JP2018127660A - Surface treated copper foil, copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated copper foil which can satisfactorily reduce transmission loss even when used for a high-frequency circuit board and has good fine circuit formability. A surface-treated copper foil having a copper foil and a surface-treated layer containing a roughening-treated layer on one or both surfaces of the copper foil, wherein the surface-treated layer contains Co and is a surface-treated layer. A surface-treated copper foil having a Co content ratio of 15% by mass or less (excluding 0% by mass) and a ten-point average roughness Rz of 1.4 μm or less on the outermost surface of the surface-treated layer. [Selection diagram] Fig. 4

Description

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

  Printed wiring boards have made great progress over the last half century and are now used in almost all electronic devices. In recent years, with the increasing demand for miniaturization and high performance of electronic devices, high density mounting of mounted components and high frequency of signals have progressed, and excellent high frequency response is required for printed wiring boards.

  The high frequency board is required to reduce transmission loss in order to ensure the quality of the output signal. The transmission loss mainly consists of a dielectric loss due to the resin (substrate side) and a conductor loss due to the conductor (copper foil side). The dielectric loss decreases as the dielectric constant and dielectric loss tangent of the resin decrease. In a high-frequency signal, the conductor loss is mainly caused by a decrease in the cross-sectional area through which the current flows due to the skin effect that only the surface of the conductor flows as the frequency increases, and the resistance increases.

  As a technique aimed at reducing the transmission loss of the high-frequency copper foil, for example, Patent Document 1 covers one or both surfaces of a metal foil surface with silver or a silver alloy metal, and the silver or silver alloy coating. A metal foil for a high-frequency circuit is disclosed in which a coating layer other than silver or a silver alloy is applied on the layer thinner than the thickness of the silver or silver alloy coating layer. And according to this, it is described that it is possible to provide a metal foil in which the loss due to the skin effect is reduced even in an ultra-high frequency region used in satellite communications.

  Patent Document 2 discloses that the integrated intensity (I (200)) of (200) plane obtained by X-ray diffraction on the rolled surface after recrystallization annealing of the rolled copper foil is the X-ray diffraction of fine powder copper. Roughening treatment after I (200) / I0 (200)> 40 with respect to the obtained integrated strength (I0 (200)) of (200) plane, and after performing roughening treatment by electrolytic plating on the rolled surface The arithmetic average roughness (hereinafter referred to as Ra) of the surface is 0.02 μm to 0.2 μm, the ten-point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm, and for printed circuit boards A roughened rolled copper foil for high-frequency circuits, characterized by being a material, is disclosed. And it is described that according to this, the printed circuit board which can be used under the high frequency exceeding 1 GHz can be provided.

  Further, Patent Document 3 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm made of bump-shaped protrusions. And according to this, it describes that the electrolytic copper foil excellent in the high frequency transmission characteristic can be provided.

Further, Patent Document 4 is a surface-treated copper foil in which a surface treatment layer is formed on at least one surface, the surface treatment layer includes a roughening treatment layer, and the total of Co, Ni, and Fe in the surface treatment layer The adhesion amount is 300 μg / dm ² or less, the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the ratio of the three-dimensional surface area to the two-dimensional surface area measured by a laser microscope on the surface treatment layer surface is 1.0 to 1.9, surface roughness Rz JIS of at least one surface is 2.2 μm or less, surface treatment layers are formed on both surfaces, and surface roughness Rz JIS of both surfaces Discloses a surface-treated copper foil having a thickness of 2.2 μm or less. And according to this, it is described that it is possible to provide a surface-treated copper foil in which transmission loss is satisfactorily suppressed even when used for a high-frequency circuit board.

Japanese Patent No. 4161304 Japanese Patent No. 4770425 JP 2004-244656 A Japanese Patent No. 5710737

  Various studies have been made on the control of transmission loss of copper foil when used for a high-frequency circuit board as described above, but there is still a lot of room for development. In recent years, along with the high integration of semiconductors, the miniaturization of the circuit of the printed wiring board used therein has progressed, and further improvement of the fine circuit formability of the copper foil is also desired.

  In the surface-treated copper foil having a copper foil and a surface-treated layer including a roughened layer on one or both surfaces of the copper foil, the Co content ratio in the surface-treated layer, and the surface-treated layer It has been found that by controlling the ten-point average roughness Rz on the outermost surface, transmission loss can be satisfactorily reduced even when used for a high-frequency circuit board, and fine circuit formability is improved.

  The present invention has been completed on the basis of the above knowledge. In one aspect, the present invention is a surface-treated copper foil having a copper foil and a surface-treated layer including a roughened layer on one or both sides of the copper foil. The surface treatment layer contains Co, and the Co content in the surface treatment layer is 15% by mass or less (excluding 0% by mass), and the ten-point average roughness of the outermost surface of the surface treatment layer It is a surface-treated copper foil whose Rz is 1.4 μm or less.

In one embodiment, the surface-treated copper foil of the present invention has a total adhesion amount of the surface-treated layer of 1.0 to 5.0 g / m ² .

  In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Ni, and the content ratio of Ni in the surface-treated layer is 8% by mass or less (excluding 0% by mass).

In still another embodiment of the surface-treated copper foil of the present invention, the adhesion amount of Co in the surface-treated layer is 30 to 2000 μg / dm ² .

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Ni, and the amount of Ni deposited on the surface-treated layer is 10 to 1000 μg / dm ² .

  In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer is selected from the group consisting of the roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. One or more layers.

  In yet another embodiment, the surface-treated copper foil of the present invention is used for a copper-clad laminate or a printed wiring board used under a high frequency exceeding 1 GHz.

  Another aspect of the present invention is a copper foil with a carrier having an intermediate layer and an ultrathin copper layer in this order on one or both sides of the carrier, wherein the ultrathin copper layer is the present invention. It is a copper foil with a carrier which is a surface-treated copper foil.

  In another aspect, the present invention is a laminate having the surface-treated copper foil of the present invention or the copper foil with carrier of the present invention.

  In one embodiment, the laminate of the present invention is a laminate comprising the copper foil with a carrier of the present invention and a resin, and a laminate in which part or all of the end face of the copper foil with a carrier is covered with the resin. It is.

  According to still another aspect of the present invention, the carrier-attached copper foil of the present invention is arranged from the carrier side or the ultrathin copper layer side to the carrier side or the pole of another carrier-attached copper foil of the present invention. It is the laminated body laminated | stacked on the thin copper layer side.

  In still another aspect, the present invention is a method for producing a printed wiring board using the surface-treated copper foil of the present invention or the copper foil with a carrier of the present invention.

  In yet another aspect of the present invention, the step of preparing the surface-treated copper foil of the present invention or the copper foil with carrier of the present invention and an insulating substrate, the step of laminating the surface-treated copper foil and the insulating substrate A step of forming a copper clad laminate, or a step of forming a copper clad laminate via a step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; and Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

  In yet another aspect of the present invention, the step of forming a circuit on the surface-treated layer side surface of the surface-treated copper foil of the present invention, or the surface of the ultrathin copper layer side of the copper foil with a carrier of the present invention or Forming a circuit on the carrier-side surface, the surface-treated layer-side surface of the surface-treated copper foil, or the ultra-thin copper layer-side surface or the carrier-side surface of the copper foil with carrier so that the circuit is buried Forming the resin layer on the substrate, and after forming the resin layer, removing the surface-treated copper foil, or after peeling the carrier or the ultrathin copper layer, the ultrathin copper layer. Or it is a manufacturing method of a printed wiring board including the process of exposing the circuit buried in the resin layer by removing the carrier.

