatment layer and / or the surface treatment layer on the glossy surface side is preferably 0.315 μm or less, more preferably 0.292 μm or less, more preferably 0.230 μm or less, even more preferably 0.200 μm or less, still more preferably 0.180 μm or less, even more preferably 0.120 μm or less, and most preferably 0 It may be controlled to 115 μm or less. The lower limit of the root mean square height Sq of the glossy surface before providing the roughening layer and / or the surface treatment layer on the glossy surface side is not particularly limited, but is generally 0.001 μm or more, preferably 0.8. It is 010 μm or more, more preferably 0.050 μm or more, and further preferably 0.100 μm or more.
By providing the root mean square height Sq of the glossy surface before providing the roughening layer and / or surface treatment layer on the glossy surface side, the roughening treatment layer and / or the surface treatment layer is provided. Since the surface roughness Sa and / or the root mean square height Sq on the glossy surface side after the control can be controlled within the above range, the pitch of the circuit formed using the electrolytic copper foil is determined by L / S. (Line / space) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less is possible.

As for the electrolytic copper foil which concerns on embodiment of this invention, the deposition surface side is the following conditions:
(A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more Satisfy at least one of 0.35 or less. By satisfying at least one of the above conditions on the deposition surface side, the surface on the deposition surface side has an appropriate roughness, so that the adhesion of the solder resist can be improved.

Here, in this specification, the “maximum peak height Sp” represents the maximum value of the height from the average surface. The “maximum valley depth Sv” represents the absolute value of the minimum value of the height from the average surface. “Maximum height Sz” represents the distance from the highest point to the lowest point on the surface. “Cultosis Sku” represents the sharpness of the height distribution. When Sku = 3, the height distribution is a normal distribution, and when Sku> 3, the surface has many sharp peaks and valleys. <3 indicates that the surface is flat. The “skewness Ssk” represents the symmetry of the height distribution. The height distribution is vertically symmetric when Ssk = 0, and the surface has many fine peaks when Ssk> 0. A surface having many fine valleys when Ssk <0.
From the viewpoint of stably securing the adhesiveness of the solder resist, the precipitation surface side is preferably at least 2, more preferably at least 3, more preferably at least 4, and even more preferably at least 5, particularly preferably. It is appropriate to satisfy at least 6 and most preferably all 7 conditions.

The surface roughness Sa on the deposition surface side is preferably 0.120 μm or more, more preferably 0.130 μm or more, and further preferably 0.140 μm or more from the viewpoint of stably securing the adhesion of the solder resist. The upper limit of the surface roughness Sa on the precipitation side is not particularly limited, but is generally 2.000 μm or less, preferably 1.800 μm or less, more preferably 1.500 μm or less, and most preferably 1.000 μm or less. is there.

The root-mean-square height Sq on the precipitation surface side is preferably 0.130 μm or more, more preferably 0.140 μm or more, and further preferably 0.150 μm or more, from the viewpoint of stably securing the adhesion of the solder resist. is there. The upper limit of the root mean square height Sq on the precipitation side is not particularly limited, but is generally 2.000 μm or less, preferably 1.800 μm or less, more preferably 1.500 μm or less, and most preferably 1.500 μm or less. 300 μm or less.

The maximum peak height Sp on the deposition surface side is preferably 1.050 μm or more, more preferably 1.100 μm or more, and further preferably 1.200 μm or more, from the viewpoint of stably securing the adhesion of the solder resist. The upper limit of the maximum peak height Sp on the deposition surface side is not particularly limited, but is generally 10.000 μm or less, preferably 9.000 μm or less, more preferably 8.000 μm or less, and most preferably 7.000 μm or less. is there.

The maximum valley depth Sv on the precipitation surface side is preferably 0.740 μm or more, more preferably 0.800 μm or more, and still more preferably 0.900 μm or more from the viewpoint of stably securing the adhesion of the solder resist. The upper limit of the maximum valley depth Sv on the precipitation surface side is not particularly limited, but is generally 10.000 μm or less, preferably 9.000 μm or less, and more preferably 8.000 μm or less.

The maximum height Sz on the deposition surface side is preferably 1.800 μm or more, more preferably 1.900 μm or more, further preferably 2.000 μm or more, most preferably, from the viewpoint of stably securing the adhesion of the solder resist. 2. It is 200 μm or more. The upper limit of the maximum height Sz on the deposition surface side is not particularly limited, but is generally 20.000 μm or less, preferably 18.000 μm or less, more preferably 15.000 μm or less, and most preferably 14.000 μm or less. is there.

The kurtosis Sku on the precipitation surface side is preferably 2.80 or more and 4.00 or less, more preferably 2.85 or more and 3.90 or less, and still more preferably 2.10 from the viewpoint of stably securing the adhesiveness of the solder resist. It is 90 or more and 3.80 or less.

The skewness Ssk on the deposition surface side is preferably 0.00 or more and 0.26 or less, more preferably 0.01 or more and 0.20 or less, from the viewpoint of stably securing the adhesion of the solder resist.

The electrolytic copper foil according to the embodiment of the present invention that satisfies the conditions on the deposition surface side as described above is the production condition of the electrolytic copper foil (for example, the linear velocity of the electrolytic solution, the current density, the concentration of the component added to the electrolytic solution, etc. ) Can be obtained by controlling.

The electrolytic copper foil according to the embodiment of the present invention preferably has a normal temperature tensile strength of 30 kg / mm ² or more. As used herein, “room temperature tensile strength” refers to a tensile strength at room temperature, which 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. From the viewpoint of stably obtaining this effect, the normal temperature tensile strength is more preferably 35 kg / mm ² or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a room temperature elongation of 3% or more. Here, “room temperature elongation” in this specification is an elongation at room temperature and means a value 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. From the viewpoint of stably obtaining this effect, the room temperature elongation is more preferably 4% or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a high-temperature tensile strength of 10 kg / mm ² or more. In the present specification, the “high temperature tensile strength” means a tensile strength at 180 ° C., which 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. From the viewpoint of stably obtaining this effect, the high temperature tensile strength is more preferably 15 kg / mm ² or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a high temperature elongation of 2% or more. In this specification, “high temperature elongation” means elongation at 180 ° C., which 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. From the viewpoint of stably obtaining this effect, the high temperature elongation is preferably 3% or more, more preferably 6% or more, and further preferably 15% or more.

