WO2018207785A1

WO2018207785A1 - Electrolytic copper foil, production method therefor, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor

Info

Publication number: WO2018207785A1
Application number: PCT/JP2018/017823
Authority: WO
Inventors: 賢二犬飼; 友一岩崎; 小林　洋介; 一彦飯田
Original assignee: Ｊｘ金属株式会社
Priority date: 2017-05-09
Filing date: 2018-05-08
Publication date: 2018-11-15
Also published as: TW201900934A; TWI690622B

Abstract

An electrolytic copper foil having a surface treatment layer on the glossy surface side thereof. In this electrolytic copper foil, the root mean square height Sq of the surface of the surface treatment layer is no more than 0.550 µm and the total amount of Zn included in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn is at least 70 µg/dm2. Alternatively, the surface roughness Sa of the surface of the surface treatment layer is no more than 0.470 µm and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn included in the surface treatment layer is at least 70 µg/dm2.

Description

Electrolytic copper foil and manufacturing method thereof, copper-clad laminate, printed wiring board and manufacturing method thereof, electronic device and manufacturing method thereof

The present disclosure relates to an electrolytic copper foil and a manufacturing method thereof, a copper-clad laminate, a printed wiring board and 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 is formed on the copper foil by etching.
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 circuit on the electrolytic copper foil, and thus it cannot be said that the circuit formability is sufficient.

On the other hand, when the surface of the electrolytic copper foil is smooth, there is a problem that sufficient adhesiveness cannot be obtained when bonding to the insulating substrate (resin substrate). In particular, since printed wiring boards are often exposed to high temperatures, the electrolytic copper foil has little decrease in adhesion to an insulating substrate (resin substrate) under high temperature conditions (that is, excellent heat resistance). It has been demanded.
As a method for improving the adhesion between the electrolytic copper foil and the insulating substrate (resin substrate), it is known to perform a roughening treatment or the like on the surface of the electrolytic copper foil. , Circuit formability) may be affected.
For this reason, the conventional technique has a problem that it is difficult to achieve both improvement in heat resistance and improvement in circuit formability.

Some embodiments of the present invention have been made in order to solve the above-described problems, and circuit formation properties and heat resistance (especially, suppressing adhesion deterioration when bonded to an insulating substrate). It is an object of the present invention to provide an electrolytic copper foil excellent in (effect) and a method for producing the same.
In addition, some embodiments of the present invention provide a copper clad laminate using an electrolytic copper foil that is excellent in circuit formability and heat resistance (particularly, an effect of suppressing a decrease in adhesiveness when adhered to an insulating substrate). It is an object of the present invention to provide a printed wiring board and a manufacturing method thereof, and an electronic device and a manufacturing method thereof.

As a result of intensive studies to solve the above problems, the present inventors have found that the surface roughness Sa and / or the root mean square height of the surface of the surface treatment layer in the electrolytic copper foil having the surface treatment layer on the glossy surface side. Focusing on the fact that the total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn is related to heat resistance, the surface treatment layer The surface roughness Sa and / or the root mean square height Sq, and the total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn are controlled within a specific range. As a result, it has been found that both heat resistance and circuit formability can be improved, and several embodiments of the present invention have been completed.

That is, the electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer on the glossy surface side,
The root mean square height Sq of the surface of the surface treatment layer is 0.550 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg. / Dm ² or more.

Moreover, the electrolytic copper foil according to another embodiment of the present invention has a surface treatment layer on the glossy surface side,
The surface roughness Sa of the surface treatment layer is 0.470 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm ^2. That's it.

Moreover, the manufacturing method of the electrolytic copper foil which concerns on embodiment of this invention, after producing electrolytic copper foil using an electrolytic drum, surface-treats to the glossy surface of the said electrolytic copper foil, and forms a surface treatment layer,
The surface roughness Sa of the surface of the electrolytic drum is 0.270 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm ² or more. It is.

Moreover, the manufacturing method of the electrolytic copper foil which concerns on another embodiment of this invention is, after producing electrolytic copper foil using an electrolytic drum, surface-treating to the glossy surface of the said electrolytic copper foil, and forming a surface treatment layer And
The root mean square height Sq of the surface of the electrolytic drum is 0.315 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm ² or more.

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 electronic device manufacturing method according to the embodiment of the present invention uses a printed wiring board.

According to some embodiments of the present invention, an electrolytic copper foil excellent in circuit formability and heat resistance and a method for producing the same 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 heat resistance, a printed wiring board, a manufacturing method thereof, an electronic device, and a manufacturing method thereof are provided. can do.

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

The electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer on the glossy surface side, and the root mean square height Sq of the surface of the surface treatment layer is 0.550 μm or less and / or the surface of the surface treatment layer. The surface roughness Sa is 0.470 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm ² or more.
Here, in this specification, the “glossy surface of the electrolytic copper foil” means the surface on the drum side (shiny surface: S surface) when the electrolytic copper foil is produced, and “deposition of electrolytic copper foil” "Surface" means the surface (matte surface: M surface) opposite to the drum when the electrolytic copper foil is produced.
Hereinafter, the preferable aspect of the electrolytic copper foil which concerns on embodiment of this invention is demonstrated.

<Electrolytic copper foil having a surface treated layer other than the roughened layer on the glossy surface>
In one aspect, the electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer other than the roughening treatment layer on the glossy surface side, and the surface roughness Sa of the surface of the surface treatment layer is 0.270 μm or less. And / or the root mean square height Sq of the surface of the surface treatment layer is 0.315 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm ² or more.

