KR20180064311A - Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device - Google Patents

Abstract

Provided is a surface treated copper foil. According to the present invention, appropriate transmission loss reduction is possible even in the event of use in a high frequency circuit board. In addition, the peel strength of the surface treated copper foil and resin is improved after lamination with the resin and heating for a predetermined time at a predetermined temperature (10 days at 180 degrees Celsius). The surface treated copper foil includes a copper foil and a surface treatment layer on one or both sides of the copper foil. The surface treatment layer has a primary particle layer or has the primary particle layer and a secondary particle layer in this order from the copper foil side. The surface treatment layer contains Zn and the Zn adhesion amount in the surface treatment layer is at least 150 micrograms per square decimeter. The surface treatment layer does not contain Ni or, in a case where the surface treatment layer contains Ni, the Ni adhesion amount in the surface treatment layer is 800 micrograms per square decimeter or less. The surface treatment layer does not contain Co or, in a case where the surface treatment layer contains Co, the Co adhesion amount in the surface treatment layer is 3,000 micrograms per square decimeter or less. The top surface of the surface treatment layer has a 10 point average illumination (Rz) of 1.5 micrometers or less.

Description

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

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

Printed circuit boards have made great strides over the past half century, and today they have been used in almost all electronic devices. In recent years, with increasing demand for miniaturization and high performance of electronic devices, mounting of high-density mounting parts and signal high frequency have been advanced, and excellent high frequency response to printed wiring boards has been demanded.

In the high frequency substrate, reduction of the transmission loss is required in order to secure 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 tangent of the resin become smaller. In the high-frequency signal, the conductor loss is mainly caused by the decrease in the cross-sectional area through which the current flows due to the surface effect that the current flows only on the surface of the conductor as the frequency becomes higher.

As a technique for reducing the transmission loss of the high frequency copper foil, for example, Patent Document 1 discloses a technique of coating a silver or silver alloy metal on one surface or both surfaces of a surface of a metal foil, And a coating layer other than the silver or silver alloy is thinner than the thickness of the silver or silver alloy coating layer. According to this, it is described that a metal foil having a reduced loss due to the surface effect can be provided even in a very high frequency region such as that used in satellite communication.

Patent Document 2 discloses that the integrated intensity (I (200)) of the (200) plane obtained by X-ray diffraction on the rolled surface after the recrystallization annealing of the rolled copper foil is an integral (200) / I ₀ (200) > 40 with respect to the strength (I ₀ (200)) and the arithmetic average roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment by electrolytic plating is applied to the rolled surface Wherein the copper foil is a material for a printed circuit board, wherein the copper foil is a material for a printed circuit board having a thickness of 0.02 mu m to 0.2 mu m and a ten point average roughness (Rz) of 0.1 mu m to 1.5 mu m. According to this, it is disclosed that a printed circuit board usable at a high frequency exceeding 1 GHz can be provided.

Patent Document 3 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is an irregular surface having a surface roughness of 2 탆 to 4 탆 which is formed of a lump-shaped protrusion. According to this, it is described that an electrolytic copper foil having excellent high-frequency transmission characteristics can be provided.

Patent Document 1: Japanese Patent Publication No. 4161304 Patent Document 2: Japanese Patent Publication No. 4704025 Patent Document 3: JP-A-2004-244656

Although various studies have been made on the control of the transfer loss of the copper foil when used in a high frequency circuit board as described above, there still remains much room for development. The surface-treated copper foil needs to have good peel strength (peel strength) between the surface-treated copper foil and the resin after being laminated with the resin from the surface treatment layer side and heated at a predetermined temperature and for a predetermined period of time have.

The inventors of the present invention have found that the present inventors have found that when a predetermined metal deposition amount in a surface treatment layer obtained by forming a primary particle layer on a copper foil or a surface treatment layer obtained by forming a primary particle layer and a secondary particle layer and a 10- Rz), it is possible to satisfactorily reduce the transmission loss even when used in a high-frequency circuit board. Further, the laminate is laminated with a resin and heated at a predetermined temperature and a predetermined time (at 180 DEG C for 10 days) And peel strength (peel strength) of the resin are improved.

The present invention is completed on the basis of the above finding and is a surface treated copper foil having a copper foil on one side and a surface treatment layer on one or both sides of the copper foil, , Or a primary particle layer and a secondary particle layer in this order from the copper foil side, the surface treatment layer contains Zn, the adhesion amount of Zn in the surface treatment layer is 150 占 퐂 / dm2 or more, The treatment layer does not contain Ni, or when the surface treatment layer contains Ni, the adhesion amount of Ni in the surface treatment layer is 800 占 퐂 / dm2 or less, and the surface treatment layer does not contain Co , Or when the surface treatment layer contains Co, the adhesion amount of Co in the surface treatment layer is 3000 占 퐂 / dm2 or less and the 10-point average roughness (Rz) of the outermost surface treatment layer is 1.5 占 퐉 Or less It is night.

According to another aspect of the present invention, there is provided a surface treated copper foil having a copper foil and a surface treatment layer on one or both surfaces of the copper foil, wherein the surface treatment layer has a primary particle layer, Wherein the surface treatment layer contains Zn and Mo, the total deposition amount of Zn and Mo in the surface treatment layer is 200 占 퐂 / dm2 or more, and the surface treatment layer contains Ni is not contained, or when the surface treatment layer contains Ni, the Ni adhesion amount in the surface treatment layer is 800 占 퐂 / dm2 or less and the surface treatment layer does not contain Co, Wherein the coating amount of Co in the surface treatment layer is 3000 mu g / dm < 2 > or less and the 10 point average roughness (Rz) of the outermost surface treatment layer is 1.5 mu m or less when the surface treatment layer contains Co It is a copper foil.

In another embodiment of the surface treated copper foil of the present invention, the surface treatment layer comprises Co.

In another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer contains Ni.

In one embodiment of the surface-treated copper foil of the present invention, the surface treatment layer includes Co and Ni, and the total amount of Co and Ni in the surface treatment layer is 3500 占 퐂 / dm2 or less.

In the surface-treated copper foil of the present invention, the surface-treated copper foil and the resin are prepared, and after the surface-treated copper foil is laminated with the resin from the surface treatment layer side, The peel strength at peeling is 0.5 kg / cm or more.

In another embodiment of the surface-treated copper foil of the present invention, the peel strength is 0.7 kg / cm or more.

In the surface-treated copper foil of the present invention, the surface treatment layer may be formed on the primary particle layer or the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti,

(B) a chromate treatment layer

Or both in this order from the copper foil side.

In the surface-treated copper foil of the present invention, the surface treatment layer may be formed on the primary particle layer or the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti,

(B) a chromate treatment layer

Or both, and a silane coupling treatment layer in this order from the copper foil side.

In the surface-treated copper foil of the present invention, the surface treatment layer may be formed on the primary particle layer or the secondary particle layer by using any one or both of a Ni-Zn alloy layer and a chromate treatment layer In this order from the copper foil side.

In the surface-treated copper foil of the present invention, the surface treatment layer may be formed on the primary particle layer or the secondary particle layer with one or both of a Ni-Zn alloy layer and a chromate treatment layer and a silane And a coupling treatment layer in this order from the copper foil side.

The surface-treated copper foil of the present invention is, in another embodiment, a resin layer on the surface of the surface treatment layer.

The surface-treated copper foil of the present invention is used in a high-frequency circuit board in another embodiment.

According to another aspect of the present invention, there is provided a carrier-coated copper foil having an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of a carrier, wherein the ultra-thin copper layer is a copper foil with a carrier, .

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

In another aspect, the present invention is a laminate comprising a copper foil with a carrier and a resin according to the present invention, wherein a part or all of an end surface of the copper foil with a carrier is covered with the resin.

According to another aspect of the present invention, there is provided a method for manufacturing a copper-clad laminate, wherein one carrier-coated copper foil of the present invention is provided on the carrier side or the ultra-thin copper layer side, Layer laminate.

In 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.

According to another aspect of the present invention, there is provided a process for preparing a surface-treated copper foil of the present invention or a copper foil with a carrier of the present invention 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 a step of peeling a carrier of the copper foil with a carrier after laminating the copper foil with a carrier and the insulating substrate, Forming process, and

And thereafter forming a circuit according to any one of a semi-additive method, a subtractive method, a partial additive method, and a modified semi-additive method.

According to another aspect of the present invention, there is provided a method of manufacturing a surface-treated copper foil, comprising the steps of: forming a circuit on the surface-treated layer side surface of the surface-treated copper foil of the present invention; Forming process,

Forming a resin layer on the surface-treated layer side surface of the surface-treated copper foil or the surface of the ultra-thin copper layer of the carrier-coated copper foil or the carrier-side surface so that the circuit is buried;

A circuit buried in the resin layer is exposed by removing the surface treated copper foil after forming the resin layer or removing the ultra thin copper layer or the carrier after the carrier or the ultra thin copper layer is peeled off And a method for manufacturing a printed wiring board.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: laminating a carrier substrate with a carrier-

A step of providing two layers of a resin layer and a circuit at least once on the surface of the carrier-coated copper foil opposite to the side laminated with the resin substrate;

And peeling the carrier or the ultra-thin copper layer from the carrier-adhered copper foil after forming the two layers of the resin layer and the circuit.

