TW201900939A - Electrolytic copper foil, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor - Google Patents

Abstract

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

Description

 Electrolytic copper foil, copper-clad laminate, printed wiring board, and 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) on a copper clad laminate after the copper foil, and then forming a conductor pattern (circuit) on the copper foil by etching.

In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, high-density encapsulation of mounted components, high-frequency signals, and the like have been progressing, and the printed wiring boards are required to be miniaturized. Spacing) or corresponding to high frequency.

Therefore, in order to refine the conductor pattern by using the electrolytic copper foil, it is proposed to add an additive such as a sulfur-containing compound that acts as a brightening agent to the electrolytic solution to prepare a surface-smoothed electrolytic copper foil on the side of the deposition surface. Thereafter, 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, in the method of Patent Document 1, under the influence of the additive contained in the electrolytic solution, in the production of the electrolytic copper foil, the copper foil is likely to wrinkle due to recrystallization at normal temperature and shrinkage thereof. Further, when such wrinkles are generated, the electrolytic copper foil and the insulating substrate (resin substrate) are subsequently wrinkled. When the electrodeposited copper foil is wrinkled, the fine pitch becomes difficult when the conductor pattern is formed on the electrodeposited copper foil, and thus the circuit formation property is difficult to be sufficient. Further, the electrolytic copper foil of Patent Document 1 also has a problem that mechanical properties (for example, tensile strength, high-temperature elongation, etc.) are likely to change under the influence of an additive added to the electrolytic solution.

On the other hand, in order to ensure insulation and prevent short-circuiting, a solder resist is applied to the conductor pattern, and therefore, the surface of the electrodeposited copper foil to be a conductor pattern is required to have good adhesion to the solder resist. However, if the surface of the electrodeposited copper foil to be a conductor pattern is smooth, there is a problem that the adhesion to the solder resist is lowered. Therefore, the surface of the electrodeposited copper foil to be a conductor pattern requires a certain degree of roughness.

In order to improve the adhesion to the insulating substrate, the electrodeposited copper foil is required to have a smoother surface in contact with the insulating substrate, and the surface of the conductor pattern is required to ensure the adhesion of the solder resist. A certain degree of roughness is required.

In order to solve the above-mentioned problems, a plurality of embodiments of the present invention have been made to provide an electrolytic copper foil excellent in circuit formability and adhesion of a solder resist.

In addition, it is an object of the present invention to provide a copper clad laminate for an electrolytic copper foil which is excellent in adhesion between a circuit formation property and a solder resist, a printed wiring board, a method for producing the same, and an electronic device and a method for producing the same .

The inventors of the present invention have made an effort to solve the above problems, and have found that the surface roughness Sa and/or the root mean square height Sq of the shiny side of the electrodeposited copper foil are controlled to a specific range, and the electrolytic copper foil is At least one of the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk on the deposition surface side is controlled to a specific range, whereby The shiny surface is in a surface state excellent in adhesion to the insulating substrate, and the deposited surface is in a surface state excellent in adhesion of the solder resist. As a result, the circuit formation property and the solder resist adhesion can be achieved. Several embodiments of the invention.

In other words, the electrodeposited copper foil according to the embodiment of the present invention has a shiny surface and a precipitated surface, and has a roughened layer on the glossy surface side, and the root mean square height Sq of the shiny surface is 0.550 μm or less, and the deposition surface side satisfies the lower side. At least one of the conditions stated:

(a) Surface roughness Sa is 0.115 μm or more

(b) The root mean square height Sq is 0.120 μm or more

(c) The maximum peak height Sp is 0.900 μm or more

(d) The maximum valley depth Sv is 0.600 μm or more

(e) The maximum height Sz is 1.500 μm or more

(f) The kurtosis Sku is 2.75 or more and 4.00 or less

(g) The skewness Ssk is 0.00 or more and 0.35 or less.

Further, the electrodeposited copper foil according to another embodiment of the present invention has a shiny surface and a precipitated surface, and has a roughened layer on the shiny side, and the surface roughness Sa on the shiny side is 0.470 μm or less, and the deposited surface side Meet at least one of the following conditions:

(a) Surface roughness Sa is 0.115 μm or more

(b) The root mean square height Sq is 0.120 μm or more

(c) The maximum peak height Sp is 0.900 μm or more

(d) The maximum valley depth Sv is 0.600 μm or more

(e) The maximum height Sz is 1.500 μm or more

(f) The kurtosis Sku is 2.75 or more and 4.00 or less

(g) The skewness Ssk is 0.00 or more and 0.35 or less.

Further, the electrodeposited copper foil according to another embodiment of the present invention has a shiny surface and a precipitated surface, and has no roughening treatment layer on the gloss surface side, and the surface roughness Sa on the gloss surface side is 0.270 μm or less. The side meets at least one of the following conditions:

(a) Surface roughness Sa is 0.115 μm or more

(b) The root mean square height Sq is 0.120 μm or more

(c) The maximum peak height Sp is 0.900 μm or more

(d) The maximum valley depth Sv is 0.600 μm or more

(e) The maximum height Sz is 1.500 μm or more

(f) The kurtosis Sku is 2.75 or more and 4.00 or less

(g) The skewness Ssk is 0.00 or more and 0.35 or less.

Further, the electrodeposited copper foil according to another embodiment of the present invention has a shiny surface and a precipitated surface, and has no roughening treatment layer on the glossy surface side, and the root mean square height Sq of the gloss surface side is 0.315 μm or less, and the precipitation is performed. The face side satisfies at least one of the following conditions:

(a) Surface roughness Sa is 0.115 μm or more

(b) The root mean square height Sq is 0.120 μm or more

(c) The maximum peak height Sp is 0.900 μm or more

(d) The maximum valley depth Sv is 0.600 μm or more

(e) The maximum height Sz is 1.500 μm or more

(f) The kurtosis Sku is 2.75 or more and 4.00 or less

(g) The skewness Ssk is 0.00 or more and 0.35 or less.

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-described electrolytic copper foil.

Further, 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 an insulating substrate to form a copper clad laminate, and then adding, subtracting, and partially adding the copper clad laminate. The circuit is formed by either the method of forming or improving the semi-additive method.

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, the printed wiring board is used.

According to some embodiments of the present invention, an electrolytic copper foil excellent in circuit formability and adhesion of a solder resist can be provided. Further, according to some embodiments of the present invention, a copper clad laminate for an electrolytic copper foil excellent in circuit formability and solder resist adhesion, a printed wiring board, a method for producing the same, and an electronic device and a method of manufacturing the same can be provided .

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

Hereinafter, an embodiment of the electrolytic copper foil of the present invention will be described.

The electrolytic copper foil according to the embodiment of the present invention has a shiny surface and a deposited surface.

Here, in the present specification, "electrolytic copper foil" means a copper foil and a copper alloy foil produced by using an electrolytic drum by the principle of electroplating.

In addition, in the present specification, the "glossy surface of the electrolytic copper foil" means the surface (shiny surface: S surface) on the side of the drum when the electrolytic copper foil is produced, and the "precipitation surface of the electrolytic copper foil" Refers to the surface (mat face: M side) opposite to the drum when the electrolytic copper foil is produced.

In addition, in the present specification, the "surface roughness Sa of the glossy side" and the root mean square height Sq of the glossy side are provided with a roughened layer and/or surface on the shiny side of the electrolytic copper foil (raw foil). In the case of treating the layer, it means the surface roughness Sa and the root mean square height Sq of the surface (the outermost surface) after the layer is disposed, respectively. In addition, the "surface roughness Sa of the glossy surface" and the root mean square height Sq of the glossy surface mean the surface of the glossy surface before the roughening treatment layer and/or the surface treatment layer (the outermost layer) Surface roughness Sa and root mean square height Sq.