Examples of copper and copper alloy that are materials of the electrolytic copper foil (raw foil) according to the embodiment of the present invention include pure copper; Sn-containing copper; Ag-containing copper; Ti, W, Mo, Cr, Zr, Mg, Ni , Sn alloy, Ag, Co, Fe, As, P, and the like are added. For example, an electrolytic copper foil formed from a copper alloy is an alloy element (e.g., Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Co) in an electrolytic solution used when manufacturing the electrolytic copper foil. 1 or more elements selected from the group consisting of Fe, As and P).
The thickness of the electrolytic copper foil (raw foil) is not particularly limited, but is typically 0.5 μm to 3000 μm, preferably 1.0 μm to 1000 μm, more preferably 1.0 μm to 300 μm, more preferably 1. 0 μm to 100 μm, more preferably 3.0 μm to 75 μm, more preferably 4 μm to 40 μm, still more preferably 5 μm to 37 μm, still more preferably 6 μm to 28 μm, still more preferably 7 μm to 25 μm, most preferably 8 μm to 19 μm Is

<Method for producing electrolytic copper foil (raw foil)>
The electrolytic copper foil (raw foil) is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath. Examples of electrolysis conditions are shown below.
(Electrolysis conditions)
Electrolyte composition: 50 to 150 g / L Cu, 60 to 150 g / L H ₂ SO ₄
Current density: 30 to 120 A / dm ²
Electrolyte linear flow rate: 1.5-5 m / s
Electrolyte temperature: 50-60 ° C
Additive: 20 to 80 mass ppm of chloride ion, 0.01 to 5.0 mass ppm of Nicawa Note that the treatment liquid used in the electrolysis, etching, surface treatment or plating described in this specification (etching liquid, The remainder of the electrolyte etc. is water unless otherwise specified.

The electrolytic drum used has a surface roughness Sa of the drum surface in order to control the surface roughness Sa and / or the root mean square height Sq of the glossy surface of the formed electrolytic copper foil (raw foil) to a predetermined range. Sa is 0.270 μm or less and / or the root mean square height Sq is 0.315 μm or less. The surface roughness Sa of the drum surface is preferably 0.150 μm or less, and the root mean square height Sq of the drum surface is preferably 0.200 μm or less.
An electrolytic drum having a predetermined surface roughness Sa and / or root mean square height Sq on its surface can be manufactured as follows. First, the surface of a drum made of titanium or stainless steel is polished by a polishing belt having a count of 300 (P300) to 500 (P500). At this time, the polishing belt is wound by winding a predetermined width in the width direction of the drum, and rotating the drum while moving the polishing belt in the width direction of the drum at a predetermined speed. The rotation speed of the drum surface during polishing is 130 m / min 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)

In the production of conventional electrolytic copper foil (raw foil), the polishing time was 1.6 minutes to 3 minutes, but in the embodiment of the present invention, it is 3.5 minutes to 10 minutes. When wetting the drum surface with water during polishing, it should be 6 to 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 can be calculated by multiplying the total number of passes (for example, 0.5 minutes × 10 passes = 5 minutes). By increasing the number 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. Conversely, reducing the count of the polishing belt and / or reducing the rotation speed of the drum surface and / or shortening the polishing time and / or drying the drum surface during polishing, Thus, the surface roughness Sa of the drum surface and the root mean square height Sq of the drum surface can be increased. 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 the extent that Sa is reduced. Conversely, 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. The particle size of the abrasive is in accordance with FEPA (Federation of European Producers of Abbreviations) -standard 43-1: 2006, 43-2: 2006.

In addition, the surface of the drum Sa can be reduced by increasing the root mean square height Sq to a smaller extent than by reducing the root mean square root height Sq by wetting the drum surface with water during polishing. it can. Conversely, 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. it can.
By using the electrolytic drum having the predetermined surface roughness Sa and / or the root mean square height Sq produced on the surface as described above, the surface roughness Sa and / or the root mean square of the predetermined glossy surface is used. An electrolytic copper foil (raw foil) having a square root height Sq can be produced.

In addition, the surface roughness Sa and the root mean square height Sq of the surface of the electrolytic drum can be measured as follows.
-A resin film (polyvinyl chloride) is immersed in a solvent (acetone) to swell.
-The swollen resin film is brought into contact with the surface of the electrolytic drum, 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 are set as the surface roughness Sa and the root mean square height Sq of the electrolytic drum surface.

On the other hand, at least one of the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk on the deposition surface side of the electrolytic copper foil is predetermined. In order to control within this range, the linear velocity of the electrolytic solution, the current density, and the concentration of the component added to the electrolytic solution may be adjusted.
In general, the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku and the skewness Ssk on the deposition surface side of the electrolytic copper foil are increased. If you want to reduce the linear flow rate of the electrolyte, increase the current density, increase the concentration of chloride ions in the electrolyte, or set the concentration of glue in the electrolyte in the range of 0 to several ppm. Or an additive having an action of increasing the surface roughness may be added to the electrolytic solution. Further, the above value tends to increase as the roughness of the electrolytic drum used increases.
Conversely, it is desired to reduce the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk of the electrolytic copper foil. In such a case, an additive having an effect of smoothing the electrolytic copper foil is added, the concentration of chloride ions in the electrolytic solution is 0 or extremely low, or the concentration of glue in the electrolytic solution is 10 ppm or more. You can increase the range. Further, the above values tend to decrease as the roughness of the electrolytic drum used decreases.

<Roughening treatment and surface treatment>
The surface treatment is not particularly limited, and examples thereof include heat treatment, rust prevention treatment, chromate treatment, and silane coupling treatment.
Here, in this specification, a layer formed by roughening treatment is a “roughening treatment layer”, a layer formed by heat resistance treatment is a “heat resistant layer”, and a layer formed by rust prevention treatment is a “rust prevention layer”. The layer formed by the chromate treatment is called “chromate treatment layer”, and the layer formed by the silane coupling treatment is called “silane coupling treatment layer”.

A roughening treatment layer may be provided on at least one of the glossy surface and the precipitation surface of the electrolytic copper foil according to the embodiment of the present invention in order to improve the adhesion to the insulating substrate (resin substrate). The roughening treatment is not particularly limited, and can be performed by electrodepositing roughened particles on the surface of the electrolytic copper foil. For example, roughened particles of copper or copper alloy may be electrodeposited on the surface of the electrolytic copper foil. The roughened particles can be fine, and the shape thereof can be any of a needle shape, a rod shape, or a particle shape. 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. Etc. Further, after electrodepositing the roughened particles of copper or copper alloy, it is possible to perform a roughening treatment in which secondary particles and tertiary particles are further electrodeposited with nickel, cobalt, copper, zinc alone or an alloy.