According to another aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising the steps of: preparing at least one resin layer and two layers of circuits on at least one side of the laminate of the present invention;

And peeling the carrier or the ultra-thin copper layer from the carrier-coated copper foil constituting the laminate after the two layers of the resin layer and the circuit are formed.

According to another aspect of the present invention, there is provided a method of manufacturing an electronic device using a printed wiring board manufactured by the method of the present invention.

According to the present invention, it is possible to satisfactorily reduce the transmission loss even when used in a high frequency circuit board, and furthermore, after lamination with a resin and heating at a predetermined temperature and for a predetermined period of time (180 DEG C for 10 days) The peel strength (fill strength) of the surface treated copper foil can be improved.

Figs. 1A to 1C are schematic views of a wiring board section in a process up to circuit plating and resist removal, which are related to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
2D to F are schematic views of a wiring board section in a process from the lamination of the resin and the copper foil with the second layer of carrier to laser drilling, which is related to a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention .
3G to 3I are schematic views of a wiring board section in a process from a via fill formation to a first layer carrier peeling, which is related to a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
4A to 4K are schematic views of a wiring board section in a process from flash etching to bump-copper filler formation, which is related to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.

≪ Surface treated copper foil &

The surface-treated copper foil of the present invention has a copper foil and a surface treatment 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 is etched with 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 having a frequency of 1 GHz or higher to be transmitted using a circuit of the circuit board. More preferably, the frequency of the signal is at least 3 GHz, more preferably at least 5 GHz, more preferably at least 8 GHz, more preferably at least 10 GHz, more preferably at least 15 GHz, even more preferably at least 18 GHz Is preferably 20 GHz or more, more preferably 30 GHz or more, more preferably 38 GHz or more, and even more preferably 40 GHz or more.

<Copper>

The shape of the copper foil usable in the present invention is not particularly limited. Typically, the copper foil used in the present invention may be an electrolytic copper foil or a rolled copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Rolled copper foil is often applied to applications requiring flexibility.

(JIS H3100 alloy No. C1100) or oxygen free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011) or tantalum copper (JIS H3100 alloy No. C1201, C1220 or JIS H3100 alloy No. C1011) commonly used as a conductor pattern of a printed wiring board Cu, Ag, Cu, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, and / or the like, in addition to high purity copper, A copper alloy to which Mg and the like are added, and a copper alloy such as a Colson type copper alloy to which Ni and Si are added can also be used. A copper foil and a copper alloy foil having a known composition can also be used. In the present specification, when the term "copper foil" is used alone, it also includes a copper alloy foil.

The thickness of the copper foil is not particularly limited, but may be 1 to 1000 占 퐉, 1 to 500 占 퐉, 1 to 300 占 퐉, 3 to 100 占 퐉, 5 to 70 占 퐉, or 6 to 35 占 퐉, Mu m, or 9 to 18 mu m.

In another aspect of the present invention, there is provided a carrier-coated copper foil having an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of a carrier, wherein the ultra-thin copper layer is the surface-treated copper foil of the present invention. When the copper foil with a carrier is used in the present invention, a surface treatment layer such as the following roughening treatment layer is provided on the surface of the ultra-thin copper layer. Other embodiments of the copper foil with a carrier will be described later.

<Surface Treatment Layer>

The surface treatment layer has a primary particle layer or a primary particle layer and a secondary particle layer in this order from the copper foil side. The primary particle layer and the secondary particle layer are formed by an electroplating layer. The characteristics of the secondary particles are one or a plurality of particles grown on the primary particles. Or the secondary particle layer is the normal plating grown on the primary particle. The secondary particles may have a dendritic shape. That is, when the term "secondary particle layer" is used in the present specification, a normal plating layer such as coating plating is also included. The secondary particle layer may be a layer having one or more layers formed by coarsely grained particles or a layer having one or more normal plating layers and may be a layer formed by coarsely grained particles and a layer having one or more normal plating layers . The surface treatment layer may have one or a plurality of different layers other than the primary particle layer or the secondary particle layer.

The primary particle layer is a layer in which the coarse particles directly formed on the copper foil and the coarse particles superimposed on the coarse particles have the same composition as the coarse particles directly formed on the copper foil or the coarse particles directly formed on the copper foil Is a layer containing harmonic grains having the same elements as the elements contained in the grains. The secondary particle layer is a coarse particle formed on the coarse particle contained in the primary particle layer and has a composition different from that of the coarse particle forming the primary particle layer or an element containing no coarse particles forming the primary particle layer As a layer containing harmonic particles.

When the presence or absence of the elements constituting the primary particles and / or the secondary particles and / or the concentration or the amount of the elements can not be measured, the primary particles and the secondary particles are, for example, Particles that are superimposed when observed with a slit-type electron microscope photograph, in which particles existing on the copper foil side (lower side) and non-overlapping particles are used as primary particles and particles existing on other particles as superimposed particles are determined as secondary particles can do.

In one aspect of the surface-treated copper foil of the present invention, the surface treatment layer contains Zn and the adhesion amount of Zn in the surface treatment layer is 150 占 퐂 / dm2 or more. When the adhesion amount of Zn is less than 150 占 퐂 / dm2, heat resistance may be poor when used as a surface treated copper foil for a high frequency circuit board. The deposition amount of Zn is preferably 155 占 퐂 / dm2 or more, preferably 165 占 퐂 / dm2 or more, preferably 180 占 퐂 / dm2 or more, preferably 200 占 퐂 / dm2 or more, preferably 250 Dm2 or more, preferably 270 占 퐂 / dm2 or more, preferably 280 占 퐂 / dm2 or more, more preferably 290 占 퐂 / dm2 or more. The upper limit of the Zn deposition amount is not particularly limited but is typically 50000 占 퐂 / dm2 or less, for example, 30000 占 퐂 / dm2 or less, for example, 10,000 占 퐂 / dm 2 or less, for example, 3000 μg / dm 2 or less, for example, 2000 μg / dm 2 or less, for example, 1000 μg / dm 2 or less.

In the present invention, the adhesion amounts of elements such as Zn, Ni, Co, and Mo in the surface treatment layer are specified. However, in the case where the surface treatment layer is present on both surfaces of the copper foil, Layer, and is not the total value of the elements (for example, Zn and the like) contained in the surface treatment layer formed on both sides.

In another aspect of the surface-treated copper foil of the present invention, the surface treatment layer contains Zn and Mo, and the total deposition amount of Zn and Mo in the surface treatment layer is 200 占 퐂 / dm2 or more. If the total deposition amount of Zn and Mo is less than 200 / / dm 2, there is a fear that heat resistance is poor when used as a surface-treated copper foil for a high frequency circuit board. The total deposition amount of Zn and Mo is preferably 250 占 퐂 / dm2 or more, more preferably 300 占 퐂 / dm2 or more, more preferably 340 占 퐂 / dm2 or more, still more preferably 360 占 퐂 / dm2 More preferably not less than 400 μg / dm 2, more preferably not less than 420 μg / dm 2, more preferably not less than 450 μg / dm 2, more preferably not less than 460 μg / dm 2, 500 μg / dm 2 or more. The upper limit of the total deposition amount of Zn and Mo is not particularly limited but is typically 100000 ㎍ / dm 2 or less, for example, 50000 / / dm 2 or less, for example, 30000 / / dm 2 or less, For example, not more than 10,000 μg / dm 2, for example not more than 8,000 μg / dm 2, such as not more than 5,000 μg / dm 2, for example not more than 3,000 μg / dm 2, for example not more than 1000 μg /

When the surface treatment layer of the surface-treated copper foil of the present invention does not contain Co, or when the surface treatment layer contains Co, the adhesion amount of Co in the surface treatment layer is 3000 占 퐂 / dm2 or less. If the Co amount exceeds 3,000 g / dm 2, the high-frequency transmission characteristics may deteriorate. The coating amount of Co is more preferably 2900 占 퐂 / dm2 or less, more preferably 2800 占 퐂 / dm2 or less, further preferably 2790 占 퐂 / dm2 or less, more preferably 2700 占 퐂 / dm2 or less, More preferably 2500 占 퐂 / dm2 or less, still more preferably 1,500 占 퐂 / dm2 or less, still more preferably 1000 占 퐂 / dm2 or less. In the case where the surface treatment layer contains Co, the lower limit of the amount of Co deposited on the surface treatment layer is not particularly limited. Typically, however, the amount of adhesion of Co is larger than 0 占 퐂 / For example, at least 0.1 g / dm2, such as at least 1 g / dm2, such as at least 2 g / dm2, such as at least 3 g / dm2, such as at least 4 g / For example, 10 μg / dm 2 or more, for example, 15 μg / dm 2 or more, for example, 20 μg / dm 2 or more. When the surface treatment layer contains Co, the effect of improving the weather resistance of the surface-treated copper foil may be exhibited as compared with the case of not including Co.

