TWI526303B - Surface-processed copper foil, laminated circuit board, carrier copper foil, printed wiring board, printed circuit board, electronic machine and printed wiring board manufacturing method - Google Patents

Description

Surface-treated copper foil, laminated board, copper foil with carrier, printed wiring board, printed circuit board, electronic device, and printed wiring board manufacturing method

The present invention relates to a method of manufacturing a surface-treated copper foil, a laminated board, a copper foil with a carrier, a printed wiring board, a printed circuit board, an electronic device, and a printed wiring board.

Printed wiring boards have made significant progress in the past half century and are now used in almost all electronic machines. In recent years, the demand for miniaturization and high performance of electronic devices has increased, and high-density mounting of components and high-frequency signals have been developed, and high-frequency correspondence is required for printed wiring boards.

In order to ensure the quality of the output signal, it is required to reduce the transmission loss for the substrate for high frequency. The transmission loss mainly includes dielectric loss caused by the resin (substrate side) and conductor loss caused by the conductor (copper foil side). The dielectric constant and dielectric loss tangent of the resin are reduced, and the dielectric loss is reduced. In the high-frequency signal, the main reason for the conductor loss is that the higher the frequency, the smaller the cross-sectional area of the current flow due to the skin effect of the current flowing only on the surface of the conductor, and the higher the resistance.

As a technique for reducing the transmission loss of the high-frequency copper foil, for example, Patent Document 1 discloses a metal foil for a high-frequency circuit which is coated with silver or a silver alloy on one surface or both surfaces of a metal foil surface. A coating layer other than silver or a silver alloy is added to the silver or silver alloy coating layer in a thickness thinner than the thickness of the silver or silver alloy coating layer. Also, it is described that a metal can be provided Foil, which reduces the loss caused by the skin effect even in ultra-high frequency regions such as those used in satellite communications.

Further, Patent Document 2 discloses a roughened copper foil for roughening a high-frequency circuit, which is characterized in that (X) is obtained by X-ray diffraction in a rolling surface after recrystallization annealing of a rolled copper foil. The integral intensity of the surface (I(200)) is the integrated intensity (I ₀ (200)) of the (200) plane obtained by X-ray diffraction of the fine powder copper, which is I (200) / I ₀ (200 >40, the arithmetic mean roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment by the plating of the rolled surface is 0.02 μm to 0.2 μm, and the ten-point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm, which is a material for a printed circuit board. Further, it is described that a printed circuit board which can be used at a high frequency exceeding 1 GHz can be provided.

Further, Patent Document 3 discloses an electrolytic copper foil characterized in that one of the surfaces of the copper foil is an uneven surface having a surface roughness of 2 to 4 μm composed of a knob-like projection. Further, it is described that an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided.

[Patent Document 1] Japanese Patent No. 4161304

[Patent Document 2] Japanese Patent No. 4704025

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-244656

It is known that the conductor loss caused by the conductor (copper foil side) is caused by the increase of the resistance due to the skin effect as described above, and the resistance has not only the influence of the resistance of the copper foil itself but also the resistance of the surface treatment layer. The influence of the surface treatment layer is formed by roughening treatment on the surface of the copper foil in order to ensure adhesion to the resin substrate. Specifically, the roughness of the surface of the copper foil is a main factor of conductor loss, and roughness The smaller the transmission loss, the smaller the transmission loss.

The inventors further advance the relationship between the roughness of the surface of the copper foil and the transmission loss. After intensive research, it was found that the smaller the roughness of the surface of the copper foil, the less the transmission loss, especially if the roughness of the surface of the copper foil is reduced to some extent, the reduction of transmission loss and the roughness of the surface of the copper foil. The relationship has changed significantly, and it is difficult to reduce the transmission loss well by merely controlling the roughness of the surface of the copper foil.

An object of the present invention is to provide a surface-treated copper foil, a laminate, a copper foil with a carrier, a printed wiring board, a printed circuit board, an electronic device, and a printed wiring board which are excellent in suppressing transmission loss even when used for a high-frequency circuit board. method.

The inventors of the present invention have a significant change in the relationship between the decrease in transmission loss and the roughness of the surface of the copper foil if the roughness of the surface of the copper foil is reduced to some extent, and it is difficult to control the surface of the copper foil only by controlling the roughness of the surface of the copper foil. The reason for reducing the transmission loss was studied. It was found that the type of metal treated on the surface of the copper foil and its adhesion amount are other factors that affect the transmission loss, and these factors are controlled together with the roughness of the surface of the copper foil. A surface-treated copper foil which satisfactorily suppresses transmission loss even when used for a high-frequency circuit substrate can be obtained.

The present invention based on the above findings is a surface-treated copper foil formed with a surface treatment layer in which the x-axis is set as the total adhesion amount of Co, Ni, Fe, and Mo in the surface treatment layer (μg). /dm ² ), in the adhesion amount-surface roughness chart in which the y-axis is set to the surface roughness Rz (μm) of the surface-treated surface, the surface-treated copper foil is located in an area surrounded by the following four lines, x =0, y=0, y=-0.000189x+1.400000, and y=-0.002333x+9.333333.

In one embodiment of the surface-treated copper foil of the present invention, in the above-mentioned adhesion amount-surface roughness chart, it is located in a region surrounded by the following four straight lines, x=0, y=0, y=-0.000183x+1.100000, and y=-0.002200x+7.150000.

In another embodiment of the surface-treated copper foil of the present invention, the surface roughness Rz is 1.3 or less.

In still another embodiment of the surface-treated copper foil of the present invention, the surface roughness Rz is 1.0 or less.

In still another embodiment of the surface-treated copper foil of the present invention, it is used for a flexible printed wiring board.

In still another embodiment of the surface-treated copper foil of the present invention, it is used for a high-frequency circuit substrate of 5 GHz or more.

In still another embodiment of the surface-treated copper foil of the present invention, it does not have a roughened layer.

In still another embodiment of the surface treated copper foil of the present invention, it has a roughened layer.

In still another embodiment of the surface-treated copper foil of the present invention, a resin layer is provided on the surface of the surface treatment layer.

In still another embodiment of the surface-treated copper foil of the present invention, the resin layer contains a dielectric.

In another aspect, the invention provides a copper foil with a carrier having an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier. The ultra-thin copper layer is the surface-treated copper foil of the present invention.

In one embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultra-thin copper layer sequentially on one side of the carrier, and has a roughened layer on the other surface of the carrier.

Still another aspect of the invention is a laminated board comprising a surface-treated copper foil of the present invention and a resin substrate.

Still another aspect of the invention is a printed wiring board using the laminated board of the invention as a material.

Still another aspect of the invention is a printed circuit board using the laminate of the present invention as a material.

Still another aspect of the invention is an electronic machine using the printed wiring board of the invention or the printed circuit board of the invention.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified semi-additive method The circuit is formed by either method.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; and attaching the circuit to the carrier a surface of the copper foil on the side of the ultra-thin copper layer is formed with a resin layer; a circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and after the carrier is peeled off, the ultra-thin copper layer is removed. Thereby, the circuit buried in the resin layer formed on the surface of the ultra-thin copper layer is exposed.

