TW201900934A - Electrolytic copper foil, manufacturing method thereof, copper-clad laminate, printed wiring board, and manufacturing method thereof, and electronic device and manufacturing method thereof - Google Patents

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 [mu]m 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 [mu]g/dm2. Alternatively, the surface roughness Sa of the surface of the surface treatment layer is no more than 0.470 [mu]m 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 [mu]g/dm2.

Description

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

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

The printed wiring board is generally manufactured by forming an insulating substrate (for example, a resin substrate) and a copper foil to form a copper clad laminate, and then etching the copper foil to form a conductor pattern.

In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, the development of high-density mounting of components and high-frequency signals, etc., has also required the miniaturization of conductor patterns on printed wiring boards. Or high frequency response.

Therefore, in order to refine the conductor pattern by using the electrolytic copper foil, it is proposed in Patent Document 1 to add an additive such as a sulfur-containing compound that acts as a brightening agent to the electrolytic solution to prepare an electrolytic copper foil having a smooth surface on the deposition surface side. After that, an electric circuit is formed on the electrolytic copper foil.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-162172

However, the method of Patent Document 1 is susceptible to wrinkles in the copper foil due to recrystallization at normal temperature and shrinkage at the time of producing the electrolytic copper foil due to the influence of the additive contained in the electrolytic solution. Further, in the case where such wrinkles are generated, wrinkles are also generated in the subsequent process of the electrolytic copper foil and the insulating substrate (resin substrate). When the electrolytic copper foil is wrinkled, it is difficult to perform fine pitching when the electrolytic copper foil is formed into a circuit. Therefore, the circuit formation property is insufficient.

On the other hand, when the surface of the electrodeposited copper foil is smooth, there is a problem that sufficient adhesion cannot be obtained when it is followed by an insulating substrate (resin substrate). In particular, in many cases, the printed wiring board is also exposed to a high temperature, so that the electrolytic copper foil is required to have a low decrease in adhesion to the insulating substrate (resin substrate) under high temperature conditions (that is, excellent heat resistance).

As a method of improving the adhesion between the electrodeposited copper foil and the insulating substrate (resin substrate), it is known that the surface of the electrodeposited copper foil is roughened or the like, but the roughening treatment affects the fine pitch (that is, circuit formability). situation.

Therefore, in the prior art, it has been difficult to achieve both the improvement of heat resistance and the improvement of circuit formation property.

In order to solve the above-described problems, the present invention has been made to provide an electrolytic copper excellent in circuit formability and heat resistance (especially, the effect of suppressing the decrease in adhesion in the case of an insulating substrate). Foil and its manufacturing method.

In addition, it is an object of the present invention to provide a copper-clad laminate and a printed wiring of an electrolytic copper foil which are excellent in circuit formability and heat resistance (especially, the effect of suppressing the decrease in adhesion with an insulating substrate). Board and its manufacturing method, as well as an electronic machine and a method of manufacturing the same.

In order to solve the above problems, the present inventors have made an effort to find that the surface roughness Sa and/or the root mean square height Sq of the surface of the surface treatment layer are focused on the electrolytic copper foil having the surface treatment layer on the glossy side. It is related to circuit formability, 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 is related to heat resistance, and the surface roughness Sa and/or the surface of the surface treatment layer are both The square root 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 to a specific range, thereby achieving improvement in heat resistance and circuit formation. The invention is enhanced to accomplish several embodiments of the invention.

In other words, the electrodeposited copper foil according to the embodiment of the present invention has a surface treatment layer on the side of the glossy surface, and 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 contained in the surface treatment layer is The total amount of Mo or the total amount of Mo and Zn is 70 μg/dm ² or more.

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

Further, in the method for producing an electrolytic copper foil according to the embodiment of the present invention, after the electrolytic copper foil is produced by using an electrolytic drum, the shiny surface of the electrolytic copper foil is surface-treated to form a surface-treated layer, and the surface of the electrolytic roller is roughened. The degree Sa is 0.270 μm or less, 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 is 70 μg/dm ² or more.

Further, in the method for producing an electrolytic copper foil according to another embodiment of the present invention, after the electrolytic copper foil is produced by using an electrolytic drum, the shiny surface of the electrolytic copper foil is surface-treated to form a surface-treated layer, and the surface of the electrolytic drum is The root mean square height Sq is 0.315 μm or less, 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 is 70 μg/dm ² or more.

Moreover, the copper clad laminate of the embodiment of the present invention has the above-described electrolytic copper foil.

Moreover, the printed wiring board according to the embodiment of the present invention has the above-described electrolytic copper foil.

Moreover, the method for producing a printed wiring board according to the embodiment of the present invention uses the above-mentioned electrodeposited copper foil.

Moreover, a method of manufacturing a printed wiring board according to another embodiment of the present invention includes the steps of: laminating the electrolytic copper foil and the insulating substrate to form a copper clad laminate, and then performing a semi-additive method, a subtractive method, and a partial addition. The method or any of the modified semi-additive methods forms a circuit.

Moreover, an electronic device according to an embodiment of the present invention includes the above printed wiring board.

Further, in the method of manufacturing an electronic device according to the embodiment of the present invention, a printed wiring board is used.

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.

Moreover, according to some embodiments of the present invention, it is possible to provide a copper-clad laminate using an electrolytic copper foil excellent in circuit formability and heat resistance, a printed wiring board, a method for producing the same, and an electronic device and a method for producing the same.

Fig. 1(a) is an SEM image of the shiny side of the electrolytic copper foil of Example 2 before the surface treatment layer is formed, and (b) is an SEM image of the shiny side of the electrolytic copper foil of Example 10 before the surface treatment layer is formed. image.

The electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer on the glossy side, and the root mean square height Sq of the surface of the surface treated layer is 0.550 μm or less and/or the surface roughness Sa of the surface of the surface treated layer is 0.470 μm. Hereinafter, 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 70 μg/dm ² or more.

Here, in the present specification, the "glossy surface of the electrolytic copper foil" means the surface of the drum side when the electrolytic copper foil is produced (gloss surface: S surface), and the "precipitation surface of the electrolytic copper foil" means electrolytic production. The surface on the opposite side of the copper foil from the roller (matte side: M side).

Hereinafter, preferred aspects of the electrolytic copper foil according to the embodiment of the present invention will be described.

<Electrolyzed copper foil having a surface treatment layer other than the roughened layer on the glossy side>

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

In the electrodeposited copper foil having the above configuration, the surface roughness Sa of the surface of the surface treated layer is set to 0.270 μm or less and/or the root mean square height Sq of the surface of the surface treated layer is set to 0.315 μm. Hereinafter, the distance between the circuits formed using the electrolytic copper foil may be set to a fine pitch of L/S (line/gap) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less.

The surface roughness Sa of the surface of the surface treatment layer is preferably 0.230 μm or less, more preferably 0.180 μm or less, further preferably 0.150 μm or less, and most preferably 0.133 μm or less from the viewpoint of improving the effect of the fine pitch. . In addition, the lower limit of the surface roughness Sa of the surface 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 still more preferably 0.100 μm or more.

Further, from the viewpoint of improving the effect of the fine pitch, the root mean square height Sq of the surface of the surface treated layer is preferably 0.200 μm or less, more preferably 0.180 μm or less. In addition, the lower limit of the root mean square height Sq of the surface 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 still more preferably 0.100 μm or more.

As described above, when the surface roughness Sa of the surface 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 formation property is improved. On the other hand, since the unevenness of 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 anchoring effect of the unevenness is lowered. In particular, there is a concern about a decrease in the adhesion between the electrolytic copper foil and the insulating substrate (resin substrate) under high temperature conditions. Therefore, it is important to increase the heat resistance by setting the total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn to 70 μg/dm ² or more.

The heat resistance can be improved by controlling the total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the total amount of Mo and Zn to 70 μg/dm ² or more. 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 preferably 80 μg/dm ² or more, and more preferably 85 μg/dm ² or more, from the viewpoint of further improving the heat resistance. , more preferably 90μg / dm ² or more, more preferably 95μg / dm ² or more, more preferably 100μg / dm ² or more, more preferably 105μg / dm ² or more, more preferably 110μg / dm ² or more, more preferably 115μg A / dm ^2, more preferably 120 g A / dm ^2, more preferably 125 g A / dm ^2, more preferably 130 [mu] A / dm ^2, more preferably 135μg / dm ² or more, more preferably 140 [mu] A / dm ^2, more preferably 150μg / dm ² or more, more preferably 200μg / dm ² or more, more preferably 250μg / dm ² or more, more preferably 300μg / dm ² or more. The total amount of Zn contained in the surface treatment layer, the total amount of Mo, or the upper limit of the total amount of Mo and Zn is not particularly limited, and is typically 6000 μg/dm ² or less, preferably 5000 μg/dm ² or less, more preferably It is 400 μg/dm ² or less.