In addition, in the present specification, "surface roughness Sa on the deposition surface side", "root mean square height Sq on the deposition surface side", "maximum peak height Sp on the deposition surface side", and "maximum valley depth Sv on the deposition surface side" The "maximum height Sz" on the side of the deposition surface, the kurtosis Sku on the side of the deposition surface, and the skewness Ssk on the side of the precipitation surface are provided on the deposition surface of the electrolytic copper foil (raw foil). In the case of the surface treatment layer, it means the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, respectively, of the surface (the outermost surface) after the layer is disposed. Kurtosis Sku and skewness Ssk.

<Electrochemical copper foil having no roughened layer on the glossy side>

In one aspect, the electrolytic copper foil according to the embodiment of the present invention does not have a roughened layer on the glossy side, and the surface roughness Sa on the glossy side is 0.270 μm or less and/or the root mean square height Sq of the glossy side. It is 0.315 μm or less.

Here, in the present specification, the "surface roughness Sa" is a parameter indicating the roughness of the three-dimensional expansion of Ra, and represents an average value of the absolute values of the height differences of the respective points with respect to the average surface of the surface. In addition, the "root mean square height Sq" is a parameter indicating the roughness of the three-dimensional expansion of Rq, indicating the standard deviation of the distance from the average surface of the surface.

By controlling the surface roughness Sa of the glossy side and/or the root mean square height Sq of the glossy side to the above range, the adhesion to the insulating substrate is improved, and the distance between the circuits formed using the electrolytic copper foil is It is possible to achieve 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 shiny side of the electrolytic copper foil is preferably 0.230 μm or less, more preferably 0.180 μm or less, still more preferably 0.150 μm or less, and most preferably 0.133, from the viewpoint of improving the effect of the fine pitch. Below μm. Further, the lower limit of the surface roughness Sa of the shiny side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.100 μm or more.

In addition, the root mean square height Sq of the shiny side of the electrolytic copper foil is preferably 0.200 μm or less, and more preferably 0.180 μm or less from the viewpoint of improving the effect of the fine pitch. Further, the lower limit of the root mean square height Sq of the shiny side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.100 μm or more.

<Electrochemical copper foil having a roughened treatment layer on the glossy side>

In another aspect, the electrolytic copper foil according to the embodiment of the present invention has a roughened layer on the glossy side, and the surface roughness Sa on the glossy side is 0.470 μm or less and/or the root mean square height Sq on the glossy side. It is 0.550 μm or less.

In general, the electrodeposited copper foil having the roughened layer on the shiny side has a fine pitch reduction, but the surface roughness of the glossy side and/or the root mean square height Sq of the glossy side are controlled to In the above range, the adhesion to the insulating substrate is improved, and the distance between the circuits formed using the electrolytic copper foil can be L/S (line/gap) = 22 μm or less / 22 μm or less, preferably 20 μm or less / 20 μm or less. The micro pitch.

The surface roughness Sa of the shiny side of the electrolytic copper foil is preferably 0.385 μm or less, more preferably 0.380 μm or less, still more preferably 0.355 μm or less, and still more preferably 0.340, from the viewpoint of improving the effect of the fine pitch. It is preferably not more than 0.3 m, more preferably 0.300 μm or less, further preferably 0.295 μm or less, further preferably 0.230 μm or less, and most preferably 0.200 μm or less. Further, the lower limit of the surface roughness Sa of the shiny side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.100 μm or more.

In addition, the root mean square height Sq of the shiny side of the electrolytic copper foil is preferably 0.490 μm or less, more preferably 0.450 μm or less, still more preferably 0.435 μm or less, from the viewpoint of improving the effect of the fine pitch. It is 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. Further, the lower limit of the root mean square height Sq of the shiny side of the electrolytic copper foil is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, more preferably 0.050 μm or more, and still more preferably 0.100 μm or more.

The electrolytic copper foil of the embodiment of the present invention having the surface roughness Sa and/or the root mean square height Sq of the glossy surface side as described above can be provided with a roughening treatment layer and/or a surface treatment layer by controlling the gloss side. Obtained from the surface roughness Sa of the front gloss surface 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 gloss surface before the roughening treatment layer and/or the surface treatment layer is provided on the gloss side is preferably controlled to 0.270 μm or less. The thickness is preferably 0.230 μm or less, more preferably 0.180 μm or less, further preferably 0.150 μm or less, further preferably 0.133 μm or less, and further preferably 0.130 μm or less, and most preferably 0.120 μm or less. Further, the lower limit of the surface roughness Sa of the shiny surface before the roughening treatment layer and/or 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, and more preferably 0.050. It is preferably μm or more, and more preferably 0.100 μm or more.

By controlling the surface roughness Sa of the shiny surface before the roughening treatment layer and/or the surface treatment layer on the glossy side to the above range, the gloss side after the roughening treatment layer and/or the surface treatment layer is provided Since the surface roughness Sa and/or the root mean square height Sq are controlled to the above range, L/S (line/gap) = 22 μm or less / 22 μm or less can be realized with respect to the distance between circuits formed using the electrolytic copper foil. It is a fine pitch of 20 μm or less / 20 μm or less.

In addition, 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 roughening treatment layer and/or the surface treatment layer is provided on the glossy surface side is preferably controlled to 0.315 μm or less. More preferably, it is 0.292 μm or less, more preferably 0.230 μm or less, further preferably 0.200 μm or less, further preferably 0.180 μm or less, and 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 roughening treatment layer and/or the surface treatment layer is provided on the shiny side is not particularly limited, but is generally 0.001 μm or more, preferably 0.010 μm or more, and more preferably It is 0.050 μm or more, and more preferably 0.100 μm or more.

By setting the root mean square height Sq of the glossy surface before the roughening treatment layer and/or the surface treatment layer on the glossy side to the above range, the gloss surface after the roughening treatment layer and/or the surface treatment layer can be provided Since the surface roughness Sa and/or the root mean square height Sq of the side are controlled to the above range, L/S (line/gap) = 22 μm or less / 22 μm or less, and more, can be realized with respect to the distance between circuits formed using the electrolytic copper foil. It is preferably a fine pitch of 20 μm or less / 20 μm or less.

In the electrodeposited copper foil according to the embodiment of the present invention, the deposition surface side satisfies at least one of the following conditions:

(a) Surface roughness Sa is 0.115 μm or more

(b) The root mean square height Sq is 0.120 μm or more

(c) The maximum peak height Sp is 0.900 μm or more

(d) The maximum valley depth Sv is 0.600 μm or more

(e) The maximum height Sz is 1.500 μm or more

(f) The kurtosis Sku is 2.75 or more and 4.00 or less

(g) The skewness Ssk is 0.00 or more and 0.35 or less.

When the deposition surface side satisfies at least one of the above conditions, the surface on the deposition surface side has an appropriate roughness, and as a result, the adhesion of the solder resist can be improved.

Here, in the present specification, "maximum peak height Sp" means the maximum value of the height from the average surface of the surface. Further, the "maximum valley depth Sv" represents the absolute value of the minimum value of the height from the average surface of the surface. In addition, the "maximum height Sz" represents the distance from the highest point to the lowest point of the surface. In addition, "kurtness Sku" indicates the sharpness of the height distribution. When Sku=3, it indicates that the height distribution is a normal distribution. When Sku>3, it indicates that there are many sharp peaks or valleys on the surface. When Sku<3, Indicates that the surface is flat. In addition, the "skewness Ssk" indicates the symmetry of the height distribution. When Ssk=0, it indicates that the height distribution is vertically symmetrical. When Ssk>0, it indicates that the surface of the small peak is large. When Ssk<0, it indicates smallness. The surface of the valley is more.

From the viewpoint of stably ensuring the adhesion of the solder resist, the deposition surface side preferably satisfies at least two conditions, more preferably satisfies at least three conditions, and further preferably satisfies at least four conditions, and further preferably In order to satisfy at least 5 conditions, it is preferable to satisfy at least 6 conditions, and it is preferable to satisfy all of the 7 conditions.

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

The root mean square height Sq of the deposition surface side is preferably 0.130 μm or more, more preferably 0.140 μm or more, and still more preferably 0.150 μm or more from the viewpoint of stably ensuring the adhesion of the solder resist. Further, the upper limit of the root mean square height Sq on the deposition surface side is not particularly limited, but is generally 2.000 μm or less, preferably 1.800 μm or less, more preferably 1.500 μm or less, and most preferably 1.300 μm or less.