  In yet another aspect of the present invention, the step of laminating the carrier-side surface or the ultrathin copper layer-side surface of the copper foil with a carrier of the present invention and a resin substrate, and laminating the resin substrate of the copper foil with a carrier A step of providing two layers of a resin layer and a circuit at least once on the surface opposite to the coated side, and after forming the two layers of the resin layer and the circuit, the carrier or the carrier from the copper foil with carrier It is the manufacturing method of a printed wiring board including the process of peeling an ultra-thin copper layer.

  In yet another aspect of the present invention, the step of providing at least one layer of a resin layer and a circuit on one or both surfaces of the laminate of the present invention, and two layers of the resin layer and the circuit Is formed, and then the carrier or the ultrathin copper layer is peeled off from the carrier-attached copper foil constituting the laminate.

  In still another aspect, the present invention is a method for manufacturing an electronic device using the printed wiring board manufactured by the method of the present invention.

  According to the present invention, it is possible to provide a surface-treated copper foil capable of satisfactorily reducing transmission loss even when used for a high-frequency circuit board and having good fine circuit formability.

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. It is a schematic schematic diagram of the calculation method of the cross section of the width direction of a circuit pattern, and an etching factor. It is a cross-sectional schematic diagram of the polyimide resin board | substrate and copper circuit in the acid-resistance evaluation test of an Example. It is the surface schematic diagram of the polyimide resin board | substrate and copper circuit in the acid-proof evaluation test of an Example.

<Surface treated copper foil>
The surface-treated copper foil of the present invention has a copper foil and a surface-treated layer on one or both surfaces of the copper foil. After the surface-treated copper foil of the present invention is bonded to an insulating substrate, the surface-treated copper foil can be etched into a target conductor pattern to finally produce a printed wiring board. The surface-treated copper foil of the present invention may be used as a surface-treated copper foil for a high-frequency circuit board. Here, the high-frequency circuit board refers to a circuit board in which the frequency of a signal transmitted using the circuit of the circuit board is 1 GHz or more. Preferably, the frequency of the signal is 3 GHz or more, more preferably 5 GHz or more, more preferably 8 GHz or more, more preferably 10 GHz or more, more preferably 15 GHz or more, more preferably 18 GHz or more, more preferably 20 GHz or more, more preferably. Is 30 GHz or more, more preferably 38 GHz or more, more preferably 40 GHz or more, more preferably 45 GHz or more, more preferably 48 GHz or more, more preferably 50 GHz or more, more preferably 55 GHz or more, more preferably 58 GHz or more.

<Copper foil>
There is no restriction | limiting in particular in the form of the copper foil which can be used for this invention, Typically, the copper foil used in this invention may be either an electrolytic copper foil or a rolled copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Rolled copper foil is often used for applications that require flexibility.
Copper foil materials include tough pitch copper (JIS H3100 alloy number C1100), oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), and phosphorus deoxidized copper (JIS H3100), which are usually used as conductor patterns for printed wiring boards. In addition to high-purity copper such as alloy number C1201, C1220 or C1221) and electrolytic copper, for example, copper containing Sn, copper containing Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Copper alloys such as a copper alloy to which Zr and / or Mg or the like are added, and a Corson-based copper alloy to which Ni and Si or the like are added can also be used. Moreover, the copper foil and copper alloy foil which have a well-known composition can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.
The thickness of the copper foil is not particularly limited, but for example, 1 to 1000 μm, alternatively 1 to 500 μm, alternatively 1 to 300 μm, alternatively 3 to 100 μm, alternatively 5 to 70 μm, alternatively 6 to 35 μm, alternatively 9 to 18 μm. It is.
In another aspect, the present invention is a copper foil with a carrier having an intermediate layer and an ultrathin copper layer in this order on one side or both sides of the carrier, wherein the ultrathin copper layer is It is a surface-treated copper foil. When using copper foil with a carrier in this invention, surface treatment layers, such as the following roughening process layers, are provided in the ultra-thin copper layer surface. In addition, another embodiment of the copper foil with a carrier will be described later.

<Surface treatment layer>
The surface treatment layer of the surface-treated copper foil of the present invention contains Co, and the content ratio of Co in the surface treatment layer is 15% by mass or less (excluding 0% by mass). By setting the Co content ratio to 15% by mass or less, high-frequency transmission characteristics can be improved. The content ratio of Co is preferably 14% by mass or less, more preferably 13% by mass or less, more preferably 12% by mass or less, and more preferably 11% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 9 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 7.5 mass% or less, 7 mass% or less Is more preferable, and it is still more preferable that it is 6.5 mass% or less. Moreover, when the surface treatment layer of the surface-treated copper foil contains Co, the fine circuit formability may be improved. The Co content in the surface treatment layer is preferably 0% by mass or more, preferably greater than 0% by mass, preferably 0.05% by mass or more, and 0.09% by mass or more. Preferably, it is 0.1% by weight or more, preferably 0.15% by weight or more, preferably 0.18% by weight or more, preferably 0.2% by weight or more, It is preferably 0.5% by mass or more, preferably 0.8% by mass or more, preferably 0.9% by mass or more, and preferably 1.0% by mass or more. It is preferably 5% by mass or more, preferably 2.0% by mass or more, preferably 2.5% by mass or more, preferably 3.0% by mass or more, and 3.5% by mass. % Or more Preferably, it is preferable that 4.0 wt% or more.

The amount of Co deposited on the surface treatment layer is preferably 30 μg / dm ² or more. If the amount of Co deposited is 30 μg / dm ² or more, the solubility in an etching solution during circuit fabrication is good, and the fine wiring formability may be improved. Further, the amount of Co deposited on the surface treatment layer is preferably 2000 μg / dm ² or less. Further, when the amount of Co adhesion is 2000 μg / dm ² or less, the high-frequency transmission characteristics may be further improved. The adhesion amount of Co in the surface treatment layer is preferably 35 μg / dm ² or more, preferably 40 μg / dm ² or more, preferably 45 μg / dm ² or more, and 50 μg / dm ² or more. preferably there is preferably at 55 [mu] g / dm ² or more, preferably 60 [mu] g / dm ² or more, preferably is preferably 100 [mu] g / dm ² or more and 150 [mu] g / dm ² or more, 200 [mu] g / Dm ² or more, preferably 250 μg / dm ² or more, preferably 300 μg / dm ² or more, preferably 350 μg / dm ² or more, and 400 μg / dm ² or more. it is preferred, it is preferred that it is preferably 450 [mu] g / dm ² or more and 500 [mu] g / dm ² or more, Is preferably 50 [mu] g / dm ² or more, preferably 600 [mu] g / dm ² or more. Further, the adhesion amount of Co in the surface treatment layer is preferably at 1950μg / dm ² or less, preferably is preferably 1900μg / dm ² or less, 1850μg / dm ² or less, 1800 [mu] g / dm ² preferably less, is preferably 1750μg / dm ² or less, preferably 1700μg / dm ² or less, preferably is preferably 1650μg / dm ² or less, 1600μg / dm ² or less 1550 μg / dm ² or less, preferably 1500 μg / dm ² or less, preferably 1450 μg / dm ² or less, preferably 1400 μg / dm ² or less, 1350 μg / dm ² or less. it is preferably, preferably not less 1300μg / dm ² or less Is preferably at 1250μg / dm ² or less, preferably 1200 [mu] g / dm ² or less, preferably 1150μg / dm ² or less, preferably 1100μg / dm ² or less, 1050μg / dm ² or less is preferably, it is preferably 1000 [mu] g / dm ² or less, is preferably 950μg / dm ² or less.