<Electrochemical copper foil having a surface treatment layer containing at least a roughened layer on the glossy side>

In another aspect, the electrolytic copper foil according to the embodiment of the present invention has a surface treatment layer containing at least a roughened layer on the side of the glossy surface, 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 treated layer is 0.550 μm or less, and the total amount of Zn contained in the surface treated layer, the total amount of Mo, or the total amount of Mo and Zn is 70 μg/dm ² or more.

In general, in the electrolytic copper foil having the roughened layer on the shiny side, the fine pitch is lowered, but in the electrolytic copper foil having the above configuration, by the surface of the surface treated layer The surface roughness Sa is set to 0.470 μm or less and/or the root mean square height Sq of the surface of the surface treated layer is set to 0.550 μm or less, and L/S (line/gap) can be performed for the distance between circuits formed using the electrolytic copper foil. ) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less.

The surface roughness Sa of the surface of the surface treatment layer is preferably 0.385 μm or less, more preferably 0.380 μm or less, still more preferably 0.355 μm or less, still more preferably 0.340 μm or less from the viewpoint of the effect of improving the fine pitch. Further, it is preferably 0.300 μm or less, more preferably 0.295 μm or less, further preferably 0.230 μm or less, and most preferably 0.200 μm or less. In addition, the lower limit of the surface roughness Sa of the surface 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 still more preferably 0.100 μm or more.

Further, from the viewpoint of improving the effect of the fine pitch, the root mean square height Sq of the surface of the surface treated layer is preferably 0.490 μm or less, more preferably 0.450 μm or less, still more preferably 0.435 μm or less, and further preferably 0.400 μm or less, more preferably 0.395 μm or less, further preferably 0.330 μm or less, and most preferably 0.290 μm or less. In addition, the lower limit of the root mean square height Sq of the surface 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 still more preferably 0.100 μm or more.

The electrodeposited copper foil of the embodiment of the present invention having the surface roughness Sa and/or the root mean square height Sq of the surface of the surface treatment layer as described above can be controlled by the gloss surface before the surface treatment layer is provided on the gloss side. Obtained by the surface roughness Sa and/or the root mean square height Sq.

In other words, in order to obtain the electrodeposited copper foil according to the embodiment of the present invention, the surface roughness Sa of the shiny surface before the surface treatment layer is provided on the glossy side is preferably controlled to 0.270 μm or less, more preferably 0.230 μm or less, or more. It is preferably 0.180 μm or less, more preferably 0.150 μm or less, further preferably 0.133 μm or less, further preferably 0.130 μm or less, and most preferably 0.120 μm or less. In addition, the lower limit of the surface roughness Sa of the shiny surface before the surface treatment layer is provided 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, and further preferably. It is 0.100 μm or more.

By controlling the surface roughness Sa of the glossy surface before the surface treatment layer is provided on the glossy side to the above range, the surface roughness Sa and/or the root mean square height Sq of the surface of the surface treatment layer can be controlled to the above range. Therefore, the distance between the circuits formed using the electrolytic copper foil can be made fine pitch of L/S (line/gap) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less.

Moreover, in order to obtain the electrolytic copper foil according to the embodiment of the present invention, the root mean square height Sq of the shiny surface before the surface treatment layer is provided on the shiny side is preferably controlled to 0.315 μm or less, more preferably 0.292 μm or less. More preferably, it is 0.230 μm or less, further preferably 0.200 μm or less, further preferably 0.180 μm or less, further preferably 0.120 μm or less, and most preferably 0.115 μm or less. Further, the lower limit of the root mean square height Sq of the shiny surface before the surface treatment layer is provided on the glossy 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, and further Preferably, it is 0.100 μm or more.

The surface roughness Sa and/or the root mean square height Sq of the surface of the surface treatment layer can be controlled to the above range by controlling the root mean square height Sq of the gloss surface before the surface treatment layer is provided on the glossy side to the above range. Therefore, the distance between the circuits formed using the electrolytic copper foil can be made fine pitch of L/S (line/gap) = 22 μm or less / 22 μm or less, more preferably 20 μm or less / 20 μm or less.

Further, when 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 70 μg/dm ² or more, the electrolytic copper foil of the embodiment of the present invention can be controlled by forming the surface treatment layer. The conditions (for example, the Zn concentration, the current density, the treatment temperature, the treatment time, and the like in the treatment liquid (plating solution) when forming the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, and the like) are obtained. The conditions at this time are not particularly limited as long as they are appropriately set depending on the type of the surface treatment layer to be formed. Further, by increasing the Zn concentration in the plating solution, the total amount of Zn (Zn adhesion amount) contained in the surface treatment layer can be increased. Moreover, by increasing the Mo concentration in the plating solution, the total amount of Mo (Mo deposition amount) contained in the surface treatment layer can be increased.

The electrolytic copper foil according to the embodiment of the present invention preferably has a room temperature tensile strength of 30 kg/mm ² or more in the electrolytic copper foil (raw foil) after the surface treatment. Here, in the present specification, "normal temperature tensile resistance" is the tensile strength at room temperature, which means that it 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 less likely to occur during the treatment. From the viewpoint of stably obtaining this effect, the normal temperature tensile resistance is more preferably 35 kg/mm ² or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has an ordinary temperature elongation of 3% or more of the electrolytic copper foil (raw foil) after the surface treatment. Here, in the present specification, "normal temperature elongation" is an elongation at room temperature, which means measured according to IPC-TM-650. If the room temperature elongation is 3% or more, the effect is not easily broken. From the viewpoint of stably obtaining this effect, the room temperature elongation is more preferably 4% or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a high-temperature tensile strength of 10 kg/mm ² or more in the electrolytic copper foil (green foil) after the surface treatment. In the present specification, "high temperature tensile resistance" is a tensile strength at 180 ° C, which means that it is measured according to IPC-TM-650. When the high-temperature tensile strength is 10 kg/mm ² or more, the effect of wrinkles when attached to the resin is less likely to occur. From the viewpoint of stably obtaining this effect, the high-temperature tensile strength is more preferably 15 kg/mm ² or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a high temperature elongation of 2% or more of the electrolytic copper foil (raw foil) after the surface treatment. In the present specification, "high temperature elongation" is an elongation at 180 ° C, which means measured according to IPC-TM-650. When the high temperature elongation is 2% or more, it is effective in preventing cracks in the circuit. The high temperature elongation is preferably 3% or more, more preferably 6% or more, and still more preferably 15% or more from the viewpoint of stably obtaining the effect.

The electrolytic copper foil according to the embodiment of the present invention preferably has a heat-resistant peeling strength of 0.90 kg/cm or more. Here, in the present specification, the "heat-resistant peeling strength" means that the electrolytic copper foil of the embodiment of the present invention and the insulating substrate (resin substrate) are heat-pressed for 2 hours at a pressure of 20 kgf/cm ² at 180 ° C. The obtained laminated body was formed into a circuit having a circuit width of 10 mm by etching, and then heated at 190 ° C for 1 hour in an atmosphere, and then floated in a solder plating bath heated to 270 ° C. Peel strength between the circuit and the insulating substrate after 20 seconds. The peel strength was determined by measuring the 90-degree peel strength according to JIS C6471:1995, by measuring the strength at the time of peeling the insulating substrate (resin substrate) and the circuit at an angle of 90 degrees and at a speed of 50 mm/min. The peel strength was measured twice, and the average value was used.

The electrolytic copper foil (raw foil) before the surface treatment used in 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, in the present specification, "electrolytic copper foil (raw foil)" means a copper foil and a copper alloy foil produced by using an electrolytic cylinder by the principle of electroplating. Examples of the copper and copper alloy which are the raw materials of the copper foil and the copper alloy foil include pure copper, Sn-doped copper, Ag-doped copper, and Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, and Ag. Copper alloys such as Co, Fe, As, and P. The copper alloy foil (raw foil) may be added with an alloying element (for example, selected from the group consisting of Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Co, Fe, As) in the electrolytic solution used in the production of the electrolytic copper foil. And one or more elements of the group consisting of P).

The thickness of the electrolytic copper foil (raw foil) is not particularly limited, and is typically 0.5 μm to 3000 μm, preferably 1.0 μm to 1000 μm, more preferably 1.0 μm to 300 μm, still more preferably 1.0 μm to 100 μm, and still more preferably It is 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, and most preferably 8 μm to 19 μm.

<Manufacturing method of electrolytic copper foil (raw foil)>

Electrolytic copper foil (raw foil) is produced by electrolyzing copper from a copper sulfate plating bath on a titanium or stainless steel drum. Examples of the electrolysis conditions are shown below.

(electrolysis conditions)

Electrolyte composition: 50~150g/L Cu, 60~150g/L H ₂ SO ₄

Current density: 30~120A/dm ²

Electrolyte temperature: 50~60°C

Additive: 20~80ppm chloride ion, 0.01~10.0ppm glue

In addition, the remainder of the treatment liquid (etching liquid, electrolyte solution, etc.) used for electrolysis, etching, surface treatment, plating, etc. which are described in this specification is water, unless it is not specifically described.