In the electrolytic copper foil having the above configuration, the surface roughness Sa of the surface treatment layer is 0.270 μm or less and / or the root mean square height Sq of the surface of the surface treatment layer is 0.315 μm or less. Thus, the pitch of the circuit formed using the electrolytic copper foil can be fine pitches of 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 of the surface treatment layer is preferably 0.230 μm or less, more preferably 0.180 μm or less, still more preferably 0.150 μm or less, and most preferably 0. 0 μm from the viewpoint of enhancing the effect of fine pitch. 133 μm or less. The lower limit of the surface roughness Sa of the surface treatment layer 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 0.100 μm or more. It is.

Further, the root mean square height Sq of the surface treatment layer is preferably 0.200 μm or less, and 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 of the surface treatment layer 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 0. ≧ 100 μm.
As described above, when the surface roughness Sa of the surface treatment layer is controlled to 0.270 μm or less and / or the root mean square height Sq of the surface of the surface treatment layer is controlled to 0.315 μm or less, the circuit formability is On the other hand, since the unevenness on the surface of the surface treatment layer is reduced, the adhesion between the electrolytic copper foil and the insulating substrate (resin substrate) due to the anchor effect of the unevenness may be reduced. In particular, there is a concern about a decrease in adhesion between the electrolytic copper foil and the insulating substrate (resin substrate) under high temperature conditions. Therefore, as described below, the heat resistance can be improved by setting the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer to 70 μg / dm ² or more. is important.

The heat resistance can be improved by controlling the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer to 70 μg / dm ² or more. From the viewpoint of further improving the heat resistance, the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is preferably 80 μg / dm ² or more, more preferably 85 μg / dm ² or more, more preferably 90 [mu] g / dm ² or more, more preferably 95μg / dm ² or more, more preferably 100 [mu] g / dm ² or more, more preferably 105μg / dm ² or more, more preferably 110 .mu.g / dm ² or more, more preferably 115μg / dm ² or more, more preferably 120 [mu] g / dm ² or more, more preferably 125 [mu] g / dm ² or more, more preferably 130μg / dm ² or more, more preferably 135μg / dm ² or more, more preferably 140 [mu] g / dm ² or more, more preferably 150 [mu] g / dm ² or more, more preferably 200 [mu] g / dm ² or more, more preferably 2 0 Pg / dm ² or more, more preferably 300 [mu] g / dm ² or more. The total amount of Zn contained in the surface treatment layer, the total amount of Mo, or although the total amount of the upper limit of the Mo and Zn is not particularly limited, typically 6000μg / dm ² or less, preferably 5000 [mu] g / dm ² or less More preferably, it is 400 μg / dm ² or less.

<Electrolytic copper foil having a surface treatment layer including at least a roughening treatment layer on the glossy surface>
In another aspect, the electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer including at least a roughening treatment layer on the glossy surface side, and the surface roughness Sa of the surface of the surface treatment layer is 0. 470 μm or less and / or the root mean square height Sq of the surface of the surface treatment layer is 0.550 μm or less, and the total amount of Zn, the total amount of Mo, or Mo and Zn contained in the surface treatment layer The total amount is 70 μg / dm ² or more.

In general, in the electrolytic copper foil having the roughened layer on the glossy surface side, fine pitch may be reduced. However, in the electrolytic copper foil having the above-described configuration, the surface roughness of the surface of the surface-treated layer may be reduced. The pitch of the circuit formed using the electrolytic copper foil is adjusted to L / S by setting the thickness Sa to 0.470 μm or less and / or the root mean square height Sq of the surface of the surface treatment layer to 0.550 μm or less. (Line / space) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less.
The surface roughness Sa of the surface treatment layer is preferably 0.385 μm or less, more preferably 0.380 μm or less, more preferably 0.355 μm or less, and still more preferably 0. 0, from the viewpoint of enhancing the effect of fine pitch. It is 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 of the surface treatment layer 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 0.100 μm or more. It is.

Further, the root mean square height Sq of the surface treatment layer is preferably 0.490 μm or less, more preferably 0.450 μm or less, more preferably 0.435 μm or less, from the viewpoint of enhancing the effect of fine pitch formation. More preferably, it is 0.400 μm or less, more 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 of the surface treatment layer 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 0. ≧ 100 μm.

The electrolytic copper foil according to the embodiment of the present invention having the surface roughness Sa and / or the root mean square height Sq of the surface treatment layer as described above is a gloss before the surface treatment layer is provided on the glossy surface side. It can be obtained by controlling the surface roughness Sa and / or the root mean square height Sq.

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 surface treatment layer on the glossy surface side is preferably 0.270 μm or less, more preferably 0. It may be controlled to 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. The lower limit of the surface roughness Sa of the glossy surface before providing 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 0.050 μm or more. More preferably, it is 0.100 μm or more.
By controlling the surface roughness Sa of the glossy surface before providing the surface treatment layer on the glossy surface side in the above range, the surface roughness Sa and / or the root mean square height Sq of the surface of the surface treatment layer is set as described above. Therefore, the pitch of the circuit formed by using the electrolytic copper foil is L / S (line / space) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less. Can be realized.