According to the present invention, it is possible to provide a surface-treated copper foil, a laminate, a copper foil with a carrier, a printed wiring board, a printed circuit board, an electronic device, and a printed wiring board which are excellent in suppressing transmission loss even when used for a high-frequency circuit board. method.

1 is an example and a comparative example in which the x-axis is a total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo, and the y-axis is a surface roughness Rz (μm) of the surface-treated surface. The amount of adhesion - surface roughness chart.

2A to 2C are schematic views showing a cross section of a wiring board in a step of plating a circuit and removing a resist in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

3D to 3F are patterns of a cross section of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening using the specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention. Figure.

4G to FIG. 4 are schematic views showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier, in a specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention.

5J to K are schematic views showing a cross section of the wiring board in a step from flash etching to forming a bump or a copper pillar in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

(copper foil substrate)

The form of the copper foil substrate which can be used in the present invention is not particularly limited, and it can be typically used in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by using a copper sulfate plating bath on a drum of titanium or stainless steel to electrolyze copper, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. Calendered copper foil is used in most cases for applications requiring flexibility.

As a material of the copper foil substrate, in addition to high-purity copper such as refined copper or oxygen-free copper which is generally used as a conductor pattern of a printed wiring board, for example, Sn-doped copper, Ag-doped copper, such as Cr, Zr may be used. Or a copper alloy such as Mg or a copper alloy to which a Cason copper alloy such as Ni or Si is added. Further, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

Further, the thickness of the copper foil substrate is not particularly limited, and is, for example, 1 to 1000 μm, or 1 to 500 μm, or 1 to 300 μm, or 3 to 100 μm, or 5 to 70 μm, or 6 to 35 μm. Or it is 9~18μm.

Further, the present invention is another aspect of the invention, a copper foil with a carrier, which has a carrier, an intermediate layer, and an extremely thin copper layer in this order, and the ultra-thin copper layer is the surface-treated copper foil of the present invention. That is, in the present invention, in another aspect, a copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order can be used as the copper foil substrate. In the present invention, in the case of using a copper foil with a carrier, a surface treatment layer such as a roughening treatment layer is provided on the surface of the ultra-thin copper layer. Further, another embodiment of the copper foil with a carrier will be described below.

(surface treatment layer)

On the surface of the copper foil substrate (when the ultra-thin copper layer with the carrier copper foil is used as the copper foil substrate, the surface of the ultra-thin copper layer) is preferably formed to ensure the use with the resin substrate. A surface treatment layer selected from the group consisting of a roughening treatment, a rustproof treatment, a heat treatment treatment, a weather resistance treatment, an acid resistance treatment, and a decane treatment. That is, in this manner, the surface treatment layer of the present invention is formed on the joint surface with the resin (matte surface (M surface)). The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening treatment can also be fine. Further, after the roughening treatment, a cover plating treatment can be performed. The surface treatment layer formed by the roughening treatment, the rustproof treatment, the heat treatment, the weather resistance treatment, the acid resistance treatment, the decane treatment, the immersion treatment in the treatment liquid, or the plating treatment may further contain a layer selected from Cu, Ni. Any one or a combination of any one or more of Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, and Ge.

(adhesion metal amount and surface roughness)

Regarding the surface-treated copper foil, the smaller the surface roughness Rz is, the smaller the transmission loss is. However, if the surface roughness Rz is reduced to some extent, the amount of adhesion of a specific metal in the surface treatment layer is greater than the surface roughness. Significantly affect the transmission loss. According to the study by the present inventors, it is understood that among such surface-treated metal species, Co, Ni, Fe, and Mo having relatively high magnetic permeability and relatively low conductivity have an influence on transmission loss. Therefore, the surface-treated copper foil of the present invention is controlled in the surface treatment layer in terms of the total adhesion amount of Co, Ni, Fe, and Mo and the surface roughness Rz. Specifically, various manufacturing steps were carried out, and the total adhesion amount of Co, Ni, Fe, and Mo in the surface treatment layer and the surface roughness Rz were measured to measure the transmission loss. As a result, it was found that the x-axis was set as the surface treatment layer. The total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo, and the y-axis is the surface roughness Rz (μm) of the surface-treated surface, and the adhesion amount-surface roughness chart is drawn as follows: Straight line: x=0, y=0, y=-0.000189x+1.400000, and y=-0.002333x+9.333333

The copper foil that is controlled in the surrounding area satisfactorily suppresses transmission loss even when used for a high-frequency circuit board.

In the surface-treated copper foil of the present invention, since the total adhesion amount of Co, Ni, Fe, and Mo and the surface roughness Rz are in a region surrounded by the above four straight lines, it is preferably used for, for example, 5 GHz or more. The high-frequency circuit board of 20 GHz or more can also suppress the transmission loss to a very small value of 4 dB/10 cm or less.

This area is shown in the adhesion amount-surface roughness chart of Fig. 1. As can be seen from Fig. 1, the total adhesion amount of Co, Ni, Fe, and Mo is controlled so as to increase the relationship with the surface roughness Rz with respect to the surface roughness Rz, but it is not simply fixed. The increase was controlled in such a manner that the ratio of increase was decreased in the vicinity of the self-adhesion amount of 3700 μg/dm ² .

Further, in the above-described adhesion amount-surface roughness chart, the surface-treated copper foil of the present invention is preferably controlled in a region surrounded by four straight lines, x=0, y=0, y=-0.000183x+ 1.100000, and y=-0.002200x+7.150000.

Further, among the four straight lines defining the region, the straight line x=0 may be a straight line of x=1, 3, 5, 10, or 100.

Further, among the four straight lines defining the region, the straight line y=0 may be a straight line of y=0.001, 0.01, 0.05, 0.10, 0.20, or 0.30.

In addition, when the value of the total adhesion amount of Co, Ni, Fe, and Mo is large, it is more excellent in heat resistance, weather resistance, acid resistance, and the like.

When the value of the surface roughness Rz is large, the peel strength is further increased.

Further, in the above-described adhesion amount-surface roughness chart, the surface-treated copper foil of the present invention is preferably controlled in a region surrounded by four straight lines, x=0, y=0, y=-0.000189x+ 1.400000, and x=445. When the value of the total adhesion amount of Co, Ni, Fe, and Mo is small, even if Rz is not set to such a small value, the transmission loss is small. Further, since Ni has an adverse effect on the alkali etching property, when the adhesion amount of Ni is 445 μg/dm ² or less, the alkali etching property is improved, which is preferable. From the viewpoint of improving the alkali etching property, the above straight line x = 445 and further preferably x = 400, more preferably x = 350, more preferably x = 300, more preferably x = 250, more preferably x = 200. .

Further, in the above-described adhesion amount-surface roughness chart, the surface-treated copper foil of the present invention is preferably controlled in a region surrounded by four straight lines, x=0, y=0, y=-0.000183x+ 1.100000, and x=445. When the value of the total adhesion amount of Co, Ni, Fe, and Mo is small, even if Rz is not set to such a small value, the transmission loss is small. Further, since Ni has an adverse effect on the alkali etching property, when the adhesion amount of Ni is 445 μg/dm ² or less, the alkali etching property is improved, which is preferable. From the viewpoint of improving the alkali etching property, the above straight line x = 445 is more preferably x = 400, further preferably x = 350, more preferably x = 300, still more preferably x = 250, more preferably x = 200. .