When performing a roughening process, a heat-resistant layer or a rust prevention layer is formed on the surface of a roughening process layer, and also a chromate process layer or a silane coupling process layer is formed in the surface.
When the roughening treatment is not performed as the surface treatment, a heat-resistant layer or a rust-preventing layer is formed on the surface of the electrolytic copper foil, and a chromate treatment layer or a silane coupling treatment layer is further formed on the surface.
The above heat-resistant layer, rust prevention layer, chromate treatment layer and silane coupling treatment layer may all be a single layer, but may be formed of a plurality of layers (for example, two or more layers, 3 Layer or more).

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

The specific processing conditions are as follows.
(Liquid composition 1)
CuSO ₄ .5H ₂ O: 39.3 to 120 g / L
H ₂ SO ₄ : 10 to 150 g / L
Na ₂ WO ₄ · 2H ₂ O: 0 to 90 mg / L
W: 0-50mg / L
Sodium dodecyl sulfate: 0-50mg
As: 0 to 2000 mg / L

(Electroplating condition 1)
Temperature: 30-70 ° C
(Current condition 1)
Current density: 25 to 110 A / dm ²
Plating time: 0.5 to 20 seconds (Liquid composition 2)
CuSO ₄ .5H ₂ O: 78 to 314 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: 1-60 seconds

Cobalt - - Copper as roughening layer when forming a nickel alloy plating layer by electrolytic plating, the content of ^{15mg / dm 2 ~ 40mg / dm} 2 of copper, the content of ^{100μg / dm 2 ~ 3000μg / dm} 2 cobalt, and it is preferable that the content is ternary alloy layer such that the nickel ^{100μg / dm 2 ~ 1500μg / dm} 2. When the Co content is less than 100 μg / dm ² , the heat resistance and the etching property may be lowered. On the other hand, if the Co content exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, and etching stains may occur, and acid resistance and chemical resistance may decrease. Moreover, heat resistance may fall that Ni content is less than 100 microgram / dm < ² >. On the other hand, if the Ni content exceeds 1500 μg / dm ² , the etching residue may increase. Preferred Co content is ^{1000μg / dm 2 ~ 2500μg / dm} 2, preferably Ni content is ^{500μg / dm 2 ~ 1200μg / dm} 2.
Here, “etching spots” in this specification means that Co remains without being dissolved when etched with copper chloride. Further, “etching residue” means that Ni remains without being dissolved when alkali etching is performed with ammonium chloride.

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: 10-20 g / L Cu, 1-10 g / L Co, 1-10 g / L Ni
pH: 1 to 4
Temperature: 30-50 ° C
Current density: 20-30 A / dm ²
Plating time: 1-5 seconds

Another example of a plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: 10-20 g / L Cu, 1-10 g / L Co, 1-10 g / L Ni
pH: 1 to 4
Temperature: 30-50 ° C
Current density: 30 to 45 A / dm ²
Plating time: 0.1 to 2.0 seconds

In the roughening treatment for forming the above-mentioned roughening treatment layer, the surface roughness Sa and / or the root mean square height Sq on the glossy surface side can be reduced by shortening the plating time. On the other hand, in the surface treatment for forming the roughening layer, the surface roughness Sa and / or the root mean square height Sq on the glossy surface side can be increased by increasing the plating time.
Further, in the roughening treatment for forming the above-mentioned roughening treatment layer, the surface roughness Sa and / or the root mean square height Sq on the glossy surface side can be reduced by increasing the current density and extremely shortening the plating time. It can be made smaller. On the other hand, in the process for forming the roughened layer, the surface roughness Sa and / or the root mean square height Sq on the glossy surface side is increased by increasing the current density and increasing the plating time. Can do.

A surface treatment layer may be provided on at least one of the glossy surface side and the deposition surface side of the electrolytic copper foil according to the embodiment of the present invention. Although it does not specifically limit as a surface treatment layer, It is preferable that it is 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. Generally, when a roughening treatment layer is formed on at least one of the glossy surface side and the precipitation surface side of the electrolytic copper foil, a heat-resistant layer or a rust prevention layer is formed on the surface, and a chromate treatment layer or A silane coupling treatment layer is formed.

The electrolytic copper foil according to the embodiment of the present invention may be provided with a resin layer on at least one of the glossy surface side and the deposition surface side. This resin layer is generally formed on the roughening treatment layer or the surface treatment layer. Although it does not specifically limit as a resin layer, It is preferable that it is an insulating resin layer.

It does not specifically limit as a heat-resistant layer and / or a rust prevention layer, A well-known thing can be used. The heat-resistant layer and / or rust-proof layer is made of, for example, nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. It can be a layer containing one or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum It may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of group elements, iron and tantalum. The heat-resistant layer and / or rust-proof layer is made 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 group 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. In the case of the nickel-zinc alloy layer, it is preferable to contain 50 mass% to 99 mass% of nickel and 50 mass% to 1 mass% of zinc, excluding inevitable impurities. The total content of zinc and nickel in the nickel-zinc alloy layer is preferably 5 mg / m ² to 1000 mg / m ² , more preferably 10 mg / m ² to 500 mg / m ² , still more preferably 20 mg / m ² to 100 mg / m ^2. m ² . Further, the ratio of the nickel content to the zinc content in the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel content / zinc content) is preferably 1.5 to 10. Further, the nickel content of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg / m ² to 500 mg / m ² , more preferably 1 mg / m ² to 50 mg / m ^2. preferable.

For example, the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer having a content of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and a content of 1 mg / m 2. A tin layer of ² to 80 mg / m ² , preferably 5 mg / m ² to 40 mg / m ² may be sequentially laminated. The nickel alloy layer may be composed of any one of nickel-molybdenum, nickel-zinc, and nickel-molybdenum-cobalt. The heat-resistant layer and / or rust-preventing layer preferably has a total content of nickel or a nickel alloy and tin of 2 mg / m ² to 150 mg / m ² and 10 mg / m ² to 70 mg / m ² . It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer preferably has [nickel or nickel content in nickel alloy] / [tin content] = 0.25 to 10, preferably 0.33 to 3. More preferred.

The chromate treatment layer is a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer can be any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, 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. .

The silane coupling agent used for the silane coupling treatment is not particularly limited, and known ones can be used. Examples of silane coupling agents include amino silane coupling agents, epoxy silane coupling agents, methacryloxy silane coupling agents, mercapto silane coupling agents, and the like. Specifically, as a silane coupling agent, vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, γ -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, Triazinesilane, γ-mercaptopropyltrimethoxysilane, and the like can be used. In addition, a silane coupling agent can be used individually or in mixture of 2 or more types. Of the various silane coupling agents, an amino silane coupling agent or an epoxy silane coupling agent is preferably used.

Specific examples of the amino silane coupling agent include 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 ) Trimethoxysilane, 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 and the like can be mentioned.