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 surface treatment layer on the glossy surface side is preferably 0.315 μm or less, more preferably Is controlled to 0.292 μm or less, more preferably 0.230 μm or less, further preferably 0.200 μm or less, further preferably 0.180 μm or less, still more preferably 0.120 μm or less, and most preferably 0.115 μm or less. Good. The lower limit of the root mean square height Sq of the glossy surface before providing 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 0. It is 0.050 μm or more, more preferably 0.100 μm or more.
By controlling the root mean square height Sq of the glossy surface before providing the surface treatment layer on the glossy side to the above range, the surface roughness Sa and / or the root mean square height of the surface of the surface treatment layer is controlled. Since Sq can be controlled within the above range, the pitch of the circuit formed using the electrolytic copper foil is L / S (line / space) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less. Fine pitch can be achieved.

Moreover, the electrolytic copper foil which concerns on embodiment of this invention whose total amount of Zn contained in a surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn is 70 microgram / dm < ² > or more is a surface treatment layer. The conditions (for example, Zn concentration, current density, processing temperature, processing time, etc. in the processing solution (plating solution) when forming the heat-resistant layer, the rust prevention layer, the chromate treatment layer, etc.) are controlled. Can be obtained by: The conditions at this time may be set as appropriate according to the type of the surface treatment layer to be formed, and are not particularly limited. Note that by increasing the Zn concentration in the plating solution, the total amount of Zn contained in the surface treatment layer (Zn adhesion amount) can be increased. Moreover, the total amount (Mo adhesion amount) of Mo contained in the surface treatment layer can be increased by increasing the Mo concentration in the plating solution.

As for the electrolytic copper foil which concerns on embodiment of this invention, it is preferable that the normal temperature tensile strength of the electrolytic copper foil (raw foil) after surface treatment is 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 normal temperature elongation of 3% or more of the surface-treated electrolytic copper foil (raw foil). 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.

As for the electrolytic copper foil which concerns on embodiment of this invention, it is preferable that the high temperature tensile strength of the electrolytic copper foil (raw foil) after surface treatment is 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.

In the electrolytic copper foil according to the embodiment of the present invention, the high temperature elongation of the electrolytic copper foil (raw foil) after the surface treatment is preferably 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.

The electrolytic copper foil according to the embodiment of the present invention preferably has a heat-resistant peel strength of 0.90 kg / cm or more. Here, in the present specification, “heat-resistant peel strength” refers to thermocompression bonding of an electrolytic copper foil and an insulating substrate (resin substrate) according to an embodiment of the present invention at 180 ° C. for 2 hours at a pressure of 20 kgf / cm ^2. After forming a circuit having a circuit width of 10 mm by etching the electrolytic copper foil of the laminate, the laminate was heated at 190 ° C. for 1 hour in an air atmosphere and then heated to 270 ° C. It means the peel strength between the circuit and the insulating substrate after floating for 20 seconds. The peel strength is a 90-degree peel strength performed in accordance with JIS C6471: 1995, and measures the strength when the insulating substrate (resin substrate) and the circuit are peeled off at a speed of 50 mm / min at an angle of 90 degrees. It is required by doing. The peel strength is measured twice and the average value is taken.

The electrolytic copper foil (raw foil) before the surface treatment used for the electrolytic copper foil according to the embodiment of the present invention is not particularly limited as long as it has the above characteristics. Here, “electrolytic copper foil (raw foil)” in the present specification means a copper foil and a copper alloy foil produced by using an electrolysis drum using the principle of electroplating. Examples of copper and copper alloy that are copper foil and copper alloy foil include: pure copper; Sn-containing copper; Ag-containing copper; Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Co, Fe , Copper alloy to which As, P and the like are added. Copper alloy foil (raw foil) is an alloy element (for example, Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Co, Fe, As) in the electrolytic solution used when producing the electrolytic copper foil. And one or more elements selected from the group consisting of 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 It 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 temperature: 50-60 ° C
Additives: 20 to 80 ppm chlorine ion, 0.01 to 10.0 ppm glue Note that the treatment liquid (etching liquid, electrolytic liquid, etc.) used in the electrolysis, etching, surface treatment or plating described in this specification The balance 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.

<Surface treatment>
The surface treatment is not particularly limited, and examples thereof include roughening treatment, heat resistance treatment, rust prevention treatment, chromate treatment, and silane coupling treatment. In this specification, the layer formed by the roughening treatment is the “roughening treatment layer”, the layer formed by the heat treatment is the “heat resistant layer”, the layer formed by the rust prevention treatment is the “rust prevention layer”, and chromate. A layer formed by the treatment is referred to as a “chromate treatment layer”, and a layer formed by the silane coupling treatment is referred to as a “silane coupling treatment layer”.
It is preferable that the electrolytic copper foil which concerns on embodiment of this invention contains 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 in a surface treatment layer.

The roughening treatment is performed in order to improve the adhesion with 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 the roughening treatment is performed as the surface treatment, a heat-resistant layer or a rust prevention layer is formed on the surface of the roughening treatment layer, and a chromate treatment layer or a silane coupling treatment layer is further formed on 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.