Regarding the electrolytic drum to be used, in order to control the surface roughness Sa and/or the root mean square height Sq of the shiny surface of the formed electrolytic copper foil (raw foil) to a specific range, the surface roughness Sa of the surface of the drum is set. The ratio is 0.270 μm or less and/or the root mean square height Sq is set to 0.315 μm or less. The surface roughness Sa of the surface of the drum is preferably 0.150 μm or less, and the root mean square height Sq of the surface of the drum is preferably 0.200 μm or less.

An electrolytic drum having a surface having a specific surface roughness Sa and/or a root mean square height Sq can be produced in the following manner. First, the surface of a titanium or stainless steel drum is ground by a grinding tape having a size of 300 (P300) to 500 (P500). At this time, the polishing tape is wound only in a specific width in the width direction of the drum, and the polishing belt is rotated at a specific speed in the width direction of the drum to rotate the drum. The rotational speed of the surface of the drum during grinding is set to be 130 m/min to 190 m/min. Further, the polishing time is a product of the time of one point passing through the surface of the drum (the position in the width direction) and the number of strokes in one stroke of the polishing belt. Further, the time during which the above-mentioned one stroke passes through one point of the drum surface is defined as the 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. In addition, the primary stroke of the polishing tape means that the surface of the circumferential direction of the roller is polished one time from the end of the axis (width) of the roller (the width direction of the electrolytic copper foil) to the other end by the polishing tape. That is, the polishing time is represented by the following formula.

Grinding time (minutes) = width of the grinding belt per 1 stroke (cm / time) / moving speed of the grinding belt (cm / minute) × number of strokes (times)

In the production of the conventional electrolytic copper foil (raw foil), the polishing time is set to 1.6 minutes to 3 minutes, but in the embodiment of the present invention, it is 3.5 minutes to 10 minutes, and in the embodiment of the present invention, When the surface of the drum is wetted with water during grinding, it is set to 6 minutes to 10 minutes. As an example of the calculation of the polishing time, for example, when the moving speed is 20 cm/min by a polishing tape having a width of 10 cm, the polishing time of one stroke of one surface of the drum surface is 0.5 minute. It can be calculated by multiplying it by the total number of strokes (for example, 0.5 minute × 10 strokes = 5 minutes). The surface roughness Sa of the drum surface can be reduced by increasing the grain size of the abrasive belt and/or increasing the rotational speed of the drum surface, and/or extending the grinding time, and/or wetting the surface of the drum with water during grinding. And the root mean square height Sq of the drum surface. Conversely, by reducing the grain size of the abrasive belt, and/or reducing the rotational speed of the drum surface, and/or shortening the grinding time, and/or drying the drum surface during grinding, the surface roughness of the drum surface can be increased. The root mean square height Sq of the Sa and the drum surface. Further, by extending the polishing time, the surface roughness Sa can be reduced, and the root mean square height Sq can be reduced to the extent that Sa is smaller. On the contrary, by shortening the polishing time, the surface roughness Sa can be increased, and the root mean square height Sq can be increased to a degree larger than the surface roughness Sa. Further, the particle size number of the above abrasive tape means the particle size of the abrasive material used for the abrasive tape. Moreover, the particle size of the abrasive material is based on FEPA (Federation of European Producers of Abrasives) - standard 43-1: 2006, 43-2:2006.

Further, by wetting the surface of the drum with water during polishing, the root mean square height Sq can be reduced, and the surface roughness Sa can be reduced to the extent that the root mean square height Sq becomes smaller. On the contrary, by drying the surface of the drum during polishing, the root mean square height Sq can be increased, and the surface roughness Sa can be increased to the extent that the root mean square height Sq becomes larger.

By using the electrolytic drum having the specific surface roughness Sa and/or the root mean square height Sq prepared in the above manner, the surface roughness Sa and/or the root mean square height Sq having a specific shiny surface can be produced. Electrolytic copper foil (raw foil).

Further, the surface roughness Sa and the root mean square height Sq of the surface of the electrolytic drum can be measured as follows.

‧ The resin film (polyvinyl chloride) is immersed in a solvent (acetone) to swell it.

‧ The swelled resin film is brought into contact with the surface of the electrolytic drum, and acetone is volatilized from the resin film, and then the resin film is peeled off, and a replica of the surface of the electrolytic drum is taken.

‧ The replica was measured by a laser microscope, and the values of the surface roughness Sa and the root mean square height Sq were measured.

Then, the values of 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 surface of the electrolytic drum.

<surface treatment>

The surface treatment is not particularly limited, and examples thereof include a roughening treatment, a heat-resistant treatment, a rust-preventing treatment, a chromate treatment, and a decane coupling treatment. In the present specification, a layer formed by roughening treatment is referred to as a "roughening layer", and a layer formed by heat-resistant treatment is referred to as a "heat-resistant layer", and a layer formed by rust-preventing treatment is used. The layer formed by the chromate treatment is referred to as a "chromate treatment layer", and the layer formed by the decane coupling treatment is referred to as a "decane coupling treatment layer".

In the electrodeposited copper foil according to the embodiment of the present invention, it is preferable that the surface treatment layer contains one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer.

The roughening treatment is performed in order to improve the adhesion to the insulating substrate (resin substrate). The roughening treatment is not particularly limited, and it can be carried out by electrodepositing the roughened particles on the surface of the electrolytic copper foil. For example, it is only necessary to electrodeposit the roughened particles of copper or copper alloy on the surface of the electrolytic copper foil. The roughened particles may be fine, and the shape may be any one of a needle shape, a rod shape, or a particle shape. The roughening treatment layer may be composed of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing any one or more. Layers, etc. Further, after roughening particles of copper or a copper alloy may be electrodeposited, a secondary process of further depositing secondary particles or tertiary particles by a simple substance such as nickel, cobalt, copper or zinc or an alloy may be performed.

When the roughening treatment is performed as a surface treatment, a heat-resistant layer or a rust-preventing layer is formed on the surface of the roughened layer, and further, a chromate-treated layer or a decane coupling treatment layer is 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 further, a chromate-treated layer or a decane coupling treatment layer is formed on the surface.

Further, the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may each be a single layer or may be formed in multiple layers (for example, two or more layers, three or more layers, or the like).

The roughening treatment layer can be formed using an electrolytic bath composed of at least one or more kinds of sulfuric acid or copper sulfate containing a substance selected from the group consisting of an alkyl sulfate salt, a tungsten ion, and an arsenic ion. In order to prevent falling powder and to improve peeling strength, the roughening treatment layer is preferably subjected to blanket plating in an electrolytic bath composed of sulfuric acid or copper sulfate.

The specific conditions of the roughening treatment are as follows.

(plating solution composition 1)

CuSO ₄ ‧5H ₂ O: 39.3~120g/L

H ₂ SO ₄ : 10~150g/L

Na ₂ WO ₄ ‧2H ₂ O: 0~90mg/L

W: 0~50mg/L

Sodium lauryl sulfate: 0~50mg

As: 0~2000mg/L

(plating condition 1)

Temperature: 30~70°C

(current condition 1)

Current density: 25~110A/dm ²

Coarse coulomb amount: 50~500As/dm ²

Plating time: 0.5~20 seconds

(plating solution composition 2)

CuSO ₄ ‧5H ₂ O: 78~314g/L

H ₂ SO ₄ : 50~200g/L

(plating condition 2)

Temperature: 30~70°C

(current condition 2)

Current density: 5~50A/dm ²

Coarse coulomb amount: 50~300As/dm ²

Plating time: 1~60 seconds

When a copper-cobalt-nickel alloy plating layer is formed as a roughened layer, it is preferably copper having a content of 15 mg/dm ² to 40 mg/dm ² by electroplating, and the content is 100 μg/dm ² ~ 3000μg / dm ² of cobalt, and the content is 100μg / dm ² ~ 1500μg / 3 membered dm ² of nickel-based alloy layer. When the Co content is less than 100 μg/dm ² , heat resistance and etching property may be lowered. On the other hand, when the Co content exceeds 3000 μg/dm ² , there is a case where it is necessary to take into consideration the influence of magnetic properties, and etching spots are generated, and acid resistance and chemical resistance are lowered. Further, when the Ni content is less than 100 μg/dm ² , the heat resistance may be lowered. On the other hand, when the Ni content exceeds 1500 μg/dm ² , there is a case where the etching residue is increased. The preferred Co content is ^{1000μg / dm 2 ~ 2500μg / dm} 2, Ni content is preferably of ^{500μg / dm 2 ~ 1200μg / dm} 2.

Here, in the present specification, "etching spots" means that when etching is performed by copper chloride, Co remains without being dissolved. Moreover, the "etching residue" means that when alkali etching is performed by ammonium chloride, Ni remains without being dissolved.