The silane coupling treatment layer is preferably 0.05 mg / m ² to 200 mg / m ² , more preferably 0.15 mg / m ² to 20 mg / m ² , still more preferably 0.3 mg / m ^{2 in} terms of silicon atoms. It is appropriate that it is provided in a range of ˜2.0 mg / m ² . In this range, the adhesion between the insulating substrate (resin substrate) and the electrolytic copper foil can be further improved.

The resin layer may be an adhesive layer, or may be a semi-cured (B-stage) insulating resin layer for bonding. The semi-cured state (B stage state) is a state where 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 be a layer containing a thermosetting resin or a thermoplastic resin. Although the kind of thermosetting resin and thermoplastic resin is not specifically limited, For example, an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin etc. are mentioned. These can be used individually or in mixture of 2 or more types.

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 formed from a composition containing a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeletal material and the like. The resin layer may be, for example, International Publication No. 2008/004399, International Publication No. 2008/053878, International Publication No. 2009/084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application Laid-Open No. 11-140281, Patent No. No. 3184485, International Publication No. 97/02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, Japanese Patent Application Laid-Open No. 2002-359444, Japanese Patent Application Laid-Open No. 2002-359444, 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 40251177, Japanese Patent Application Laid-Open No. 2004-349654, and Japanese Patent No. 2004-349654. Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-2005 Japanese Patent No. 62506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. 2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-. No. 326923, Japanese Patent Application Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. 2006/028207, Japanese Patent No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication No. 2006/134868, Japanese Patent No. No. 5046927, JP 2009-173017 A, International Publication No. 2007/105635, Japanese Patent No. 5180815, International Publication No. 2008/114858, International Publication No. 2009/008471, Japanese Unexamined Patent Publication No. 2011-14727, Country Substances described in JP2009 / 001850, WO2009 / 145179, WO2011 / 068157, JP2013-19056A (resin, resin curing agent, compound, curing accelerator, dielectric Body, reaction catalyst, cross-linking agent, polymer, prepreg, skeletal material, etc.) and / or resin layer forming method and forming apparatus.

For example, the resin is dissolved in a solvent such as methyl ethyl ketone (MEK) and toluene to form a resin solution, which is applied onto the electrolytic copper foil, the roughening treatment layer or the surface treatment layer by a known method such as a roll coater method, If necessary, it is heated and dried to remove the solvent to bring it to the B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 ° C. to 250 ° C., preferably 130 ° C. to 200 ° C.

An electrolytic copper foil having a resin layer is a mode in which a predetermined wiring pattern is formed after the resin layer is superposed on an insulating substrate (resin substrate), and the entire resin layer is thermocompressed to thermally cure the resin layer. used.

When the electrolytic copper foil with the resin layer is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the thickness of the resin layer can be set such that interlayer insulation can be ensured, or a copper-clad laminate can be produced even if no prepreg material is used. In addition, the surface smoothness can be further improved by undercoating an insulating resin on the surface of the substrate.

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 the resin layer is not particularly limited, but is preferably 0.1 μm to 80 μm. When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the electrolytic copper foil with the resin layer is laminated on the base material provided with the inner layer material without interposing the prepreg material, It may be difficult to ensure interlayer insulation between the circuit. 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 desired 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 or the like are likely to occur during handling, and excessive resin flow may occur during thermocompression bonding with the inner layer material, making smooth lamination difficult. is there.

Moreover, as another product form of the electrolytic copper foil with a resin layer, it is also possible to sell it in a form in which a semi-cured resin layer is formed on the glossy surface or the surface treatment layer.

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

A method for manufacturing a printed wiring board according to an embodiment of the present invention includes forming a copper-clad laminate by laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention, then a semi-additive method, a modified semi-additive method, Forming a circuit by either a partial additive method or a subtractive method. Here, the insulating substrate may include an inner layer circuit.

In this specification, the “semi-additive method” means 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 conductor pattern is formed using electroplating and etching.

Therefore, the printed wiring board manufacturing method according to the embodiment of the present invention using the semi-additive method,
A step of laminating an electrolytic copper foil and an insulating substrate (resin substrate) according to an embodiment of the present invention;
Removing all the electrolytic copper foil by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole and / or a blind via in the resin exposed by removing the electrolytic copper foil by etching;
Performing a desmear process on a region including through holes and / or blind vias;
Providing an electroless plating layer for a region including resin and through-holes and / or blind vias;
Providing a plating resist on the electroless plating layer;
After exposing the plating resist, removing the plating resist in the region where the circuit is formed;
A step of providing an electroplating layer in a region where a circuit is formed after removing the plating resist;
Removing the plating resist;
Removing an electroless plating layer in a region other than a region where a circuit is formed by flash etching or the like.

In another aspect of the method for manufacturing a printed wiring board according to the embodiment of the present invention using a semi-additive method,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a through hole and / or a blind via in the electrolytic copper foil and the insulating substrate (resin substrate);
Performing a desmear process on a region including through holes and / or blind vias;
Removing all the electrolytic copper foil by a method such as etching or plasma using a corrosive solution such as acid,
A step of providing an electroless plating layer for the resin exposed by removing the electrolytic copper foil by etching or the like and the region including the through hole and / or the blind via;
Providing a plating resist on the electroless plating layer;
After exposing the plating resist, removing the plating resist in the region where the circuit is formed;
A step of providing an electroplating layer in a region where a circuit is formed after removing the plating resist;
Removing the plating resist;
Removing an electroless plating layer in a region other than a region where a circuit is formed by flash etching or the like.

In another aspect of the method for manufacturing a printed wiring board according to the embodiment of the present invention using a semi-additive method,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a through hole and / or a blind via in the electrolytic copper foil and the insulating substrate (resin substrate);
Removing all the electrolytic copper foil by a method such as etching or plasma using a corrosive solution such as acid,
Performing a desmear process on a region including through holes and / or blind vias;
A step of providing an electroless plating layer for the resin exposed by removing the electrolytic copper foil by etching or the like and the region including the through hole and / or the blind via;
Providing a plating resist on the electroless plating layer;
After exposing the plating resist, removing the plating resist in the region where the circuit is formed;
A step of providing an electroplating layer in a region where a circuit is formed after removing the plating resist;
Removing the plating resist;
Removing an electroless plating layer in a region other than a region where a circuit is formed by flash etching or the like.

In another aspect of the method for manufacturing a printed wiring board according to the embodiment of the present invention using a semi-additive method,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Removing all 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;
After exposing the plating resist, removing the plating resist in the region where the circuit is formed;
A step of providing an electroplating layer in a region where a circuit is formed after removing the plating resist;
Removing the plating resist;
And a step of 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.