When the surface treatment layer of the surface-treated copper foil of the present invention does not contain Ni, or when the surface treatment layer contains Ni, the Ni adhesion amount in the surface treatment layer is 800 占 퐂 / dm2 or less. If the amount of Ni adhered exceeds 800 占 퐂 / dm2, the high-frequency transmission characteristic may deteriorate. The adhesion amount of Ni is more preferably not more than 750 μg / dm 2, still more preferably not more than 600 μg / dm 2, still more preferably not more than 400 μg / dm 2, still more preferably not more than 250 μ m 2 . In the case where the surface treatment layer contains Ni, the lower limit of the Ni deposition amount in the surface treatment layer is not particularly limited, but typically, for example, the adhesion amount of Ni is greater than 0 / / For example, at least 0.1 g / dm2, such as at least 1 g / dm2, such as at least 2 g / dm2, such as at least 3 g / dm2, such as at least 4 g / For example, 10 μg / dm 2 or more, for example, 15 μg / dm 2 or more, for example, 20 μg / dm 2 or more. When the surface treatment layer contains Ni, the chemical resistance of the surface-treated copper foil may be improved as compared with the case where the surface treatment layer contains no Ni.

In the surface-treated copper foil of the present invention, it is preferable that the surface treatment layer further contains Co and Ni, and the total deposition amount of Co and Ni in the surface treatment layer is 3500 占 퐂 / dm2 or less. If the total amount of Co and Ni exceeds 3500 占 퐂 / dm2, the high-frequency transmission characteristic may be deteriorated. The total deposition amount of Co and Ni is more preferably 3100 占 퐂 / dm2 or less, still more preferably 1900 占 퐂 / dm2 or less, still more preferably 1400 占 퐂 / dm2 or less. The lower limit of the total deposition amount of Co and Ni in the surface treatment layer is not particularly limited when the surface treatment layer contains Co and Ni. For example, not less than 0.1 μg / dm 2, such as not less than 1 μg / dm 2, such as not less than 2 μg / dm 2, such as not less than 3 μg / For example, 5 μg / dm 2 or more, such as 10 μg / dm 2 or more, such as 15 μg / dm 2 or more, for example, 20 μg / For example, at least 30 μg / dm 2, for example at least 40 μg / dm 2, such as at least 50 μg / dm 2, such as at least 60 μg / dm 2, such as at least 70 μg / dm 2. Further, when the surface treatment layer contains Co and Ni, the chemical resistance and weather resistance of the surface-treated copper foil may be improved as compared with the case of not containing Co and Ni.

The deposition amount of the element contained in the surface treatment layer can be adjusted by increasing the concentration of the element in the surface treatment liquid used for forming the surface treatment layer and / or increasing the current density when the surface treatment is plating , And / or by increasing the surface treatment time (electrification time at the time of plating), or the like. The deposition amount of the element contained in the surface treatment layer is preferably set 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, the current density is lowered , And / or by shortening the surface treatment time (electrification time at the time of plating).

In the surface-treated copper foil of the present invention, the 10-point average roughness (Rz) of the outermost surface treatment layer is 1.5 占 퐉 or less. If the 10-point average roughness (Rz) of the outermost surface layer of the surface treatment layer exceeds 1.5 탆, there is a fear that the high-frequency transmission characteristics may deteriorate. The 10-point average roughness (Rz) of the outermost surface layer of the surface treatment layer is more preferably 1.3 占 퐉 or less, further preferably 1.1 占 퐉 or less, further preferably 1.0 占 퐉 or less, further preferably 0.9 占 퐉 or less. Means a surface of the outermost (outermost) layer of the plurality of layers when the surface treatment layer is formed by a plurality of layers formed by surface treatment. Then, the 10-point average roughness (Rz) is measured on the outermost (outermost) layer surface of the plurality of layers. The lower limit of the 10-point average roughness (Rz) of the outermost surface layer of the surface treatment layer is not particularly limited, but is typically 0.01 탆 or more, for example, 0.05 탆 or more, for example, 0.1 탆 or more.

The surface treatment layer of the surface-treated copper foil of the present invention may be formed on the primary particle layer or the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti,

(B) a chromate treatment layer

Or both of them may be arranged in this order from the copper foil side.

Further, the surface-treated layer of the surface-treated copper foil of the present invention may be formed on the primary particle layer or the secondary particle layer,

(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti,

(B) a chromate treatment layer

And the silane coupling treatment layer may be disposed in this order from the copper foil side.

The surface-treated layer of the surface-treated copper foil of the present invention may have one or both of the Ni-Zn alloy layer and the chromate treatment layer on the primary particle layer or the secondary particle layer in this order from the copper foil side.

Further, the surface-treated layer of the surface-treated copper foil of the present invention may be formed such that one or both of a Ni-Zn alloy layer and a chromate treatment layer and a silane coupling treatment layer are formed on the primary particle layer or the secondary particle layer It may be in this order.

In addition, the Ni-Zn alloy layer described above means a layer of an alloy containing Ni and Zn. The Ni-Zn alloy layer may be a layer in which the total concentration of Ni and Zn is 80 atomic% or more. The total concentration of Ni and Zn can be measured by summing the concentration of Ni atoms and the concentration of Zn atoms obtained by analyzing atomic concentrations of Ni and Zn in the depth direction using XPS or the like. The Ni-Zn alloy layer may be a layer composed only of Ni and Zn.

The surface-treated copper foil of the present invention is obtained by preparing the surface-treated copper foil and a resin, laminating the surface-treated copper foil with the resin from the surface treatment layer side, etching the surface-treated copper foil to prepare a circuit having a width of 10 mm, A peel strength of 0.5 kg / cm or more when the circuit is peeled in the 90 占 direction, and a peel strength of 0.7 kg / cm or more can be achieved.

In the surface-treated copper foil of the present invention, the surface-treated copper foil and the resin are prepared, the surface-treated copper foil is laminated with the resin from the surface treatment layer side, the surface-treated copper foil is etched to prepare a circuit having a width of 10 mm, It is possible to achieve a peel strength of not less than 0.4 kg / cm and a peel strength of not less than 0.5 kg / cm when the circuit is peeled from the resin in the 90 占 direction after heating the circuit at 180 占 폚 under atmospheric pressure for 10 days.

The above-mentioned resin and the above-described lamination conditions are any one, two, or three of the following (1) to (3). That is, the peel strength obtained based on any one of the following conditions (1) to (3) is preferably within the above range.

(1) Resin: liquid crystal polymer resin which is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 m

Lamination conditions: pressure 3.5 MPa, heating temperature 300 DEG C, heating time 10 minutes

(2) Resin: low dielectric polyimide resin, thickness 50 m

Lamination conditions: pressure 4 MPa, heating temperature 300 DEG C, heating time 10 minutes

(3) Resin: polytetrafluoroethylene, thickness 50 탆

<Transmission Loss>

When the transmission loss is small, attenuation of the signal is suppressed when a signal is transmitted at a high frequency, so that it is possible to transmit a stable signal in a circuit that transmits a signal at a high frequency. Therefore, a small value of the transmission loss is preferable because it is suitable for use in a circuit application for transmitting a high-frequency signal. The surface-treated copper foil was laminated with a commercially available liquid crystal polymer resin (Vecstar CTZ manufactured by Kuraray Co., Ltd., thickness: 50 탆, resin as a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), , And the transmission loss is measured at a frequency of 20 GHz and a frequency of 40 GHz by using a network analyzer HP8720C manufactured by HP and the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / More preferably less than 4.1 dB / 10 cm, and even more preferably less than 3.7 dB / 10 cm.

<Copper with Carrier>

The carrier-adhered copper foil according to another embodiment of the present invention has an intermediate layer and an ultra-thin copper layer in this order on one side or both sides of the carrier. And the extremely thin copper layer is one of the above-described embodiments of the present invention.

<Carrier>

The carrier usable in the present invention is typically a metal foil or a resin film such as a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, a foil, an iron alloy foil, a stainless steel foil, an aluminum foil, And is provided in the form of a resin film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin film, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyamide film and a polyamide imide film.

The carriers usable in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolytically precipitating copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Examples of the material of the copper foil 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 phosphorus pentoxide and electric copper, , Ag-containing copper, a copper alloy containing Cr, Zr or Mg added thereto, or a copper alloy such as a Colson-type copper alloy containing Ni and Si added. A known copper alloy can also be used. In the present specification, when the term &quot; copper foil &quot; is used singly, copper alloy foil is also included.