In the surface-treated copper foil of the present invention, the total adhesion amount of the surface-treated layer is preferably 1.0 g / m ² or more. The total adhesion amount of the surface treatment layer is the total adhesion amount of elements constituting the surface treatment layer. Examples of the elements constituting the surface treatment layer include Cu, Ni, Co, Cr, Zn, W, As, Mo, P, and Fe. When the total adhesion amount of the surface treatment layer is 1.0 g / m ² or more, the adhesion between the surface treatment copper foil and the resin may be improved. It is preferable that the total adhesion amount of the surface treatment layer is 5.0 g / m ² or less. When the total adhesion amount of the surface treatment layer is 5.0 g / m ² or less, the high frequency transmission characteristics may be further improved. The total adhesion amount of the surface treatment layer is preferably 1.05 g / m ² or more, more preferably 1.1 g / m ² or more, and preferably 1.15 g / m ² or more. preferably at .2g / m ² or more, preferably at 1.25 g / m ² or more, preferably at 1.3 g / m ² or more, preferably at 1.35 g / m ² or more . Further, the total adhesion amount of the surface treatment layer is preferably 4.8 g / m ² or less, more preferably 4.6 g / m ² or less, and preferably 4.4 g / m ² or less. It is preferably 4.3 g / m ² or less, preferably 4.0 g / m ² or less, preferably 3.5 g / m ² or less, and 3.0 g / m ² or less. Is preferably 2.5 g / m ² or less, preferably 2.0 g / m ² or less, preferably 1.9 g / m ² or less, and 1.8 g / m ² or less. located in preferably, preferably at 1.7 g / m ² or less, preferably at 1.65 g / m ² or less, preferably at 1.60 g / m ² or less, 1.55 g / m ² it is preferably less, preferably at 1.50 g / m ² or less, is 1.45 g / m ² or less Is more preferably 1.43 μg / dm ² or less, and even more preferably 1.4 g / m ² or less.

  It is preferable that the surface treatment layer of the surface-treated copper foil contains Ni. When the surface treatment layer of the surface-treated copper foil contains Ni, there may be an effect that the acid resistance is improved. The surface treatment layer preferably contains Ni, and the Ni content in the surface treatment layer is preferably 8% by mass or less (excluding 0% by mass). When the Ni content is 8% by mass or less, the high-frequency transmission characteristics of the surface-treated copper foil may be further improved. The content ratio of Ni in the surface treatment layer is more preferably 7.5% by mass or less, more preferably 7% by mass or less, more preferably 6.5% by mass or less, and 6% by mass. More preferably, it is more preferably 5.5% by mass or less, more preferably 5% by mass or less, more preferably 4.8% by mass or less, and 4.5% by mass. More preferably, it is more preferably 4.2% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.8% by mass or less. The Ni content in the surface treatment layer is preferably 0% by mass or more, preferably greater than 0% by mass, preferably 0.05% by mass or more, and 0.09% by mass or more. Preferably, it is 0.1% by mass or more, preferably 0.15% by mass or more, preferably 0.18% by mass or more, and 0.2% by mass or more. Is preferably 0.5% by mass or more, preferably 0.8% by mass or more, preferably 0.9% by mass or more, and preferably 1.0% by mass or more. 1.1% by mass or more, preferably 1.2% by mass or more, preferably 1.3% by mass or more, and preferably 1.4% by mass or more. .5% by mass or more There it is preferable.

It is preferable that the surface treatment layer contains Ni, and the adhesion amount of Ni in the surface treatment layer is 10 μg / dm ² or more. When the adhesion amount of Ni is 10 μg / dm ² or more, the acid resistance of the surface-treated copper foil may be good. Further, the adhesion amount of Ni in the surface treatment layer is preferably 1000 μg / dm ² or less. If the adhesion amount of Ni is 1000 μg / dm ² or less, the high frequency transmission characteristics may be further improved. The adhesion amount of Ni is preferably 20 μg / dm ² or more, preferably 30 μg / dm ² or more, preferably 40 μg / dm ² or more, and preferably 50 μg / dm ² or more. preferably at 100 [mu] g / dm ² or more, preferably at 120 [mu] g / dm ² or more, preferably at 140 [mu] g / dm ² or more, preferably at 160 [mu] g / dm ² or more, at 180 [mu] g / dm ² or more preferably there is preferably at 200 [mu] g / dm ² or more, preferably at 220μg / dm ² or more, preferably at 240 [mu] g / dm ² or more, preferably at 260μg / dm ² or more, 280 [mu] g / Dm ² or more is preferable. The coating weight of the Ni is preferably equal to or less than 950μg / dm ^2, preferably at 900 [mu] g / dm ² or less, preferably at 850μg / dm ² or less, that is 800 [mu] g / dm ² or less preferably, preferably at 750 [mu] g / dm ² or less, preferably at 700 [mu] g / dm ² or less, preferably at 650μg / dm ² or less, preferably at 600 [mu] g / dm ² or less, 550μg / dm ² less and even preferable, preferably at 500 [mu] g / dm ² or less, preferably at 450 [mu] g / dm ² or less, preferably at 400 [mu] g / dm ² or less, preferably at 350 [mu] g / dm ² or less 300 μg / dm ² or less, preferably 250 μg / dm ² or less, and preferably 200 μg / dm ² or less. Preferred, preferably at 180 [mu] g / dm ² or less, preferably at 160 [mu] g / dm ² or less.

  In the present invention, the total adhesion amount of the surface treatment layer, the Co content rate in the surface treatment layer, the Ni content rate, and the adhesion amount of elements such as Co, Ni, etc. Is present in the surface treatment layer on one side and is not the total value of elements (for example, Co) contained in the surface treatment layer formed on both sides.

  In addition, the adhesion amount of the element contained in the surface treatment layer is such that the concentration of the element in the surface treatment liquid used when forming the surface treatment layer is increased and / or when the surface treatment is plating. The current density can be increased by increasing the current density and / or increasing the surface treatment time (the energization time for plating). In addition, the adhesion amount of the element contained in the surface treatment layer is such that the concentration of the element in the surface treatment liquid used when forming the surface treatment layer is lowered and / or when the surface treatment is plating. It is possible to reduce the current density by reducing the current density and / or shortening the surface treatment time (the energization time for plating).

  In the surface-treated copper foil of the present invention, the ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.4 μm or less. When the ten-point average roughness Rz of the outermost surface of the surface treatment layer exceeds 1.4 μm, there is a possibility that a problem that high-frequency transmission characteristics deteriorate. The ten-point average roughness Rz of the outermost surface of the surface treatment layer is more preferably 1.3 μm or less, still more preferably 1.1 μm or less, and even more preferably 0.9 μm or less. The “outermost surface of the surface treatment layer” is the surface of the outermost layer (outermost surface) of the plurality of layers when the surface treatment layer is formed by a plurality of layers formed by the surface treatment. means. And ten-point average roughness Rz is measured about the surface of the outermost layer (outermost surface) of the plurality of layers. The lower limit of the ten-point average roughness Rz on the outermost surface of the surface treatment layer is not particularly limited, but is typically 0.01 μm or more, for example 0.05 μm or more, for example 0.1 μm or more.

  The surface treatment layer of the surface-treated copper foil of the present invention has a roughening treatment layer. The surface of the copper foil after degreasing is generally intended to improve the peel strength of the copper foil after lamination on the surface of the copper foil that adheres to the resin base, that is, the roughened surface. In addition, it is formed by performing “fist-bump” -shaped electrodeposition. Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off. In the present invention, such a pretreatment and finishing treatment are referred to as “roughening treatment”.

  The roughening treatment layer in the surface-treated copper foil of the present invention can be produced, for example, by forming secondary particles after forming primary particles under the following conditions.