In this specification, the “modified semi-additive method” means that an electrolytic copper foil is laminated on an insulating substrate, a non-circuit forming part is protected by a plating resist, and a copper thickening of the circuit forming part is performed by electrolytic plating. It means a method of forming a circuit on an insulating substrate by removing the resist and removing the electrolytic copper foil other than the circuit forming part by (flash) etching.

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

In another aspect of the method for manufacturing a printed wiring board according to the embodiment of the present invention using the modified semi-additive method,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a plating resist on the electrolytic copper foil;
After exposing the plating resist, removing the plating resist in the region where the circuit is formed;
A step of providing an electroplating layer in a region where a circuit is formed after removing the plating resist;
Removing the plating resist;
And a step of 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.

In this specification, the “partial additive method” means that a conductive circuit is formed by applying a catalyst nucleus on a substrate provided with a conductor layer and, if necessary, a substrate provided with a hole for a through hole or a via hole, and etching it. A method of manufacturing a printed wiring board by forming a solder resist or a plating resist as necessary, and then thickening the conductive circuit, through holes, via holes, etc. by electroless plating treatment means.

Therefore, the printed wiring board manufacturing method according to the embodiment of the present invention using the partly additive method, in one aspect,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a through hole and / or a blind via in the electrolytic copper foil and the insulating substrate;
Performing a desmear process on a region including through holes and / or blind vias;
Providing catalyst nuclei for regions containing 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 no solder resist or plating resist is provided.

In this specification, the “subtractive method” means a method of forming a conductor pattern by selectively removing unnecessary portions of the copper foil on the copper-clad laminate by etching or the like.

Therefore, the printed wiring board manufacturing method according to the embodiment of the present invention using the subtractive method, in one aspect,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a through hole and / or a blind via in the electrolytic copper foil and the insulating substrate;
Performing a desmear process on a region including through holes and / or blind vias;
Providing an electroless plating layer for a region including through holes and / or blind vias;
Providing an electroplating layer on the surface of the electroless plating layer;
Providing an etching resist on the surface of the electrolytic plating layer and / or the electrolytic copper foil;
Exposing the etching resist to form a circuit pattern;
A step of forming a circuit by removing the electrolytic copper foil, 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;
And a step of removing the etching resist.

The printed wiring board manufacturing method according to the embodiment of the present invention using the subtractive method, in another aspect,
A step of laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention;
Providing a through hole and / or a blind via in the electrolytic copper foil and the insulating substrate;
Performing a desmear process on a region including through holes and / or blind vias;
Providing an electroless plating layer for a region including through holes and / or blind vias;
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 and / or 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 acid to form a circuit;
And a step of removing the etching resist.

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

Hereinafter, although an embodiment of the present invention is described in detail by an example and a comparative example, the present invention is not limited by these.
1. Preparation of electrolytic copper foil (Examples 1 to 18, Comparative Examples 1 and 2)
A rotating drum (electrolytic drum) made of titanium was prepared. Next, the surface of the electrolytic drum was polished under the 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 with a count polishing belt shown in Table 1. At this time, the polishing belt was wound by winding a predetermined width in the drum width direction and rotating the drum while moving the polishing belt in the drum width direction. Table 1 shows the rotational speed of the drum surface during 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, in the electrolytic cell, the above-described electrolytic drum and electrodes were disposed around the electrolytic drum with a predetermined distance between the electrodes. 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 described in Table 2 was reached while rotating the electrolytic drum.
<Electrolysis conditions>
Electrolyte composition: 100 g / L Cu, 100 g / L H ₂ SO ₄
Current density: 90 A / dm ²
Electrolyte flow rate: 2.0 m / sec Electrolyte temperature: 60 ° C
Additives: 60 ppm by weight of chloride ion, glue (Examples 1, 2, 5, 6 and 10-12, and in Comparative Example 1, 0.02 ppm, Examples 3, 4, 7-9 and 13) In -18, it was set to 4.5 ppm.)

In Comparative Example 2, electrolysis was performed under the following conditions, and copper was deposited on the surface of the electrolytic drum until the thickness described in Table 2 was reached.
<Electrolysis conditions>
Electrolyte composition: 50 to 150 g / L Cu, 60 to 150 g / L H ₂ SO ₄
Current density: 10 to 80 A / dm ²
Electrolyte flow rate: 1.5-5 m / sec Electrolyte temperature: 50-60 ° C
Additive: 10 to 100 mass ppm of chloride ion, 10 to 100 mass ppm of bis (3sulfopropyl) disulfide, 10 to 100 mass ppm of tertiary amine compound The following compounds are used as the tertiary amine compound. It was.

In the above chemical formula, R ₁ and R ₂ are both methyl groups. The tertiary amine compound can be obtained, for example, by mixing a predetermined amount of Deconal Ex-314 manufactured by Nagase ChemteX Corporation and dimethylamine and reacting at 60 ° C. for 3 hours.

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

For Examples 1 to 4 and 10 and Comparative Examples 1 and 2, the following (1) to (4) were applied to the surface (glossy surface) of the electrolytic copper foil (raw foil) produced as described above on the electrolytic drum side. ) Was performed in this order. Further, for Examples 1 and 2 and Comparative Examples 1 and 2, the following (2) to (2) to the surface (deposition surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above The processing shown in (4) was performed in this order. For Example 10, the following treatments (1) to (4) were performed on the surface (deposition surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above. It carried out in this order. Moreover, about Example 3, the process shown to the following (3) was implemented with respect to the surface (deposition surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as mentioned above. Moreover, about Example 4, the process shown to the following (4) was implemented with respect to the surface (precipitation surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as mentioned above.

(1) Roughening treatment Roughened particles were electrodeposited on the surface using a copper roughening plating bath consisting of Cu, H ₂ SO ₄ , As and W described below.
(Liquid composition 1)
CuSO ₄ .5H ₂ O: 120 g / L
H ₂ SO ₄ : 120 g / L
Na ₂ WO ₄ · 2H ₂ O: 20 mg / L
Sodium dodecyl sulfate: 30mg
As: 1mg / L

(Electroplating condition 1)
Temperature: 40 ° C
(Current condition 1)
Current density: 70 A / dm ²
Plating time: 2 seconds (Liquid composition 2)
CuSO ₄ .5H ₂ O: 240 g / L
H ₂ SO ₄ : 120 g / L
(Electroplating condition 2)
Temperature: 55 ° C
(Current condition 2)
Current density: 20 A / dm ²
Plating time: 7 seconds

(2) Barrier treatment (heat-resistant treatment)
Nickel zinc alloy plating was performed.
(Liquid composition)
Ni: 13 g / L
Zn: 5 g / L
pH: 2
(Electroplating conditions)
Temperature: 40 ° C
Current density: 8 A / dm ²

(3) Chromate treatment Zinc chromate treatment was performed.
(Liquid composition)
CrO ₃ : 2.5 g / L
Zn: 0.7 g / L
Na ₂ SO ₄ : 10 g / L
pH: 4.8
(Zinc chromate condition)
Temperature: 54 ° C
Current density: 0.7 A / dm ²

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

Examples 5 to 8 and 14 to 18 are shown in the following (1) to (5) with respect to the surface (glossy surface) of the electrolytic copper foil (raw foil) produced as described above on the electrolytic drum side. Processing was performed in this order. For Examples 5 to 8 and 15 to 18, the following (2) to (2) to the surface (precipitation surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above: The processing shown in 5) was performed in this order. Moreover, about Example 14, the process shown to the following (4) and (5) with respect to the surface (precipitation surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as mentioned above. It carried out in this order.