The thickness of the carrier which can be used in the present invention is not particularly limited, but it may be suitably adjusted to a suitable thickness after acting as a carrier, for example, 5 mu m or more. However, if it is too thick, the production cost becomes high, and therefore, it is generally preferable to be 35 mu m or less. Thus, the thickness of the carrier is typically from 8 to 70 占 퐉, more typically from 12 to 70 占 퐉, and more typically from 18 to 35 占 퐉. From the viewpoint of reducing the raw material cost, it is preferable that the thickness of the carrier is small. Therefore, the thickness of the carrier is typically from 5 to 35 μm, preferably from 5 to 18 μm, preferably from 5 to 12 μm, preferably from 5 to 11 μm And preferably not less than 5 占 퐉 and not more than 10 占 퐉. Further, when the thickness of the carrier is small, folded wrinkles are liable to occur at the time of passing through the carrier. It is effective to smooth the conveying roll of the copper foil manufacturing apparatus with a carrier or shorten the distance between the conveying roll and the next conveying roll in order to prevent the occurrence of folds. Further, in the case where a copper foil with a carrier is used in the embedding method (the embedded method), which is one of the methods for producing a printed wiring board, the rigidity of the carrier is required to be high. Therefore, when used in the landfill method, the carrier preferably has a thickness of 18 to 300 탆, preferably 25 to 150 탆, more preferably 35 to 100 탆, more preferably 35 to 70 탆 desirable.

The primary particle layer and the secondary particle layer may be provided on the surface of the carrier opposite to the surface on which the ultra-thin copper layer is provided. The provision of the primary particle layer and the secondary particle layer on the surface opposite to the surface of the carrier on which the ultra-thin copper layer is provided is to deposit the carrier on a support such as a resin substrate from the surface side having the primary particle layer and the secondary particle layer The carrier and the resin substrate are not easily peeled off.

Hereinafter, an example of the production conditions when an electrolytic copper foil is used as a carrier is shown.

<Electrolyte Composition>

Copper: 90 ~ 110g / L

Sulfuric acid: 90 to 110 g / L

Chlorine: 50 to 100 ppm

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

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

The amine compound may be an amine compound of the following formula.

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

[Chemical Formula 1]

Wherein R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group and an alkyl group.

<Manufacturing Conditions>

Current density: 70 ~ 100A / dm2

Electrolyte temperature: 50 to 60 ° C

Electrolyte flux: 3 ~ 5 m / sec

Electrolysis time: 0.5 to 10 minutes

<Middle layer>

An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is a structure in which the extremely thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with a carrier on the insulating substrate and the ultra-thin copper layer can be peeled off from the carrier after the laminating step to the insulating substrate And is not particularly limited. For example, the intermediate layer of the copper foil with a carrier of the present invention may be formed of an alloy containing at least one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, One or more species selected from the group consisting of The intermediate layer may be a plurality of layers.

For example, the intermediate layer may be a single metal layer made of a single element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, A layer made of a hydrate or an oxide or an organic material of one or more elements selected from the group consisting of Mo, Ti, W, P, Cu, Al and Zn; , A single metal layer composed of one element selected from the group consisting of W, P, Cu, Al and Zn or a single metal layer composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, And an alloy layer composed of one or two or more elements selected from the group of elements.

When the intermediate layer is provided on only one side, it is preferable to provide a rust prevention 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 a part of the adhered metal such as chromium or zinc may be a hydrate or an oxide.

Further, for example, the intermediate layer can be formed by stacking nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium on the carrier in this order. Since the adhesive force between nickel and copper is higher than the adhesion between chrome and copper, when the ultra-thin copper layer is peeled off, it is peeled from the interface between the ultra-thin copper layer and chromium. In addition, nickel in the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultra-thin copper layer. The nickel adhesion amount in the intermediate layer is preferably 100 μg / dm 2 to 40000 μg / dm 2, more preferably 100 μg / dm 2 to 4000 μg / dm 2, more preferably 100 μg / Dm 2 or less, more preferably 100 μg / dm 2 or more and less than 1000 μg / dm 2, and the adhesion amount of chromium in the intermediate layer is preferably 5 μg / dm 2 or more and 100 μg / dm 2 or less.

<Ultra-thin copper layer>

On the middle layer, an ultra-thin copper layer is provided. Another layer may be provided between the intermediate layer and the ultra thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and is used in a general electrolytic copper foil to form a copper foil at a high current density. . The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically from 0.5 to 12 占 퐉, more typically from 1 to 5 占 퐉, more typically from 1.5 to 5 占 퐉, and more typically from 2 to 5 占 퐉. Further, an extremely thin copper layer may be provided on both sides of the carrier.

<Formation Conditions of Primary Particle Layer and Secondary Particle Layer>

A primary particle layer is formed on the copper foil in the case of the surface-treated copper foil or on the ultra-thin copper layer in the case of the carrier-adhered copper foil, or the primary particle layer and the secondary particle layer are formed in this order. The conditions for forming the primary particle layer and the secondary particle layer are shown below. This indicates a suitable example. For example, if the adhesion strength to the resin used is sufficient and the initial peeling is in the range of 0.5 kg / cm or more, The plating conditions other than the indication are not a problem. The present invention includes these.

Primary particle layer

In the case of treatment with the primary particle plating solution (II) after the treatment with the primary particle plating solution (I), it is possible to form the primary particle layer under the following conditions.

(Treatment with primary particle plating solution (I)

<Electrolyte Composition>

Copper: 5 to 10 g / L

Sulfuric acid: 70 to 80 g / L

<Manufacturing Conditions>

Current density: 50 to 55 A / dm 2

Electrolyte temperature: 35 ° C

Delivery time: 0.5-1.6 seconds

(Treatment with primary particle plating solution (II)

<Electrolyte Composition>

Copper: 20 to 50 g / L

Sulfuric acid: 60 to 100 g / L

<Manufacturing Conditions>

Current density: 4 to 10 A / dm 2

Electrolyte temperature: 35 ~ 45 ℃

Delivery time: 1.4 to 2.5 seconds

In the case of forming the primary particle layer only by the treatment with the primary particle plating solution (I), the treatment is carried out under the conditions described in the following treatment 1 with the primary particle plating solution (I) or treatment 2 with the primary particle plating solution (I) It is possible to do.

(Treatment with primary particle plating solution (I) 1)

<Electrolyte Composition>

Copper: 10 ~ 45g / L

Cobalt: 5 ~ 30g / L

Nickel: 5 to 30 g / L

pH: 2.8 to 3.2

<Manufacturing Conditions>

Current density: 30 ~ 45A / dm2

Electrolyte temperature: 30 ~ 40 ℃

Delivery time: 0.3 to 0.8 seconds

(Treatment with primary particle plating solution (I) 2)

<Electrolyte Composition>

Copper: 5 ~ 15g / L

Nickel: 3 to 30 g / L

pH: 2.6-3.0

<Manufacturing Conditions>

Current density: 50 to 70 A / dm 2

Electrolyte temperature: 30 ~ 40 ℃

Electrolysis time: 0.3 to 0.9 seconds

Secondary particle layer

In the case of forming the secondary particle layer, it is possible to carry out by treatment with the following secondary particle plating solution (I) or secondary particle plating solution (II).

(Treatment with secondary particle plating solution (I)) [

<Electrolyte Composition>

Copper: 10 ~ 15g / L

Cobalt: 5 to 15 g / L

Nickel: 5 to 15 g / L

pH: 2.8 to 3.2

<Manufacturing Conditions>

Current density: 30 ~ 35A / dm2

Electrolyte temperature: 33 ~ 37 ℃

Electrolysis time: 0.5 to 1.0 second

(Treatment with secondary particle plating solution (II)) [

<Electrolyte Composition>

Copper: 5 ~ 12g / L

Nickel: 2 to 11 g / L

pH: 2.8

<Manufacturing Conditions>

Current density: 55 to 65 A / dm 2

Electrolyte temperature: 35 ~ 40 ℃

Electrolysis time: 0.3 to 0.9 seconds

&Lt; Coating plating &

When the secondary particle layer is formed on the primary particle layer, the secondary particle layer is coated with plating. The layer formed by the coating plating may be a Zn-Cr alloy layer, a Ni-Mo alloy layer, a Zn layer, a Co-Mo alloy layer, a Co-Ni alloy layer, a Ni-W alloy layer, a Ni-P alloy Ni alloy layer, a Ni-Al alloy layer, a Co-Zn alloy layer, a Co-P alloy layer, a Zn-Co alloy layer, a Ni layer, a Co layer, a Cr layer, an Al layer, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, Co and the like, such as a Ni-Sn layer or a Zn-Ni alloy layer A metal layer composed of one kind of element or two or three kinds selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Or an alloy layer composed of two or more kinds of elements selected from the above-mentioned element group.