Further, in the above-described adhesion amount-surface roughness chart, the surface-treated copper foil of the present invention is preferably controlled in a region surrounded by four straight lines, x=3010, y=0, y=-0.000189x+ 1.400000, and y=-0.002333x+9.333333.

When the value of the total adhesion amount of Co, Ni, Fe, and Mo is large, the effect of improving chemical resistance is obtained.

Further, in the above-described adhesion amount-surface roughness chart, the surface-treated copper foil of the present invention is preferably controlled in a region surrounded by three straight lines, that is, X = 3010, y = 0, and y = - 0.002200x+7.150000.

When the value of the total adhesion amount of Co, Ni, Fe, and Mo is large, the effect of improving chemical resistance is obtained.

When the surface roughness Rz is in the above region, it is not particularly limited, and in order to further suppress transmission loss, it is preferably controlled to 1.3 μm or less, more preferably 1.0 μm or less, and even more preferably 0.9 μm or less. The control is preferably 0.8 μm or less, more preferably 0.7 μm or less, and even more preferably 0.6 μm or less.

(Manufacturing method of surface-treated copper foil)

In the present invention, in order to increase the peeling strength of the copper foil after lamination, in order to increase the peeling strength of the copper foil after lamination, the copper foil substrate (the ultra-thin copper layer of the rolled copper foil or the electrolytic copper foil or the copper foil with the carrier) is bonded to the resin substrate. In order to carry out the roughening treatment of the surface of the copper foil after degreasing. In general, the electrolytic copper foil has irregularities at the time of manufacture, and the convex portion of the electrolytic copper foil is reinforced by the roughening treatment to further increase the unevenness. The surface of the rolled copper foil or the double-sided flat electrolytic copper foil or the copper foil with a carrier prepared by the copper sulfate electrolyte containing a leveling agent is smoother than the surface of the deposition surface of the usual electrolytic copper foil. Fine irregularities can be formed by subjecting the smoothed surface to a roughening treatment under specific conditions. In the present invention, the roughening treatment may be performed by, for example, any one selected from the group consisting of Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, and Ge. The plating of one or more alloys or the surface treatment of an organic substance or the like is performed. In the case where normal copper plating or the like is used as the pre-treatment before roughening, after the roughening, as the surface treatment, the metal may be coated with the metal in order to impart heat resistance and chemical resistance. Further, any one or a group selected from the group consisting of Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, and Ge may be used without performing the roughening treatment. Plating of the above alloys. Then, as the surface treatment, there is a case where the metal is coated by plating in order to impart heat resistance and chemical resistance. In the case of roughening treatment, there is an advantage that the adhesion strength to the resin is increased. Further, in the case where the roughening treatment is not performed, since the manufacturing steps of the surface-treated copper foil are simplified, the productivity can be improved, the cost can be reduced, and the roughness can be reduced. By adjusting the liquid composition, plating time and current density of the plating treatment on the surface of the copper foil, the total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo in the surface treatment layer of the present invention can be controlled. The relationship between the surface roughness Rz (μm) of the surface treated surface.

Further, in order to control the surface roughness Rz (μm) of the surface-treated surface of the surface-treated copper foil, the TD roughness (Rz) of the surface of the treated side of the copper foil (copper foil substrate) before surface treatment is controlled in advance and Gloss is also important. Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is 0.20 to 0.80 μm, preferably 0.20 to 0.50 μm, and the gloss of the rolling direction (MD) at an incident angle of 60 degrees is 350 to 800. %, preferably 500~800%, and if more conventional The surface treatment increases the current density and shortens the surface treatment time, thereby reducing the surface roughness Rz after the surface treatment. Such a copper foil can be produced by subjecting an oil film equivalent of a rolling oil to rolling (high gloss rolling), chemical polishing such as chemical etching, or electrolytic polishing in a phosphoric acid solution, and adding An electrolytic copper foil is produced by using a specific additive. Thus, the surface roughness (Rz) and the glossiness of the TD of the copper foil before the treatment are set to the above range, whereby the surface roughness (Rz) of the copper foil after the treatment can be easily controlled.

Further, regarding the copper foil before the surface treatment, the 60 degree gloss of MD is preferably from 500 to 800%, more preferably from 501 to 800%, still more preferably from 510 to 750%. If the 60-degree gloss of the MD of the copper foil before the surface treatment is less than 500%, there is a case where Rz is higher than 500%, and if it exceeds 800%, there is a problem that it is difficult to manufacture.

Further, the high gloss rolling can be carried out by setting the oil film equivalent specified in the following formula to 13,000 to 18,000.

Oil film equivalent = {(calendering oil viscosity [cSt]) × (penetration speed [mpm] + roll peripheral speed [mpm])} / {(roller bite angle [rad]) × (material's lodging stress [kg / Mm ² ])}

The rolling oil viscosity [cSt] is a dynamic viscosity of 40 °C.

In order to set the oil film equivalent to 13,000 to 18,000, it is sufficient to use a low-viscosity rolling oil or a known method such as slowing the penetration speed.

Further, the electrolytic copper foil having the surface roughness Rz and the glossiness within the above range can be produced by the following method.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm.

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

[with carrier copper foil]

The copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier. Further, the ultra-thin copper layer is the surface-treated copper foil according to the embodiment of the present invention.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, for example, a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, and an insulation. A resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like) is provided.

As the carrier which can be used in the present invention, copper foil is preferably used. The reason is: copper foil Since the electrical conductivity is high, it is easy to form an intermediate layer and an extremely thin copper layer thereafter. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by using a copper sulfate plating bath on a drum of titanium or stainless steel to electrolyze copper, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, copper alloy such as Cr, Zr or Mg, or Ni and Si may be added. Caston copper alloy copper alloy.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to exhibit a thickness suitable as a carrier, and may be, for example, 5 μm or more. However, if the production cost is increased if it is too thick, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically from 12 to 70 μm, more typically from 18 to 35 μm.

Further, with respect to the carrier used in the present invention, the surface roughness Rz of the surface of the extremely thin copper layer subjected to the surface treatment can be controlled by controlling the surface roughness Rz and the glossiness of the side on which the intermediate layer is formed in the following manner. And gloss.

For the carrier used in the present invention, it is also important to control the roughness (Rz) and gloss of the TD of the surface on the side on which the intermediate layer is formed in advance before the formation of the intermediate layer. Specifically, the surface roughness (Rz) of the TD of the carrier before the formation of the intermediate layer is 0.20 to 0.80 μm, preferably 0.20 to 0.50 μm, and the gloss of the rolling direction (MD) at an incident angle of 60 degrees is 350 to 800. %, preferably 500 to 800%. Such a copper foil can be produced by subjecting an oil film equivalent of a rolling oil to rolling (high gloss rolling), chemical polishing such as chemical etching, or electrolytic polishing in a phosphoric acid solution, and adding An electrolytic copper foil is produced by using a specific additive. Thus, the surface roughness (Rz) and the glossiness of the TD of the copper foil before the treatment are set to the above range, whereby the surface roughness (Rz) of the copper foil after the treatment can be easily controlled.