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

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

The maximum height Sz of the deposition surface side is preferably 1.800 μm or more, more preferably 1.000 μm or more, further preferably 2.000 μm or more, and most preferably 2.200 μm or more from the viewpoint of stably ensuring the adhesion of the solder resist. Further, the upper limit of the maximum height Sz on the deposition surface side is not particularly limited, but is generally 20.000 μm or less, preferably 18.000 μm or less, more preferably 15.000 μm or less, and most preferably 14.000 μm or less.

The kurtosis Sku of the deposition surface side is preferably 2.80 or more and 4.00 or less, more preferably 2.85 or more and 3.90 or less, and further preferably 2.90 or more and 3.80 or less from the viewpoint of stably ensuring the adhesion of the solder resist.

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

The electrolytic copper foil according to the embodiment of the present invention which satisfies the conditions of the deposition surface side as described above can be controlled by the manufacturing conditions of the electrolytic copper foil (for example, the linear velocity of the electrolytic solution, the current density, the concentration of the component added to the electrolytic solution, etc.) ) and get.

The electrolytic copper foil according to the embodiment of the present invention preferably has a tensile strength at room temperature of 30 kg/mm ² or more. Here, in the present specification, "normal temperature tensile strength" means tensile strength at room temperature, which means measured according to IPC-TM-650. When the tensile strength at normal temperature is 30 kg/mm ² or more, there is an effect that wrinkles are less likely to occur during handling. From the viewpoint of stably obtaining this effect, the normal temperature tensile strength is more preferably 35 kg/mm ² or more.

The electrolytic copper foil according to the embodiment of the present invention preferably has a room temperature elongation of 3% or more. Here, in the present specification, "normal temperature elongation" means an elongation at room temperature, which means that it is measured in accordance with IPC-TM-650. If the room temperature elongation is 3% or more, there is an effect that it 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 tensile strength of 10 kg/mm ² or more. In the present specification, "high temperature tensile strength" means a tensile strength at 180 ° C, which means that it is measured in accordance with 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. In the present specification, "high temperature elongation" means an elongation at 180 ° C, which means that it is measured in accordance with 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.

Examples of the copper and copper alloy which are the raw materials of the electrolytic copper foil (raw foil) according to the embodiment of the present invention include pure copper; Sn-doped copper; Ag-doped copper; and Ti, W, Mo, Cr, Zr, and Mg are added. , copper alloys such as Ni, Sn, Ag, Co, Fe, As, P, and the like. For example, an electrolytic copper foil formed of a copper alloy may be added with an alloying element by an electrolytic solution used in the production of an electrolytic copper foil (for example, selected from the group consisting of Ti, W, Mo, Cr, Zr, Mg, Ni, Sn, Ag, Manufactured from one or more of the group consisting of Co, Fe, As, and 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 further It is preferably 3.0 μm to 75 μm, more preferably 4 μm to 40 μm, further preferably 5 μm to 37 μm, further preferably 6 μm to 28 μm, further preferably 7 μm to 25 μm, and most preferably 8 μm. 19 μm.

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

The electrolytic copper foil (raw foil) is produced by analyzing copper electricity from a copper sulfate plating bath onto a drum made of titanium or stainless steel. Hereinafter, an example of electrolysis conditions will be described.

(electrolysis conditions)

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

Current density: 30~120A/dm ²

Electrolytic line flow rate: 1.5~5m/s

Electrolyte temperature: 50~60°C

Additive: 20~80ppm ppm of chloride ion, 0.01~5.0ppmppm of animal 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 mentioned.

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 of the surface of the drum Sa is set to 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 electrolysis drum having a specific surface roughness Sa and/or a root mean square height Sq on the surface can be produced in the following manner. First, the surface of a titanium or stainless steel drum is ground using a grinding belt having a particle size number of 300 (P300) to 500 (P500). At this time, the polishing tape is wound at a specific width in the width direction of the drum, and the polishing belt is moved in the width direction of the drum at a specific speed, and the drum is rotated to perform polishing. 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 passing through the surface of the drum (the position in the width direction) at one point in the first pass of the polishing belt and the number of passes. Further, the time during which one point of the surface of the drum passes through the first pass is set to a value obtained by dividing the width of the polishing belt by the moving speed of the rotating belt in the width direction of the rotating belt. In addition, the primary pass of the polishing tape means one end to the other end of the shaft (width) direction of the rotating cylinder (the width direction of the electrolytic copper foil), and the surface of the rotating cylinder in the circumferential direction is ground once with a polishing tape. That is, the polishing time is represented by the following formula.

Grinding time (minutes) = width of grinding belt per pass (cm/time) / moving speed of grinding belt (cm/min) × number of passes (times)

In the manufacture 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 set to 3.5 minutes to 10 minutes, and in the embodiment of the present invention, In the case where 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 polishing belt has a width of 10 cm and the moving speed is 20 cm/min, the polishing time of one turn of the surface of the drum is 0.5 minute. It can be calculated by multiplying the total number of passes by the polishing time (for example, 0.5 minute × 10 passes = 5 minutes). The surface roughness 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. Degree Sa and the root mean square height Sq of the drum surface. Conversely, the surface of the drum surface can be increased by reducing the number of grain of the abrasive belt, and/or reducing the rotational speed of the surface of the drum, and/or shortening the grinding time, and/or drying the surface of the drum during grinding. The roughness Sa and the root mean square height Sq of the surface of the drum. Further, by extending the polishing time, the surface roughness Sa can be reduced, and the root mean square height Sq can be reduced to a greater extent than Sa. 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 greater extent than the surface roughness Sa becomes larger. Further, the particle size number of the above-mentioned abrasive tape means the particle size of the abrasive for the abrasive tape. Further, 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 grinding, the root mean square height Sq can be reduced, and the surface roughness Sa can be reduced to a greater extent than the root mean square height Sq becomes smaller. On the other hand, by drying the surface of the drum during grinding, the root mean square height Sq can be increased, and the surface roughness Sa can be increased to a greater extent than the root mean square height Sq.

By using an electrolytic drum having a specific surface roughness Sa and/or a root mean square height Sq as described above, a surface roughness Sa and/or a root mean square height having a specific glossy surface can be produced. Sq 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.

‧ The swollen resin film is brought into contact with the surface of the electrolysis drum, and after the acetone is volatilized from the resin film, the resin film is peeled off, and a replica of the surface of the electrolysis drum is collected.

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

Further, 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.

On the other hand, in order to at least one of the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk on the deposition surface side of the electrolytic copper foil. The control is a specific range, and it is only necessary to adjust the linear velocity of the electrolyte, the current density, and the concentration of the component added to the electrolyte.

In general, the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk of the deposition surface side of the electrolytic copper foil are to be increased. In the case of a value, it is only necessary to reduce the linear flow rate of the electrolyte, or to increase the current density, or to increase the concentration of chloride ions in the electrolyte, or to increase the concentration of the animal glue in the electrolyte in the range of 0 to several ppm, or It is sufficient to add an additive having an effect of increasing the surface roughness to the electrolytic solution. Further, the above value tends to increase as the roughness of the electrolytic drum to be used becomes larger.

On the other hand, in order to reduce the surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the kurtosis Sku, and the skewness Ssk of the deposition surface side of the electrolytic copper foil, In this case, an additive having a function of smoothing the electrolytic copper foil is added, or the concentration of the chloride ion in the electrolytic solution is lowered to 0 or extremely low, or the concentration of the animal glue in the electrolytic solution is increased in a range of 10 ppm or more. Just fine. Further, the above value tends to decrease as the roughness of the electrolytic drum to be used becomes smaller.

<Coarsening and surface treatment>

The surface treatment is not particularly limited, and examples thereof include heat-resistant treatment, rust-preventing treatment, chromate treatment, and decane coupling treatment.