(Primary particle plating conditions)
An example of the primary particle plating conditions is as follows.
Liquid composition: Copper 10-20 g / L, sulfuric acid 50-100 g / L
Liquid temperature: 25-50 degreeC
Current density: 1 to 58 A / dm ²
Coulomb amount: 1.5 to 70 As / dm ²

(Plating conditions for secondary particles)
An example of secondary particle plating conditions is as follows.
Liquid composition: Copper 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L
pH: 2-3
Liquid temperature: 30-50 degreeC
Current density: 20 to 50 A / dm ²
Coulomb amount: 12-50 As / dm ²

  The surface treatment layer may include a roughening treatment layer and one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. Note that each of the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

As the heat-resistant layer and rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. Further, the heat-resistant layer and / or the rust-preventing layer may contain oxides, nitrides and silicides containing the above-mentioned elements. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer is a nickel - molybdenum alloy, nickel - zinc alloys, nickel - molybdenum -You may be comprised by either 1 type of a cobalt alloy and a nickel- tin alloy.

  In the present specification, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

  The silane coupling treatment layer may be formed using a known silane coupling agent, such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, triazine silane. You may form using silane coupling agents, such as. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  In addition, on the surface of copper foil, ultrathin copper layer, roughening treatment layer, heat-resistant layer, rust prevention layer, silane coupling treatment layer or chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-111169A, Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A Processing can be performed.

<Transmission loss>
When the transmission loss is small, attenuation of the signal when performing signal transmission at a high frequency is suppressed, so that a stable signal transmission can be performed in a circuit that transmits the signal at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency. After bonding the surface-treated copper foil with a commercially available liquid crystal polymer resin (Vecstar CTZ manufactured by Kuraray Co., Ltd., thickness 50 μm, a resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), When a microstrip line is formed by etching so that the characteristic impedance is 50Ω, a transmission coefficient is measured using a network analyzer HP8720C manufactured by HP, and a transmission loss at a frequency of 40 GHz is obtained. Is preferably less than 7.5 dB / 10 cm, more preferably less than 7.3 dB / 10 cm, more preferably less than 7.1 dB / 10 cm, more preferably less than 7.0 dB / 10 cm, and more preferably less than 6.9 dB / 10 cm. 6.8dB / 10cm or less is more preferable , More preferably less than 6.7dB / 10 cm, more preferably less than 6.6 dB / 10 cm, less than 6.5 dB / 10 cm is more preferred.

<Copper foil with carrier>
The copper foil with a carrier which is another embodiment of the present invention has an intermediate layer and an ultrathin copper layer in this order on one side or both sides of the carrier. And the said ultra-thin copper layer is the surface treatment copper foil which is one embodiment of the above-mentioned this invention.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCP (liquid crystal polymer) film, fluororesin film, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyamide film, and polyamideimide film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include tough pitch copper (JIS H3100 alloy number C1100), oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), high-purity copper such as phosphorous deoxidized copper and electrolytic copper, and Sn Copper alloys such as copper containing, copper containing Ag, copper alloys added with Cr, Zr, Mg, etc., and Corson copper alloys added with Ni, Si, etc. can also be used. Moreover, a well-known copper alloy can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.
In addition, you may provide a primary particle layer and a secondary particle layer in the surface on the opposite side to the surface in the side which provides the ultra-thin copper layer of a carrier. Providing the primary particle layer and the secondary particle layer on the surface opposite to the surface on the side on which the ultrathin copper layer of the carrier is provided means that the carrier is transferred from the surface side having the primary particle layer and the secondary particle layer to the resin substrate, etc. When it is laminated on the support, there is an advantage that the carrier and the resin substrate are hardly separated.

Below, an example of manufacturing conditions in the case of using electrolytic copper foil as a carrier is shown.
<Electrolyte composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

  The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.

(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.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance Or a single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al It can be constructed by forming an alloy layer made of a selected one or more elements from the configured group of elements in Zn.

When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, more typically 1.5 to 4 μm, and more typically 2 to 3.5 μm. In addition, you may provide an ultra-thin copper layer on both surfaces of a carrier.

  The method of using the surface-treated copper foil of the present invention and / or the carrier-attached copper foil of the present invention is well known to those skilled in the art. For example, the surface of the surface-treated copper foil and / or the ultrathin copper layer is made of paper. Base material phenolic resin, paper base material epoxy resin, synthetic fiber cloth base material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, Bonded to an insulating substrate such as polyimide film, liquid crystal polymer, fluororesin, polyamide resin, low dielectric polyimide film, etc. (in the case of copper foil with carrier, peel off the carrier after thermocompression bonding) to make a copper clad laminate, Etching the bonded surface-treated copper foil and / or ultra-thin copper layer into the desired conductor pattern, and finally producing a printed wiring board Kill.

<Resin layer>
The surface-treated copper foil of the present invention may include a resin layer on the surface of the surface-treated layer. Also, an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, or chromate A resin layer may be provided on the surface of the layer, the silane coupling layer, or the Ni—Zn alloy layer. The resin layer is more preferably formed on the outermost surface of the surface-treated copper foil.
The copper foil with a carrier of the present invention may include a resin layer on the primary particle layer or the secondary particle layer, and on the heat-resistant layer, the rust preventive layer, the chromate treatment layer, or the silane coupling treatment layer.

  The resin layer may be an adhesive or may be a semi-cured (B stage) insulating resin layer for bonding. The semi-cured state (B stage) is a state where there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and further a curing reaction occurs when subjected to heat treatment. including.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin , Polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin , Polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting poly Nylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having a crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) Propane, phosphorus-containing phenolic compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin , Isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin. It can be mentioned resins as preferred.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins , Biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a mixture of two or more types, or a hydrogenated product of the epoxy resin Or a halogenated compound can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO2006 / 028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  These resins described above are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin liquid, which is used on the surface-treated copper foil and / or the ultrathin copper layer, or the heat-resistant layer, On the surface treatment layer including the rust layer, the chromate film layer, the silane coupling agent layer, etc., for example, by a roll coater method or the like, and then heated and dried as necessary to remove the solvent and remove the B stage. Put it in a state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

  The surface-treated copper foil provided with the resin layer and / or the copper foil with carrier (copper foil with carrier with resin) is laminated on the base material and then thermocompression bonded over the resin layer. When it is a copper foil with a carrier, the carrier is peeled off to expose an ultrathin copper layer (which is naturally exposed on the surface of the intermediate layer side of the ultrathin copper layer), It is used in such a manner that a predetermined wiring pattern is formed on the surface-treated copper foil or ultrathin copper layer.

  When this surface-treated copper foil with resin and / or copper foil with carrier is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

  In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.

  The thickness of the resin layer is preferably 0.1 to 80 μm. When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.

  On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer having a desired thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

  Furthermore, as another product form of the copper foil with a carrier with resin, the surface treatment layer of the ultra-thin copper layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling treatment It is also possible to manufacture in the form of a resin-coated copper foil in which no carrier is present after coating the layer with a resin layer to make it a semi-cured state and then peeling the carrier.

A printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown. In addition, a printed wiring board can be similarly manufactured even if it uses the surface-treated copper foil of this invention as an ultra-thin copper layer of copper foil with a carrier.