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 to 20 g/L of Cu, 1 to 10 g/L of Co, 1~10g/L of Ni

pH: 1~4

Temperature: 30~50°C

Current density: 20~30A/dm ²

Plating time: 1~5 seconds

Another example of the plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows: plating bath composition: 10-20 g/L of Cu, 1 to 10 g/L of Co , 1~10g/L of Ni

pH: 1~4

Temperature: 30~50°C

Current density: 30~45A/dm ²

Plating time: 0.1~2.0 seconds

Further, in the roughening 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 made small by shortening the plating time. On the other hand, in the surface treatment for forming the roughened layer described above, the surface roughness Sa and/or the root mean square height Sq of the surface of the surface treated layer can be increased by extending the plating time.

Further, in the roughening treatment for forming the roughened layer, the surface roughness Sa and/or the root mean square height Sq of the surface of the surface treatment layer can be further reduced by increasing the current density and making the plating time very short. . On the other hand, in the above-described process of 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 further increased by increasing the current density and extending the plating time.

The electrodeposited copper foil according to the embodiment of the present invention may have a surface treatment layer on the side of the deposition surface. The surface treatment layer formed on the side of the deposition surface is not particularly limited, and is preferably one selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane-coupled treatment layer. More than one layer. Generally, a heat-resistant layer or a rust-preventive layer is formed on the surface of the roughened layer, and a chromate-treated layer or a decane-coupled layer is formed thereon.

The electrodeposited copper foil according to the embodiment of the present invention may have a resin layer on one side or both sides of the gloss side and the deposition side. The resin layer is generally formed on the surface treatment layer. The resin layer is not particularly limited, and is preferably an insulating resin layer.

The heat-resistant layer and/or the rust-preventing layer are not particularly limited, and those known to the public can be used. The heat-resistant layer and/or the rust-proof layer may be, for example, selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and The layer of one or more elements of the group of yttrium may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver. A metal layer or an alloy layer composed of one or more elements selected from the group consisting of a platinum group element, iron, and lanthanum. Moreover, the heat-resistant layer and/or the rust-preventing layer may comprise a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. And an oxide, a nitride or a telluride of one or more elements of the group consisting of. Further, the heat-resistant layer and/or the rust-preventing 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% by mass to 99% by mass of nickel and 50% by mass to 1% by mass of zinc in addition to unavoidable impurities. The total content of zinc and nickel in the nickel-zinc alloy layer is preferably from 5 mg/m ² to 1000 mg/m ² , more preferably from 10 mg/m ² to 500 mg/m ² , still more preferably from 20 mg/m ² to 100 mg/m. ² . Further, the ratio of the nickel content to the zinc content (=nickel content/zinc content) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is preferably 1.5 to 10. Further, the nickel content of the nickel-zinc alloy layer or the nickel-zinc alloy layer is preferably from 0.5 mg/m ² to 500 mg/m ² , more preferably from 1 mg/m ² to 50 mg/m ² .

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

The chromate treatment layer is a layer treated with a solution comprising chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium (may be metals, alloys, oxides, nitrides, sulfides, etc.) Any form). Specific examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate; or a chromate treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Processing layers, etc.

The decane coupling agent used in the decane coupling treatment is not particularly limited, and a known one can be used. Examples of the decane coupling agent include an amine decane coupling agent, an epoxy decane coupling agent, a methacryloxy decane coupling agent, and a fluorenyl decane coupling agent. Specifically, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxypropyl group can be used. Trimethoxydecane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N -3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like. Further, the decane coupling agent may be used singly or in combination of two or more. Further, among the above various decane coupling agents, an amine decane coupling agent or an epoxy decane coupling agent is preferably used.

Specific examples of the amine-based decane coupling agent include N-(2-aminoethyl)-3-aminopropyltrimethoxydecane and 3-(N-styrylmethyl-2-amine Ethylethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyl Trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3- Aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl- 3-aminopropyl)trimethoxynonane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl) Trimethoxy decane, aminophenyl trimethoxy decane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyl Tris(methoxyethoxyethoxy)decane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N-benzylamino Ethylaminopropyl)trimethoxy Decane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, (N,N-dimethyl-3-aminopropyl)trimethoxydecane, γ-aminopropyl Triethoxy decane, N-β (aminoethyl) γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3 - Aminopropyltrimethoxydecane, and the like.

The decane coupling treatment layer is suitably from 0.05 mg/m ² to 200 mg/m ² , more preferably from 0.15 mg/m ² to 20 mg/m ² , and still more preferably 0.3 mg/by conversion. Set in the range of m ² ~2.0mg/m ² . In the case of this range, the adhesion between the insulating substrate (resin substrate) and the electrolytic copper foil can be further improved.

The resin layer may be a layer of an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer is superposed and stored even if the surface is not adhered by a finger, and the hardening reaction is generated when the heat treatment is performed.

Further, the resin layer may be a layer containing a thermosetting resin or a thermoplastic resin. The type of the thermosetting resin and the thermoplastic resin is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polyvinyl acetal. Resin, amine ester resin, etc. These may be used alone or in combination of two or more.

The resin layer may be composed of a well-known resin, a resin hardener, a compound, a hardening accelerator, a dielectric (a dielectric containing an inorganic compound and/or an organic compound, a dielectric containing a metal oxide, or the like may be used. A composition of a body, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, or the like. In addition, the resin layer may be, for example, International Publication No. 2008/004399, International Publication No. 2008/053878, International Publication No. 2009/084533, Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. Japanese Patent No. 3,184,485, International Publication No. 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open Japanese Patent Publication No. 2003-359444, Japanese Patent Publication No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Application Publication No. 2004-82687, Japanese Patent No. Japanese Patent No. 4025177, Japanese Patent Publication No. 2004-349654, Japanese Patent No. 4,286,060, Japanese Patent Laid-Open Publication No. 2005-262506, 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 Laid-Open Patent Publication No. 2006-257153, Japanese Laid-Open Patent Publication No. 2007-326923, and JP-A-2008- Japanese Laid-Open Patent Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Nos. Japanese Laid-Open Patent Publication No. 2009-173017, International Publication No. 2007/105635, Japanese Patent No. 5180815, International Publication No. 2008/114858, International Publication No. 2009/008471, Japanese Patent Laid-Open No. 2011-14727, International A substance (resin, a resin curing agent, a compound, a curing accelerator, and a medium) disclosed in Japanese Laid-Open Patent Publication No. 2009/001850, the International Publication No. 2009/145179, the International Publication No. 2011/068157, and the Japanese Patent Publication No. 2013-19056 The electric body, the reaction catalyst, the crosslinking agent, the polymer, the prepreg, the skeleton material, and the like, and/or the method of forming the resin layer, and the forming apparatus are formed.

For example, the resin is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin liquid, which is applied to an electrolytic copper foil or a surface treatment layer by a known method such as a roll coater method. Then, if necessary, heat drying is performed to remove the solvent, thereby setting the B-stage state. In the drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 ° C to 250 ° C, preferably 130 ° C to 200 ° C.

The electrodeposited copper foil having a resin layer is used by superimposing the resin layer on an insulating substrate (resin substrate), thermolating the entire resin layer, and thermally curing the resin layer to form a specific wiring pattern.

When the above-mentioned electrolytic copper foil with a resin layer is used, the number of sheets of the prepreg material used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be such that the thickness of the interlayer insulation can be ensured, or the copper clad laminate can be produced even if the prepreg material is not used at all. Further, the surface of the substrate may be coated with an insulating resin to further improve the smoothness of the surface.

Moreover, when the prepreg material is not used, there are the following advantages: the material cost of the prepreg material is saved, and the lamination step is also simplified, so that it is economically advantageous, and the prepreg material is used. The thickness of the multilayer printed wiring board manufactured by the thickness is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

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 adhesion is lowered, and it is difficult to secure the inner layer material when the carrier-attached copper foil with the resin layer is laminated on the substrate having the inner layer material without interposing the prepreg material. The case of interlayer insulation between circuits. On the other hand, when the thickness of the resin layer is made thicker than 80 μm, it is difficult to form a resin layer having a desired thickness by one application step, and it takes an unnecessary material cost and the number of steps, which is economically disadvantageous. Further, since the resin layer formed is inferior in flexibility, cracks and the like are likely to occur during the treatment, and excessive resin flow occurs during thermocompression bonding with the inner layer material, so that it is difficult to form a smooth layer.

Further, another form of the electrolytic copper foil with a resin layer may be sold as a resin layer having a semi-hardened state on the shiny side or the surface treated layer.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the present specification, the "printed wiring board" includes a printed wiring board on which electronic components are mounted, a printed circuit board, a printed circuit board, a flexible printed wiring board, and a rigid printed wiring board.

Moreover, an electronic device can be produced using a printed wiring board, an electronic device can be produced using a printed circuit board on which an electronic component is mounted, or an electronic device can be produced using a printed circuit board on which an electronic component is mounted. Hereinafter, an example of a manufacturing procedure of a plurality of printed wiring boards using the electrolytic copper foil of the embodiment of the present invention will be described.

A method of manufacturing a printed wiring board according to an embodiment of the present invention includes the steps of: laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate to form a copper clad laminate, and then adding a semi-additive method and a modified semi-additive method A method of forming a circuit by either a partial addition method or a subtractive method. Here, the insulating substrate may be one in which an inner layer circuit is mounted.