Here, 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 is treated by rust prevention. The layer formed is referred to as a "rust-proof layer", and the layer formed by the chromate treatment is referred to as a "chromate treatment layer", and the layer formed by the coupling treatment of decane is referred to as a "decane coupling treatment layer". .

In order to improve the adhesion to the insulating substrate (resin substrate), at least one surface of the shiny surface and the deposited surface of the electrolytic copper foil according to the embodiment of the present invention may be provided with a roughened layer. The roughening treatment is not particularly limited, and it can be carried out by electrodepositing the roughened particles onto the surface of the electrolytic copper foil. For example, it is only necessary to electrodeposit the roughened particles of copper or copper alloy to the surface of the electrolytic copper foil. The roughened particles may be fine, and the shape may be needle-shaped, rod-shaped or particulate. The roughening treatment layer may be composed of any element 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 elemental substances. Layers, etc. Further, after the roughened particles of copper or a copper alloy are electrodeposited, a roughening treatment may be further performed by further electrodepositing secondary particles or tertiary particles using a simple substance such as nickel, cobalt, copper or zinc or an alloy.

In the case of the roughening 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-coupled layer is formed on the surface.

When the roughening treatment as the surface treatment is not performed, 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 thereof.

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, but may be formed in a plurality of 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 of sulfuric acid-copper sulfate containing at least one selected from the group consisting of an alkyl sulfate salt, a tungsten ion, and an arsenic ion. The roughening treatment layer is preferably plated by an electrolytic bath composed of sulfuric acid-copper sulfate in order to prevent falling powder and to improve peeling strength.

The specific processing conditions are as follows.

(liquid 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

Plating time: 0.5~20 seconds

(liquid 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

In the case of forming a copper-cobalt-nickel alloy plating layer as a roughening layer, it is preferably made into a copper 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 / dm ² of Ni as the ternary 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 , it is not preferable in the case where the influence of magnetism is necessary, and there is a case where an etching spot is 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 spot" means that when etching is performed using copper chloride, Co remains without being dissolved. In addition, the "etching residue" means that when alkali etching is performed using ammonium chloride, Ni remains without being dissolved.

One of the plating baths and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating layer 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 plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating layer are 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 on the glossy surface side can be made small by shortening the plating time. On the other hand, in the surface treatment for forming the roughened layer, the surface roughness Sa and/or the root mean square height Sq on the glossy side 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 on the glossy surface side can be made smaller by increasing the current density and greatly shortening the plating time. On the other hand, in the process of forming the roughened layer, the surface roughness Sa and/or the root mean square height Sq on the glossy side can be made larger by increasing the current density and extending the plating time.

Further, a surface treatment layer may be provided on at least one of the shiny side and the deposited side of the electrodeposited copper foil according to the embodiment of the present invention. The surface treatment layer is not particularly limited, and is preferably one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. In general, when a roughened layer is formed on at least one of the shiny side and the deposited side of the electrolytic copper foil, a heat-resistant layer or a rust-preventing layer is formed on the surface thereof, and chromate treatment is formed thereon. The layer or decane coupling treatment layer.

In the electrodeposited copper foil according to the embodiment of the present invention, a resin layer may be provided on at least one side of the gloss side and the deposition side. The resin layer is generally formed on the roughened layer or the surface treated 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. In addition, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. An oxide, a nitride or a telluride of one or more elements of the group consisting of iron and strontium. Further, the heat-resistant layer and/or the rust-preventive layer may be a copper-zinc alloy layer, a zinc-nickel alloy layer, a nickel-cobalt alloy layer, a copper-nickel alloy layer, or a chromium-zinc alloy layer. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat resistant layer and/or the rustproof 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 layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 1.5 to 10. Further, the nickel content of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 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-preventive layer may be a nickel or nickel alloy layer having a content of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and a content of 1 mg/m. The tin layer of ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² , is sequentially laminated. 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-preventive layer preferably have a total content of nickel or a nickel alloy and tin of from 2 mg/m ² to 150 mg/m ² , more preferably from 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive 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 liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium (may be metals, alloys, oxides, nitrides, sulfides). Any form). Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromium treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Acid salt treatment layer, etc.

The decane coupling agent used for 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-glycidoxy propyl propylene can be used. Trimethoxy decane, 4-glycidyl butyl trimethoxy decane, γ-aminopropyl triethoxy decane, N-β-(aminoethyl)-γ-aminopropyltrimethoxy Decane, N-3-(4-(3-aminopropoxy)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-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane 3-(2-N-benzyl Aminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-aminopropyl) Trimethoxy decane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxy Baseline, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(Amino B And γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, and the like.

The decane coupling treatment layer is preferably 0.05 mg/m ² to 200 mg/m ² , more preferably 0.15 mg/m ² to 20 mg/m ² , still more preferably 0.3 mg/m ² in terms of ruthenium atom. Set within the range of ~2.0 mg/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 in a semi-hardened state (B-stage state) to be used next. The semi-hardened state (B-stage state) includes that the insulating resin layer can be stacked and stored even if it is touched by a finger, and the insulating resin layer can be stored in a state of hardening reaction.

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, polyurethane resin, and the like. These can be used individually or in mixture of 2 or more types.

The resin layer is composed of a 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) It is preferred to form a composition of 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. 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. 4,174,415, International Publication No. 2004/005588, Japanese Laid-Open Patent Publication No. 2006-257153, Japanese Laid-Open Patent Publication No. 2007-326923 Japanese Patent No. 50-249169, Japanese Patent No. 5024930, International Publication No. 2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. 2006/134868, Japanese Patent No. 5046927 Bulletin, 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 Substances (resin, resin curing agent, compound, hardening accelerator, and the like) disclosed in Japanese Laid-Open Patent Publication No. 2009/001850, International Publication No. 2009/145179, International Publication No. 2011/068157, and JP-A-2013-19056 It is formed by a method of forming a dielectric body, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like, and/or a resin layer.

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, a roughened layer or a surface by a known method such as a roll coating method. On the treatment layer, the solvent is removed by heating and drying as needed, thereby making it a B-stage state. Drying may be carried out, for example, using a hot air drying oven, and the drying temperature may be from 100 ° C to 250 ° C, preferably from 130 ° C to 200 ° C.

The electrolytic copper foil having a resin layer is used in such a manner that after the resin layer and the insulating substrate (resin substrate) are superposed, the entire resin layer is thermocompression bonded to thermally cure the resin layer, and thereafter, a specific wiring pattern is formed.

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 set to ensure the thickness of the interlayer insulation, or the copper-clad laminate can be produced even if the prepreg material is not used at all. Further, an insulating resin primer may be applied to the surface of the substrate to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the following advantages are obtained: the material cost of the prepreg material is saved, and the lamination step is also simplified, so that it is advantageous in the economical aspect, and is only equivalent to the prepreg material. 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 made thinner than 0.1 μm, the adhesion force is lowered, and when the electrodeposited copper foil with the resin layer is laminated on the substrate having the inner layer material without interposing the prepreg material, it is difficult to ensure The case of interlayer insulation between the circuit and the inner layer material. On the other hand, when the thickness of the resin layer is made thicker than 80 μm, it is difficult to form the resin layer of the target thickness by one application step, and the extra material cost and the number of steps are consumed, which is disadvantageous in terms of economy. Further, since the resin layer formed is inferior in flexibility, cracking or the like is likely to occur during handling, and excessive pressure of the resin may cause excessive resin flow during the thermal pressure bonding of the inner layer material to make it difficult to smoothly Laminated.

Further, as another form of the electrolytic copper foil with a resin layer, a resin layer in a semi-hardened state may be formed on a glossy surface or a surface treatment layer.

Further, the printed circuit board is completed by mounting the electronic component 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.

Further, an electronic device can be produced using a printed wiring board, or an electronic device can be manufactured using a printed circuit board on which electronic components are mounted, or an electronic device can be produced using a printed circuit board on which electronic components are 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 for producing a printed wiring board according to an embodiment of the present invention includes the steps of: forming a copper-clad laminate by laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate, and then improving the semi-additive method by a semi-additive method A circuit is formed by any of a partial addition method or a subtractive method. Here, the insulating substrate may be a circuit including an inner layer.