  In one embodiment of the method for producing a printed wiring board according to the present invention, the copper foil with carrier according to the present invention (hereinafter referred to as “copper foil with carrier” and “ultra-thin copper layer” is read as surface-treated copper foil, A printed wiring board may be manufactured by replacing “ultra-thin copper layer side” with “surface treatment layer side.” When replaced as described above, a printed wiring board is manufactured assuming that there is no description of the carrier. And the step of preparing an insulating substrate, the step of laminating the copper foil with carrier and the insulating substrate, and the layering of the copper foil with carrier and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate. Then, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-additive method, a partly additive method, and a subtractive method. By any method, including a step of forming a circuit. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

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

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

  In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.
In the above-described printed wiring board manufacturing method, “ultra-thin copper layer” is used as a carrier, “carrier” is read as an ultra-thin copper layer, and a circuit is formed on the carrier-side surface of the copper foil with carrier. It is also possible to manufacture a printed wiring board by embedding a circuit with resin.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 3H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  According to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, when removing the ultrathin copper layer by flash etching as shown in FIG. In addition, the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

  Moreover, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having the said board | substrate or resin layer, the copper foil with a carrier used for the first layer is supported, and since it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer and known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification, Organic compound foils can be used.

Further, the method for producing a printed wiring board of the present invention includes a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing at least once a resin layer and a circuit on the surface of the copper layer with carrier on the opposite side of the copper layer side surface or the carrier side surface, and forming two layers of the resin layer and the circuit Then, a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultrathin copper layer from the carrier-attached copper foil may be used. As a specific example of the coreless construction method, first, an ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated to form a laminate (copper-clad laminate, copper-clad laminate). (Also referred to as a laminate). Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. You may laminate | stack another copper foil with a carrier from the carrier side or the ultra-thin copper layer side to the resin layer formed in the carrier side surface or the ultra-thin copper layer side surface. Also, centering on the resin substrate or resin or prepreg, on the surface side of both the resin substrate or resin or prepreg, in the order of carrier / intermediate layer / ultra thin copper layer or ultra thin copper layer / intermediate layer / carrier. A laminated body having a structure in which a copper foil with a carrier is laminated or a structure laminated in the order of “carrier / intermediate layer / ultra thin copper layer / resin substrate or resin or prepreg / carrier / intermediate layer / ultra thin copper layer”. Laminate or “laminate / intermediate layer / ultra-thin copper layer / resin substrate / carrier / intermediate layer / ultra-thin copper layer” in the order of laminate or “ultra-thin copper layer / intermediate layer / carrier / resin” You may use the laminated body which has the structure laminated | stacked in order of "board | substrate / carrier / intermediate layer / ultra-thin copper layer" in the above-mentioned printed wiring board manufacturing method (coreless construction method). And, on the exposed surface of the ultra-thin copper layer or carrier at both ends of the laminate, another resin layer is provided, and after further providing a copper layer or a metal layer, the copper layer or the metal layer is processed. A circuit may be formed. Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed one or more times (build-up method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the production of the coreless substrate described above, a laminate having a configuration of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer described later using two copper foils with a carrier, Laminate having a structure of carrier / intermediate layer / ultra thin copper layer / ultra thin copper layer / intermediate layer / carrier, or a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer It is also possible to produce a laminated body and use the laminated body as a center. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer. The above-mentioned laminated body has other surfaces between the surface of the ultrathin copper layer, the surface of the carrier, between the carrier, between the ultrathin copper layer and the ultrathin copper layer, and between the ultrathin copper layer and the carrier. You may have a layer. The other layer may be a resin substrate or a resin layer. In this specification, “surface of ultrathin copper layer”, “surface of ultrathin copper layer side”, “surface of ultrathin copper layer”, “surface of carrier”, “surface of carrier side”, “carrier surface”, “ "Surface of laminated body" and "laminated body surface" means an ultrathin copper layer, a carrier, and a laminated body, if the ultrathin copper layer surface, carrier surface, and laminated body surface have other layers, the other layer The concept includes the surface (outermost surface). Moreover, it is preferable that a laminated body has the structure of an ultra-thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra-thin copper layer. This is because, when a coreless substrate is manufactured using the laminate, an ultrathin copper layer is disposed on the coreless substrate side, so that a circuit can be easily formed on the coreless substrate using the modified semi-additive method. In addition, since the thickness of the ultrathin copper layer is thin, it is easy to remove the ultrathin copper layer, and it becomes easier to form a circuit on the coreless substrate using the semi-additive method after the ultrathin copper layer is removed. .
In this specification, “laminate” not specifically described as “laminate A” or “laminate B” indicates a laminate including at least laminate A and laminate B.

  In the above coreless substrate manufacturing method, a printed wiring board is manufactured by a build-up method by covering part or all of the end face of the copper foil with carrier or the above-mentioned laminated body (including laminated body A) with a resin. In doing so, it is possible to prevent infiltration of the chemical solution between one copper foil with a carrier and another copper foil with a carrier constituting the intermediate layer or laminate, and an ultrathin copper layer due to the infiltration of the chemical solution, The separation of the carrier and the corrosion of the copper foil with the carrier can be prevented, and the yield can be improved. As used herein, “resin that covers part or all of the end face of the copper foil with carrier” or “resin that covers part or all of the end face of the laminate” may be a resin that can be used for the resin layer or a known resin. Can be used. Further, in the above-described coreless substrate manufacturing method, the carrier-attached copper foil or laminate when viewed in plan, the carrier-attached copper foil or laminate portion (a laminate portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery of the laminated copper foil with carrier and another copper foil with carrier may be covered with resin or prepreg. Moreover, the laminated body (laminated body A) formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact each other so that isolation | separation is possible. Further, when viewed in plan in the copper foil with carrier, the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultrathin copper layer, or one copper foil with carrier and another copper with carrier) It may be formed by being covered with a resin or a prepreg over the entire outer periphery or the entire surface of the laminated portion. In addition, when viewed in plan, the resin or prepreg is preferably larger than the copper foil with carrier or the laminate or the laminated portion of the laminate, and the resin or prepreg is laminated on both sides of the carrier-attached copper foil or laminate, It is preferable to use a laminated body having a configuration in which the attached copper foil or the laminated body is bound (wrapped) with a resin or a prepreg. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Covered copper foil with carrier or laminated part of laminated body (laminated part of carrier and ultrathin copper layer, or laminated part of one copper foil with carrier and another copper foil with carrier) is resin or When the prepreg or the like is firmly attached, it may be necessary to remove the laminated portion by cutting or the like.

  The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention. Moreover, the said carrier side surface or said ultra-thin copper layer side surface of said one copper foil with a carrier and the said carrier side surface or said ultra-thin copper layer side surface of said another copper foil with a carrier are as needed. Alternatively, a laminate obtained by directly laminating through an adhesive may be used. Further, the carrier or ultrathin copper layer of the one copper foil with carrier and the carrier or ultrathin copper layer of the other copper foil with carrier may be joined. Here, in the case where the carrier or the ultrathin copper layer has a surface treatment layer, the “joining” includes a mode in which the carriers or the ultrathin copper layer are joined to each other via the surface treatment layer. Further, part or all of the end face of the laminate may be covered with resin.

Lamination of carriers, ultrathin copper layers, carriers and ultrathin copper layers, and copper foils with a carrier can be performed by the following method, for example, in addition to superimposing.
(A) Metallurgical joining method: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, Friction stir welding), brazing;
(B) Mechanical joining method: caulking, joining with rivets (joining with self-piercing rivets, joining with rivets), stitcher;
(C) Physical joining method: adhesive, (double-sided) adhesive tape

  By joining part or all of one carrier and part or all of the other carrier or part or all of the ultrathin copper layer using the joining method, one carrier and the other carrier or pole A laminated body constituted by laminating thin copper layers and contacting the carriers or the carrier and the ultrathin copper layer in a separable manner can be produced. When one carrier and the other carrier or ultrathin copper layer are weakly bonded and one carrier and the other carrier or ultrathin copper layer are laminated, one carrier and the other carrier or ultrathin copper layer Even without removing the junction with the thin copper layer, one carrier and the other carrier or ultrathin copper layer can be separated. In addition, when one carrier and the other carrier or ultrathin copper layer are strongly bonded, the portion where one carrier and the other carrier or ultrathin copper layer are bonded is cut or chemically polished ( One carrier and the other carrier or the ultrathin copper layer can be separated by removing them by etching or the like.