Specific conditions for the roughening treatment are as follows.
(Plating solution 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
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds (Plating solution 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 roughening treatment layer described above, the surface roughness Sa and / or the root mean square height Sq of the surface treatment layer can be reduced by shortening the plating time. . On the other hand, in the surface treatment for forming the roughened layer, the surface roughness Sa and / or the root mean square height Sq of the surface of the surface-treated layer can be increased by increasing the plating time.
Further, in the roughening treatment for forming the above-mentioned roughened layer, the surface roughness Sa and / or the root mean square height of the surface of the surface-treated layer is increased by increasing the current density and extremely shortening the plating time. Sq can be further reduced. On the other hand, in the process for forming the roughening treatment layer, the surface roughness Sa and / or the root mean square height Sq of the surface treatment layer is increased by increasing the current density and lengthening the plating time. can do.

The electrolytic copper foil according to the embodiment of the present invention may have a surface treatment layer on the deposition surface side. Although it does not specifically limit as a surface treatment layer formed in the precipitation surface side, One or more types selected from the group which consists of a roughening process layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. A layer is preferred. In general, a heat-resistant layer or a rust-preventing layer is formed on the surface of the roughening treatment layer, and a chromate treatment layer or a silane coupling treatment layer is formed thereon.

The electrolytic copper foil according to the embodiment of the present invention may have a resin layer on one or both of the glossy surface side and the deposition surface side. This resin layer is generally formed on 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) or toluene to form a resin liquid, which is applied onto the electrolytic copper foil or the surface treatment layer by a known method such as a roll coater method, and then heated as necessary. B stage is obtained by drying and removing the solvent. 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 carrier-attached copper foil with the resin layer is laminated on the base material provided with the inner layer material without interposing the prepreg material, the inner layer material It may be difficult to ensure interlayer insulation with 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 required, 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.

In one aspect, a method for manufacturing a printed wiring board according to an embodiment of the present invention using a subtractive 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;
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 37, Comparative Example 1)
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 an electrolytic bath under the following conditions, and copper was deposited on the surface of the electrolytic drum while rotating the electrolytic drum until the thickness became 18 μm.
<Electrolysis conditions>
Electrolyte composition: 100 g / L Cu, 100 g / L H ₂ SO ₄
Current density: 90 A / dm ²
Electrolyte temperature: 60 ° C
Additives: 60 mass ppm of chlorine ion, glue (Examples 1, 2, 5, 6, 10 to 12, 15, 16, 19, 20, and 24 to 26, and in Comparative Example 1, 0.02 ppm) In Examples 3, 4, 7 to 9, 13, 14, 17, 18, 21 to 23, and 27 to 37, it was set to 4.5 ppm.)

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

Example 1
The surface treatment (glossy surface) on the electrolytic drum side of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (4).
(1) Roughening treatment After electrodepositing roughened particles on the glossy surface of an electrolytic copper foil (raw foil) using the plating solution 1 (pH 1 or less) having the following composition under the following plating condition 1, A roughening layer (Cu-As-W) was formed by further electrodepositing the roughened particles under the following plating condition 2 using the plating solution 2 (pH 0.3 or lower).
<Composition of plating solution 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
<Plating condition 1>
Temperature: 40 ° C
Current density: 70 A / dm ²
Plating time: 2 seconds

<Plating solution 2 composition>
CuSO ₄ .5H ₂ O: 240 g / L
H ₂ SO ₄ : 120 g / L
<Plating condition 2>
Temperature: 55 ° C
Current density: 20 A / dm ²
Plating time: 7 seconds

(2) Heat resistance treatment (barrier treatment)
A heat-resistant layer (Ni—Zn) was formed by performing nickel-zinc alloy plating under the following plating conditions using a plating solution (pH 2) having the following composition.
<Plating solution composition>
Ni: 13 g / L
Zn: 12 g / L
<Plating conditions>
Temperature: 40 ° C
Current density: 0.2 A / dm ²
Plating time: 2.89 seconds

(3) Chromate treatment A zinc chromate treatment layer was formed by performing zinc chromate treatment under the following plating conditions using a plating solution (pH 4.8) having the following composition.
<Plating solution composition>
CrO ₃ : 2.5 g / L
Zn: 2.0 g / L
Na ₂ SO ₄ : 10 g / L
<Plating conditions>
Temperature: 54 ° C
Current density: 1.0 A / dm ²
(4) Silane coupling treatment A silane coupling treatment layer A was formed by spraying a silane coupling treatment liquid having a tetraethoxysilane content of 0.4 vol% and a pH of 7.5.

(Example 2)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 1 except that (2) the plating time in the heat treatment was changed to 2.96 seconds. It was.
(Example 3)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 1 except that (2) the plating time in the heat treatment was changed to 2.75 seconds. It was.
Example 4
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 1 except that (2) the plating time in the heat treatment was changed to 2.82 seconds. It was.