Further, regarding the carrier before the formation of the intermediate layer, the 60 degree gloss of MD is preferably from 500 to 800%, more preferably from 501 to 800%, still more preferably from 510 to 750%. If the 60-degree gloss of the MD of the copper foil before the surface treatment is less than 500%, there is a case where the Rz is higher than 500%. After 800%, there is a problem that is difficult to manufacture.

Further, the high gloss rolling can be carried out by setting the oil film equivalent specified in the following formula to 13,000 to 18,000.

Oil film equivalent = {(calendering oil viscosity [cSt]) × (penetration speed [mpm] + roll peripheral speed [mpm])} / {(roller bite angle [rad]) × (material's lodging stress [kg / Mm ² ])}

The rolling oil viscosity [cSt] is a dynamic viscosity of 40 °C.

In order to set the oil film equivalent to 13,000 to 18,000, it is sufficient to use a low-viscosity rolling oil or a known method such as slowing the penetration speed.

Further, the electrodeposited copper foil having the surface roughness Rz and the glossiness within the above range can be produced by the following method. The electrolytic copper foil can be used as a carrier.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent 1 ((bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

Further, a roughened layer may be provided on the surface opposite to the surface on the side where the ultra-thin copper layer of the carrier is provided. The roughening treatment layer may be provided by a known method, or may be provided by the above-described roughening treatment. a roughened layer is provided on a surface opposite to the surface on the side where the ultra-thin copper layer is provided on the carrier, and when the carrier layer is supported on a support such as a resin substrate from the surface side of the roughened layer, the carrier has a carrier and The resin substrate is not easily peeled off.

<intermediate layer>

An intermediate layer is disposed on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with the carrier on the insulating substrate, and the insulating layer is laminated on the other hand. After the step of the substrate, the very thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or more of these oxides and organic compounds. Also, the intermediate layer may be a plurality of layers.

Further, for example, the intermediate layer may be configured by forming an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer or an alloy layer selected from one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. A layer composed of a hydrate or an oxide selected from one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed thereon.

Further, for example, the intermediate layer may be configured by forming one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer or an alloy layer selected from one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. Forming a single metal layer selected from one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or selected from the group consisting of Cr, Ni, Co, Fe An alloy layer composed of one or more elements of the element group consisting of Mo, Ti, W, P, Cu, Al, and Zn.

Further, in the intermediate layer, a known organic substance can be used as the organic substance, and any one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid are preferably used. For example, as a specific nitrogen-containing organic compound, it is preferred to use 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzo) as a triazole compound having a substituent. Triazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol or the like is preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid or the like is preferably used.

Further, for example, the intermediate layer may be formed by sequentially laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer on the carrier. Since the bonding strength between nickel and copper is higher than the bonding strength between chromium and copper, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and the chromium-containing layer is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer. The intermediate layer is preferably nickel, deposition amount 100μg / dm ² or more and 40000μg / ² or less dm, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² Hereinafter, it is more preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a Ni plating layer on the opposite side of the carrier. The chromium layer of the above intermediate layer can be provided by chrome plating or chromate treatment.

If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer affects the surface roughness Rz and the glossiness of the surface of the extremely thin copper layer after the surface treatment, and thus the surface of the surface of the extremely thin copper layer The thickness of the intermediate layer is preferably from 1 to 1000 nm, preferably from 1 to 500 nm, preferably from 2 to 200 nm, preferably from 2 to 100 nm, more preferably from 3 to 60 nm. Furthermore, the intermediate layer may also be disposed on both sides of the carrier.

<very thin copper layer>

An extremely thin copper layer is disposed on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer having the carrier is a surface-treated copper foil according to an embodiment of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. It is typically from 0.5 to 12 μm, more typically from 1.5 to 5 μm. Further, before the ultra-thin copper layer is provided on the intermediate layer, in order to reduce the pinhole of the ultra-thin copper layer, strike plating using a copper-phosphorus alloy may be performed. The base plating may be, for example, a copper pyrophosphate plating solution. Furthermore, an extremely thin copper layer may be provided on both sides of the carrier.

Further, the ultra-thin copper layer of the present application is formed under the following conditions. It is to control the surface roughness Rz and the glossiness of the surface of the ultra-thin copper layer by forming a smooth ultra-thin copper layer.

. Electrolyte composition

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

Leveling agent 1 ((bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

. Manufacturing conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to copper thickness and current density)

[Resin layer on the surface treated surface]

A resin layer may be provided on the surface-treated surface of the surface-treated copper foil of the present invention. The above resin layer may also be an insulating resin layer. Further, in the surface-treated copper foil of the present invention, the "surface-treated surface" is subjected to a surface treatment such as a heat-resistant layer, a rust-preventing layer, or a weather-resistant layer after the roughening treatment. The surface of the surface-treated copper foil after the surface treatment was carried out. In the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the "surface-treated surface" is subjected to a roughening treatment to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, and the like. In the case of surface treatment, it refers to the surface of the ultra-thin copper layer after the surface treatment.

The resin layer may be a bonding agent or an insulating resin layer in a semi-hardened state (B-stage state) for bonding. The semi-hardened state (B-stage state) includes that the insulating resin layer can be stacked and stored even when the surface is in contact with the finger, and the insulating resin layer can be stored. The treatment produces a state of hardening reaction.

The resin layer may be a bonding resin, that is, a bonding agent, or may be an insulating resin layer in a semi-hardened state (B-stage state) for bonding. The semi-hardened state (B-stage state) includes a non-adhesive feeling even when the surface is in contact with a finger, and the insulating resin layer can be stacked and stored, and if it is subjected to heat treatment, a curing reaction occurs.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. No., International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003- No. 304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, and Japanese Patent No. 4286060 Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, and Japanese Special Publication 2009-6702 No. 9, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471 , Japan Special Open 2011-14727, International Public Publication No. WO2009/001850, International Public Publication No. WO2009/145179, The materials described in JP-A-2011-068157 and JP-A-2013-19056 (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, The skeleton material or the like and/or the method of forming the resin layer and the forming device are formed.

Further, the type of the resin layer is not particularly limited, and examples thereof include, for example, an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, and a maleimide. Compound, poly-m-butylene iminoimide compound, maleimide-based resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin, polyether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, Polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bis-xenylene diimide Resin, thermosetting polyphenylene ether resin, cyanate resin, acid anhydride, acid anhydride, linear polymer with crosslinkable functional group, polyphenylene ether resin, 2,2-double (4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin, helium oxygen Alkyl modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, One or more resins selected from the group consisting of a phenoxy group, a polymer epoxy resin, an aromatic polyamine, a fluororesin, a bisphenol, a block copolymer polyimine resin, and a cyanoester resin.

Moreover, those having two or more epoxy groups in the epoxy resin may be used without any particular problem as long as they are usable for electronic materials. Further, the epoxy resin is preferably an epoxy resin which is epoxidized using a compound having two or more epoxy propyl groups in its molecule. Further, it may be selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac type Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac epoxy resin, naphthalene ring Oxygen resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, epoxidized propylamine type epoxy resin, triglycidyl isocyanurate , a glycidyl compound such as N,N-diepoxypropylaniline, a glycidyl ester compound such as diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, or a biphenol One or a mixture of two or more of an aldehyde varnish type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetraphenylethane type epoxy resin, or a hydrogenated or halogenated epoxy resin may be used. body.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. Further, the phosphorus-containing epoxy resin is preferably derived, for example, from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in its molecule. Epoxy resin obtained in the form of an object.