In the present 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, and a pattern is formed, and a conductor pattern is formed by plating and etching.

Therefore, the method for producing a printed wiring board according to the embodiment of the present invention using the semi-additive method is a step comprising the steps of laminating an electrolytic copper foil and an insulating substrate (resin substrate) according to an embodiment of the present invention. a step of completely removing the electrolytic copper foil by etching or plasma etching using an etching solution such as an acid; and removing a through hole and/or a blind hole by removing the resin exposed by the electrolytic copper foil by etching; a step of removing a desmear by a region including a via hole and/or a blind via; a step of providing an electroless plating layer to a resin, and a region including the via hole and/or the blind via hole; and an electroless plating layer a step of providing a plating resist on the top; a step of removing the plating resist in the region where the circuit is formed after the exposure of the plating agent; and a step of providing a plating layer in the region where the circuit is formed by removing the plating resist; a step of resisting the plating agent; and a step of removing the electroless plating layer in a region outside the region where the circuit is formed by rapid etching or the like.

A method of manufacturing a printed wiring board according to an embodiment of the present invention using a semi-additive method is another aspect comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; and electrolytic copper foil And a step of providing a through hole and/or a blind hole in the insulating substrate (resin substrate); a step of removing the slag treatment on the region including the through hole and/or the blind hole; etching or plasma etching by etching the solution using an acid or the like Method for completely removing electrolytic copper foil; removing resin exposed by electrolytic copper foil by etching or the like, and providing an electroless plating layer in a region including through holes and/or blind holes; a step of providing a plating resist on the coating layer; a step of removing the plating resist in the region where the circuit is formed after the exposure of the plating agent; and a step of providing the plating layer in the region where the circuit is formed by removing the plating resist a step of removing the plating resist; and a step of removing the electroless plating layer in a region outside the region where the circuit is formed by rapid etching or the like.

A method of manufacturing a printed wiring board according to an embodiment of the present invention using a semi-additive method is another aspect comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; and electrolytic copper foil And a step of providing a through hole and/or a blind hole in the insulating substrate (resin substrate); a step of completely removing the electrolytic copper foil by etching or plasma etching using an acid or the like; and including through holes and/or blind holes a step of removing the desmear treatment; a step of removing the resin exposed by the electrolytic copper foil by etching or the like, and providing an electroless plating layer in a region including the through hole and/or the blind hole; and electroless plating a step of providing a plating resist on the coating layer; a step of removing the plating resist in the region where the circuit is formed after the exposure of the plating agent; and a step of providing the plating layer in the region where the circuit is formed by removing the plating resist a step of removing the plating resist; and a step of removing the electroless plating layer in a region outside the region where the circuit is formed by rapid etching or the like.

A method of manufacturing a printed wiring board according to an embodiment of the present invention using a semi-additive method is another aspect comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; a step of completely removing the electrolytic copper foil by etching or plasma etching or the like; a step of providing an electroless plating layer on the surface of the resin exposed by removing the electrolytic copper foil by etching; and an electroless plating layer a step of providing a plating resist on the top; a step of removing the plating resist in the region where the circuit is formed after the exposure of the plating agent; and a step of providing a plating layer in the region where the circuit is formed by removing the plating resist; a step of resisting the plating agent; 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 rapid etching or the like.

In the present specification, the "modified semi-additive method" means a method of laminating an electrolytic copper foil on an insulating substrate, protecting a non-circuit forming portion by a plating resist, and performing thick copper of the circuit forming portion by electroplating. After the plating, the plating resist is removed, and the electrolytic copper foil other than the circuit forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating substrate.

Therefore, the method for producing a printed wiring board according to an embodiment of the present invention using the modified semi-additive method is a step comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; a step of providing a through hole and/or a blind hole in the electrolytic copper foil and the insulating substrate; a step of removing the slag treatment on the region including the through hole and/or the blind hole; and providing electroless plating in the region including the through hole and/or the blind hole a step of plating a layer; a step of providing a plating resist to the electrolytic copper foil; a step of forming a circuit by electroplating after the plating resist is provided; a step of removing the plating resist; and removing the borrowing by rapid etching The step of removing the electrolytic copper foil exposed by the plating resist.

A method of manufacturing a printed wiring board according to an embodiment of the present invention using a modified semi-additive method is another aspect comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; a step of providing a plating resist on the copper foil; a step of removing the plating resist in the region where the circuit is formed after the exposure of the plating agent; and a step of providing the plating layer in the region where the circuit for forming the plating resist is removed a step of 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 rapid etching or the like.

In the present specification, the "partial addition method" means a method in which a catalyst core is provided on a substrate on which a conductor layer is provided, and a via hole or a via hole is formed as needed, and etching is performed to form a catalyst core. The conductor circuit is provided with a solder resist or a plating resist as needed, and then subjected to thick plating on a conductor circuit, a via hole, a via hole, or the like by electroless plating, thereby manufacturing a printed wiring board.

Therefore, the method for producing a printed wiring board according to an embodiment of the present invention using a partial addition method is in one aspect, comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; a step of providing a through hole and/or a blind hole in the foil and the insulating substrate; a step of removing the slag treatment on the area including the through hole and/or the blind hole; and applying a catalyst core to the area including the through hole and/or the blind hole a step of providing a resist on the electrolytic copper foil; a step of exposing the resist to form a circuit pattern; and removing the electrolytic copper foil and the catalyst core by etching or plasma etching using an acid or the like a step of removing a resist; removing a resist or an anti-plating agent on the surface of the insulating substrate exposed by the electrolytic copper foil and the catalyst core by etching or plasma etching using an acid or the like; And the step of providing an electroless plating layer in a region where no solder resist or anti-plating agent is provided.

In the present specification, the "reduction 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 method for producing a printed wiring board according to the embodiment of the present invention using the subtractive method is a step comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; and electrolytic copper foil And a step of providing a through hole and/or a blind hole in the insulating substrate; performing a desmear treatment step on the region including the through hole and/or the blind hole; and providing an electroless plating layer on the region including the through hole and/or the blind hole a step of providing a plating layer on the surface of the electroless plating layer; a step of providing a resist on the surface of the plating layer and/or the electrolytic copper foil; and a step of exposing the resist to form a circuit pattern; a step of removing an electrolytic copper foil, an electroless plating layer, and the above plating layer to form an electric circuit by etching or plasma etching of an etching solution such as acid; and a step of removing the resist.

A method for producing a printed wiring board according to an embodiment of the present invention using a subtractive method is a step comprising the steps of: laminating an electrolytic copper foil and an insulating substrate according to an embodiment of the present invention; and electrolytic copper foil and insulating a step of providing a through hole and/or a blind hole in the substrate; a step of removing the slag treatment on the area including the through hole and/or the blind hole; and an step of providing an electroless plating layer on the area including the through hole and/or the blind hole a step of forming a mask on the surface of the electroless plating layer; a step of providing a plating layer on the surface of the electroless plating layer not forming the mask; and providing a resist on the surface of the plating layer and/or the electrolytic copper foil; a step of exposing the resist to form a circuit pattern; a step of forming an electric circuit by removing an electrolytic copper foil and an electroless plating layer by etching or plasma etching using an acid or the like; and removing the resist step.

Furthermore, the step of providing a through hole and/or a blind hole, and the subsequent desmear step may not be performed.

[Examples]

Hereinafter, embodiments of the present invention will be described in detail by way of examples and comparative examples, but the invention is not limited thereto.

1. Production of electrolytic copper foil

(Examples 1 to 37, Comparative Example 1)

Prepare a titanium rotating drum (electrolytic drum). Next, the surface of the electrolytic drum was ground under the conditions described in Table 1, and an electrolytic drum having a specific surface roughness Sa and a root mean square height Sq was prepared. Specifically, the surface of the electrolytic drum was ground by the abrasive tape of the particle size number described in Table 1. At this time, the polishing tape is wound only in a specific width in the width direction of the drum, and the polishing belt is rotated in the width direction of the drum to rotate the drum, thereby performing polishing. The rotational speed of the surface of the drum at the time of grinding is shown in Table 1. Further, the polishing time is based on the width of the polishing tape and the moving speed of the polishing tape, and is the product of the time of one pass of the roller surface and the number of strokes in one stroke. Here, the primary stroke of the polishing tape means that the surface of the circumferential direction of the rotary drum is polished once from the end portion in the axial direction (the width direction of the electrolytic copper foil) to the other end portion by the polishing tape. That is, the polishing time is represented by the following formula.