In the present specification, the "semi-additive method" means a method in which thin electroless plating is performed on an insulating substrate or a copper foil seed layer, and after forming a pattern, a conductor pattern is formed by plating and etching.

Therefore, the method for producing a printed wiring board according to an embodiment of the present invention using a semi-additive method includes the following steps: a step of laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate (resin substrate); a step of removing all of the electrolytic copper foil by etching or plasma etching using an etching solution such as an acid; a step of providing a via hole and/or a blind via a resin exposed by etching to remove the electrolytic copper foil; a step of desmear treatment in the region of the through hole and/or the blind hole; a step of providing an electroless plating layer on the resin and a region including the through hole and/or the blind hole; on the electroless plating layer a step of providing a plating resist layer; a step of removing the plating resist layer for forming a region of the circuit after exposing the plating layer; and a step of disposing the plating layer in a region where the plating resist layer is formed for forming the circuit; a step of removing the plating resist layer; and a step of removing the electroless plating layer located in a region other than the region where the circuit is formed by flash etching or the like.

In another aspect, the method for producing a printed wiring board according to an embodiment of the present invention using a semi-additive method includes the steps of: laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; and electrolytic copper foil and a step of providing a through hole and/or a blind hole in an insulating substrate (resin substrate); a step of removing a slag treatment on a region including the through hole and/or the blind hole; etching or plasma etching using an etching solution using an acid or the like a step of removing all of the electrolytic copper foil; a step of providing an electroless plating layer on a resin exposed by removing the electrolytic copper foil by etching or the like, and a region including the through hole and/or the blind hole; and electroless plating a step of providing a plating resist layer on the layer; a step of removing the plating resist layer for forming a region of the circuit after exposing the plating layer; and providing a plating layer in a region where the plating resist layer is formed to form a circuit a step of removing the plating resist layer; and a step of removing the electroless plating layer located in a region other than the region where the circuit is formed by rapid etching or the like.

In another aspect, the method for producing a printed wiring board according to an embodiment of the present invention using a semi-additive method includes the steps of: laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; and electrolytic copper foil and a step of providing a through hole and/or a blind hole in an insulating substrate (resin substrate); a step of removing all of 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 performing desmear treatment; a step of providing an electroless plating layer on a resin exposed by removing the electrolytic copper foil by etching or the like, and a region including the via hole and/or the blind hole; and electroless plating a step of providing a plating resist layer on the layer; a step of removing the plating resist layer for forming a circuit region after exposing the plating layer; and providing a plating layer in a region where the plating resist layer is formed to form a circuit a step of removing the plating resist layer; and a step of removing the electroless plating layer located in a region other than the region where the circuit is formed by rapid etching or the like.

In another aspect of the method for producing a printed wiring board according to an embodiment of the present invention using a semi-additive method, the step of laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; using acid or the like a step of removing all of the electrolytic copper foil by etching or etching of the etching solution; a step of providing an electroless plating layer on the surface of the resin exposed by removing the electrolytic copper foil by etching; on the electroless plating layer a step of providing a plating resist layer; a step of removing the plating resist layer for forming a region of the circuit after exposing the plating layer; and a step of disposing the plating layer in a region where the plating resist layer is formed for forming the circuit; a step of removing the plating resist layer; and a step of removing the electroless plating layer and the electrolytic copper foil located 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 the non-circuit forming portion with a plating resist layer, and performing thick copper plating on the circuit forming portion by electroplating. After the layer, the resist is removed, and the electrolytic copper foil other than the circuit forming portion is removed by (rapid) etching, whereby an electric circuit is formed 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 includes the following steps: a step of laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; 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 region including the through hole and/or the blind hole; and providing an electroless plating on the region including the through hole and/or the blind hole a step of layering; a step of providing a plating resist layer on the electrolytic copper foil; a step of forming a circuit by electroplating after the plating resist layer is provided; a step of removing the plating resist layer; and removing the plating resist by rapid etching The step of removing the electrolytic copper foil exposed by the coating.

In another aspect, the method for producing a printed wiring board according to an embodiment of the present invention using the modified semi-additive method includes the steps of: laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; and electrolytic copper foil a step of providing a plating resist layer; a step of removing the plating resist layer for forming a region after the plating layer is exposed; and a step of providing a plating layer for removing the plating layer from the region for forming the circuit a step of removing the plating resist layer; and a step of removing the electroless plating layer and the electrolytic copper foil located 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 of providing a catalyst core on a substrate formed by providing a conductor layer, a hole formed by a via hole or a via hole as needed. And etching to form a conductor circuit, and if necessary, providing a solder resist or a plating resist layer, and then performing thick plating on a conductor circuit, a via hole, a via hole, or the like by electroless plating treatment, thereby manufacturing printing Wiring board.

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

In the present specification, the "reduction method" means a method of selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like to form a conductor pattern.

Therefore, the method for producing a printed wiring board according to the embodiment of the present invention using the subtractive method includes the following steps: a step of laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; and an electrolytic copper foil and a step of providing a through hole and/or a blind hole in the insulating substrate; a step of removing the slag treatment on the area including the through hole and/or the blind hole; and providing an electroless plating layer on the area 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 an etching resistant layer on the surface of the electrolytic plating layer and/or the electrolytic copper foil; and a step of exposing the etching layer to form a circuit pattern; The step of forming an electric circuit by removing an electrolytic copper foil, an electroless plating layer, and the above electrolytic plating layer by etching or plasma etching using an etching solution such as an acid; and removing the etching resistant layer.

In another aspect, the method for producing a printed wiring board according to the embodiment of the present invention using the subtractive method includes the steps of: laminating an electrolytic copper foil according to an embodiment of the present invention and an insulating substrate; 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 on which the mask is not formed; and providing an anti-reflection on the surface of the electrolytic plating layer and/or the electrolytic copper foil a step of etching a layer; a step of exposing the etching layer to form a circuit pattern; and removing the electrolytic copper foil and the electroless plating layer by etching or plasma etching using an acid or the like to form a circuit And the step of removing the anti-etching layer.

Further, 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 18, Comparative Examples 1 and 2)

Prepare a titanium 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 electrolysis drum was ground using the polishing tape of the number of the grain numbers described in Table 1. At this time, the polishing tape is wound at a specific width in the width direction of the drum, and the polishing belt is moved in the width direction of the drum, and the drum is rotated to perform 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 a product of the time passing through one point of the surface of the drum and the number of passes in one pass obtained by the width of the polishing tape and the moving speed of the polishing tape. Here, the primary pass of the polishing tape means one end portion to the other end portion in the axial direction (the width direction of the electrolytic copper foil), and the surface in the circumferential direction of the rotary cylinder is polished once by the polishing tape. That is, the polishing time is expressed by the following formula.

Grinding time (minutes) = width of grinding belt per pass (cm/time) / moving speed of grinding belt (cm/min) × number of passes (times)

Next, the electrolysis drum is placed in an electrolytic cell, and electrodes are disposed around the electrolysis drum with a specific interelectrode distance therebetween. Next, electrolysis was carried out in an electrolytic cell under the following conditions, and the electrolysis drum was rotated to deposit copper on the surface of the electrolysis drum until it became the thickness described in Table 2.

<Electrolysis conditions>

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

Current density: 90A/dm ²

Electrolyte flow rate: 2.0m / sec

Electrolyte temperature: 60 ° C

Additive: 60 ppm by mass of chloride ion, animal glue (in Examples 1, 2, 5, 6 and 10 to 12, and Comparative Example 1, set to 0.02 ppm, in Examples 3, 4, 7 to 9 and In 13~18, it is set to 4.5ppm).

In Comparative Example 2, electrolysis was carried out under the following conditions to deposit copper on the surface of the electrolysis drum until it became the thickness described in Table 2.