(when the resin layer contains a dielectric (dielectric filler))

The resin layer may also contain a dielectric (dielectric filler).

When a dielectric material (dielectric filler) is contained in any of the above resin layers or resin compositions, it can be used for forming a capacitor layer to increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) used was BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), and PbLaTiO ₃ . A dielectric powder of a composite oxide having a perovskite structure such as PbLaZrO (commonly known as PLZT) or SrBi ₂ Ta ₂ O ₉ (commonly known as SBT).

The dielectric (dielectric filler) may also be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder property of the dielectric (dielectric filler) is preferably from 0.01 μm to 3.0 μm, preferably 0.02 μm. The range of 2.0 μm. Further, when a photo is taken by a scanning electron microscope (SEM) on a dielectric body, and a straight line is drawn on the particles of the dielectric body on the photo, the length of the straight line crossing the dielectric particles is longest. The length of part of the dielectric particles is set to the diameter of the dielectric particles. Further, the average value of the particle diameters of the measurement field-directed dielectrics is defined as the particle diameter of the dielectric.

Dissolving the resin and/or resin composition and/or compound contained in the above resin layer in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cyproterone, N-methyl-2- A resin liquid (resin varnish) is prepared in a solvent such as pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, and is coated, for example, by a roll coating method or the like. It is placed on the roughened surface of the surface-treated copper foil, and then heated and dried as necessary to remove the solvent to be in a B-stage state. Drying may be carried out, for example, using a hot air drying oven, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved in a solvent to form a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Resin solution. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone to dissolve at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Further, the resin layer is preferably a semi-hardened resin film having a resin overflow flow rate in the range of 5% to 35% when measured in accordance with MIL-P-13949G in the MIL standard (US Military Standard).

In the present specification, the resin overflow rate is based on MIL-P-13949G in the MIL standard, and a sample of four 10 cm squares is sampled from a surface-treated copper foil to which a resin having a resin thickness of 55 μm is attached. The film samples were laminated under the conditions of a pressure of 171 ° C, a pressurization pressure of 14 kgf / cm ² , and a pressurization time of 10 minutes, and the results of measuring the resin outflow weight at this time were The value calculated based on the number 1.

The surface-treated copper foil (resin-treated copper foil with resin) provided with the above-mentioned resin layer is used in such a manner that after the resin layer and the substrate are overlapped, the entire resin is thermocompression-bonded to thermally harden the resin layer. Then, in the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the carrier is peeled off to expose the ultra-thin copper layer (of course, the exposed portion is the intermediate layer of the extremely thin copper layer) The surface of the side) forms a specific wiring pattern from the surface on the opposite side to the side where the surface-treated copper foil is roughened.

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

Furthermore, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, so that it is economically advantageous, and the thickness of the multilayer printed wiring substrate to be manufactured is thinned as a prepreg material. The thickness of the layer can be made to have an advantage of a very thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 120 μm.

When the thickness of the resin layer is less than 0.1 μm, the bonding strength is lowered, and when the resin-coated surface-treated copper foil is laminated on the substrate having the inner layer material without interposing the prepreg, it is difficult to ensure the inside. The case of interlayer insulation between circuits of layer materials. On the other hand, when the thickness of the resin layer is made thicker than 120 μm, it is difficult to form a resin layer having a target thickness by one application step, and it takes an extra material cost and man-hour, which is disadvantageous in terms of economy. Happening.

Further, in the case where a surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, in order to reduce the thickness of the multilayer printed wiring board, it is preferable to set the thickness of the above resin layer to 0.1 μm. More preferably, it is 0.5 μm to 5 μm, and more preferably 1 μm to 5 μm.

Hereinafter, examples of the manufacturing steps of a plurality of printed wiring boards using the copper foil with a carrier of the present invention are shown.

In an embodiment of the method for manufacturing a printed wiring board according to the present invention, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and the copper foil and the insulating substrate with the carrier a laminate layer is formed by laminating the carrier-attached copper foil and the insulating substrate so that the ultra-thin copper layer side faces the insulating substrate, and then the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and then borrowing The circuit is formed by any one of a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate may also be provided as an inner layer circuit.

In the present invention, the semi-additive method refers to a method of forming a conductor pattern by plating and etching after performing thin electroless plating on an insulating substrate or a copper foil seed layer.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is removed by etching or plasma etching using an acid or the like. Providing a through hole or/and a blind via in the resin exposed by removing the ultra-thin copper layer by etching; removing the adhesive containing the above-mentioned perforated or/and blind via a slag treatment; providing an electroless plating layer on the resin and the region containing the perforation or/and the blind hole; providing a plating resist on the electroless plating layer; exposing the plating resist to the above, and then removing the formed a plating resist in a region of the circuit; a plating layer disposed in a region where the circuit is formed by removing the plating resist; removing the plating resist; removing the shape by rapid etching or the like An electroless plating layer in a region other than the region of the above circuit.

In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; Providing an electroless plating layer on a surface of the resin exposed by removing the ultra-thin copper layer by etching; on the electroless plating layer a plating resist is disposed; the plating resist is exposed, and then the plating resist is removed from the region where the circuit is formed; and the plating layer is disposed in the region where the circuit is formed by removing the plating resist; A plating resist; an electroless plating layer and an extremely thin copper layer in a region other than the region where the above-described circuit is formed are removed by rapid etching or the like.

In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and increasing a copper thickness of the circuit forming portion by plating. The resist is removed, and the metal foil other than the circuit forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer exposed on the carrier is peeled off and the insulating substrate is provided with a perforation or/and a blind hole; Performing desmear treatment on the perforated or/and blind via regions; providing an electroless plating layer on the region containing the perforated or/and blind vias; and plating the surface of the extremely thin copper layer exposed by peeling the carrier After the plating resist is disposed, the circuit is formed by electroplating; the plating resist is removed; and the ultra-thin copper layer exposed by removing the plating resist is removed by rapid etching.

Further, a step of forming a circuit on the resin layer may be performed by laminating another carrier-attached copper foil from the ultra-thin copper layer side on the resin layer, and forming the circuit using a carrier-attached copper foil bonded to the resin layer. step. Further, other copper foil with a carrier adhered to the above resin layer may be the copper foil with a carrier of the present invention. Further, the step of forming a circuit on the resin layer may be carried out by any one of a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Further, the copper foil with a carrier on which the circuit is formed on the surface may have a substrate or a resin layer on the surface of the carrier on which the carrier copper foil is attached.

A method of manufacturing a printed wiring board of the present invention using a modified semi-additive method In one embodiment, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the insulating substrate and peeling off the copper carrier a carrier for foil; a plating resist disposed on the extremely thin copper layer exposed by peeling off the carrier; exposing the plating resist, and then removing the plating resist in the region where the circuit is formed; A plating resist is formed in a region where the circuit is formed; a plating resist is removed; and an electroless plating layer and an extremely thin copper layer in a region other than the region where the circuit is formed are removed by rapid etching or the like.

In the present invention, the partial addition method refers to a method of providing a catalyst core on a substrate formed by providing a conductor layer and, if necessary, opening a hole for a via hole or a via hole. Etching is performed to form a conductor circuit, and if necessary, a solder resist or a plating resist is provided, and a via hole or a via hole is thickened by an electroless plating treatment on the conductor circuit to manufacture a printed wiring board.