Also, a step of providing at least one layer of the resin layer and the circuit on the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, the carrier of the laminate is provided with a carrier. The printed wiring board which does not have a core is producible by implementing the process of peeling the said ultra-thin copper layer or carrier from copper foil. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.
The resin substrate, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. An accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like may be included. In addition, the above-mentioned copper foil with a carrier or laminated body may be smaller than resin, a prepreg, a resin substrate, or a resin layer when planarly viewed.

  The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board and the like. For example, for a rigid PWB, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base Epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film for FPC Fluorine resin can be used. In addition, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the copper circuit is covered with a coverlay after the copper circuit is formed, so that the film and the copper circuit are not easily peeled off, and the peel strength is reduced. The film can be prevented from peeling off from the copper circuit.

  Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example. That is, other aspects or modifications included in the present invention are included.

In the raw foils of Example 6 and Comparative Example 5, a rolled copper foil TPC having a thickness of 12 μm (tough pitch copper standardized in JIS H3100 C1100, made of JX Metal, surface ten-point average roughness Rz = 0.7 μm) It was used. For the raw foils of Example 7 and Comparative Example 6, 12 μm thick electrolytic copper foil (JX metal HLP foil, 10-point average roughness Rz = 0.7 μm of the surface of the precipitation surface (M surface)) was used. The surface treatment layer was provided on the precipitation surface (M surface).
Moreover, the copper foil with a carrier manufactured with the following method was used for the raw foil of Examples 1-5, 8-15, and Comparative Examples 1-4.
In Examples 1 to 5, 8, 10 to 15, and Comparative Examples 1 to 4, an electrolytic copper foil (JTC metal JTC foil) having a thickness of 18 μm was prepared as a carrier, and for Example 9, the above-described thickness of 18 μm was prepared. Standard rolled copper foil TPC was prepared as a carrier. Under the following conditions, an intermediate layer was formed on the surface of the carrier, and an ultrathin copper layer having a thickness (1 μm or 3 μm) shown in Table 1 was formed on the surface of the intermediate layer. When the carrier was an electrolytic copper foil, an intermediate layer was formed on the glossy surface (S surface).

-Examples 1-5, 8-15 and Comparative Examples 1-4
<Intermediate layer>
(1) Ni layer (Ni plating)
An Ni layer having an adhesion amount of 3000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Liquid temperature: 55-65 degreeC
Current density: 10 A / dm ²
(2) Cr layer (electrolytic chromate treatment)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm ² is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
<Ultrathin copper layer>
Next, after the surface of the Cr layer formed in (2) was washed with water and pickled, the thickness described in Table 1 (1 μm or 3 μm on the Cr layer on a continuous roll-to-roll type continuous plating line. ) Was electroplated under the following conditions to produce a carrier-attached copper foil.
Copper concentration: 90-110 g / L
Sulfuric acid concentration: 90-110 g / L
Chloride ion concentration: 50-90ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
In addition, 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: 100 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec

<Roughening treatment 1, roughening treatment 2>
Subsequently, using the plating bath described in Table 3, as shown in Table 1, roughening treatment 1 was performed. For Examples 3, 12 to 14, and Comparative Examples 1, 5, and 6, the roughening treatment 2 was performed as shown in Table 1 using the plating bath shown in Table 3 following the roughening treatment 1. It was.

<Heat-resistant treatment, rust-proof treatment>
Subsequently, for Examples 2, 3, and 10 to 14, heat treatment was performed as described in Table 1 using the plating bath described in Table 4. Furthermore, about Examples 10 and 11, the rust prevention process was performed as described in Table 1 using the plating bath described in Table 4.

<Chromate treatment, silane coupling treatment>
Then, the following electrolytic chromate processes were performed about Examples 1-5, 8-15, and Comparative Examples 1-6.
Electrolytic chromate treatment liquid composition: potassium dichromate 1-1g / L
Liquid temperature: 40-60 degreeC
pH: 0.5-10
Current density: 0.01 to 2.6 A / dm ²
Energization time: 0.05 to 30 seconds Then, about Examples 1-5, 7-15, and Comparative Examples 1-6, the silane coupling process using the following diaminosilane was performed.
Silane coupling treatment Silane coupling agent: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane Silane coupling agent concentration: 0.5 to 1.5 vol%
Process temperature: 20-70 degreeC
Processing time: 0.5-5 seconds

(Total adhesion amount of surface treatment layer)
-Identification of the number of roughening particles before etching The surface side having the surface treatment layer of Examples and Comparative Examples was photographed at a magnification of 10,000 with a scanning electron microscope (SEM). The number of roughened particles was counted in three arbitrary fields of view of the obtained photograph having a size of 5 μm × 5 μm. The arithmetic average value of the roughened particles in the three fields of view was defined as the number of roughened particles per field of view. In addition, the roughening particle | grains in which a part of roughening particle | grains are contained in the visual field were also counted as roughening particle | grains.

-Execution of etching Etching was performed for 0.5 seconds under the following conditions.
(Etching conditions)
・ Etching type: Spray etching ・ Spray nozzle: Full cone type ・ Spray pressure: 0.10 MPa
・ Etching temperature: 30 ℃
・ Etching solution composition:
H ₂ O ₂ 18g / L
H ₂ SO ₄ 92 g / L
Cu 8g / L
Additive JFE Co., Ltd. FE-830IIW3C Appropriate amount Remaining water In addition, in order to prevent erosion by an etching liquid, the surface which is not etched was masked with acid-resistant tape or prepreg.

Measurement of the number of roughened particles on the sample surface after etching and determination of the etching end time The number of roughened particles on the sample surface after etching was measured in the same manner as described above.
When the number of roughened particles was 5% or more and 20% or less of the number of roughened particles before etching, the etching was terminated.
Whether or not the aforementioned number of roughened particles is a number of 5% or more and 20% or less of the number of roughened particles before etching is determined by a value A of the following formula being 5% or more and 20% or less. Depending on whether or not.
A (%) = number of rough particles after etching (number / 25 μm ² ) / number of rough particles before etching (number / 25 μm ² ) × 100%
The reason for setting the above-mentioned etching termination standard is that the copper foil or the ultrathin copper layer under the surface treatment layer may be etched at the location where the roughened particles on the sample surface do not exist. When the number of roughened particles exceeded 20% of the number of roughened particles before etching, the etching was again performed for 0.5 seconds. Then, the measurement of the number of roughened particles and the etching for 0.5 second were repeated until the number of roughened particles became 20% or less of the number of roughened particles before etching. When the number of roughened particles is less than 5% of the number of roughened particles before etching during the first 0.5 second etching, the etching time is set to 0 to 0.05 seconds or more. Any time within the range of 4 seconds or less (eg, 0.05 seconds, 0.1 seconds, 0.15 seconds, 0.2 seconds, 0.25 seconds, 0.3 seconds, 0.35 seconds or 0. 4 seconds), the number of roughened particles on the surface of the sample after the etching is measured. The total etching time in which the number of roughened particles was 5% or more and 20% or less of the number of roughened particles before etching was defined as the etching end time.

・ Measurement of the weight of the sample before etching Sample size: 10 cm square sheet (10 cm square sheet punched with a press)
Sampling of sample: Arbitrary 3 places In addition, the precision balance which can measure to four digits after a decimal point was used for the weight measurement of a sample. And the measured value of the obtained weight was used for the said calculation as it was.
Aswan Corporation IBA-200 was used for the precision balance. As the press machine, HAP-12 manufactured by Noguchi Press Co., Ltd. was used.
In addition, you may measure the above-mentioned weight including masking members, such as an acid-proof tape or a prepreg used at the time of implementation of the following etching. In that case, also in the measurement of the sample weight after the etching described later, the weight including the masking member is measured. Moreover, when a sample is a copper foil with a carrier, you may measure the above-mentioned weight including a carrier. In that case, even in the measurement of the sample weight after etching described later, the weight including the carrier is measured.