(1) Roughening treatment Roughening treatment was performed in the following plating bath and plating conditions in order to electrodeposit the roughened particles of the ternary copper-cobalt-nickel alloy plating on the surface.
Plating bath composition: 16 g / L Cu, 10 g / L Co, 10 g / L Ni
pH: 1 to 4
Temperature: 30 ° C
Current density: 30 A / dm ²
Plating time: 2 seconds

(2) Heat-resistant treatment Co—Ni alloy plating was performed. The Co—Ni alloy plating conditions are described below.
(Electrolytic solution composition)
Co: 10 g / L
Ni: 20 g / L
pH: 1.0 to 3.5
(Electrolyte temperature)
35 ° C
(Current condition)
Current density 10A / dm ²
Plating time: 1 second

(3) Rust prevention treatment Zinc-nickel alloy plating was performed.
(Liquid composition)
Ni: 15 g / L
Zn: 50 g / L
pH: 3-4
(Electroplating conditions)
Temperature: 50 ° C
Current density: 0.3 A / dm ²
Plating time: 2.43 seconds for Examples 5 and 8, 2.61 seconds for Example 6, 2.32 seconds for Example 7, 0.5 to 5 seconds for Examples 14-18

(4) Chromate treatment Zinc chromate treatment was performed.
(Liquid composition)
CrO ₃ : 2.5 g / L
Zn: 0.7 g / L
Na ₂ SO ₄ : 10 g / L
pH: 4.8
(Zinc chromate condition)
Temperature: 54 ° C
Current density: 0.7 A / dm ²

(5) Silane coupling treatment (Liquid composition)
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane content: 0.4 vol%
pH: 7.5
Application method: Spray of solution

Regarding Example 9, the following (1) was applied to the electrolytic drum side surface (glossy surface) and the opposite surface (deposition surface) of the electrolytic copper foil (raw foil) produced as described above. The processes shown in (3) were performed in this order.

(1) Barrier treatment (heat-resistant treatment)
Nickel-zinc alloy plating was performed.
(Liquid composition)
Ni: 13 g / L
Zn: 5 g / L
pH: 2
(Electroplating conditions)
Temperature: 40 ° C
Current density: 8 A / dm ²

(2) Chromate treatment Zinc chromate treatment was performed.
(Liquid composition)
CrO ₃ : 2.5 g / L
Zn: 0.7 g / L
Na ₂ SO ₄ : 10 g / L
pH: 4.8
(Zinc chromate condition)
Temperature: 54 ° C
Current density: 0.7 A / dm ²

(3) Silane coupling treatment (Liquid composition)
Tetraethoxysilane content: 0.4 vol%
pH: 7.5
Application method: Spray of solution

After the above treatment, a resin layer was formed on the surface of the surface treatment layer under the following conditions.
(Resin synthesis example)
To a 2 liter three-necked flask equipped with a reflux condenser equipped with a condenser tube with a ball on a trap with a stainless steel vertical stirring bar, a nitrogen introduction tube and a stopcock, 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 and cooled to near room temperature, and then 3, 4, 3 ′, 4 '-Biphenyltetracarboxylic dianhydride 29.42 g (100 mmol), 2,2-bis {4- (4-aminophenoxy) phenyl} propane 82.12 g (20 mmol), 200 g of NMP, and toluene 40g was added and after mixing 1 hour 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, Kay-Isei Chemical Co., Ltd.) has 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), dissolved and mixed at 60 ° C. for 20 minutes to obtain a resin solution. After that, the resin solution was applied to the surface of the surface treatment layer of the electrolytic copper foil using a reverse roll coating machine, and dried at 120 ° C. for 3 minutes and at 160 ° C. for 3 minutes in a nitrogen atmosphere. Then, heat treatment was performed at 300 ° C. for 2 minutes to prepare an electrolytic copper foil provided with a resin layer. The thickness of the resin layer was 2 μm.

For Examples 11 to 13, the surface (glossy surface) on the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above was subjected to the roughening treatment shown in (1) below. The same processes (2) to (5) as in Examples 5 to 8 and 14 were performed in this order. Further, in Examples 11 to 13, the surface (glossy surface) opposite to the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above was compared with (2) to ( The same process as 5) was performed in this order.

(1) Roughening treatment Roughening treatment was performed in the following plating bath and plating conditions in order to electrodeposit the roughened particles of the ternary copper-cobalt-nickel alloy plating on the surface.
Plating bath composition: 10-20 g / L Cu, 1-10 g / L Co, 1-10 g / L Ni
pH: 1 to 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 and glossy surface side roughness Sa and root mean square height Sq>
The surface roughness Sa and the root mean square height Sq on the glossy surface and the glossy surface side are ISO-25178-2: 2012 with respect to the glossy surface of the electrolytic copper foil before and after the roughening treatment and / or the surface treatment. The measurement was performed using a laser microscope OLS4100 (LEXT OLS 4100) manufactured by Olympus. At this time, in a laser microscope, measurement of 200 μm × 1000 μm area (specifically 200,000 μm ² ) was performed at three locations using an objective lens 50 times, 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 the 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 (when the measurement surface is a curved surface), the surface roughness Sa and the root mean square height Sq were calculated after performing plane correction. The environmental temperature at the time of measuring the surface roughness Sa with a laser microscope was set to 23 to 25 ° C.

<Deposition surface side roughness Sa, root mean square height Sq, maximum peak height Sp, maximum valley depth Sv, maximum height Sz, kurtosis Sku and skewness Ssk>
The surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the kurtosis Sku and the skewness Ssk on the precipitation surface side are the electrolytic copper after the roughening treatment and / or the surface treatment. Based on ISO-25178-2: 2012, measurement was performed on the deposited surface of the foil using a laser microscope OLS4100 (LEXT OLS 4100) manufactured by Olympus. The measurement conditions at this time were the same as the measurement conditions for the glossy surface and the surface roughness Sa and the root mean square height Sq on the glossy surface side.