Therefore, in an embodiment of the method for manufacturing a printed wiring board of the present invention using a partial addition method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer exposed on the carrier is peeled off and the insulating substrate is provided with a perforation or/and a blind hole; Performing desmear treatment on the region of the perforation or/and the blind hole; imparting a catalyst core to the region containing the perforation or/and the blind hole; and providing an etching resist on the surface of the extremely thin copper layer exposed by peeling the carrier; Exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the catalyst core by using etching or plasma etching of an acid or the like to form a circuit; removing the etching resist; a surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an acid or the like, and providing a solder resist or a plating resist; Is provided above the solder resist or plating resist in the plating zone is provided in the electroless plating layer.

In the present invention, the subtractive method refers to a method of selecting by etching or the like. An unnecessary portion of the copper foil on the copper clad laminate is selectively removed to form a conductor pattern.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier are provided with perforations or/and blind vias; Or / and the area of the blind hole is subjected to desmear treatment; an electroless plating layer is provided on the region containing the above-mentioned perforated or/and blind holes; a plating layer is disposed on the surface of the electroless plating layer; and the plating layer or/and the above-mentioned electrode An etching resist is disposed on the surface of the thin copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer, the electroless plating layer and the above are removed by etching or plasma etching using an acid or the like A circuit is formed to form a circuit; the above etching resist is removed.

In another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After the carrier-attached copper foil is laminated with the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier are provided with perforations or/and blind vias; Or / and the area of the blind hole is subjected to desmear treatment; an electroless plating layer is provided on the region containing the above-mentioned perforated or/and blind holes; a mask is formed on the surface of the electroless plating layer; and the above-mentioned electroless electricity is not formed in the mask a plating layer is disposed on the surface of the plating layer; an etching resist is disposed on the surface of the plating layer or/and the ultra-thin copper layer; and the etching resist is exposed to form a circuit pattern; etching or plasma is performed by etching the solution using an acid or the like And the like, removing the ultra-thin copper layer and the electroless plating layer to form a circuit; and removing the etching resist.

The step of providing a perforation or/and a blind hole, and the subsequent desmear step may also be omitted.

Here, the printing using the copper foil with the carrier of the present invention will be described in detail using the drawings. A specific example of a method of manufacturing a brushed wiring board. Here, the copper foil with a carrier having the ultra-thin copper layer in which the roughened layer is formed is exemplified, but the invention is not limited thereto, and even a very thin copper layer having a roughened layer is not used. The carrier copper foil with a carrier can also implement the manufacturing method of the following printed wiring board similarly.

First, as shown in FIG. 2-A, a copper foil with a carrier (first layer) having an extremely thin copper layer having a roughened layer formed on its surface is prepared.

Then, as shown in FIG. 2-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a specific shape.

Then, as shown in FIG. 2-C, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Then, as shown in FIG. 3-D, the resin layer is laminated on the ultra-thin copper layer by covering the circuit plating layer (by burying the circuit plating layer), and then the other carrier is bonded from the very thin copper layer side. Copper foil (layer 2).

Then, as shown in Fig. 3-E, the carrier was peeled off from the carrier copper foil of the second layer.

Then, as shown in FIG. 3-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Then, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.

Then, as shown in FIG. 4-H, a circuit plating layer is formed on the via fill material as in the above-described FIG. 2-B and FIG.

Then, as shown in Fig. 4-I, the carrier was peeled off from the carrier-attached copper foil of the first layer.

Then, as shown in FIG. 5-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Then, as shown in FIG. 5-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in the above manner.

The above-mentioned other carrier copper foil (the second layer) can use the copper carrier of the present invention. As the foil, a conventional copper foil with a carrier can be used, and a usual copper foil can also be used. Further, in the circuit of the second layer shown in FIG. 4-H, a layer or a plurality of layers may be formed, or may be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method performs such circuit formation.

The copper foil with a carrier of the present invention preferably controls the chromatic aberration of the surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer, or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably controls the chromatic aberration of the roughened surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the surface-treated copper foil of the present invention, the "roughening treatment surface" is subjected to surface treatment for providing a heat-resistant layer, a rust-preventing layer, a weather-resistant layer, or the like after the roughening treatment. It refers to the surface of the surface-treated copper foil (very thin copper layer) after the surface treatment. Further, in the case where the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the "roughening treatment surface" is used to provide a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after the roughening treatment. In the case of surface treatment, the surface of the ultra-thin copper layer after the surface treatment is performed.

(1) In the formula of the surface of the ultra-thin copper layer, the color difference ΔE* ab based on JISZ8730 is 45 or more.

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is added, and the combination is expressed by the L* a* b color system based on JIS Z8730. The index is expressed in the form of ΔL: black and white, Δa: red green, Δb: yellow blue. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

The above color difference can be adjusted by increasing the current density when the ultra-thin copper layer is formed, reducing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by providing a roughening treatment layer by roughening the surface of the ultra-thin copper layer. In the case where the roughening treatment layer is provided, it is possible to increase the current density (for example, 40 to 60 A/by using an electrolytic solution containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. Dm ² ), and adjust the processing time (for example, 0.1 to 1.3 seconds). When the roughened layer is not provided on the surface of the ultra-thin copper layer, it can be achieved by using a plating bath in which the concentration of Ni is twice or more of other elements, in an extremely thin copper layer or Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer Set a lower current density (0.1~1.3A/dm ² ) and a longer processing time (20 seconds to 40 seconds) than conventional processing.

In the case of the difference in the surface of the ultra-thin copper layer, if the color difference ΔE* ab based on JIS Z8730 is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil, the contrast between the extremely thin copper layer and the circuit becomes As a result, the visibility is improved, and the positional alignment of the circuit can be performed with high precision. The surface of the ultra-thin copper layer based on JIS Z8730 has a color difference ΔE* ab of preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the chromatic aberration on the surface of the ultra-thin copper layer is controlled as described above, the contrast with the circuit plating layer becomes clear, and the visibility becomes good. Therefore, in the manufacturing step of the printed wiring board as described above, for example, as shown in FIG. 2-C, the circuit plating layer can be formed accurately at a specific position. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating layer is buried in the resin layer, the circuit is removed by rapid etching, for example, as shown in FIG. 5-J. The plating layer is protected by a resin layer, and its shape is maintained, whereby it is easy to form a fine circuit. Further, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the wiring of the circuit is favorably suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIGS. 5-J and 5-K, the exposed surface of the circuit plating layer is recessed from the resin layer, so that it is easy to form a convex on the circuit plating layer, respectively. The block, which in turn forms a copper pillar, increases manufacturing efficiency.

Further, as the resin, a known resin or a prepreg can be used. For example, it can be impregnated with BT (bis-s-butylene diimine III) A prepreg of glass cloth of resin or BT resin, ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, the resin layer and/or the resin and/or the prepreg described in the present specification can be used as the above-mentioned resin.