-Measurement of weight of sample after etching After masking the surface of the sample opposite to the side having the surface treatment layer, the surface treatment surface side of the sample was etched for the etching end time. Thereafter, the weight of the sample was measured. In addition, since the sample observed with the scanning electron microscope deposits noble metals, such as platinum, in the case of observation with a scanning electron microscope, a sample weight becomes larger than the weight of an actual sample. Therefore, the weight of the sample after etching was measured using a sample that was not observed with a scanning electron microscope. The roughening treatment layer is substantially uniformly formed on the copper foil or the ultrathin copper layer. Therefore, it was judged that a sample that was not observed with a scanning electron microscope may be used.

-Calculation of total adhesion amount of surface treatment layer Total adhesion amount of surface treatment layer (g / m ² ) = {(weight of sample of 10 cm square sheet before etching (g / 100 cm ² )) − (10 cm square after etching) weight of the sample sheet ^{(g / 100cm 2))}} × 100 (m 2 / 100cm 2)
The arithmetic average value of the total adhesion amount of the three surface treatment layers was taken as the value of the total adhesion amount of the surface treatment layer.

(Measurement of Co content, Ni content, Co, and Ni adhesion amount in the surface treatment layer)
The amount of Co and Ni deposited was determined by dissolving an ICP emission spectrophotometer manufactured by SII (model: Measurements were made by ICP emission analysis using SPS3100). The arithmetic average value of the adhesion amounts of Co and Ni in the three samples was taken as the value of the adhesion amounts of Co and Ni.
In Examples and Comparative Examples in which a surface treatment layer is provided on both sides of a copper foil, masking is performed by attaching an acid-resistant tape on one side, or thermocompression bonding a prepreg such as FR4, and the like. The amount of adhesion of Co, Ni and other elements was measured. Then, the masking is removed and the amount of Co, Ni and other elements deposited on the other side is measured, or another sample is used to measure the amount of Co, Ni and other elements on the other side. The amount of adhesion was measured. The values shown in Table 2 were values on one side. About the copper foil which provided the surface treatment layer on both surfaces, the adhesion amount of Co, Ni, and another element became the same value on both surfaces. When Co, Ni and other elements are not dissolved in a nitric acid aqueous solution having a concentration of 20% by mass, a solution capable of dissolving Co, Ni and other elements (for example, nitric acid concentration: 20% by mass, hydrochloric acid) The concentration may be measured by the above-described ICP issuance analysis after dissolution using a mixed aqueous solution of nitric acid and hydrochloric acid having a concentration of 12% by mass. Note that a known liquid, a known acidic liquid, or a known alkaline liquid may be used as the liquid capable of dissolving Co and Ni.
In addition, when the unevenness of the copper foil or the ultrathin copper layer is large and the thickness of the copper foil or the ultrathin copper layer is 1.5 μm or less, the thickness of the surface treatment layer side is dissolved by 1 μm. Sometimes, the surface treatment component on the side opposite to the surface treatment layer and the component of the intermediate layer of the copper foil with carrier may also dissolve. Therefore, in such a case, 30% of the thickness of the copper foil or ultrathin copper layer is dissolved from the surface of the copper foil or ultrathin copper layer on the surface treatment layer side.
The “adhesion amount” of an element means the adhesion amount (mass) of the element per unit unit area (1 dm ² or 1 m ² ) of the sample.
Further, the Co content and the Ni content in the surface treatment layer were calculated by the following equations.
Co content (%) in surface treatment layer = Co adhesion amount (μg / dm ² ) / Total adhesion amount of surface treatment layer (g / m ² ) × 10 ⁻⁴ (g / m ² ) / (μg / dm ² ) × 100
Ni content in surface treatment layer (%) = Ni adhesion amount (μg / dm ² ) / total adhesion amount of surface treatment layer (g / m ² ) × 10 ⁻⁴ (g / m ² ) / (μg / dm ² ) × 100

(Measurement of ten-point average roughness Rz)
The surface roughness Rz (ten-point average roughness) of the surface of the roughening treatment layer was measured using a contact roughness meter Surfcorder SE-3C stylus type roughness meter manufactured by Kosaka Laboratory Co., Ltd. according to JIS B0601-1982 It was measured. Rz was arbitrarily measured at 10 locations, and the average value at 10 locations of Rz was defined as the Rz value.

(Measurement of transmission loss)
About each sample, after bonding with a liquid crystal polymer resin substrate (Vecstar CTZ made by Kuraray Co., Ltd.-thickness 50 μm, resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), characteristics are obtained by etching. A microstrip line was formed so that the impedance was 50Ω, and a transmission coefficient was measured using a network analyzer N5247A manufactured by HP, and a transmission loss at a frequency of 40 GHz was obtained. In addition, after laminating | stacking the above-mentioned sample with a liquid crystal polymer resin substrate, about the sample whose thickness of copper foil is thinner than 3 micrometers, the total thickness of copper foil and copper plating was 3 micrometers by carrying out copper plating. Moreover, after laminating the above-mentioned sample with the liquid crystal polymer resin substrate, when the thickness of the copper foil was thicker than 3 μm, the copper foil was etched to a thickness of 3 μm.

(Measurement of peel strength)
About each sample, it bonded together with the liquid crystal polymer resin substrate (Kuraray Co., Ltd. Vecstar CTZ-thickness 50 micrometers, resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxy naphthoic acid (ester)) from the surface treatment layer side. . Thereafter, when the sample was a copper foil with a carrier, the carrier was peeled off. When the thickness of the sample copper foil or ultrathin copper layer is thinner than 18 μm, copper plating is performed on the surface of the copper foil or ultrathin copper layer, and the total thickness of the copper foil or ultrathin copper layer and the copper plating is 18 μm. It was. Moreover, when the thickness of the sample copper foil or ultrathin copper layer was thicker than 18 μm, the thickness of the copper foil or ultrathin copper layer was set to 18 μm by etching. The peel strength was measured according to a 90 ° peeling method (JIS C 6471 8.1) by pulling the liquid crystal polymer resin substrate side with a load cell. The peel strength was measured for three samples for each example and each comparative example. And the arithmetic mean value of the peel strength of 3 samples of each Example and each comparative example was made into the value of the peel strength of each Example and each comparative example. The peel strength is preferably 0.5 kN / m or more.

(Fine wiring formability)
Each sample of Examples and Comparative Examples was bonded to a liquid crystal polymer resin substrate (Vecstar CTZ manufactured by Kuraray Co., Ltd., thickness 50 μm, a resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)). . Thereafter, when the sample was a copper foil with a carrier, the ultrathin copper layer was peeled off from the carrier. Then, about the sample whose thickness of copper foil or ultra-thin copper layer of a sample is thinner than 3 micrometers, the total thickness of copper foil or ultra-thin copper layer and copper plating was 3 micrometers. Moreover, when the thickness of the copper foil or the ultrathin copper layer was thicker than 3 μm, the copper foil was etched to a thickness of 3 μm. Subsequently, after applying a photosensitive resist on the copper foil or ultra-thin copper layer or copper-plated surface on the liquid crystal polymer resin substrate, 50 L / S = 5 μm / 5 μm wide circuits were printed by an exposure process, The etching process which removes the unnecessary part of a copper foil, an ultra-thin copper layer, or a copper plating surface was performed on the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, and the circuit bottom width (the length of the base X) and the etching factor when the circuit top width became 4 μm were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 5 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. By using this etching factor, it is possible to easily determine whether the etching property is good or bad. In the present invention, an etching factor of 6 or more is etching property: ◎◎, 5 or more and less than 6 is etching property: ◎, 4 or more and less than 5 is etching property: ◯, 3 or more and less than 4 is etching property: ○, less than 3, or Impossibility of calculation was evaluated as etching property: x. In the table, “connection” in “the length of the base X” indicates that the circuit cannot be formed because it is connected to an adjacent circuit at least at the base.