Grinding time (minutes) = width of the grinding belt per 1 stroke (cm / time) / moving speed of the grinding belt (cm / minute) × number of strokes (times)

Next, the electrolytic drum is placed in an electrolytic cell, and electrodes are disposed at a predetermined distance between the electrodes around the electrolytic drum. Next, electrolysis was carried out in an electrolytic cell 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>

Composition of electrolyte: 100g/L of Cu, 100g/L of H ₂ SO ₄

Current density: 90A/dm ²

Electrolyte temperature: 60 ° C

Additive: 60 ppm by mass of chloride ion and gel (in Examples 1, 2, 5, 6, 10 to 12, 15, 16, 19, 20, and 24 to 26 and Comparative Example 1 as 0.02 ppm) Example 3, 4, 7~9, 13, 14, 17, 18, 21~23, 27~37 is set to 4.5ppm)

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

(Example 1)

The surface (glossy surface) on the side of the electrolytic drum of the electrolytic copper foil (raw foil) produced in the above manner was subjected to surface treatment in the following order (1) to (4).

(1) roughening treatment

The plating solution 1 having the following composition (pH 1 or less) was used, and after the roughened particles were electrodeposited on the shiny surface of the electrolytic copper foil (raw foil) under the following plating conditions 1, the following plating solution was used. 2 (pH value of 0.3 or less), the roughened particles were further electrodeposited under the following plating conditions 2 to form a roughened layer (Cu-As-W).

<plating solution 1 composition>

CuSO ₄ ‧5H ₂ O: 120g/L

H ₂ SO ₄ : 120g/L

Na ₂ WO ₄ ‧2H ₂ O: 20 mg/L

Sodium lauryl sulfate: 30mg

As: 1mg/L

<plating condition 1>

Temperature: 40 ° C

Current density: 70A/dm ²

Plating time: 2 seconds

<plating solution 2 composition>

CuSO ₄ ‧5H ₂ O: 240g/L

H ₂ SO ₄ : 120g/L

<plating condition 2>

Temperature: 55 ° C

Current density: 20A/dm ²

Plating time: 7 seconds

(2) Heat treatment (barrier treatment)

A nickel-zinc alloy plating was performed under the plating conditions described below using a plating solution (pH 2) having the following composition, thereby forming a heat-resistant layer (Ni-Zn).

<plating fluid composition>

Ni: 13g/L

Zn: 12g/L

<plating conditions>

Temperature: 40 ° C

Current density: 0.2A/dm ²

Plating time: 2.89 seconds

(3) chromate treatment

The zinc chromate treatment layer was formed by performing a zinc chromate treatment under the plating conditions described below using a plating solution having the following composition (pH 4.8).

<plating fluid composition>

CrO ₃ : 2.5g / L

Zn: 2.0g/L

Na ₂ SO ₄ : 10g/L

<plating conditions>

Temperature: 54 ° C

Current density: 1.0A/dm ²

(4) decane coupling treatment

The decane coupling treatment liquid having a tetraethoxy decane content of 0.4 vol% and a pH of 7.5 was sprayed to form a decane coupling treatment layer A.

(Example 2)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (2) the plating time in the heat-resistant treatment to 2.96 seconds.

(Example 3)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (2) the plating time in the heat-resistant treatment to 2.75 seconds.

(Example 4)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (2) the plating time in the heat-resistant treatment to 2.82 seconds.

(Example 5)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

The roughened particles are electrodeposited on the shiny side of the electrolytic copper foil (raw foil) under the plating conditions described below by using a plating solution having the following composition (pH 1 to 4), thereby forming a roughened layer ( Cu-Co-Ni (1)).

<plating fluid composition>

Cu: 16g/L

Co: 10g/L

Ni: 10g/L

<plating conditions>

Temperature: 30 ° C

Current density: 30A/dm ²

Plating time: 2 seconds

(2) Heat treatment

A heat-resistant layer (Co-Ni) was formed by plating a Co-Ni alloy under the plating conditions described below using a plating solution having the following composition (pH 1.0 to 3.5).

<plating fluid composition>

Co: 10g/L

Ni: 20g/L

<plating conditions>

Temperature: 35 ° C

Current density 10A/dm ²

Plating time: 1 second

(3) Anti-rust treatment

A rust-preventing layer (Zn-Ni) was formed by plating a Zn-Ni alloy under the plating conditions described below using a plating solution having the following composition (pH 3-4).

<plating fluid composition>

Ni: 15g/L

Zn: 50g/L

<plating conditions>

Temperature: 50 ° C

Current density: 0.3A/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) decane coupling treatment

The decane coupling treatment liquid having a N-(2-aminoethyl)-3-aminopropyltrimethoxydecane content of 0.4 vol% and a pH of 7.5 was sprayed to form a decane coupling treatment layer B.

(Example 6)

The surface treatment was carried out in the same manner as in Example 5 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (2.6) the plating time in the rustproof treatment to 2.61 seconds.

(Example 7)

The surface treatment was carried out in the same manner as in Example 5 except that the plating time in the (3) rust-preventing treatment was changed to 2.32 seconds on the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 8)

The same surface treatment as in Example 5 was carried out on the shiny side of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 9)

The glossy surface of the electrolytic copper foil (raw foil) produced in the above manner was subjected to surface treatment in the following order (1) to (3).

(1) Heat 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, thereby forming 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) decane coupling treatment

The decane coupling treatment layer A was formed under the same conditions as in Example 1.

(Embodiment 10)

The same surface treatment as in Example 2 was carried out on the shiny side of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 11)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

The roughened particles are electrodeposited on the shiny side of the electrolytic copper foil (raw foil) under the plating conditions described below by using a plating solution having the following composition (pH 1 to 4), thereby forming a roughened layer ( Cu-Co-Ni (2)).

<plating fluid composition>

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

<plating conditions>

Temperature: 30~50°C

Current density: 35~45A/dm ²

Plating time: 0.1~1.5 seconds

(2) Heat treatment

A heat-resistant layer (Co-Ni) was formed under the same conditions as in Example 5.

(3) Anti-rust treatment

A rustproof 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) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Embodiment 12)

The surface treatment was carried out in the same manner as in Example 11 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to 2.55 seconds in the (3) rust-preventing treatment.

(Example 13)

The same surface treatment as in Example 11 was carried out on the shiny side of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 14)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

A roughened layer (Cu-Co-Ni(1)) was formed under the same conditions as in Example 5.

(2) Heat treatment

A heat-resistant layer (Co-Ni) was formed under the same conditions as in Example 5.

(3) Anti-rust treatment

A rustproof 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) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 15)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (3) the plating time in the heat-resistant treatment to 3.79 seconds.

(Embodiment 16)

The surface treatment was carried out in the same manner as in Example 15 except that the plating surface of the electrolytic copper foil (raw foil) produced in the above manner was changed to (b) the plating time in the heat-resistant treatment to 4.89 seconds.

(Example 17)

The surface treatment was carried out in the same manner as in Example 15 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (2) the plating time in the heat-resistant treatment to 6.40 seconds.

(Embodiment 18)

The surface treatment was carried out in the same manner as in Example 15 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (6.8) the plating time in the heat-resistant treatment to 6.88 seconds.

(Embodiment 19)

The surface treatment was carried out in the same manner as in Example 5 except that the plating time in the (3) rust-preventing treatment was changed to 6.66 seconds in the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner.

(Embodiment 20)

The surface treatment was carried out in the same manner as in Example 19 except that the plating time in the (3) rust-preventing treatment was changed to 6.95 seconds in the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 21)

The surface treatment was carried out in the same manner as in Example 19 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (8) the plating time in the rustproof treatment to 8.17 seconds.

(Example 22)

The surface treatment was carried out in the same manner as in Example 19 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (9.2) the plating time in the rustproofing treatment to 9.27 seconds.

(Example 23)

The surface treatment was carried out in the same manner as in Example 9 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (1) the plating time in the heat-resistant treatment to 11.70 seconds.

(Example 24)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (1) the plating time in the heat-resistant treatment to 15.15 seconds.

(Embodiment 25)

The surface treatment was carried out in the same manner as in Example 11 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to 15.64 seconds in (3) the rust-preventing treatment.

(Example 26)

The surface treatment was carried out in the same manner as in Example 11 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to 15.16 seconds in (3) the rust-preventing treatment.

(Example 27)

The surface treatment was carried out in the same manner as in Example 11 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to 4.63 seconds in the (3) rust-preventing treatment.

(Embodiment 28)

The surface treatment was carried out in the same manner as in Example 5 except that the plating time in the (3) rust-preventing treatment was changed to 2.43 seconds in the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner.

(Example 29)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

The roughened particles are electrodeposited on the shiny side of the electrolytic copper foil (raw foil) under the plating conditions described below by using a plating solution having the following composition (pH 1 to 4), thereby forming a roughened layer ( Cu-Co-Ni-Mo).

<plating fluid composition>

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

Mo: 1~5g/L

<plating conditions>

Temperature: 30~50°C

Current density: 20~30A/dm ²

Plating time: 1~5 seconds

(2) Heat treatment

A heat-resistant layer (Co-Ni) was formed under the same conditions as in Example 5.

(3) Anti-rust treatment

A rustproof 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) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Embodiment 30)

The glossy surface of the electrolytic copper foil (raw foil) produced in the above manner was subjected to surface treatment in the following order (1) to (4).