Further, the copper foil with a carrier used in the first layer may have a substrate or a resin layer on the surface of the copper foil with the carrier. By having the substrate or the resin layer, the copper foil with a carrier used in the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, as long as the substrate or the resin layer has an effect of supporting the copper foil with a carrier used in the first layer, all of the substrate or the resin layer can be used. For example, as the substrate or the resin layer, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, or an inorganic substance described in the specification of the present application can be used. A foil of a compound, a plate of an organic compound, or a foil of an organic compound.

The surface-treated copper foil of the present invention can be bonded to the resin substrate from the surface treatment layer side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics suitable for use in a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber cloth substrate ring can be used for the rigid PWB. Oxygen resin, fluororesin impregnated cloth, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin, glass cloth substrate epoxy resin, etc., flexible printed circuit board (FPC) A polyester film or a polyimide film, a liquid crystal polymer (LCP) film, a fluororesin, and a fluororesin-polyimine composite material are used. Further, since the dielectric loss of the liquid crystal polymer (LCP) is small, it is preferable to use a liquid crystal polymer (LCP) film for the printed wiring board for high-frequency circuit use.

In the case of the rigid PWB, the bonding method is prepared by impregnating a substrate such as a glass cloth with a resin to cure the resin to a semi-hardened prepreg. This can be carried out by overlapping the copper foil with the prepreg and heating and pressurizing. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film is laminated to a copper foil under high temperature and high pressure via a bonding agent or without using a bonding agent. The laminate or the polyimide precursor can be coated, dried, hardened, or the like, whereby a laminate can be produced.

The laminate of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, it can be used for single-sided PWB, double-sided PWB, and multilayer PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be used for rigid PWB, flexible PWB (FPC), and soft and hard composite PWB.

[Examples]

A rolled copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 18 μm or an electrolytic copper foil having a thickness of 18 μm was prepared as the copper foil substrates of Examples 1 to 35 and Comparative Examples 1 to 28. Further, the copper foil substrate can be controlled by the above method to control the surface roughness Rz and gloss before surface treatment.

Further, the copper foil with a carrier described below was prepared as the copper foil substrate of Examples 36 to 40.

For Examples 36 to 38 and 40, an electrolytic copper foil having a thickness of 18 μm was prepared as a carrier, and in Example 39, a rolled copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 18 μm was prepared as a carrier. Further, an intermediate layer was formed on the surface of the carrier under the following conditions, and an extremely thin copper layer was formed on the surface of the intermediate layer. Further, the carrier may, if necessary, control the surface roughness Rz and glossiness of the surface before the formation of the surface intermediate layer on the side where the intermediate layer is formed by the above method.

. Example 36

<intermediate layer>

(1) Ni layer (Ni plating)

The carrier was subjected to electroplating on a continuous roll-to-roll type continuous plating line under the following conditions, thereby forming a Ni layer of an adhesion amount of 1000 μg/dm ² . The specific plating conditions are described below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss: saccharin, butylene glycol, etc.

Sodium dodecyl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Then, after the surface of the Ni layer formed in (1) is washed with water and pickled, and then subjected to electrolytic chromate treatment on the Ni layer under the following conditions on a roll-to-roll continuous plating line, A Cr layer having an adhesion amount of 11 μg/dm ² was attached.

Potassium dichromate: 1~10g/L, zinc: 0g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

<very thin copper layer>

Then, after the surface of the Cr layer formed in (2) is washed with water and pickled, and then subjected to electroplating on a roll-to-roll type continuous plating line, the thickness is 1.5 μm formed on the Cr layer. An extremely thin copper layer is used to make an extremely thin copper foil with a carrier.

Copper concentration: 90~110g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

Further, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

. Example 37

<intermediate layer>

(1) Ni-Mo layer (nickel-molybdenum alloy plating)

The carrier was subjected to electroplating on a roll-to-roll continuous plating line under the following conditions, thereby forming a Ni-Mo layer having an adhesion amount of 3000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) Ni hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 36 except that the thickness of the ultra-thin copper layer was 2 μm.

. Example 38

<intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 36.

(2) Organic layer (organic layer formation treatment)

Then, after the surface of the Ni layer formed in (1) was washed with water and pickled, the surface of the Ni layer was sprayed with a liquid temperature of 40 ° C containing a concentration of 1 to 30 g/L of carboxybenzotriazole (CBTA) under the following conditions. The aqueous solution having a pH of 5 was sprayed for 20 to 120 seconds to form an organic layer.

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 36 except that the thickness of the ultra-thin copper layer was changed to 3 μm.

. Example 39, 40

<intermediate layer>

(1) Co-Mo layer (cobalt-molybdenum alloy plating)

The carrier was subjected to electroplating on a roll-to-roll continuous plating line under the following conditions, thereby forming a Co-Mo layer of an adhesion amount of 4000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Co: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 36 except that the thickness of the ultra-thin copper layer was set to 5 μm in Example 39 and 3 μm in Example 40.

Then, the rolled copper foil, the electrolytic copper foil, and the copper foil with a carrier prepared in Examples 1 to 40 and Comparative Examples 1 to 28 were plated under the conditions shown in Tables 1 to 3 as a surface treatment. Table 1 shows the liquid composition, pH, temperature, and current density of each of the liquids 1 to 11. Tables 2 and 3 show that the plating treatments 1 to 4 are sequentially performed by the bath composition and time described. Further, after the plating, heat resistance is ensured by Zn, Ni or alloy plating and chromate treatment, and the peel strength is improved by coating the amine-based decane.

The coating conditions of the amino decane are as follows.

. Amino decane: N-2-(aminoethyl)-3-aminopropyltrimethoxydecane

. Decane concentration: 5.0 vol% (remaining part: water)

. Processing temperature: 45~55°C

. Processing time: 5 seconds

. Drying after decane treatment: 100 ° C × 3 seconds

Further, the surface treatments of Examples 5, 11, 18, 20, 21, 25, 26, 27, 31, 34, 40, and Comparative Example 27 correspond to a smooth plating treatment (surface treatment without non-roughening treatment), The surface treatment in the examples and comparative examples corresponds to the roughening treatment.

Each of the samples of the examples and the comparative examples produced in the above manner was subjected to various evaluations as described below.

<Measurement of adhesion amount>

For measuring the adhesion amount of various metals of the surface treatment layer, a film of a surface of a copper foil of 50 mm × 50 mm was dissolved in a solution in which HNO ₃ (2% by weight) and HCl (5% by weight) were mixed, and ICP emission was used for spectroscopy. The analysis device (manufactured by SII NanoTechnology Co., Ltd., SFC-3100) quantifies the metal concentration in the solution, and calculates the amount of metal per unit area (μg/dm ² ). At this time, in order to prevent the metal adhesion amount which is opposite to the surface to be measured from being mixed, it is shielded as necessary and analyzed. Further, the measurement was carried out on a sample obtained by performing the above-described Zn, Ni or the alloy plating, the chromate treatment, and the amine-based decane treatment.

<Measurement of Surface Roughness Rz>

The ten-point average roughness of the surface-treated surface was measured in accordance with JIS B0601-1994 using a contact roughness meter SP-11 manufactured by Kosaka Research Institute Co., Ltd. The measurement position was changed under the conditions of a measurement reference length of 0.8 mm, an evaluation length of 4 mm, a cutoff value of 0.25 mm, and a feed rate of 0.1 mm/sec, and the measurement was performed 10 times, and the value of 10 measurements was obtained.