(Acid resistance)
Polyamic acid (U-Vanice-A, BPDA (biphenyltetracarboxylic dianhydride) system manufactured by Ube Industries) is applied on each sample of Examples and Comparative Examples, dried at 100 ° C., cured at 315 ° C., and polyimide A copper-clad laminate having a resin substrate (BPDA (biphenyltetracarboxylic dianhydride) polyimide) and a copper foil was formed. Thereafter, when the sample was a copper foil with a carrier, the ultrathin copper layer was peeled off from the carrier. Then, about the sample whose thickness of copper foil or ultra-thin copper layer of a sample is thinner than 3 micrometers, the total thickness of copper foil or ultra-thin copper layer and copper plating was 3 micrometers. Moreover, when the thickness of the copper foil or the ultrathin copper layer was thicker than 3 μm, the copper foil was etched to a thickness of 3 μm. Subsequently, a photosensitive resist is applied to the copper foil or ultrathin copper layer or copper plating surface on the polyimide resin substrate, and then 50 L / S = 5 μm / 5 μm wide circuits (wirings) are printed by the exposure process. And the etching process which removes the unnecessary part of a copper foil, an ultra-thin copper layer, or a copper plating surface was performed on the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued until the circuit top width reached 4 μm. Thereafter, the polyimide resin substrate having a copper circuit was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 1 minute, and the interface between the polyimide resin substrate and the copper circuit was observed with an optical microscope. (See FIGS. 6 and 7) Then, the width of the circuit eroded by an aqueous solution of sulfuric acid and hydrogen peroxide was observed, and the acid resistance was evaluated as follows. The width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide was the length in the width direction of the eroded portion of the circuit. Then, the maximum value of the width of the circuit eroded by the sulfuric acid and hydrogen peroxide aqueous solution in the observed circuit of the sample was defined as the width of the circuit eroded by the sulfuric acid and hydrogen peroxide aqueous solution of the sample.
The evaluation of acid resistance was as follows. “◎”: The width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is less than 0.6 μm, “◎”: The width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is 0.6 μm or more. Less than 8 μm, “◯◯”: the width of the circuit eroded by an aqueous solution of sulfuric acid and hydrogen peroxide is 0.8 μm or more and less than 1.0 μm, “◯”: the width of the circuit eroded by an aqueous solution of sulfuric acid and hydrogen peroxide Is 1.0 μm or more and less than 1.2 μm, “×”: The width of the circuit eroded by the aqueous solution of sulfuric acid and hydrogen peroxide is 1.2 μm or more. The above production conditions and evaluation results are shown in Tables 1-4.

(Evaluation results)
In each of Examples 1 to 15, transmission loss was satisfactorily suppressed and fine circuit formation was good.
In Comparative Examples 1, 5, and 6, the Co content ratio in the surface treatment layer is 0% by mass, and the ten-point average roughness Rz of the outermost surface of the surface treatment layer exceeds 1.4 μm, and the transmission loss And the fine circuit formability was poor.
In Comparative Examples 2 and 4, the Co content ratio in the surface treatment layer exceeded 15 mass%, and the transmission loss was large.
In Comparative Example 3, the Co content in the surface treatment layer was 0% by mass, and the fine circuit formability was poor.

Claims (17)

A surface-treated copper foil having a copper foil and a surface treatment layer including a roughening treatment layer on one or both surfaces of the copper foil,
The surface treatment layer contains Co, and the Co content in the surface treatment layer is 15% by mass or less (excluding 0% by mass),
The surface-treated copper foil whose 10-point average roughness Rz of the outermost surface of the said surface treatment layer is 1.4 micrometers or less. The surface-treated copper foil according to claim 1, wherein a total adhesion amount of the surface-treated layer is 1.0 to 5.0 g / m ² .   2. The surface-treated copper foil according to claim 1, wherein the surface treatment layer contains Ni, and the content ratio of Ni in the surface treatment layer is 8 mass% or less (excluding 0 mass%). The surface-treated copper foil as described in any one of Claims 1-3 whose adhesion amount of Co in the said surface treatment layer is 30-2000 microgram / dm < ² >. The surface-treated copper foil according to any one of claims 1 to 4, wherein the surface-treated layer contains Ni, and an adhesion amount of Ni in the surface-treated layer is 10 to 1000 µg / dm ² .   The said surface treatment layer has the said roughening process layer, and 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The surface-treated copper foil as described in any one.   The surface-treated copper foil as described in any one of Claims 1-6 used for the copper clad laminated board or printed wiring board used under the high frequency over 1 GHz.   It is a copper foil with a carrier which has an intermediate | middle layer and an ultra-thin copper layer in this order on the one surface of a carrier, or both surfaces, Comprising: The said ultra-thin copper layer is as described in any one of Claims 1-7. Copper foil with carrier, which is a surface-treated copper foil.   The laminated body which has the surface-treated copper foil as described in any one of Claims 1-7, or the copper foil with a carrier as described in Claim 8.   It is a laminated body containing the copper foil with a carrier of Claim 8, and resin, Comprising: The laminated body by which one part or all part of the end surface of the said copper foil with a carrier was covered with the said resin.   The copper foil with a carrier according to claim 8 is from the carrier side or the ultrathin copper layer side, and the carrier side or the ultrathin copper layer side of the copper foil with a carrier according to claim 8. Laminated body laminated on.   The manufacturing method of the printed wiring board using the surface-treated copper foil as described in any one of Claims 1-7, or the copper foil with a carrier as described in Claim 8. A step of preparing the surface-treated copper foil according to any one of claims 1 to 7 or the copper foil with a carrier according to claim 8 and an insulating substrate,
A step of forming a copper clad laminate through a step of laminating the surface-treated copper foil and the insulating substrate, or after laminating the copper foil with carrier and the insulating substrate, the carrier of the copper foil with carrier is A step of forming a copper clad laminate through a peeling step; and
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the surface-treated layer side surface of the surface-treated copper foil according to any one of claims 1 to 7, or the ultrathin copper layer side of the carrier-attached copper foil according to claim 8. Forming a circuit on the surface or the carrier side surface;
Forming a resin layer on the surface-treated layer side surface of the surface-treated copper foil, or on the ultrathin copper layer-side surface or the carrier-side surface of the carrier-attached copper foil so that the circuit is buried; and
After forming the resin layer, by removing the surface-treated copper foil, or after peeling the carrier or the ultrathin copper layer, by removing the ultrathin copper layer or the carrier, A method for manufacturing a printed wiring board, comprising a step of exposing a circuit buried in a resin layer. The step of laminating the carrier side surface or the ultrathin copper layer side surface of the copper foil with a carrier according to claim 8 and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. A step of providing two layers of a resin layer and a circuit at least once on one or both surfaces of the laminate according to any one of claims 9 to 11, and
A method for producing a printed wiring board, comprising the step of peeling the carrier or the ultrathin copper layer from a copper foil with a carrier constituting the laminate after forming the resin layer and the two layers of the circuit.   The manufacturing method of the electronic device using the printed wiring board manufactured by the method as described in any one of Claims 12-16.