(Example 5)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment Using a plating solution (pH 1 to 4) having the following composition, roughening is performed by electrodepositing roughened particles on the glossy surface of an electrolytic copper foil (raw foil) under the following plating conditions. A treatment layer (Cu—Co—Ni (1)) was formed.
<Plating solution composition>
Cu: 16 g / L
Co: 10 g / L
Ni: 10 g / L
<Plating conditions>
Temperature: 30 ° C
Current density: 30 A / dm ²
Plating time: 2 seconds

(2) Heat-resistant treatment A heat-resistant layer (Co-Ni) was formed by performing Co-Ni alloy plating under the following plating conditions using a plating solution (pH 1.0 to 3.5) having the following composition. .
<Plating solution composition>
Co: 10 g / L
Ni: 20 g / L
<Plating conditions>
Temperature: 35 ° C
Current density 10A / dm ²
Plating time: 1 second

(3) Rust prevention treatment A rust prevention layer (Zn—Ni) was formed by performing Zn—Ni alloy plating under the following plating conditions using a plating solution (pH 3 to 4) having the following composition.
<Plating solution composition>
Ni: 15 g / L
Zn: 50 g / L
<Plating conditions>
Temperature: 50 ° C
Current density: 0.3 A / dm ²
Plating time: 2.43 seconds

(4) Chromate treatment A zinc chromate treatment layer was formed under the same conditions as in Example 1.
(5) Silane coupling treatment Silane coupling treatment is performed by spraying a silane coupling treatment liquid having an N- (2-aminoethyl) -3-aminopropyltrimethoxysilane content of 0.4 vol% and a pH of 7.5. A treatment layer B was formed.

(Example 6)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 5 except that (3) the plating time in the rust prevention treatment was changed to 2.61 seconds. went.
(Example 7)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 5 except that (3) the plating time in the rust prevention treatment was changed to 2.32 seconds. went.
(Example 8)
The same surface treatment as in Example 5 was performed on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.

Example 9
The surface treatment was performed in the order of the following (1) to (3) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Heat resistance treatment (barrier treatment)
A nickel-zinc alloy plating was performed under the same conditions as in Example 1 except that the plating time was changed to 2.82 seconds to form a heat-resistant layer (Ni—Zn).
(2) Chromate treatment A zinc chromate treatment layer was formed under the same conditions as in Example 1.
(3) Silane coupling treatment A silane coupling treatment layer A was formed under the same conditions as in Example 1.

(Example 10)
The same surface treatment as in Example 2 was performed on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.

(Example 11)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment Using a plating solution (pH 1 to 4) having the following composition, roughening is performed by electrodepositing roughened particles on the glossy surface of an electrolytic copper foil (raw foil) under the following plating conditions. A treatment layer (Cu—Co—Ni (2)) was formed.
<Plating solution composition>
Cu: 10 to 20 g / L
Co: 1-10g / L
Ni: 1-10g / L
<Plating conditions>
Temperature: 30-50 ° C
Current density: 35 to 45 A / dm ²
Plating time: 0.1 to 1.5 seconds

(2) Heat-resistant treatment A heat-resistant layer (Co—Ni) was formed under the same conditions as in Example 5.
(3) Rust prevention treatment A rust prevention layer (Zn—Ni) was formed under the same conditions as in Example 5.
(4) Chromate treatment A zinc chromate treatment layer was formed under the same conditions as in Example 1.
(5) Silane coupling treatment A silane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 12)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 11 except that (3) the plating time in the rust prevention treatment was changed to 2.55 seconds. went.
(Example 13)
The same surface treatment as in Example 11 was performed on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.

(Example 14)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment A roughening treatment layer (Cu—Co—Ni (1)) was formed under the same conditions as in Example 5.
(2) Heat-resistant treatment A heat-resistant layer (Co—Ni) was formed under the same conditions as in Example 5.
(3) Rust prevention treatment A rust prevention layer (Zn—Ni) was formed under the same conditions as in Example 5 except that the plating time was 2.49 seconds.
(4) Chromate treatment A zinc chromate treatment layer was formed under the same conditions as in Example 1.
(5) Silane coupling treatment A silane coupling treatment layer B was formed under the same conditions as in Example 5.
(Example 15)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 1 except that (2) the plating time in the heat treatment was changed to 3.79 seconds. It was.
(Example 16)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 15 except that (2) the plating time in the heat treatment was changed to 4.89 seconds. It was.
(Example 17)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 15 except that (2) the plating time in the heat treatment was changed to 6.40 seconds. It was.
(Example 18)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 15 except that (2) the plating time in the heat treatment was changed to 6.88 seconds. It was.

(Example 19)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 5 except that (3) the plating time in the rust prevention treatment was changed to 6.66 seconds. went.
(Example 20)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 19 except that (3) the plating time in the rust prevention treatment was changed to 6.95 seconds. went.
(Example 21)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 19 except that (3) the plating time in the rust prevention treatment was changed to 8.17 seconds. went.
(Example 22)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 19 except that (3) the plating time in the rust prevention treatment was changed to 9.27 seconds. went.

(Example 23)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 9 except that (1) the plating time in the heat treatment was changed to 11.70 seconds. It was.
(Example 24)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the same manner as in Example 1 except that (2) the plating time in the heat treatment was changed to 15.15 seconds. It was.
(Example 25)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 11 except that (3) the plating time in the rust prevention treatment was changed to 15.64 seconds. went.
(Example 26)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 11 except that (3) the plating time in the rust prevention treatment was changed to 16.16 seconds. went.
(Example 27)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 11 except that (3) the plating time in the rust prevention treatment was changed to 4.63 seconds. went.
(Example 28)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, the surface treatment was performed in the same manner as in Example 5 except that (3) the plating time in the rust prevention treatment was changed to 18.53 seconds. went.