<Measurement of transmission loss>

For each sample having a thickness of 18 μm, the surface of each of the samples was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), and the characteristic impedance was 50 Ω by etching. In the manner of forming a microstrip line, the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. The evaluation of the transmission loss at a frequency of 20 GHz was evaluated as ◎ as less than 3.7 dB/10 cm, and as ○ at 3.7 dB/10 cm or more and less than 4.1 dB/10 cm, and 4.1 dB/10 cm or more and less than 5.0 dB/10 cm. The evaluation was Δ, and 5.0 dB/10 cm or more was evaluated as ×. Further, after attaching the carrier copper foil to the surface of the ultra-thin copper layer and the commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), the carrier was peeled off. Then, the ultra-thin copper layer was plated with copper so that the total thickness of the ultra-thin copper layer and the copper-plated layer was 18 μm. Then, the same measurement as described above was carried out.

<joinability>

First, a liquid crystal polymer film of a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.) was bonded to a copper foil provided with a coating layer (surface treatment layer) by vacuum heat and pressure.

Then, the peeling strength was measured according to the 90° peeling method (JIS C 6471 8.1) on the copper foil in which the liquid crystal polymer was laminated. Further, the copper foil with a carrier is subjected to vacuum heating and pressurization to provide the ultra-thin copper layer on the side of the coating layer (the surface-treated side) and the above-mentioned commercially available liquid crystal polymer resin (manufactured by Kuraray Co., Ltd.). After the bonding of the Vecstar CTZ-50 μm), the carrier was peeled off, and then the ultra-thin copper layer was plated with copper so that the total thickness of the ultra-thin copper layer and the copper-plated layer was 18 μm. Then, the same measurement as described above was carried out.

<alkali etching property>

Further, in Example 11 and Example 34, the copper foil in which the liquid crystal polymer was laminated was investigated for alkali etching property.

. Use of liquid medicine: A-Process manufactured by Meltex Co., Ltd.

. Temperature: 50 ° C

. Stirring speed: 200rpm

As a result, in Example 11, it was confirmed by visual observation that it was all dissolved in 300 seconds. On the other hand, in Example 34, it took 315 seconds until all dissolved. Therefore, it is understood that the alkali etching property of Example 11 is excellent.

The evaluation results are shown in Tables 4 and 5. In addition, FIG. 1 shows an example in which the x-axis is the total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo, and the y-axis is the surface roughness Rz (μm) of the surface-treated surface. Examples of adhesion and surface roughness of the comparative examples.

(Evaluation results)

In any of the examples, the x-axis is the total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo in the surface treatment layer, and the y-axis is the surface roughness Rz (μm) of the surface-treated surface. The plotted adhesion-surface roughness chart is located in the area surrounded by 4 lines of x=0, y=0, y=-0.000189x+1.400000, and y=-0.002333x+9.333333, so The transmission loss is satisfactorily suppressed to 4.0 dB/10 cm or less. Further, any of the examples has good adhesion.

On the other hand, any of the comparative examples is outside the region surrounded by the above four straight lines, and thus the transmission loss is more than 4.0 dB/10 cm and is defective.

Further, in the present embodiment, copper plating is performed using an extremely thin copper layer of a copper foil having a thickness of 18 μm or a copper foil with a carrier, and a copper foil having a total thickness of the ultra-thin copper layer and the copper plating layer is 18 μm. As described above, since there is a phenomenon in which a current is distributed only on the surface of the conductor in the high-frequency region, the thickness of the copper foil affects the impedance control, but does not seriously interfere with the transmission loss. Therefore, it is considered that the copper foil having a thickness other than 18 μm can also suppress the transmission loss by controlling the roughness of the present invention and the amount of metal to be surface-treated.

Claims (22)

A surface-treated copper foil having a surface-treated layer formed by using a x-axis as a total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo in a surface-treated layer, and a y-axis as a surface-treated surface In the adhesion amount-surface roughness chart drawn by the surface roughness Rz (μm), the surface-treated copper foil is located in a region surrounded by the following four straight lines, x=220, y=0, y=-0.000189x+1.400000 And y=-0.002333x+9.333333. The surface-treated copper foil according to claim 1 of the patent application, in the adhesion amount-surface roughness chart, is located in a region surrounded by the following four straight lines, x=220, y=0, y=-0.000183x+ 1.100000, and y=-0.002200x+7.150000. A surface-treated copper foil having a surface-treated layer formed by using a x-axis as a total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo in a surface-treated layer, and a y-axis as a surface-treated surface In the adhesion amount-surface roughness chart drawn by the surface roughness Rz (μm), the surface-treated copper foil is located in a region surrounded by the following four straight lines, x=0, y=0, y=0.30, and y= -0.002333x+9.333333. The surface-treated copper foil of claim 3, in the adhesion amount-surface roughness chart, is located in an area surrounded by the following four straight lines, x=0, y=0, y=0.30, and y=-0.002200x+7.150000. A surface-treated copper foil having a surface-treated layer formed by using a x-axis as a total adhesion amount (μg/dm ² ) of Co, Ni, Fe, and Mo in a surface-treated layer, and a y-axis as a surface-treated surface In the adhesion amount-surface roughness chart drawn by the surface roughness Rz (μm), the surface-treated copper foil is located in a region surrounded by the following four straight lines, x=0, y=0.70, y=-0.000189x+1.400000 And y=-0.002333x+9.333333. The surface-treated copper foil of claim 5, in the adhesion amount-surface roughness chart, is located in a region surrounded by three straight lines, x=0, y=0.70, and y=-0.000183x. +1.100000. The surface-treated copper foil according to any one of claims 1 to 6, wherein the surface roughness Rz is 1.3 or less. The surface-treated copper foil according to claim 7, wherein the surface roughness Rz is 1.0 or less. The surface-treated copper foil according to any one of claims 1 to 6, which is used for a flexible printed wiring board. The surface-treated copper foil according to any one of claims 1 to 6, which is used for a high-frequency circuit substrate of 5 GHz or more. The surface-treated copper foil according to any one of claims 1 to 6, which does not have a roughened layer. The surface-treated copper foil according to any one of claims 1 to 6, which has a roughened layer. The surface-treated copper foil according to any one of claims 1 to 6, which has a resin layer on the surface of the surface treatment layer. The surface-treated copper foil of claim 13, wherein the resin layer contains a dielectric. A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier, the ultra-thin copper layer being the surface-treated copper foil according to any one of claims 1 to 6. The copper foil with carrier of claim 15 is characterized in that the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other side of the carrier. A laminated board comprising a surface-treated copper foil according to any one of claims 1 to 16 and a resin substrate. A printed wiring board using a laminate having the scope of claim 17 as a material. A printed circuit board using a laminate having the scope of claim 17 as a material. An electronic machine using the printed wiring board of claim 18 or the printed circuit board of claim 19 of the patent application. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of claim 15 or 16; laminating the copper foil with the insulating substrate; and bonding the copper foil with the carrier After the insulating substrate is laminated, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil. Then, the circuit is formed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier of claim 15 or 16; and burying the circuit in the copper foil with the carrier a surface of the ultra-thin copper layer is formed with a resin layer; a circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and after the carrier is peeled off, the ultra-thin copper layer is removed, thereby The circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.