<Normal temperature tensile strength, high temperature tensile strength>
The electrolytic copper foil after the roughening treatment and / or the surface treatment was measured for normal temperature tensile strength and high temperature tensile strength according to IPC-TM-650.

<Normal temperature elongation, high temperature elongation>
The electrolytic copper foil after the roughening treatment and / or the surface treatment was measured for normal temperature elongation and high temperature elongation according to IPC-TM-650. As described above, “high temperature tensile strength” means tensile strength at 180 ° C. “High temperature elongation” means elongation at 180 ° C.

<Circuit formability>
The electrolytic copper foil after the roughening treatment and / or the surface treatment was bonded to the 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 deposition surface side until the thickness became 9 μm. And the etching resist was provided in the surface of the electrolytic copper foil after etching, exposure and image development were performed, and the resist pattern was formed. Thereafter, etching is performed with ferric chloride, and L / S = 25 μm / 25 μm, L / S = 22 μm / 22 μm, L / S = 20 μm / 20 μm, and L / S = 15 μm / 15 μm and a length of 1 mm. 20 pieces of each were formed. Subsequently, a difference (μm) between the maximum value and the minimum value of the circuit lower end width as viewed from the circuit upper surface was measured, and an average value obtained by measuring five locations was used as a result. If the difference between the maximum value and the minimum value was 2 μm or less, it was judged as having excellent circuit linearity and marked with “◎”. In addition, the case where the difference between the maximum value and the minimum value was more than 2 μm and 4 μm or less was marked as ◯. In addition, the case where the difference between the maximum value and the minimum value exceeded 4 μm was evaluated as x.

<Solder resist adhesion>
The adhesion of the solder resist was performed as follows. First, a solder resist (product name “PSR-4000AUS308” manufactured by Taiyo Ink Mfg. Co., Ltd., product name) is applied to the deposition surface side of the electrolytic copper foil after the surface treatment, followed by drying (80 ° C. × 30 minutes), post-cure (150 ° C. × 60 minutes) and post-UV (high pressure mercury lamp, 1000 mJ / cm ² ) were successively performed to form a 20-30 μm thick solder resist resin layer (coating film) to prepare a test piece. Next, this test piece was floated in a solder bath at 260 ° C. for 20 seconds, then removed from the solder layer, and swelled at the interface between the electrolytic copper foil and the solder resist (peeling between the electrolytic copper foil and the solder resist) was observed. . In this evaluation, the surface of the electrolytic copper foil that had discolored due to blistering in the area of 5% or more was x (failed), and the surface of the electrolytic copper foil that was discolored from 2% to less than 5% had discoloration of the interface due to blistering. Evaluation was made as ◯, where no discoloration of the interface due to blistering occurred, or when there was discoloration of the interface due to blistering in an area of less than 2% of the electrolytic copper foil.

Test conditions and test results are shown in Tables 2 and 3. Moreover, Fig.1 (a) is a SEM image of the glossy surface of the electrolytic copper foil of Example 2 before forming a roughening process layer and a surface treatment layer. FIG.1 (b) is the SEM image of the glossy surface of the electrolytic copper foil of Example 10 before forming a roughening process layer and a surface treatment layer.

<Evaluation results>
The electrolytic copper foil of Example 9 having no roughening treatment layer on the glossy surface side has a gloss roughness side surface roughness Sa of 0.270 μm or less and a root mean square height Sq of 0.315 μm or less, For the precipitation surface side, the surface roughness Sa is 0.115 μm or more, the root mean square height Sq is 0.120 μm or more, the maximum peak height Sp is 0.900 μm or more, and the maximum valley depth Sv is 0.600 μm or more. The maximum height Sz was 1.500 μm or more, the kurtosis Sku was 2.75 to 4.00, and the skewness Ssk was 0.00 to 0.35. The electrolytic copper foil had good circuit formability and solder resist adhesion. Moreover, this electrolytic copper foil also had good results of normal temperature tensile strength, high temperature tensile strength, normal temperature elongation and high temperature elongation.
In addition, in the electrolytic copper foils of Examples 1 to 8 and 10 to 14 having the roughened layer on the glossy surface side, the surface roughness Sa on the glossy surface side is 0.470 μm or less and the root mean square height Sq is 0. The surface roughness Sa is not less than 0.115 μm, the root mean square height Sq is not less than 0.120 μm, the maximum peak height Sp is not less than 0.900 μm, and the maximum valley depth Sv is about 550 μm or less. Was 0.600 μm or more, the maximum height Sz was 1.500 μm or more, the kurtosis Sku was 2.75 or more and 4.00 or less, and the skewness Ssk was 0.00 or more and 0.35 or less. The electrolytic copper foil had good circuit formability and solder resist adhesion. Moreover, this electrolytic copper foil also had good results of normal temperature tensile strength, high temperature tensile strength, normal temperature elongation and high temperature elongation.

On the other hand, the electrolytic copper foil of Comparative Example 1 having a roughened layer on the glossy surface side has a surface roughness Sa on the glossy surface side of more than 0.470 μm and a root mean square height Sq of 0.550 μm. It was over. Therefore, this electrolytic copper foil was not sufficient in circuit formation.
In addition, the electrolytic copper foil of Comparative Example 2 having the roughened layer on the glossy surface side has a surface roughness Sa of less than 0.115 μm and a root mean square height Sq of less than 0.120 μm and a maximum on the deposition surface side. The peak height Sp is less than 0.900 μm, the maximum valley depth Sv is less than 0.600 μm, the maximum height Sz is less than 1.500 μm, the kurtosis Sku is out of the range of 2.75 to 4.00, and the skewness Ssk is 0.00. It was outside the range of 00 to 0.35. Therefore, this electrolytic copper foil has insufficient adhesiveness of the solder resist.

As can be seen from the above results, according to the embodiment of the present invention, it is possible to provide an electrolytic copper foil excellent in circuit formability and solder resist adhesion. In addition, according to the embodiment of the present invention, a copper-clad laminate using an electrolytic copper foil excellent in circuit formability and solder resist adhesion, a printed wiring board, a manufacturing method thereof, an electronic device, and a manufacturing method thereof are provided. Can be provided.