<Electrolysis conditions>

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

Current density: 10~80A/dm ²

Electrolyte flow rate: 1.5~5m/sec

Electrolyte temperature: 50~60°C

Additive: 10 to 100 ppm by mass of chloride ion, 10 to 100 ppm by mass of bis(3-sulfopropyl) disulfide, and 10 to 100 ppm by mass of a tertiary amine compound.

Further, the following compounds were used as the above tertiary amine compound.

In the above chemical formula, R ₁ and R _{2 are} both a methyl group. Further, the above tertiary amine compound can be obtained, for example, by mixing a certain amount of Denacol Ex-314 and dimethylamine manufactured by Nagase Co., Ltd., and reacting at 60 ° C for 3 hours.

Next, the copper which was deposited on the surface of the rotating electrolytic drum was peeled off, and the electrolytic copper foil was continuously produced.

With respect to Examples 1 to 4 and 10 and Comparative Examples 1 and 2, the following (1) to (4) were sequentially applied to the surface (glossy surface) on the side of the electrolytic drum of the electrolytic copper foil (raw foil) produced as described above. ) The processing shown. Further, in Examples 1 and 2 and Comparative Examples 1 and 2, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced as described above was sequentially subjected to the following (2)~ (4) The processing shown. In addition, in the example 10, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced as described above was sequentially subjected to the treatments shown in the following (1) to (4). In addition, in the third embodiment, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced as described above was subjected to the treatment shown in the following (3). In addition, in the fourth embodiment, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced as described above was subjected to the treatment shown in the following (4).

(1) roughening treatment

The roughened particles are electrodeposited to the surface using a copper roughening plating bath described below composed of Cu, H ₂ SO ₄ , As, and W.

(liquid composition 1)

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 condition 1)

Current density: 70A/dm ²

Plating time: 2 seconds

(liquid composition 2)

CuSO ₄ ‧5H ₂ O: 240g/L

H ₂ SO ₄ : 120g/L

(plating condition 2)

Temperature: 55 ° C

(current condition 2)

Current density: 20A/dm ²

Plating time: 7 seconds

(2) Barrier treatment (heat treatment)

Nickel-zinc alloy plating is performed.

(liquid composition)

Ni: 13g/L

Zn: 5g/L

pH: 2

(plating conditions)

Temperature: 40 ° C

Current density: 8A/dm ²

(3) chromate treatment

Treatment with zinc chromate.

(liquid composition)

CrO ₃ : 2.5g / L

Zn: 0.7g/L

Na ₂ SO ₄ : 10g/L

pH: 4.8

(zinc chromate condition)

Temperature: 54 ° C

Current density: 0.7A/dm ²

(4) decane coupling treatment

(liquid composition)

Tetraethoxydecane content: 0.4 vol%

pH: 7.5

Coating method: spray of solution

In the examples 5 to 8 and 14 to 18, the surface (glossy surface) on the side of the electrolysis cylinder of the electrolytic copper foil (raw foil) produced as described above was sequentially subjected to the following (1) to (5). deal with. In addition, in the examples 5 to 8 and 15 to 18, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced as described above was sequentially subjected to the following (2) to (5). ) The processing shown. Further, in Example 14, the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced in the above manner was subjected to the treatments shown in the following (4) and (5) in order.

(1) roughening treatment

In order to electrodeposit the roughened particles of the ternary copper-cobalt-nickel alloy plating to the surface, the roughening treatment was carried out under the following plating bath and plating conditions.

Plating bath composition: 16g/L of Cu, 10g/L of Co, 10g/L of Ni

pH: 1~4

Temperature: 30 ° C

Current density: 30A/dm ²

Plating time: 2 seconds

(2) Heat treatment

Co-Ni alloy plating was performed. The Co-Ni alloy plating conditions are described below.

(electrolyte composition)

Co: 10g/L

Ni: 20g/L

pH: 1.0~3.5

(electrolyte temperature)

35°C

(current condition)

Current density: 10A/dm ²

Plating time: 1 second

(3) Anti-rust treatment

Zinc-nickel alloy plating is performed.

(liquid composition)

Ni: 15g/L

Zn: 50g/L

pH: 3~4

(plating conditions)

Temperature: 50 ° C

Current density: 0.3A/dm ²

Plating time: Examples 5 and 8 are 2.43 seconds, Example 6 is 2.61 seconds, Example 7 is 2.32 seconds, and Examples 14 to 18 are 0.5 to 5 seconds.

(4) chromate treatment

Treatment with zinc chromate.

(liquid composition)

CrO ₃ : 2.5g / L

Zn: 0.7g/L

Na ₂ SO ₄ : 10g/L

pH: 4.8

(zinc chromate condition)

Temperature: 54 ° C

Current density: 0.7A/dm ²

(5) decane coupling treatment

(liquid composition)

N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane content: 0.4 vol%

pH: 7.5

Coating method: spray of solution

In the ninth embodiment, the surface (gloss surface) on the electrorotation drum side and the surface (precipitation surface) opposite to the electrolysis drum side of the electrolytic copper foil (raw foil) produced in the above manner were sequentially subjected to the following (1). ~(3) shows the processing.

(1) Barrier treatment (heat treatment)

Nickel-zinc alloy plating is performed.

(liquid composition)

Ni: 13g/L

Zn: 5g/L

pH: 2

(plating conditions)

Temperature: 40 ° C

Current density: 8A/dm ²

(2) chromate treatment

Treatment with zinc chromate.

(liquid composition)

CrO ₃ : 2.5g / L

Zn: 0.7g/L

Na ₂ SO ₄ : 10g/L

pH: 4.8

(zinc chromate condition)

Temperature: 54 ° C

Current density: 0.7A/dm ²

(3) decane coupling treatment

(liquid composition)

Tetraethoxydecane content: 0.4 vol%

pH: 7.5

Coating method: spray of solution

After the above treatment, a resin layer was formed on the surface of the surface treatment layer under the following conditions.

(Resin Synthesis Example)

Add 3,4,3',4'-biphenyl to a 2-liter three-necked flask equipped with a stainless steel anchor stir bar, a nitrogen inlet pipe and a stopcock. 117.68 g (400 mmol) of tetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis(3-aminophenoxy)benzene, 4.0 g (40 mmol) of γ-valerolactone, and 4.8 g (60 mmol) of pyridine. 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were heated at 180 ° C for 1 hour and cooled to near room temperature, and then added 3,4,3',4'-biphenyl. 49.42g (100mmol) of tetracarboxylic dianhydride, 82.12g (200mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 200g of NMP, and 40g of toluene, mixed at room temperature After 1 hour, it was heated at 180 ° C for 3 hours to obtain a block copolymerized polyimine having a solid content of 38%. The block copolymerized polyimine is represented by the following formula (1): general formula (2) = 3:2, number average molecular weight: 70,000, and weight average molecular weight: 150,000.

The block copolymerized polyimine solution obtained in the synthesis example was further diluted with NMP to prepare a block copolymerized polyimine solution having a solid content of 10%. In the block copolymerized polyimine solution, the weight ratio of the solid component of bis(4-maleoximeiminophenyl)methane (BMI-H, KI formation) was set to 35, and the block copolymerization was carried out. The weight ratio of the solid content of the polyimine is set to 65 (that is, the weight of the solid component of the bis(4-methyleneiminephenyl)methane contained in the resin solution: the block copolymer contained in the resin solution The weight fraction of the solid content of the polyimine was 35:65), and the mixture was dissolved and mixed at 60 ° C for 20 minutes to prepare a resin solution. Thereafter, the resin solution was applied onto the surface of the surface treated layer of the electrolytic copper foil using a reverse roll coater, and dried at 120 ° C for 3 minutes at 160 ° C for 3 minutes in a nitrogen atmosphere, and finally 300. The electrolytic treatment was carried out for 2 minutes at ° C to prepare an electrolytic copper foil having a resin layer. Further, the thickness of the resin layer was set to 2 μm.