The coating plating can be carried out by treating with a coating plating liquid or the like, or by combining these. The metal layer and / or the alloy layer which can not be provided by wet plating can be prepared by a dry plating method such as sputtering, physical vapor deposition (PVD) or chemical vapor deposition (CVD).

· Treatment with plating solution (1) Zn-Cr

Liquid composition: 1 to 1 g / L of potassium dichromate, 0.1 to 5 g / l of Zn

Solution temperature: 40 to 60 ° C

pH: 0.5 to 10

Current density: 0.01 to 2.6 A / dm 2

Energization time: 0.05 to 30 seconds

· Treatment with plating solution (2) Treatment with Ni-Mo

Liquid composition: 270 to 280 g / L nickel sulfate, 35 to 45 g / L nickel chloride, 10 to 20 g / L nickel acetate, 1 to 60 g / L sodium molybdate, 10 to 50 g / L sodium citrate, 90ppm

Temperature: 20 to 65 ° C

pH: 4-12

Current density: 0.5 to 5 A / dm 2

Power-on time: 0.1 to 5 seconds

· Treatment with plating solution (3) Zn

Solution composition: Zn 1 ~ 15g / L

Solution temperature: 25 ~ 50 ℃

pH: 2-6

Current density: 0.5 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

(4) Treatment with Co-Mo

Liquid composition: Co 1 ~ 20g / L, sodium molybdate 1 ~ 60g / L, sodium citrate 10 ~ 110g / L

Solution temperature: 25 ~ 50 ℃

pH: 5 to 7

Current density: 1 to 4 A / dm 2

Power-on time: 0.1 to 5 seconds

· Treatment with coating solution (5) Co-Ni

Liquid composition: Co 1 to 20 g / L, Ni 1 to 20 g / L

Temperature: 30 ~ 80 ℃

pH: 1.5 to 3.5

Current density: 1 to 20 A / dm 2

Power supply time: 0.1 to 4 seconds

· Treatment with plating solution (6) Treatment with Zn-Ni

Solution composition: Zn 1 to 30 g / L, Ni 1 to 30 g / L

Solution temperature: 40 ~ 50 ℃

pH: 2 to 5

Current density: 0.5 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

· Treatment with plating solution (7) Treatment with Ni-W

Solution composition: Ni 1 to 30 g / L, W 1 to 300 mg / L

Temperature: 30 ~ 50 ℃

pH: 2 to 5

Current density: 0.1 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

· Treatment with coating plating solution (8) Treatment with Ni-P

Solution composition: Ni 1 to 30 g / L, P 1 to 10 g / L

Temperature: 30 ~ 50 ℃

pH: 2 to 5

Current density: 0.1 to 5 A / dm 2

Energization time: 0.01 to 0.3 seconds

<Other Surface Treatment>

After the plating, the surface may be subjected to chromate treatment, silane coupling treatment or the like. That is, at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the primary particle layer or the secondary particle layer. The heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer described above may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

In the present specification, the chromate treatment layer refers to a layer treated with a liquid containing anhydrous chromic acid, chromic acid, bichromic acid, chromic acid salt or dichromate salt. The chromate treatment layer contains elements (metals, alloys, oxides, nitrides, sulfides and the like) such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti Maybe. Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate or a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc.

As the heat-resistant layer and the rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one element selected from the group of Further, the heat-resistant layer and / or the anticorrosion layer may contain an oxide, a nitride, or a silicide including the above-described 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% of nickel and 50 wt% to 1 wt% of 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, and preferably 20 to 100 mg / m 2. Further, it is preferable that the ratio of the nickel deposition amount of the nickel-zinc alloy layer or the nickel-zinc alloy layer to the deposition amount of zinc (= deposition amount of nickel / deposition amount of zinc) is 1.5 to 10. The adhesion amount of the nickel-zinc alloy layer or nickel in the nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2. When the heat-resistant layer and / or the rust-preventive layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate does not corrode the liquid at the time when the inner wall of the through hole or the via hole comes into contact with the liquid, The adhesion between the copper foil and the resin substrate is improved.

For example, the heat resistant layer and / or the rust preventive layer may be formed of a nickel or nickel alloy layer having an adhesion amount of 1 mg / m2 to 100 mg / m2, preferably 5 mg / m2 to 50 mg / m2 and an adhesion amount of 1 mg / m2 to 80 mg / m2 M 2 to 40 mg / m 2, and the nickel alloy layer may be a nickel-molybdenum alloy, a nickel-zinc alloy, a nickel-molybdenum-cobalt alloy, or a nickel-tin alloy It may be composed of any one kind.

The silane coupling treatment layer may be formed using a known silane coupling agent, and may be an epoxy silane, an amino silane, a methacryloxy silane, a mercapto silane, a vinyl silane, an imidazole silane, a triazine silane Or the like may be used. These silane coupling agents may be used in combination of two or more. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

In addition, the surface of the copper foil, the ultra-thin copper layer, the roughened layer, the heat resistant layer, the rust-preventive layer, the silane coupling treatment layer or the chromate treatment layer can be subjected to a known surface treatment.

The surface treatment layer of the present invention may include a layer formed by the above-described surface treatment. For example, the surface treatment layer of the present invention may be formed by applying the above-mentioned coating layer and / or metal layer, and / or alloy layer, and / or heat resistant layer, and / or rustproof layer, and / A coupling treatment layer, and / or a roughening treatment layer may be included.

Thus, a copper foil with a carrier having a surface-treated copper foil and / or a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer is produced. The method of using the surface-treated copper foil and / or the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface-treated copper foil and / or the surface of the ultra-thin copper layer may be coated with paper base phenol resin, paper base epoxy resin, Resin, glass / paper composite base epoxy resin, glass / glass nonwoven composite base material epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, liquid crystal polymer, fluorine resin, polyamide resin, low dielectric polyimide film (In the case of a carrier-adhered copper foil, the carrier is peeled off after thermocompression) to form a copper-clad laminate, and a surface-treated copper foil adhered to the insulating substrate and / And finally, a printed wiring board can be manufactured.

<Resin Layer>

The surface-treated copper foil of the present invention may be provided with a resin layer on the surface of the surface treatment layer. An alloy layer or a chromate treatment layer composed of Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, A coupling treatment layer, or a Ni-Zn alloy layer may be provided on the surface of the resin layer. It is more preferable that the resin layer is formed on the outermost surface of the surface-treated copper foil.

The copper foil with a carrier of the present invention may be provided with a heat resistant layer, a rust prevention layer, a chromate treatment layer, or a resin layer on the silane coupling treatment layer on the primary particle layer or the secondary particle layer.

The resin layer may be an adhesive or may be an insulating resin layer in a semi-cured state for bonding (B stage). The semi-cured state (B stage) includes a state in which the insulating resin layer can be stacked and stored without touching even when a finger touches the surface thereof, and further a curing reaction occurs when subjected to a heat treatment.

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may include a thermoplastic resin. The kind thereof is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin (Also referred to as polyether sulfone) resin, an aromatic polyamide resin, an aromatic polyamide resin polymer, a rubbery resin, a polyamine, an aromatic polyamine, a polyamide imide Butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester-based resin, carboxylic acid-modified epoxy resin, carboxyl-modified acrylonitrile-butadiene resin, Anhydrides of polyvalent carboxylic acids, crosslinkable functionalities (4-cyanate phenyl) propane, phosphorus-containing phenol compounds, manganese naphthenate, 2,2-bis (4-glycidylphenyl) ) Propane, polyphenylene ether cyanate resin, siloxane modified polyamide imide resin, cyanoester resin, phosphazene resin, rubber modified polyamide imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, A resin containing at least one member selected from the group consisting of phenoxy, polymer epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerized polyimide resin and cyanoester resin is suitable.

The epoxy resin has two or more epoxy groups in the molecule and can be used without particular problems if it can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Further, it is also possible to use epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, alicyclic epoxy resins, Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, canceled bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, isocyanuric acid Glycidyl amine compounds such as triglycidyl and N, N-diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl type epoxy resins, A phenol novolak type epoxy resin, a trishydroxyphenyl methane type epoxy resin, and a tetraphenyl ethane type epoxy resin Or a mixture of two or more of them may be used, or a hydrogenated product or a halogenated product of the above epoxy resin may be used.

An epoxy resin containing phosphorus known as phosphorus-containing epoxy resin 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 .

The resin layer may be formed using a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric (a dielectric including an inorganic compound and / or an organic compound, a dielectric including a metal oxide, A polymer, a prepreg, and a skeleton material. The resin layer may be formed using a known forming method and a forming apparatus.