Claims (39)

1. An electrolytic copper foil having a glossy surface and a precipitation surface,
   The glossy surface has a roughening layer, the root mean square height Sq of the glossy surface is 0.550 μm or less, and the precipitation surface side has the following conditions:
   (A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more An electrolytic copper foil satisfying at least one of 0.35 or less.
2. The precipitation surface side has the following conditions:
   (A) Surface roughness Sa is 0.120 μm or more (b) Root mean square height Sq is 0.130 μm or more (c) Maximum peak height Sp is 1.050 μm or more (d) Maximum valley Depth Sv is 0.740 μm or more (e) Maximum height Sz is 1.800 μm or more (f) Kurtosis Sku is 2.80 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more The electrolytic copper foil according to claim 1, satisfying at least one of 0.26 or less.
3. The electrolytic copper foil according to claim 1 or 2, wherein the surface roughness Sa on the glossy surface side is 0.380 µm or less.
4. The electrolytic copper foil according to any one of claims 1 to 3, wherein a surface roughness Sa on the glossy surface side is 0.355 µm or less.
5. The electrolytic copper foil according to any one of claims 1 to 4, wherein a surface roughness Sa on the glossy surface side is 0.300 µm or less.
6. The electrolytic copper foil according to any one of claims 1 to 5, wherein a surface roughness Sa on the glossy surface side is 0.200 µm or less.
7. The electrolytic copper foil according to any one of claims 1 to 6, wherein a root mean square height Sq on the glossy surface side is 0.490 µm or less.
8. The electrolytic copper foil according to any one of claims 1 to 7, wherein a root mean square height Sq on the glossy surface side is 0.450 µm or less.
9. The electrolytic copper foil according to any one of claims 1 to 8, wherein a root mean square height Sq on the glossy surface side is 0.400 µm or less.
10. The electrolytic copper foil according to any one of claims 1 to 9, wherein the root mean square height Sq on the glossy surface side is 0.330 µm or less.
11. An electrolytic copper foil having a glossy surface and a precipitation surface,
    It has a roughening treatment layer on the glossy surface side, the surface roughness Sa on the glossy surface side is 0.470 μm or less, and the precipitation surface side has the following conditions:
    (A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more An electrolytic copper foil satisfying at least one of 0.35 or less.
12. The electrolytic copper foil according to claim 11, wherein the root mean square height Sq on the glossy surface side is 0.550 µm or less.
13. The electrolytic copper foil according to any one of claims 1 to 12, 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.
14. The electrolytic copper foil according to any one of claims 1 to 13, wherein a surface roughness Sa of the glossy surface before providing the roughening treatment layer on the glossy surface side is 0.130 µm or less.
15. The electrolytic copper foil according to any one of claims 1 to 14, wherein a root mean square height Sq of the glossy surface before providing the roughening layer on the glossy surface side is 0.315 µm or less.
16. The electrolytic copper foil according to any one of claims 1 to 15, 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.
17. An electrolytic copper foil having a glossy surface and a precipitation surface,
    There is no roughening layer on the glossy surface side, the surface roughness Sa on the glossy surface side is 0.270 μm or less, and the precipitation surface side has the following conditions:
    (A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more An electrolytic copper foil satisfying at least one of 0.35 or less.
18. The electrolytic copper foil according to claim 17, wherein the root mean square height Sq on the glossy surface side is 0.315 µm or less.
19. An electrolytic copper foil having a glossy surface and a precipitation surface,
    The glossy surface side does not have a roughening treatment layer, the root mean square height Sq on the glossy surface side is 0.315 μm or less, and the precipitation surface side has the following conditions:
    (A) Surface roughness Sa is 0.115 μm or more (b) Root mean square height Sq is 0.120 μm or more (c) Maximum peak height Sp is 0.900 μm or more (d) Maximum valley Depth Sv is 0.600 μm or more (e) Maximum height Sz is 1.500 μm or more (f) Kurtosis Sku is 2.75 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more An electrolytic copper foil satisfying at least one of 0.35 or less.
20. The precipitation surface side has the following conditions:
    (A) Surface roughness Sa is 0.120 μm or more (b) Root mean square height Sq is 0.130 μm or more (c) Maximum peak height Sp is 1.050 μm or more (d) Maximum valley Depth Sv is 0.740 μm or more (e) Maximum height Sz is 1.800 μm or more (f) Kurtosis Sku is 2.80 or more and 4.00 or less (g) Skewness Ssk is 0.00 or more The electrolytic copper foil according to any one of claims 17 to 19, satisfying at least one of 0.26 or less.
21. The electrolytic copper foil according to any one of claims 17 to 20, wherein a surface roughness Sa on the glossy surface side is 0.150 µm or less.
22. The electrolytic copper foil according to any one of claims 17 to 21, wherein a surface roughness Sa on the glossy surface side is 0.130 µm or less.
23. The electrolytic copper foil according to any one of claims 17 to 22, wherein a root mean square height Sq on the glossy surface side is 0.200 µm or less.
24. The electrolytic copper foil according to any one of claims 17 to 23, wherein a root mean square height Sq on the glossy surface side is 0.120 µm or less.
25. The electrolytic copper foil according to any one of claims 1 to 24, having a normal temperature tensile strength of 30 kg / mm ² or more.
26. The electrolytic copper foil according to any one of claims 1 to 25, wherein the room temperature elongation is 3% or more.
27. The electrolytic copper foil according to any one of claims 1 to 26, wherein the high-temperature tensile strength is 10 kg / mm ² or more.
28. The electrolytic copper foil according to any one of claims 1 to 27, wherein the high temperature elongation is 2% or more.
29. The electrolytic copper foil according to any one of claims 1 to 28, wherein the roughening layer is provided on the precipitation surface side.
30. 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. The electrolytic copper foil according to any one of claims 1 to 16, which is a layer.
31. One or more selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of at least one roughening treatment layer on the glossy side and the precipitation side of the electrolytic copper foil The electrolytic copper foil according to any one of claims 1 to 16, which has a surface treatment layer.
32. The electrolytic copper foil according to any one of claims 1 to 31, further comprising a resin layer on at least one of a glossy surface side and a deposition surface side of the electrolytic copper foil.
33. The electrolytic copper foil according to claim 32, wherein the resin layer is provided on the roughening treatment layer or the surface treatment layer.
34. A copper-clad laminate having the electrolytic copper foil according to any one of claims 1 to 33.
35. A printed wiring board having the electrolytic copper foil according to any one of claims 1 to 33.
36. A method for producing a printed wiring board using the electrolytic copper foil according to any one of claims 1 to 33.
37. A copper-clad laminate is produced by laminating the electrolytic copper foil according to any one of claims 1 to 33 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 method.
38. An electronic device having the printed wiring board according to claim 35.
39. A method for manufacturing an electronic device using the printed wiring board according to claim 35.

Images