In the examples 11 to 13, the surface (glossy surface) on the side of the electrolysis drum of the electrolytic copper foil (raw foil) produced as described above was subjected to the roughening treatment shown in the following (1), and then sequentially carried out and carried out. Cases 5 to 8 and 14 are treated similarly to (2) to (5). Further, in Examples 11 to 13, the surface (glossy surface) of the electrolytic copper foil (raw foil) produced in the above manner opposite to the electrolytic drum side was sequentially carried out in the same manner as in Examples 5 to 8 (2) to (2) 5) The same process.

(1) roughening treatment

In order to electrodeposit the roughened particles of the ternary copper-cobalt-nickel alloy plating to the surface, the roughening treatment was carried out under the following plating bath and plating conditions.

Plating bath composition: 10~20g/L of Cu, 1~10g/L of Co, 1~10g/L of Ni

pH: 1~4

Temperature: 30~50°C

Current density: 30~45A/dm ²

Plating time: 0.1~1.5 seconds

2. Evaluation of electrolytic copper foil

<The surface roughness Sa and the root mean square height Sq of the glossy side and the glossy side

The surface roughness Sa and the root mean square height Sq on the shiny side and the glossy side are the shiny side of the electrolytic copper foil before and after the roughening treatment and/or the surface treatment, according to ISO-25178-2:2012, using Olympus Corporation The manufactured laser microscope OLS4100 (LEXT OLS 4100) was measured. At this time, with respect to the laser microscope, the measurement of the area of 200 μm × 1000 μm (specifically, 200,000 μm ² ) of three places using 50 times of the objective lens was performed, and the surface roughness Sa and the root mean square height Sq were calculated. The arithmetic mean of the surface roughness Sa and the root mean square height Sq obtained at three places is taken as the value 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 (in the case of a curved surface), plane correction is performed, and then the surface roughness Sa and the root mean square height Sq are calculated. Further, the ambient temperature at which the surface roughness Sa was measured by a laser microscope was set to 23 to 25 °C.

<surface roughness Sa, root mean square height Sq, maximum peak height Sp, maximum valley depth Sv, maximum height Sz, kurtosis Sku, and skewness Ssk> on the deposition surface side

The surface roughness Sa, the root mean square height Sq, the maximum peak height Sp, the maximum valley depth Sv, the kurtosis Sku, and the skewness Ssk on the deposition surface side are for the electrolytic copper foil after the roughening treatment and/or the surface treatment. The precipitate was measured according to ISO-25178-2:2012 using a laser microscope OLS4100 (LEXT OLS 4100) manufactured by Olympus. The measurement conditions at this time are the same as the measurement conditions of the surface roughness Sa and the root mean square height Sq on the shiny side and the shiny side.

<Normal temperature tensile strength, high temperature tensile strength>

For the electrolytic copper foil subjected to the roughening treatment and/or the surface treatment, the tensile strength at room temperature and the tensile strength at high temperature were measured in accordance with IPC-TM-650.

<normal temperature elongation, high temperature elongation>

For the electrolytic copper foil subjected to the roughening treatment and/or the surface treatment, the room temperature elongation and the high temperature elongation were measured in accordance with IPC-TM-650. Further, as described above, "high temperature tensile strength" means a tensile strength at 180 °C. In addition, "high temperature elongation" means an elongation at 180 °C.

<circuit formation>

The electrolytic copper foil subjected to the roughening treatment and/or the surface treatment is bonded to the bis-m-butylene diimide three from the gloss side by thermocompression bonding Resin prepreg. Thereafter, the electrodeposited copper foil bonded to the prepreg was etched from the side of the deposition surface until the thickness thereof was 9 μm. Then, an anti-etching layer is provided on the surface of the electrolytic copper foil after the etching, and exposure and development are performed to form a resist pattern. Thereafter, etching was performed using ferric chloride, and 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 obtained at 5 points was measured as a result. When the difference between the maximum value and the minimum value is 2 μm or less, it is judged that the circuit has good linearity and is set to ◎. In addition, when the difference between the maximum value and the minimum value is more than 2 μm and is 4 μm or less, it is set to ○. Further, when the difference between the maximum value and the minimum value exceeds 4 μm, it is set to ×.

<Adhesiveness of solder resist>

The adhesion of the solder resist is performed in the following manner. First, a solder resist (manufactured by Sun Ink Manufacturing Co., Ltd., trade name "PSR-4000AUS308") was applied to the deposition surface side of the electrolytic copper foil after the surface treatment, and then dried sequentially (80 ° C × 30 minutes). After the curing (150 ° C × 60 minutes) and the rear UV (high pressure mercury lamp, 1000 mJ / cm ² ), a resin layer (coating film) of a solder resist of 20 to 30 μm thick was formed, thereby preparing a test piece. Next, after the test piece was floated in a solder bath at 260 ° C for 20 seconds, it was taken out from the solder layer, and the expansion at the interface between the electrolytic copper foil and the solder resist (peeling of the electrolytic copper foil and the solder resist) was observed. . In this evaluation, in the area of 5% or more of the electrolytic copper foil, the interface discoloration caused by the expansion is set to × (failed), and the area of the electrolytic copper foil of 2% or more and less than 5% exists. The discoloration of the interface caused by the expansion is ○, and the interface discoloration caused by the expansion is not caused at all, or the interface discoloration due to the expansion in the area of less than 2% of the electrolytic copper foil is set to ◎. Conduct an evaluation.

The test conditions and test results are shown in Tables 2 and 3. Further, Fig. 1(a) is an SEM image of the shiny side of the electrolytic copper foil of Example 2 before the roughening treatment layer and the surface treatment layer were formed. Fig. 1(b) is an SEM image of the shiny side of the electrolytic copper foil of Example 10 before the roughening treatment layer and the surface treatment layer were formed.

<evaluation result>

The electrodeposited copper foil of Example 9 which does not have a roughened layer on the shiny side, has a surface roughness Sa of 0.270 μm or less and a root mean square height Sq of 0.315 μm or less on the gloss surface side, and the surface roughness on the deposition surface side. The degree Sa is 0.115 μm or more, the root mean square height Sq is 0.120 μm or more, the maximum peak height Sp is 0.900 μm or more, the maximum valley depth Sv is 0.600 μm or more, the maximum height Sz is 1.500 μm or more, and the kurtosis Sku is 2.75 or more. 4.00 or less, the skewness Ssk is 0.00 or more and 0.35 or less. Further, the electrodepositive properties of the electrodeposited copper foil and the solder resist are good. Further, the electrolytic copper foil was also excellent in normal temperature tensile strength, high temperature tensile strength, normal temperature elongation, and high temperature elongation.

In addition, the electrodeposited copper foils of Examples 1 to 8 and 10 to 14 having a roughened layer on the shiny side have a surface roughness Sa of 0.470 μm or less and a root mean square height Sq of 0.550 μm or less. The surface roughness Sa is 0.115 μm or more, the root mean square height Sq is 0.120 μm or more, the maximum peak height Sp is 0.900 μm or more, the maximum valley depth Sv is 0.600 μm or more, and the maximum height Sz is 1.500 μm or more. The kurtosis Sku is 2.75 or more and 4.00 or less, and the skewness Ssk is 0.00 or more and 0.35 or less. Further, the electrodepositive properties of the electrodeposited copper foil and the solder resist are good. Further, the electrolytic copper foil was also excellent in normal temperature tensile strength, high temperature tensile strength, normal temperature elongation, and high temperature elongation.

On the other hand, in the electrolytic copper foil of Comparative Example 1 having the roughened layer on the glossy side, the surface roughness Sa on the glossy side was more than 0.470 μm, and the root mean square height Sq was also more than 0.550 μm. Therefore, the circuit formation property of this electrolytic copper foil is inadequate.

In addition, the surface roughness Sa of the electrodeposited copper foil of Comparative Example 2 having a roughened layer on the shiny side was less than 0.115 μm, the root mean square height Sq was less than 0.120 μm, and the maximum peak height Sp was not reached. 0.900 μm, the maximum valley depth Sv is less than 0.600 μm, the maximum height Sz is less than 1.500 μm, and the kurtosis Sku is outside the range of 2.75 or more and 4.00 or less, and the skewness Ssk is outside the range of 0.00 or more and 0.35 or less. Therefore, the adhesion of the solder resist of the electrolytic copper foil is insufficient.