(Example 29)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment Using a plating solution (pH 1 to 4) having the following composition, roughening is performed by electrodepositing roughened particles on the glossy surface of an electrolytic copper foil (raw foil) under the following plating conditions. A treatment layer (Cu—Co—Ni—Mo) was formed.
<Plating solution composition>
Cu: 10 to 20 g / L
Co: 1-10g / L
Ni: 1-10g / L
Mo: 1-5g / L
<Plating conditions>
Temperature: 30-50 ° C
Current density: 20-30 A / dm ²
Plating time: 1-5 seconds

(Example 30)
Surface treatment was performed in the order of the following (1) to (4) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment A roughening treatment layer (Cu—As—W) was formed under the same conditions as in Example 1.
(2) Heat-resistant treatment Using a plating solution (pH 2) having the following composition, cobalt zinc alloy plating was performed under the following plating conditions to form a heat-resistant layer (Co-Zn).
<Plating solution composition>
Co: 13 g / L
Zn: 12 g / L
<Plating conditions>
Temperature: 40 ° C
Current density: 0.2 A / dm ²
Plating time: 5.16 seconds

(3) Chromate treatment A chromate treatment layer was formed by performing a chromate treatment under the following plating conditions using a plating solution (pH 4.8) having the following composition.
<Plating solution composition>
CrO ₃ : 2.5 g / L
Na ₂ SO ₄ : 10 g / L
<Plating conditions>
Temperature: 54 ° C
Current density: 1.0 A / dm ²
(4) Silane coupling treatment Silane coupling treatment layer A was formed under the same conditions as in Example 1.

(Example 31)
The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to a surface treatment in the same manner as in Example 30 except that (2) the plating time in the heat treatment was changed to 8.33 seconds. It was.

(Example 32)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment A roughening treatment layer (Cu—Co—Ni (1)) was formed under the same conditions as in Example 5.
(2) Heat-resistant treatment A heat-resistant layer (Co—Ni) was formed under the same conditions as in Example 5.
(3) Rust prevention treatment Using a plating solution (pH 3 to 7) having the following composition, Ni—Mo alloy plating was performed under the following plating conditions to form a rust prevention layer (Ni—Mo).
<Plating solution composition>
Ni: 30 g / L
Mo: 4g / L
<Plating conditions>
Temperature: 40 ° C
Current density: 2 A / dm ²
Plating time: 8.33 seconds (4) Chromate treatment A chromate treatment layer was formed under the same conditions as in Example 30.
(5) Silane coupling treatment A silane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 33)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, (3) surface treatment was performed in the same manner as in Example 32 except that the conditions in the rust prevention treatment were changed as follows. .
(3) Rust prevention treatment A rust prevention layer (Co-Mo) was formed by performing Co-Mo alloy plating under the following plating conditions using a plating solution (pH 3 to 7) having the following composition.
<Plating solution composition>
Co: 30 g / L
Mo: 4g / L
<Plating conditions>
Temperature: 40 ° C
Current density: 2 A / dm ²
Plating time: 23.48 seconds

(Example 34)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, (3) the plating time in the rust prevention treatment is changed to 6.22 seconds, and (4) the chromate treatment is the same as in Example 1. Surface treatment was performed in the same manner as in Example 32 except that the zinc chromate treatment was performed.

(Example 35)
The surface treatment was performed in the order of the following (1) to (3) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment Using a plating solution (pH 1 to 4) having the following composition, roughening is performed by electrodepositing roughened particles on the glossy surface of an electrolytic copper foil (raw foil) under the following plating conditions. A treatment layer (Cu—Co—Ni—Zn) was formed.
<Plating solution composition>
Cu: 10 to 20 g / L
Co: 1-10g / L
Ni: 1-10g / L
Zn: 2-12 g / L
<Plating conditions>
Temperature: 30-50 ° C
Current density: 30 to 45 A / dm ²
Plating time: 0.1 to 1.5 seconds (2) Chromate treatment A zinc chromate treatment layer was formed under the same conditions as in Example 1.
(3) Silane coupling treatment A silane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 36)
Surface treatment was performed in the same manner as in Example 1 except that the conditions in (2) heat treatment were changed as follows on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(2) Heat-resistant treatment Using a plating solution (pH 10 to 13) having the following composition, Cu—Zn alloy plating was performed under the following plating conditions to form a heat-resistant layer (Cu—Zn).
<Plating solution composition>
NaOH: 80-140 g / L
NaCN: 100 to 150 g / L
CuCN: 20-30g / L
Zn (CN) 2: 15 to 20 g / L
As ₂ O ₃ : 0.01 to 1 g / L
<Plating conditions>
Temperature: 40-90 ° C
Current density: 5 A / dm ²
Plating time: 14.06 seconds

(Example 37)
Surface treatment was performed in the order of the following (1) to (5) on the glossy surface of the electrolytic copper foil (raw foil) produced as described above.
(1) Roughening treatment A roughening treatment layer (Cu—Co—Ni (1)) was formed under the same conditions as in Example 5.
(2) Heat-resistant treatment A heat-resistant layer (Zn-Ni) was formed by performing Zn-Ni alloy plating under the following plating conditions using a plating solution (pH 3 to 4) having the following composition.
<Plating solution composition>
Ni: 1-15g / L
Zn: 45 to 55 g / L
<Plating conditions>
Temperature: 40-55 ° C
Current density: 0.1 to 0.3 A / dm ²
Plating time: 11.00 seconds (3) Rust prevention treatment Rust prevention is achieved by performing Co-Ni alloy plating under the following plating conditions using a plating solution (pH 1.0 to 3.5) having the following composition. A layer (Co—Ni) was formed.
<Plating solution composition>
Co: 1-30g / L
Ni: 1-30g / L
<Plating conditions>
Temperature: 30-80 ° C
Current density 1.0 A / dm ²
Plating time: 1 to 4 seconds (4) Chromate treatment A chromate treatment layer was formed under the same conditions as in Example 30.
(5) Silane coupling treatment A silane coupling treatment layer B was formed under the same conditions as in Example 5.