(1) roughening treatment

A roughened layer (Cu-As-W) was formed under the same conditions as in Example 1.

(2) Heat treatment

The cobalt-zinc alloy plating was performed under the plating conditions described below using a plating solution (pH 2) having the following composition, thereby forming a heat-resistant layer (Co-Zn).

<plating fluid composition>

Co: 13g/L

Zn: 12g/L

<plating conditions>

Temperature: 40 ° C

Current density: 0.2A/dm ²

Plating time: 5.16 seconds

(3) chromate treatment

A chromate treatment layer was formed by performing a chromate treatment under the plating conditions described below using a plating solution having the following composition (pH 4.8).

<plating fluid composition>

CrO ₃ : 2.5g / L

Na ₂ SO ₄ : 10g/L

<plating conditions>

Temperature: 54 ° C

Current density: 1.0A/dm ²

(4) decane coupling treatment

The decane coupling treatment layer A was formed under the same conditions as in Example 1.

(Example 31)

The surface treatment was carried out in the same manner as in Example 30 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (3) the plating time in the heat-resistant treatment to 8.33 seconds.

(Example 32)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

A roughened layer (Cu-Co-Ni(1)) was formed under the same conditions as in Example 5.

(2) Heat treatment

A heat-resistant layer (Co-Ni) was formed under the same conditions as in Example 5.

(3) Anti-rust treatment

The rust-preventing layer (Ni-Mo) was formed by performing Ni-Mo alloy plating under the plating conditions described below using a plating solution having the following composition (pH 3 to 7).

<plating fluid composition>

Ni: 30g/L

Mo: 4g/L

<plating conditions>

Temperature: 40 ° C

Current density: 2A/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) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 33)

The surface of the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner was changed in the same manner as in Example 32 except that the conditions in the rust-preventing treatment were changed as described below.

(3) Anti-rust treatment

The rust-preventing layer (Co-Mo) was formed by plating a Co-Mo alloy under the plating conditions described below using a plating solution having the following composition (pH 3 to 7).

<plating fluid composition>

Co: 30g/L

Mo: 4g/L

<plating conditions>

Temperature: 40 ° C

Current density: 2A/dm ²

Plating time: 23.48 seconds

(Example 34)

With respect to the shiny surface of the electrolytic copper foil (raw foil) produced as described above, the plating time in the (3) rustproof treatment was changed to 6.22 seconds, and the same zinc chromate treatment as in Example 1 was carried out as (4) Surface treatment was carried out in the same manner as in Example 32 except for chromate treatment.

(Example 35)

The glossy surface of the electrolytic copper foil (raw foil) produced in the above manner was subjected to surface treatment in the following order (1) to (3).

(1) roughening treatment

The roughened particles are electrodeposited on the shiny side of the electrolytic copper foil (raw foil) under the plating conditions described below by using a plating solution having the following composition (pH 1 to 4), thereby forming a roughened layer ( Cu-Co-Ni-Zn).

<plating fluid composition>

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

Zn: 2~12g/L

<plating conditions>

Temperature: 30~50°C

Current density: 30~45A/dm ²

Plating time: 0.1~1.5 seconds

(2) chromate treatment

A zinc chromate treatment layer was formed under the same conditions as in Example 1.

(3) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Example 36)

The surface of the shiny surface of the electrolytic copper foil (raw foil) produced in the above manner was changed in the same manner as in Example 1 except that the conditions in the heat-resistant treatment were changed as described below (2).

(2) Heat treatment

A Cu-Zn alloy plating was performed under the plating conditions described below using a plating solution having the following composition (pH 10 to 13) to form a heat-resistant layer (Cu-Zn).

<plating fluid composition>

NaOH: 80~140g/L

NaCN: 100~150g/L

CuCN: 20~30g/L

Zn(CN) ₂ : 15~20g/L

As ₂ O ₃ : 0.01~1g/L

<plating conditions>

Temperature: 40~90°C

Current density: 5A/dm ²

Plating time: 14.06 seconds

(Example 37)

The glossy surface of the electrolytic copper foil (raw foil) produced as described above was subjected to surface treatment in the following order (1) to (5).

(1) roughening treatment

A roughened layer (Cu-Co-Ni(1)) was formed under the same conditions as in Example 5.

(2) Heat treatment

The Zn-Ni alloy plating was performed under the plating conditions described below using a plating solution having the following composition (pH 3-4) to form a heat-resistant layer (Zn-Ni).

<plating fluid composition>

Ni: 1~15g/L

Zn: 45~55g/L

<plating conditions>

Temperature: 40~55°C

Current density: 0.1~0.3A/dm ²

Plating time: 11.00 seconds

(3) Anti-rust treatment

A rust-preventing layer (Co-Ni) was formed by plating a Co-Ni alloy under the plating conditions described below using a plating solution having the following composition (pH 1.0 to 3.5).

<plating fluid composition>

Co: 1~30g/L

Ni: 1~30g/L

<plating conditions>

Temperature: 30~80°C

Current density 1.0A/dm ²

Plating time: 1~4 seconds

(4) chromate treatment

A chromate treatment layer was formed under the same conditions as in Example 30.

(5) decane coupling treatment

The decane coupling treatment layer B was formed under the same conditions as in Example 5.

(Comparative Example 1)

The surface treatment was carried out in the same manner as in Example 1 except that the plating time of the electrolytic copper foil (raw foil) produced in the above manner was changed to (1) the plating time in the heat-resistant treatment to 0.015 seconds.

2. Evaluation of electrolytic copper foil

<The surface roughness Sa and the root mean square height Sq of the surface of the glossy surface and the surface treatment layer>

The surface roughness Sa and the root mean square height Sq of the electroluminescent copper foil before and after the surface treatment were measured in accordance with ISO-25178-2:2012 using a laser microscope OLS4100 (LEXT OLS 4100) manufactured by Olympus. At this time, in the laser microscope, three areas of 200 μm × 1000 μm (specifically, 200,000 μm ² ) were measured using an objective lens at 50 times, and the surface roughness Sa and the root mean square height Sq were calculated.

The arithmetic mean values of the surface roughness Sa and the root mean square height Sq obtained at three places are respectively the values of the surface roughness Sa and the root mean square height Sq. Further, in the laser microscope measurement, when the measurement surface of the measurement result is not a flat surface (when the surface is curved), the surface roughness Sa and the root mean square height Sq are calculated after the plane correction. Further, the ambient temperature at which the surface roughness Sa was measured by a laser microscope was set to 23 to 25 °C.

<Total amount of Zn contained in the surface treatment layer, total amount of Mo, or total amount of Mo and Zn>

The electrolytic copper foil after the surface treatment was taken into a sample having a size of 10 cm × 10 cm. Next, the surface of the surface-treated layer of the sample was dissolved in an aqueous solution of nitric acid having a concentration of 20% by mass to a thickness of 1 μm, and then an ICP luminescence analyzer (Model: ICPS-7510) manufactured by Shimadzu Corporation was used. For ICP luminescence analysis, the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn were measured. The measurement sites were carried out at three locations, and the arithmetic mean of the results was taken as the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn.

In the case where a surface treatment layer is provided on both the shiny side and the deposited surface of the electrolytic copper foil, the acid-proof tape may be attached to the deposition surface side, or the prepreg such as FR4 may be thermally pressure-bonded or the like to be masked and dissolved. The surface of the glossy surface was treated to measure the total amount of Zn, the total amount of Mo, or the total amount of Mo and Zn. Further, in the case where Zn and Mo are not dissolved in a 20% by mass aqueous solution of nitric acid, a solution which can dissolve Zn and Mo (for example, a nitric acid concentration: 20% by mass, a hydrochloric acid concentration: 12% by mass of nitric acid and the like) may be used. After the solution was dissolved in a mixed aqueous solution of hydrochloric acid or the like, the measurement was carried out by the above-described ICP emission analysis. Further, a solution which can dissolve Zn and Mo can be a known solution, an acidic solution or an alkaline solution.

In the case where the thickness of the electrolytic copper foil is large and the thickness of the electrolytic copper foil is 1.5 μm or less, the surface treatment component of the precipitation surface may be dissolved when the surface of the surface treatment layer is dissolved to a thickness of 1 μm. Therefore, in such a case, it is preferable that the surface of the surface-treated layer of the electrodeposited copper foil dissolves the thickness of the electrolytic copper foil by 30%.

<Normal peel strength, heat peel strength>

After the surface-treated electrolytic copper foil and the glass epoxy substrate (FR-4) were heat-press bonded at 180 ° C for 2 hours under an applied pressure of 20 kgf/cm ² to obtain a laminated body, the laminated copper was electrolytically etched by etching. The foil forms a circuit with a circuit width of 10 mm. Thereafter, according to JIS C6471:1995, the strength (peeling strength) at the time of peeling the glass epoxy substrate and the circuit at a speed of 50 mm/min at an angle of 90 degrees was measured, thereby obtaining a normal peel strength. The measurement of the normal peel strength and the measurement of the heat-resistant peel strength described below were carried out twice, and the average values thereof were taken as the values of the normal peel strength and the heat-resistant peel strength.