From the above results, according to the embodiment of the present invention, it is possible to provide an electrolytic copper foil excellent in circuit formability and adhesion of a solder resist. Further, according to the embodiment of the present invention, it is possible to provide a copper-clad laminate having an electrolytic copper foil excellent in circuit formability and solder resist adhesion, a printed wiring board, a method for producing the same, and an electronic device and a method for producing the same.

Claims (39)

 An electrolytic copper foil having a shiny surface and a precipitation surface, and having a roughened layer on the glossy surface side, wherein the root surface height Sq of the shiny surface is 0.550 μm or less, and the deposition surface side satisfies at least the following conditions One: (a) the surface roughness Sa is 0.115 μm or more, (b) the root mean square height Sq is 0.120 μm or more, (c) the maximum peak height Sp is 0.900 μm or more, and (d) the maximum valley depth Sv is 0.600 μm or more (e). The maximum height Sz is 1.500 μm or more. (f) The kurtosis Sku is 2.75 or more and 4.00 or less (g) The skewness Ssk is 0.00 or more and 0.35 or less.    The electrodeposited copper foil according to claim 1, wherein the deposition surface side satisfies at least one of the following conditions: (a) the surface roughness Sa is 0.120 μm or more, and (b) the root mean square height Sq is 0.130 μm or more. (c) maximum peak height Sp is 1.050 μm or more (d) maximum valley depth Sv is 0.740 μm or more (e) maximum height Sz is 1.800 μm or more (f) kurtosis Sku is 2.80 or more and 4.00 or less (g) skewness Ssk is 0.00 or more and 0.26 or less.    The electrodeposited copper foil according to claim 1 or 2, wherein the surface roughness Sa of the gloss surface side is 0.380 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 3, wherein the surface roughness Sa of the glossy surface side is 0.355 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 4, wherein the surface roughness Sa of the glossy surface side is 0.300 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 5, wherein the surface roughness Sa of the glossy surface side is 0.200 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 6, wherein the root mean square height Sq of the gloss side is 0.490 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 7, wherein the root mean square height Sq of the gloss side is 0.450 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 8, wherein the root mean square height Sq of the gloss side is 0.400 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 9, wherein the root mean square height Sq of the gloss side is 0.330 μm or less.    An electrolytic copper foil having a shiny surface and a precipitated surface, and having a roughened layer on the shiny side, wherein the surface roughness Sa of the shiny surface side is 0.470 μm or less, and the deposition surface side satisfies at least the following conditions. One: (a) the surface roughness Sa is 0.115 μm or more, (b) the root mean square height Sq is 0.120 μm or more, (c) the maximum peak height Sp is 0.900 μm or more, and (d) the maximum valley depth Sv is 0.600 μm or more (e). The maximum height Sz is 1.500 μm or more. (f) The kurtosis Sku is 2.75 or more and 4.00 or less (g) The skewness Ssk is 0.00 or more and 0.35 or less.    The electrodeposited copper foil according to claim 11, wherein the root mean square height Sq of the gloss side is 0.550 μm or less.    The electrodeposited copper foil according to any one of claims 1 to 12, wherein the surface roughness Sa of the gloss surface before the roughening treatment layer is provided on the gloss 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 gloss surface before the roughening treatment layer is provided on the gloss 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 roughening treatment layer is provided on the gloss surface 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 roughening treatment layer is provided on the gloss surface side is 0.120 μm or less.    An electrolytic copper foil having a glossy surface and a precipitation surface, and having no roughening treatment layer on the glossy surface side, and having a surface roughness Sa of 0.270 μm or less on the gloss surface side, wherein the deposition surface side satisfies the following conditions At least one of: (a) the surface roughness Sa is 0.115 μm or more, (b) the root mean square height Sq is 0.120 μm or more, (c) the maximum peak height Sp is 0.900 μm or more, and (d) the maximum valley depth Sv is 0.600 μm or more ( e) The maximum height Sz is 1.500 μm or more (f) The kurtosis Sku is 2.75 or more and 4.00 or less (g) The skewness Ssk is 0.00 or more and 0.35 or less.    The electrodeposited copper foil according to claim 17, wherein the root mean square height Sq of the gloss side is 0.315 μm or less.    An electrolytic copper foil having a glossy surface and a precipitation surface, and having no roughening treatment layer on the glossy surface side, wherein the root mean square height Sq of the gloss surface side is 0.315 μm or less, and the deposition surface side satisfies the following conditions At least one of: (a) the surface roughness Sa is 0.115 μm or more, (b) the root mean square height Sq is 0.120 μm or more, (c) the maximum peak height Sp is 0.900 μm or more, and (d) the maximum valley depth Sv is 0.600 μm or more. (e) The maximum height Sz is 1.500 μm or more (f) The kurtosis Sku is 2.75 or more and 4.00 or less (g) The skewness Ssk is 0.00 or more and 0.35 or less.    The electrodeposited copper foil according to any one of the preceding claims, wherein the deposition surface side satisfies at least one of the following conditions: (a) the surface roughness Sa is 0.120 μm or more (b) mean square The root height Sq is 0.130 μm or more, (c) the maximum peak height Sp is 1.050 μm or more, (d) the maximum valley depth Sv is 0.740 μm or more, (e) the maximum height Sz is 1.800 μm or more, and (f) the kurtosis Sku is 2.80 or more and 4.00. The following (g) skewness Ssk is 0.00 or more and 0.26 or less.    The electrodeposited copper foil according to any one of claims 17 to 20, wherein the surface roughness Sa of the glossy surface side is 0.150 μm or less.    The electrodeposited copper foil according to any one of claims 17 to 21, wherein the surface roughness Sa of the glossy surface side is 0.130 μm or less.    The electrodeposited copper foil according to any one of claims 17 to 22, wherein the root mean square height Sq of the gloss side is 0.200 μm or less.    The electrodeposited copper foil according to any one of claims 17 to 23, wherein the root mean square height Sq of the gloss side is 0.120 μm or less.   The electrolytic copper foil according to any one of claims 1 to 24, which has a tensile strength at room temperature of 30 kg/mm ² or more.  The electrolytic copper foil according to any one of claims 1 to 25, which has a room temperature elongation of 3% or more.   The electrolytic copper foil according to any one of claims 1 to 26, 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 27, which has a high temperature elongation of 2% or more.    The electrodeposited copper foil according to any one of claims 1 to 28, which has a roughened layer on the side of the deposition surface.    The electrolytic copper foil according to any one of claims 1 to 16, wherein the roughening treatment layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc. Any of the constituents of the group or a layer composed of an alloy of any one or more of the simple substances.    The electrodeposited copper foil according to any one of claims 1 to 16, wherein the surface of the roughened layer on at least one of the shiny side and the deposited side of the electrodeposited copper foil has a surface selected from the group consisting of a heat-resistant layer, One or more surface treatment layers of the group consisting of a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer.    The electrodeposited copper foil according to any one of claims 1 to 3, wherein a resin layer is provided on at least one of a gloss side and a deposition surface side of the electrodeposited copper foil.    The electrodeposited copper foil according to claim 32, wherein the resin layer is provided on the roughened layer or the surface treated layer.    A copper clad laminate having the electrolytic copper foil according to any one of claims 1 to 33.    A printed wiring board having the electrolytic copper foil according to any one of claims 1 to 33.    A method of producing a printed wiring board using the electrolytic copper foil according to any one of claims 1 to 33.    A method of manufacturing a printed wiring board, comprising the steps of: laminating an electrolytic copper foil according to any one of claims 1 to 33 and an insulating substrate to form a copper clad laminate, and then semi-additively reducing The circuit is formed by any one of a method of forming, a partial addition, or a modified semi-additive.    An electronic machine having the printed wiring board of claim 35.    A method of manufacturing an electronic device using the printed wiring board of claim 35.