(Comparative Example 1)
For the glossy surface of the electrolytic copper foil (raw foil) produced as described above, (2) surface treatment was performed in the same manner as in Example 1 except that the plating time in the heat treatment was changed to 0.015 seconds. It was.

2. Evaluation of Electrolytic Copper Foil <Glossy Surface and Surface Treatment Layer Surface Roughness Sa and Root Mean Square Height Sq>
Surface gloss Sa and root mean square height using a laser microscope OLS4100 (LEXT OLS 4100) manufactured by Olympus, based on ISO-25178-2: 2012, on the glossy surface of the electrolytic copper foil before and after the surface treatment Sq was measured. 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.

<The total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn>
A sample having a size of 10 cm × 10 cm was taken from the electrolytic copper foil after the surface treatment. Next, after dissolving a 1 μm thickness from the surface of the surface treatment layer of the collected sample with an aqueous nitric acid solution having a concentration of 20% by mass, an ICP using an ICP emission spectrometer (model: ICPS-7510) manufactured by Shimadzu Corporation. The total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn was measured by emission analysis. The measurement location was performed at three locations, and the arithmetic average value of the results was defined as the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn.
In addition, when the surface treatment layer is provided on both the glossy surface and the deposited surface of the electrolytic copper foil, masking is performed by attaching an acid-resistant tape to the deposited surface side or thermocompressing a prepreg such as FR4. The surface treatment layer on the glossy surface can be dissolved to measure the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn. In addition, when Zn and Mo are not dissolved in an aqueous nitric acid solution having a concentration of 20% by mass, a solution capable of dissolving Zn and Mo (for example, nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) Measurement may be performed by the above-described ICP emission analysis after dissolution using a mixed solution of acid and hydrochloric acid. Moreover, you may use a well-known liquid, an acidic liquid, or an alkaline liquid for the liquid which can dissolve Zn and Mo.
In addition, when the electrolytic copper foil has large irregularities and the thickness of the electrolytic copper foil is 1.5 μm or less, when the surface treatment layer is dissolved by 1 μm thickness, the surface treatment component of the precipitation surface is also dissolved. May end up. Therefore, in such a case, it is desirable to dissolve 30% of the thickness of the electrolytic copper foil from the surface of the surface treatment layer of the electrolytic copper foil.

<Normal peel strength, heat-resistant peel strength>
The surface-treated electrolytic copper foil and the glass epoxy substrate (FR-4) were thermocompression bonded at 180 ° C. for 2 hours at a pressure of 20 kgf / cm ² to obtain a laminated body. A circuit having a circuit width of 10 mm was formed by etching. Then, based on JISC6471: 1995, normal peel strength was calculated | required by measuring the intensity | strength (peel intensity | strength) when the glass epoxy board | substrate and a circuit were peeled off at a speed | rate of 50 mm / min at an angle of 90 degree | times. The measurement of the normal peel strength and the measurement of the heat-resistant peel strength described later were performed twice, and the average values were taken as the values of the normal-state peel strength and the heat-resistant peel strength, respectively.
The heat-resistant peel strength is obtained by heating a laminate having a circuit formed at 190 ° C. for 1 hour in an air atmosphere, and then floating for 20 seconds in a solder plating bath heated to 270 ° C., and then measuring the peel strength. It was.
Moreover, the deterioration rate of the peel strength by a heat | fever was evaluated based on the following formula.
Degradation rate of peel strength due to heat = (normal peel strength−heat-resistant peel strength) / normal peel strength × 100

<Normal temperature tensile strength, high temperature tensile strength>
The electrolytic copper foil after 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 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 surface-treated electrolytic copper foil was bonded to a bismaleimide triazine resin prepreg by thermocompression bonding from the glossy surface side. Thereafter, the electrolytic copper foil bonded to the prepreg was etched from the side opposite to the side bonded to the prepreg to a thickness of 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.
Test conditions and test results are shown in Tables 2-5. Moreover, Fig.1 (a) is a SEM image of the glossy surface of the electrolytic copper foil of Example 2 before forming 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 surface treatment layer.

<Evaluation results>
The root mean square height Sq of the surface treatment layer is 0.550 μm or less and / or the surface roughness Sa of the surface treatment layer is 0.470 μm or less, and the total amount of Zn contained in the surface treatment layer The electrolytic copper foils of Examples 1 to 37 in which the total amount of Mo or the total amount of Mo and Zn was 70 μg / dm ² or more had good circuit formability and heat resistance. In particular, in the electrolytic copper foils of Examples 9 and 23 having the surface treatment layer other than the roughening treatment layer on the glossy surface side, the surface roughness Sa of the surface treatment layer surface is 0.270 μm or less and the surface treatment layer surface The root mean square height Sq was 0.315 μm or less.
Further, in the electrolytic copper foil of another example having a surface treatment layer including at least a roughening treatment layer on the glossy surface side, the surface roughness Sa of the surface of the surface treatment layer is 0.470 μm or less or the root mean square height. Sq was 0.550 μm or less.
On the other hand, the root mean square height Sq and the surface roughness Sa of the surface of the surface treatment layer exceed the above ranges, and the total amount of Zn, the total amount of Mo, or Mo contained in the surface treatment layer The electrolytic copper foil of Comparative Example 1 in which the total amount with Zn was less than 70 μg / dm ² did not have sufficient circuit formability and heat resistance.