These resins are dissolved in, for example, a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin solution, which is then mixed with the surface-treated copper foil and / or the ultra-thin copper layer or the heat resistant layer, Or the above-mentioned chromate film layer or the above-mentioned silane coupling agent layer by a roll coater method or the like, and then, if necessary, drying by heating to remove the solvent to obtain a B-stage state . For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

The surface-treated copper foil having the resin layer and / or the copper foil with a carrier (copper foil with a resin with a carrier) is thermally pressed to superpose the resin layer on the base material to thermally cure the resin layer, In the case of a copper foil with a carrier, the carrier is peeled to expose the ultra-thin copper layer (of course, the exposed surface is the intermediate layer side surface of the ultra-thin copper layer), and a predetermined wiring pattern is formed on the surface- Is used.

Use of the resin-coated surface-treated copper foil and / or the copper foil with a carrier can reduce the number of prepreg materials used in the production of the multilayer printed wiring board. In addition, the thickness of the resin layer can be set to ensure the interlaminar insulation, or the copper clad laminate can be manufactured without using the prepreg material at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is simplified. Therefore, the multilayer printed wiring board is economically advantageous and the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is It is advantageous in that an extremely thin multilayer printed wiring board having a thickness of 100 mu m or less can be produced.

The thickness of the resin layer is preferably 0.1 to 80 mu m. When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered. When the resin-coated copper foil with a resin is laminated on a base material having an inner layer material without interposing the prepreg material therebetween, There is a case that it becomes difficult to secure.

On the other hand, if the thickness of the resin layer is made thicker than 80 탆, it becomes difficult to form a resin layer having a desired thickness in a single coating step, resulting in economical disadvantages because extra material cost and number of steps are involved. In addition, since the formed resin layer is poor in flexibility, cracks and the like are liable to be generated during handling, and excessive resin flow may occur at the time of thermocompression bonding with the inner layer material, resulting in difficulty in smooth lamination.

Further, as another product form of the copper foil with a resin with a resin attached thereto, it is preferable that the surface treatment layer of the ultra-thin copper layer or the heat resistant layer, the anticorrosive layer or the chromate treatment layer or the silane coupling treatment layer, The carrier is peeled off to form a semi-cured resin-coated copper foil in the absence of a carrier.

A printed circuit board is completed by mounting electronic parts on a printed wiring board. In the present invention, the &quot; printed wiring board &quot; includes a printed wiring board, a printed circuit board, and a printed board on which the electronic parts are mounted.

The electronic device may be manufactured using the printed wiring board, the electronic device may be manufactured using the printed circuit board on which the electronic parts are mounted, or an electronic device may be manufactured using the printed board on which the electronic parts are mounted . Hereinafter, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier according to the present invention are presented. A printed wiring board can also be produced by using the surface-treated copper foil of the present invention as the ultra-thin copper layer of the copper foil with a carrier.

In one embodiment of the method for producing a printed wiring board according to the present invention, the carrier-attached copper foil (hereinafter referred to as &quot; carrier-bonded copper foil &quot; and &quot; Layer side &quot; to &quot; the surface-treated layer side &quot; to read the printed wiring board. [0095] When the above-described replacement is read, a printed wiring board may be manufactured without a carrier, The step of laminating the copper foil with a carrier and the insulating substrate, the step of laminating the copper foil with a carrier and the insulating substrate so that the extremely thin copper layer side faces the insulating substrate, and then peeling the carrier of the copper foil with a carrier to form a copper clad laminate Followed by a semi-additive method, a modified semi-additive method, a partially additive method, and a sub- According to any one of the method of the rack capacitive method, a step of forming a circuit. The insulating substrate may include an inner layer circuit.

In the present invention, the semi-additive method refers to a method in which thin electroless plating is performed on an insulating substrate or a copper foil sheet layer to form a pattern, followed by electroplating and etching to form a conductor pattern.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the ultra-thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming a through hole and / or a blind via in the exposed resin by removing the extremely thin copper layer by etching,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of providing an electroless plating layer on a region including the resin and the through hole and / or the blind via,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electrolytic plating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the insulating resin substrate;

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of removing all of the ultra-thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer on the region including the resin and the through hole and / or the blind via exposed by removing the extremely thin copper layer by etching or the like,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electrolytic plating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the insulating resin substrate;

A step of removing all of the ultra-thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of forming an electroless plating layer on the region including the resin and the through hole and / or the blind via exposed by removing the extremely thin copper layer by etching or the like,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electrolytic plating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of removing all of the ultra-thin copper layer exposed by peeling off the carrier by a method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer on the exposed surface of the resin by removing the extremely thin copper layer by etching,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electrolytic plating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like,

.

According to the modified semi-additive method of the present invention, the metal foil is laminated on the insulating layer, the non-circuit forming portion is protected by the plating resist, the copper of the circuit forming portion is thickened by electrolytic plating, And removing a metal foil other than the circuit forming portion by (flash) etching, thereby forming a circuit on the insulating layer.

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of providing a through hole and / or a blind via on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of providing an electroless plating layer on a region including the through hole and / or the blind via,

A step of providing a plating resist on the surface of the extremely thin copper layer exposed by peeling the carrier,

A step of forming a circuit by electrolytic plating after the plating resist is provided,

A step of removing the plating resist,

A step of removing the exposed ultra-thin copper layer by removing the plating resist by flash etching,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a modified semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a plating resist on the extremely thin copper layer exposed by peeling the carrier,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electroplating layer in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like,

.

In the present invention, the partial additive method is a method in which a substrate provided with a conductor layer and, if necessary, a catalyst core is provided on a substrate formed by drilling holes for through holes or via holes to form a conductor circuit by etching, , A solder resist or a plating resist is provided, and then a thickness is formed on the conductor circuit, a through hole, a via hole or the like by an electroless plating process, thereby producing a printed wiring board.

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the partial additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of providing a through hole and / or a blind via on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

Providing a catalyst nucleus to a region including the through hole and / or the blind via,

A step of providing an etching resist on the surface of the ultra thin copper layer exposed by peeling off the carrier,

A step of exposing the etching resist to a circuit pattern,

A step of forming a circuit by removing the extremely thin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid,

A step of removing the etching resist,

A step of forming a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the extremely thin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid,

A step of providing an electroless plating layer in a region where the solder resist or the plating resist is not provided,

.

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

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of providing a through hole and / or a blind via on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of providing an electroless plating layer on a region including the through hole and / or the blind via,

A step of 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 and / or the extremely thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely thin copper layer, 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,

A step of removing the etching resist,

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of providing a through hole and / or a blind via on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of providing an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a mask on the surface of the electroless plating layer,

A step of providing an electroplating layer on the surface of the electroless plating layer where no mask is formed,

A step of providing an etching resist on the surface of the electrolytic plating layer and / or the extremely thin copper layer,

A step of exposing the etching resist to a circuit pattern,

The step of forming a circuit by removing the extremely thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid,

A step of removing the etching resist,

.

The step of providing the through hole and / or the blind via, and the subsequent desmearing step may not be performed.

Hereinafter, a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings. Here, the case where the primary particle layer and the secondary particle layer are provided as the roughened treatment layer will be described.

First, as shown in Fig. 1-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened treatment layer formed on its surface is prepared.

Then, as shown in Fig. 1-B, a resist is coated on the roughened layer of the ultra-thin copper layer, and exposure and development are performed to etch the resist into a predetermined shape.

Then, as shown in Fig. 1-C, circuit plating is formed and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in FIG. 2-D, a resin layer is laminated on the ultra-thin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the other carrier- Is adhered from the extremely thin copper layer side.

Then, as shown in Fig. 2-E, the carrier is peeled off from the carrier-coated copper foil of the second layer.

Next, as shown in Fig. 2-F, a laser hole is formed at a predetermined position of the resin layer to expose the circuit plating to form a blind via.

Then, as shown in FIG. 3-G, copper is buried in the blind via to form a via fill.

Then, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIG. 1-B and FIG. 1-C.

Next, as shown in Fig. 3-I, the carrier is peeled off from the first layer of copper foil with a carrier.

Then, as shown in Fig. 4-J, the extremely thin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Next, as shown in Fig. 4-K, bumps are formed on the circuit plating in the resin layer, and a copper filler is formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention is manufactured.

In addition, in the above-described method for producing a printed wiring board, the "ultra-thin copper layer" is changed to a carrier, the "carrier" is changed to an ultra-thin copper layer, a circuit is formed on the carrier side surface of the copper foil with a carrier, , A printed wiring board can be manufactured.

The above-mentioned copper foil with a carrier (second layer) may be a copper foil with a carrier of the present invention, a conventional copper foil with a carrier, or a normal copper foil. Further, on the circuit of the second layer shown in FIG. 3-H, one circuit or a plurality of circuits may be additionally formed, and these circuits may be formed by a semiadditive method, a subtractive method, a partial additive method, Or by a semi-additive method.