The heat-resistant peel strength is obtained by heating the laminated body in which the circuit is formed in an air atmosphere at 190 ° C for 1 hour, and then floating in a solder plating bath heated to 270 ° C for 20 seconds, and then measuring the peel strength. Out.

Moreover, the deterioration rate of the peeling strength by heat was evaluated based on the following formula.

Deterioration rate of peel strength caused by heat = (normal peel strength - heat peel strength) / normal peel strength × 100

<Normal temperature resistance, high temperature and tensile strength>

For the surface treated electrolytic copper foil, the room temperature tensile strength and the high temperature tensile strength were measured in accordance with IPC-TM-650.

<normal temperature elongation, high temperature elongation>

For the surface-treated electrolytic copper foil, the room temperature elongation and the high temperature elongation were measured in accordance with IPC-TM-650. Further, as described above, "high temperature tensile resistance" means the tensile strength at 180 °C. Further, "high temperature elongation" means an elongation at 180 °C.

<circuit formation>

The surface-treated electrolytic copper foil is bonded to the bis-n-butylene diimide three by thermocompression bonding from the shiny side Resin prepreg. Thereafter, the electrodeposited copper foil attached to the prepreg was etched from the side opposite to the side to which the prepreg was bonded until the thickness became 9 μm. Then, a resist is provided on the surface of the electrodeposited copper foil after etching, and exposure and development are performed to form a resist pattern. Thereafter, by etching with ferric chloride, 20 lengths of 1 mm were formed by 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, respectively. Wiring. Then, the difference (μm) between the maximum value and the minimum value of the width of the lower end of the circuit observed from the upper surface of the circuit was measured, and the average value at five points was measured as a result. When the difference between the maximum value and the minimum value is 2 μm or less, it is determined that the circuit has good circuit linearity and is set to ◎. Moreover, when the difference between the maximum value and the minimum value exceeds 2 μm and is 4 μm or less, it is assumed to be ○. Further, when the difference between the maximum value and the minimum value exceeds 4 μm, it is set to ×.

The test conditions and test results are shown in Tables 2 to 5. Further, Fig. 1(a) is an SEM image of the shiny side of the electrolytic copper foil of Example 2 before the surface treatment layer was formed. Fig. 1(b) is an SEM image of the shiny side of the electrolytic copper foil of Example 10 before the surface treatment layer was formed.

<evaluation result>

The root mean square height Sq of the surface of the surface treatment layer is 0.550 μm or less and/or the surface roughness Sa of the surface of the surface treatment layer is 0.470 μm or less, the total amount of Zn contained in the surface treatment layer, the total amount of Mo or The electrolytic copper foils of Examples 1 to 37 in which the total amount of Mo and Zn was 70 μg/dm ² or more were excellent in circuit formability and heat resistance. In particular, the surface roughness Sa of the surface of the electrodeposited copper foil-based surface treatment layer of Examples 9 and 23 having the surface treatment layer other than the roughened layer on the shiny side is 0.270 μm or less, and the surface of the surface treated layer is uniform. The square root height Sq is 0.315 μm or less.

Further, the surface roughness Sa of the surface of the electrodeposited copper foil-based surface treatment layer of the other embodiment having the surface treatment layer containing at least the roughened layer on the shiny side is 0.470 μm or less, or the root mean square height Sq is 0.550 μm. the following.

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 range, 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 is less than 70 μg. The electrolytic copper foil of Comparative Example 1 of /dm ² was insufficient in circuit formability and heat resistance.

According to the above results, according to the embodiment of the present invention, it is possible to provide an electrolytic copper foil excellent in circuit formability and heat resistance and a method for producing the same. Moreover, according to the embodiment of the present invention, it is possible to provide a copper clad laminate using an electrolytic copper foil excellent in circuit formability and heat resistance, a printed wiring board, a method for producing the same, an electronic device, and a method for producing the same.

Claims (38)

An electrolytic copper foil having a surface treatment layer on a side of a glossy surface, and a root mean square height Sq of a surface of the surface treatment layer is 0.550 μm or less, a total amount of Zn contained in the surface treatment layer, and a total amount of Mo Or the total amount of Mo and Zn is 70 μg/dm ² or more.  The electrodeposited copper foil according to claim 1, wherein the surface roughness Sa of the surface of the surface treatment layer is 0.380 μm or less.    The electrodeposited copper foil according to claim 1, wherein the surface of the surface treated layer has a surface roughness Sa of 0.355 μm or less.    The electrodeposited copper foil according to claim 1, wherein the surface of the surface treated layer has a surface roughness Sa of 0.300 μm or less.    The electrodeposited copper foil according to claim 1, wherein the surface of the surface-treated layer has a surface roughness Sa of 0.200 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 5, wherein the surface of the surface treatment layer has a root mean square height Sq of 0.490 μm or less.    The electrodeposited copper foil according to claim 6, wherein the surface of the surface treatment layer has a root mean square height Sq of 0.450 μm or less.    The electrodeposited copper foil according to claim 6, wherein the surface of the surface treatment layer has a root mean square height Sq of 0.400 μm or less.    The electrodeposited copper foil according to claim 6, wherein the surface of the surface treatment layer has a root mean square height Sq of 0.330 μm or less.   An electrolytic copper foil having a surface treatment layer on a side of a glossy surface, and a surface roughness Sa of a surface of the surface treatment layer is 0.470 μm or less, a total amount of Zn contained in the surface treatment layer, a total amount of Mo or The total amount of Mo and Zn is 70 μg/dm ² or more.  The electrodeposited copper foil according to claim 10, wherein the surface of the surface treatment layer has a root mean square height Sq of 0.550 μm or less.   The electrodeposited copper foil according to any one of claims 1 to 11, wherein 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 80 μg/dm ² or more.  The electrodeposited copper foil according to any one of claims 1 to 12, wherein the surface roughness Sa of the shiny surface before the surface treatment layer is provided on the glossy surface side is 0.270 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 13, wherein the surface roughness Sa of the shiny surface before the surface treatment layer is provided on the glossy surface side is 0.130 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 14, wherein a root mean square height Sq of the gloss surface before the surface treatment layer is provided on the gloss side is 0.315 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 15, wherein a root mean square height Sq of the gloss surface before the surface treatment layer is provided on the gloss 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, which has a room temperature elongation of 3% or more.   The electrolytic copper foil according to any one of claims 1 to 18, which has a high temperature tensile strength of 10 kg/mm ² or more.  The electrolytic copper foil according to any one of claims 1 to 19, which has a high temperature elongation of 2% or more.    The electrolytic copper foil according to any one of claims 1 to 20, which has a heat-resistant peel strength of 0.90 kg/cm or more.    The electrolytic copper foil according to any one of claims 1 to 21, wherein the surface treatment layer on the glossy side comprises a layer selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treatment layer, and a decane coupling treatment layer. One or more layers in the group.    The electrodeposited copper foil according to any one of claims 1 to 22, which has a surface treatment layer on the side of the deposition surface.    The electrodeposited copper foil according to claim 23, wherein the surface treatment layer on the side of the deposition surface comprises a layer selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer. One or more layers in the group.    The electrolytic copper foil according to any one of claims 1 to 24, wherein the surface treatment layer is composed of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc. Any element of the group or a layer composed of any one or more of the alloys.    The electrodeposited copper foil according to any one of claims 1 to 25, which has a resin layer on one side or both sides of the gloss surface side and the deposition surface side.    The electrodeposited copper foil according to claim 26, wherein the resin layer is provided on the surface treatment layer.   A method for producing an electrolytic copper foil, wherein after the electrolytic copper foil is produced by using an electrolytic drum, the shiny surface of the electrolytic copper foil is surface-treated to form a surface treatment layer, and the surface roughness Sa of the surface of the electrolytic cylinder is 0.270 μm. Hereinafter, 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 70 μg/dm ² or more. A method for producing an electrolytic copper foil, wherein after the electrolytic copper foil is produced by using an electrolytic drum, the glossy surface of the electrolytic copper foil is surface-treated to form a surface treatment layer, and a root mean square height Sq of the surface of the electrolytic cylinder is 0.315 Μm or less, 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 70 μg/dm ² or more.  The method for producing an electrolytic copper foil according to claim 28, wherein the electrolytic drum has a root mean square height Sq of 0.315 μm or less.    The method for producing an electrodeposited 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 surface of the electrolytic drum has a root mean square height Sq of 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 of producing a printed wiring board using the electrolytic copper foil according to any one of claims 1 to 27.    A method of manufacturing a printed wiring board, comprising the steps of: laminating a copper-clad laminate by laminating an electrolytic copper foil and an insulating substrate according to any one of claims 1 to 27, and then performing a semi-additive method and a subtractive method A method of forming a circuit by either a partial addition method or a modified semi-additive method.    An electronic machine having the printed wiring board of claim 34.    A method of manufacturing an electronic device using the printed wiring board of claim 34.