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

Claims

An electrolytic copper foil having a surface treatment layer on the glossy surface side,
The root mean square height Sq of the surface of the surface treatment layer is 0.550 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg. Electrolytic copper foil which is / dm 2 or more.
The electrolytic copper foil according to claim 1, wherein the surface roughness Sa of the surface treatment layer is 0.380 μm or less.
The electrolytic copper foil according to claim 1, wherein the surface roughness Sa of the surface treatment layer is 0.355 μm or less.
The electrolytic copper foil according to claim 1, wherein the surface roughness Sa of the surface treatment layer is 0.300 μm or less.
The electrolytic copper foil according to claim 1, wherein the surface roughness Sa of the surface treatment layer is 0.200 μm or less.
6. The electrolytic copper foil according to claim 1, wherein a root mean square height Sq of the surface of the surface treatment layer is 0.490 μm or less.
The electrolytic copper foil according to claim 6, wherein the root mean square height Sq of the surface of the surface treatment layer is 0.450 µm or less.
The electrolytic copper foil according to claim 6, wherein the root mean square height Sq of the surface of the surface treatment layer is 0.400 µm or less.
The electrolytic copper foil according to claim 6, wherein the root mean square height Sq of the surface of the surface treatment layer is 0.330 µm or less.
An electrolytic copper foil having a surface treatment layer on the glossy surface side,
The surface roughness Sa of the surface treatment layer is 0.470 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm 2. Electrolytic copper foil that is above.
The electrolytic copper foil according to claim 10, wherein the root mean square height Sq of the surface of the surface treatment layer is 0.550 µm or less.
The electrolytic copper foil according to any one of claims 1 to 11, wherein the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 80 μg / dm 2 or more. .
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 surface treatment layer on the glossy surface side is 0.270 µm or less.
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 surface treatment layer on the glossy surface side is 0.130 µm or less.
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 surface treatment layer on the glossy surface side is 0.315 µm or less.
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 surface treatment layer on the glossy surface side is 0.120 µm or less.
The electrolytic copper foil according to any one of claims 1 to 16, which has a normal temperature tensile strength of 30 kg / mm 2 or more.
The electrolytic copper foil according to any one of claims 1 to 17, wherein the room temperature elongation is 3% or more.
The electrolytic copper foil according to any one of claims 1 to 18, wherein the high-temperature tensile strength is 10 kg / mm 2 or more.
The electrolytic copper foil according to any one of claims 1 to 19, wherein the high temperature elongation is 2% or more.
The electrolytic copper foil according to any one of claims 1 to 20, having a heat-resistant peel strength of 0.90 kg / cm or more.
The surface treatment layer on the glossy surface side includes at least one layer selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The electrolytic copper foil as described in the item.
The electrolytic copper foil according to any one of claims 1 to 22, further comprising a surface treatment layer on the deposition surface side.
The surface treatment layer on the precipitation surface side includes one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. Electrolytic copper foil of description.
The surface treatment layer is a layer made of any single substance 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 24.
The electrolytic copper foil according to any one of claims 1 to 25, further comprising a resin layer on one or both of the glossy surface side and the precipitation surface side.
The electrolytic copper foil according to claim 26, wherein the resin layer is provided on the surface treatment layer.
After producing an electrolytic copper foil using an electrolytic drum, a method for producing an electrolytic copper foil in which a surface treatment layer is formed by performing a surface treatment on the glossy surface of the electrolytic copper foil,
The surface roughness Sa of the surface of the electrolytic drum is 0.270 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / dm 2 or more. A method for producing an electrolytic copper foil.
After producing an electrolytic copper foil using an electrolytic drum, a method for producing an electrolytic copper foil in which a surface treatment layer is formed by performing a surface treatment on the glossy surface of the electrolytic copper foil,
The root mean square height Sq of the surface of the electrolytic drum is 0.315 μm or less, and the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn contained in the surface treatment layer is 70 μg / The manufacturing method of the electrolytic copper foil which is dm < 2 > or more.
The method for producing an electrolytic copper foil according to claim 28, wherein the root mean square height Sq of the electrolytic drum is 0.315 µm or less.
The method for producing an electrolytic copper foil according to any one of claims 28 to 30, wherein the surface roughness Sa of the surface of the electrolytic drum is 0.150 µm or less.
The method for producing an electrolytic copper foil according to any one of claims 28 to 31, wherein the root mean square height Sq of the surface of the electrolytic drum is 0.200 µm or less.
A copper-clad laminate having the electrolytic copper foil according to any one of claims 1 to 27.
A printed wiring board having the electrolytic copper foil according to any one of claims 1 to 27.
A method for producing a printed wiring board using the electrolytic copper foil according to any one of claims 1 to 27.
After producing the copper-clad laminate by laminating the electrolytic copper foil according to any one of claims 1 to 27 and an insulating substrate, 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.
Electronic equipment having the printed wiring board according to claim 34.
A method for manufacturing an electronic device using the printed wiring board according to claim 34.