According to the above-described method for producing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in FIG. 4-J, The plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating formation of a microcircuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved and conduction of the circuit wiring is suppressed well. Therefore, formation of a fine circuit is facilitated. Further, 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 becomes a depression from the resin layer, , The copper filler is easily formed on the copper foil, and the production efficiency is improved.

Known resins and prepregs can be used for the embedding resin. For example, glass poison prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film made by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in the present specification may be used for the embedding resin.

The carrier-coated copper foil 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 above-described substrate or resin layer, the carrier-bonded copper foil used for the first layer is supported, and wrinkles are not easily generated, which is advantageous in that the productivity is improved. Further, any substrate or resin layer can be used for the substrate or resin layer as long as it has the effect of supporting the copper foil with a carrier used in the first layer. Examples of the substrate or resin layer include a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, , A foil of an organic compound can be used.

The method for manufacturing a printed wiring board according to the present invention is characterized by comprising the steps of laminating the ultra thin copper layer side surface or the carrier side surface and the resin substrate of the copper foil with a carrier of the present invention, A step of forming two layers of a resin layer and a circuit at least once on the surface of the copper foil with a carrier on the side opposite to the side surface; and a step of forming two layers of the resin layer and the circuit, (Coreless method) including a step of peeling the ultra-thin copper layer. As a concrete example of the coreless method, a laminate (a copper clad laminate or a copper clad laminate) is produced by first laminating a resin substrate and a surface of the copper clad layer side or the carrier side of the copper clad laminate of the present invention. Thereafter, a resin layer is formed on the surface of the extremely thin copper layer side laminated with the resin substrate or on the surface of the copper foil with a carrier opposite to the carrier side surface. The resin layer formed on the carrier-side surface or the ultra-thin copper layer-side surface may be further laminated with another carrier-bonded copper foil from the carrier side or the ultra-thin copper layer side. In addition, a carrier, an intermediate layer, an ultra-thin copper layer, or an ultra-thin copper layer / intermediate layer / carrier in this order on the resin substrate, resin or prepreg, A laminate having a structure in which an attached copper foil is laminated or a laminate having a structure in which "carrier / intermediate layer / ultra-thin copper layer / resin substrate or resin / prepreg / carrier / Intermediate layer / carrier / resin substrate / carrier / intermediate layer / ultra-thin copper layer &quot; in the order of the intermediate layer / ultra thin copper layer / resin substrate / carrier / Layered structure may be used in the above-described method for producing a printed wiring board (coreless method). A circuit may be formed by providing another resin layer on the surface of the ultra-thin copper layer or carrier exposed on both ends of the laminate, further providing a copper layer or a metal layer, and then processing the copper layer or metal layer. Moreover, another resin layer may be provided on the circuit as if the circuit were buried. The circuit and the resin layer may be formed at least once (build-up method). The core-less substrate can be manufactured by peeling the ultra-thin copper layer or the carrier of each of the carrier-coated copper foil from the carrier or the ultra-thin copper layer with respect to the laminate thus formed (hereinafter also referred to as the laminate B). In the production of the above-described coreless substrate, two copper-coated copper foils may be used to form a laminate having a structure of ultra-thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra- A laminate having a structure of a layer / ultra thin copper layer / intermediate layer / carrier or a laminate having a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer may be prepared, . Two layers of a resin layer and a circuit are provided at least once on the surface of the extremely thin copper layer or the carrier on both sides of the laminate (hereinafter also referred to as the laminate A), and two layers of the resin layer and the circuit are provided one or more times, It is possible to manufacture a coreless substrate by peeling the ultra-thin copper layer or the carrier of each of the carrier-coated copper foil from the carrier or the ultra-thin copper layer. The above-described laminate may have another layer between the surface of the ultra-thin copper layer, the surface of the carrier, between the carrier and the carrier, between the ultra-thin copper layer and the ultra-thin copper layer, and between the ultra-thin copper layer and the carrier. The other layer may be a resin substrate or a resin layer. In the present specification, the term &quot; surface of ultra-thin copper layer &quot;, &quot; ultra-thin copper layer side surface &quot;, &quot; ultra-thin copper layer surface &quot;, &quot; surface of carrier, (Superficial surface) of the other layer when the extremely thin copper layer, the carrier, and the laminate have different layers on the surface of the ultra-thin copper layer, the carrier surface, and the laminate, . It is also preferable that the laminate has a structure of an ultra-thin copper layer / an intermediate layer / a carrier / a carrier / an intermediate layer / an ultra-thin copper layer. This is because a very thin copper layer is disposed on the core-less substrate side when the core-less substrate is manufactured using the above-described laminate, so that a circuit can be easily formed on the core-less substrate using the modified semi-additive method. In addition, since the thickness of the ultra-thin copper layer is thin, it is easy to remove the ultra-thin copper layer, and a circuit can be easily formed on the core-less substrate by using the semi-additive method after removal of the ultra-thin copper layer.

In the present specification, "laminate A" or "laminate B", which is not specifically described as "laminate A", refers to a laminate including at least a laminate A and a laminate B.

Further, in the above-described method for producing a coreless substrate, when a printed circuit board is manufactured by a build-up method by covering a copper foil with a carrier or a part or all of a cross section of the above-mentioned laminate (including the laminate A) It is possible to prevent the chemical liquid from penetrating between one carrier-bonded copper foil constituting the intermediate layer or the laminate and the other carrier-bonded copper foil, and to prevent the separation of the ultra-thin copper layer and the carrier and the corrosion of the carrier- And the yield can be improved. As the &quot; resin covering part or all of the cross section of the copper foil with a carrier &quot; or &quot; resin covering part or all of the cross section of the laminate, &quot; a resin usable in the resin layer or a known resin can be used. Further, in the above-described method for producing a coreless substrate, it is preferable that when the carrier-bonded copper foil or the laminate has a laminated portion of the carrier-coated copper foil or the laminate (a laminated portion of the carrier and the ultra-thin copper layer, At least a part of the outer periphery of the other copper-clad laminate of the copper foil with a carrier) may be covered with a resin or a prepreg. The laminate (laminate A) formed by the above-described production method of the coreless substrate may be constituted by bringing a pair of carrier-bonded copper foils into contact with each other so as to be separable from each other. Further, when the carrier-bonded copper foil is in a plan view, the outer periphery of the laminated portion of the carrier-adhered copper foil or laminate (the laminated portion of the carrier and the ultra-thin copper layer, or the laminated portion of one carrier- Or may be covered with a resin or prepreg over the entire surface of the entire or laminated portion. The resin or prepreg is preferably larger than the laminated portion of the copper-clad laminate or the laminate with a carrier, and the resin or prepreg is laminated on both surfaces of the copper-clad laminate or carrier with the carrier, It is preferable that the copper foil or the laminate is a laminate having a configuration in which the copper foil or the laminate is plated (wrapped or wrapped) with a resin or a prepreg. With such a constitution, when the copper foil with a carrier or the laminate is laid flat, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and the other member is covered with the lateral side of this portion, As a result, it is possible to reduce peeling off of the carrier during handling and the ultra thin copper layer or the carrier-bonded copper foil. In addition, it is possible to prevent the penetration of the chemical liquid into the interface of the laminated portion in the chemical liquid treatment step as described above by covering with the resin or the prepreg so as not to expose the outer periphery of the laminated portion of the copper- Corrosion and erosion of the copper foil can be prevented. When separating one carrier-adhered copper foil from the pair of carrier-bonded copper foils of the laminate or separating the carrier of the copper foil with the carrier and the copper foil (the ultra-thin copper layer), the carrier- Or when the laminated portion of the laminate (the laminated portion of the carrier and the ultra-thin copper layer, or the laminated portion of one carrier-bonded copper foil and another carrier-bonded copper foil) is tightly adhered firmly by resin or prepreg or the like, It may be necessary to remove the laminated portion by cutting or the like.

The laminate may be formed by laminating the carrier-coated copper foil of the present invention on the carrier side or the ultra-thin copper layer side and on the carrier side or the ultra-thin copper layer side of another carrier-coated copper foil of the present invention. The carrier-side surface or the ultra-thin copper layer-side surface of the one carrier-bonded copper foil and the carrier-side surface of the another carrier-bonded copper foil or the ultra-thin copper layer-side surface may be directly laminated The resulting laminate may be used. Further, the carrier or the ultra-thin copper layer of the one carrier-attached copper foil and the carrier or the ultra-thin copper layer of the another carrier-bonded copper foil may be bonded. Here, the &quot; bonding &quot; includes the case where the carrier or the ultra-thin copper layer has the surface treatment layer, and the case where the carrier or the ultra-thin copper layer is bonded to each other through the surface treatment layer. A part or all of the cross section of the laminate may be covered with a resin.

The lamination of the carriers, the ultra-thin copper layers, the carrier, the ultra-thin copper layer, and the carrier-bonded copper foil can be carried out by, for example, the following method.

(a) Metallurgical bonding method: 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) ;

(b) Mechanical bonding methods: caulking, joining by rivets (joining by self-piercing rivets, joining by rivets), stitchers;

(c) Physical bonding method: Adhesive, (double-sided) adhesive tape

A part or the whole of one carrier and a part or all of the other carrier or a part or all of the ultra-thin copper layer are bonded using the above-mentioned bonding method to laminate one carrier and the other carrier or ultra-thin copper layer , And a laminate composed of the carriers or the carrier and the ultra-thin copper layer in contact so as to be detachable can be manufactured. In the case where one carrier and the other carrier or ultra thin copper layer are weakly bonded and one carrier and the other carrier or ultra thin copper layer are laminated, the bonding portion between one carrier and the other carrier or ultra thin copper layer is removed The carrier can be separated from the other carrier or the ultra-thin copper layer. When one carrier is strongly bonded to the other carrier or ultra-thin copper layer, a portion where one carrier and the other carrier or ultra-thin copper layer are bonded is cut, chemically polished (etched, etc.) It is possible to separate one carrier from the other carrier or ultra-thin copper layer.

The step of forming at least one layer of the resin layer and the circuit on the laminate thus constructed, and the step of forming at least one layer of the resin layer and the circuit at least once, The copper layer or the carrier is peeled off, whereby a printed wiring board having no core can be manufactured. Two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.

The resin substrate, the resin layer, the resin, and the prepreg used in the above-described laminate may be the resin layer described in this specification, and the resin, the resin curing agent, the compound, the curing accelerator, the dielectric, A catalyst, a cross-linking agent, a polymer, a prepreg, a skeleton or the like. The above-described copper foil or laminate with a carrier may be smaller than resin or prepreg, resin substrate or resin layer when planar.

The resin substrate is not particularly limited as long as it has properties applicable to a printed wiring board and the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber base epoxy resin, A polyester film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin, or the like can be used for the FPC, and an epoxy resin, a glass / glass nonwoven fabric composite base epoxy resin and a glass cloth base epoxy resin. Further, when an LCP (liquid crystal polymer) film or a fluororesin film is used, the peeling strength between the film and the surface-treated copper foil tends to be smaller than that when a polyimide film is used. Therefore, when a LCP (liquid crystal polymer) film or a fluororesin film is used, after forming a copper circuit, the copper circuit is covered with a coverlay so that the film and the copper circuit do not peel off easily, Peeling of the film and the copper circuit can be prevented.

[Example]

The following is a description based on examples and comparative examples. Note that this embodiment is merely an example, and the present invention is not limited to this example. That is, the present invention includes other forms or modifications included in the present invention.

(Original foil) of Examples 1 to 2, 4 to 6, 9 to 16, and Comparative Examples 1 to 2, 4 and 6 to 7 was coated with a standard rolled copper foil TPC (tough Pitch copper, JX metal, 10-point average roughness (Rz) of the surface = 0.7 mu m) was used. Electrodeposited copper foil (JX metal HLP foil, 10-point average roughness (Rz) on the surface of the precipitated surface (M plane) = 0.7 탆) having a thickness of 12 탆 was applied to the raw foils of Examples 3 and 8 and Comparative Examples 3 and 5, A surface treatment layer was provided on the surface (M side).

The carrier foil of Example 7 and Comparative Example 8 was a copper foil with a carrier prepared by the following method.

In Example 7, an electrolytic copper foil having a thickness of 18 占 퐉 (JX foil made of JX metal) was prepared as a carrier, and for Comparative Example 8, a standard rolled copper foil TPC having a thickness of 18 占 퐉 as described above was prepared as a carrier. An intermediate layer was formed on the surface of the carrier under the following conditions to form a very thin copper layer 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 side).

Example 7, Comparative Example 8

<Middle layer>

(1) Ni layer (Ni plating)

The carrier was plated on a continuous plating line of the roll-to-roll type under the following conditions to form an Ni layer having an adhesion amount of 1000 μg / dm 2. Specific plating conditions will be described below.

Nickel sulfate: 270-280 g / L

Nickel chloride: 35 to 45 g / L

Nickel acetate: 10 to 20 g / L

Boric acid: 30 to 40 g / L

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 55 to 75 ppm

pH: 4 to 6

Solution temperature: 55 ~ 65 ℃

Current density: 10 A / dm 2

(2) Cr layer (electrolytic chromate treatment)

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

1 to 10 g / L of potassium dichromate, 0 g / L of zinc

pH: 7 ~ 10

Solution temperature: 40 to 60 ° C

Current density: 2A / dm 2

<Ultra-thin copper layer>

Subsequently, the surface of the Cr layer formed in (2) was washed with water and pickled. Subsequently, an extremely thin copper layer having a thickness of 1.5 탆 was formed on the Cr layer by electroplating under the following conditions on a roll- To prepare a copper foil with a carrier.

Copper concentration: 90 ~ 110g / L

Sulfuric acid concentration: 90 to 110 g / L

Chloride ion concentration: 50 to 90 ppm

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

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

Further, the following amine compounds were used as the leveling agent 2.

(2)

Wherein 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 ℃

Current density: 100 A / dm 2

Electrolyte flux: 1.5 to 5 m / sec

Subsequently, a primary particle layer, a primary particle layer and a secondary particle layer were formed on the surface of the ultra-thin copper layer of the rolled copper foil, the electrolytic copper foil or the carrier-coated copper foil under the conditions shown in Tables 1 to 3. An example in which two current conditions and a coulomb amount are described in the primary particle current condition column in Table 1 means that plating is performed under the conditions described on the left side and then further plating is performed under the conditions described on the right side . For example, in the primary particle current condition column of Example 1, "(50 A / dm 2, 65 As / dm 2) + (8 A / dm 2, 16 As / dm 2)" is described, And a current density of 50 A / dm &lt; 2 &gt; and a coulomb amount of 65 As / dm &lt; 2 &gt;, plating was performed with a current density of 8 A / dm & .

Subsequently, coated plating was formed on the primary particle layer or on the secondary particle layer in which the secondary particle layer was formed under the conditions shown in Tables 1 and 4. Further, in the case where a plurality of treatments are described in the coating plating field, it means that the treatments are carried out in order from the left-hand side. For example, in Example 2, "(2) Ni-Mo + (1) Zn-Cr" is described in the column of "Coating Plating Conditions (Table 4 is Coating Plating Solution)" in Table 1, (2) 0.17, (1) 1.0 &quot; is written in the column of &quot; (2) (2) Ni-Mo plating, and (1) Zn-Cr plating in Table 4 were carried out in the same manner as in Example 2, 1) Zn-Cr plating means 1.0 second.

<Surface treatment layer other than primary particle layer and secondary particle layer and coated plating>

After the coating plating was formed, the following electrolytic chromate treatment was carried out for Examples 3 and 5 and Comparative Example 6. In the other Examples and Comparative Examples, the following electrolytic chromate treatment was not carried out.

· Electrolytic chromate treatment

Liquid composition: Potassium dichromate 1 ~ 1 g / L

Solution temperature: 40 to 60 ° C

pH: 0.5 to 10

Current density: 0.01 to 2.6 A / dm 2

Energization time: 0.05 to 30 seconds

Thereafter, Examples 3 to 5 and 10 were subjected to silane coupling treatment using the following diamino silane.

· Silane coupling treatment

Silane coupling agent: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane

Silane coupling agent concentration: 0.5 to 1.5 vol%

Processing temperature: 20 ~ 70 ℃

Processing time: 0.5 to 5 seconds

(Measurement of ten-point average roughness (Rz)) [

The surface roughness (Rz, 10-point average roughness) of the surface of the roughened layer was measured using a contact roughness meter Surfcorder SE-3 C contact-type roughness meter manufactured by Kosaka Laboratory Co., Ltd. in accordance with JIS B0601-1982. Rz was arbitrarily measured at 10 points, and the average value of the 10 points of Rz was set as the value of Rz.

(Measurement of transmission loss)

Each sample was applied to a liquid crystal polymer resin substrate (Vecstar CTZ manufactured by Kuraray Co., Ltd., thickness: 50 mu m, resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)) and then subjected to etching so that the characteristic impedance was 50 , And the transmission coefficient was measured using a network analyzer N5247A manufactured by HP to determine a transmission loss at a frequency of 20 GHz. As a result of evaluation of the transmission loss at a frequency of 20 GHz, 4.0 dB / 10 cm or less was rated as O, and 4.1 dB / 10 cm or more was rated as x.

(Measurement of peel strength)

The surface-treated surface of the copper foil and the resin substrate described in Table 2 were bonded by a hot press to produce a copper clad laminate. A 10 mm wide circuit was fabricated by using a general copper chloride circuit etchant. The initial peel strength was measured while pulling. The produced circuit was put in an oven under the atmosphere of 180 ° C, taken out after 10 days, and pulled out in the same 90 ° direction as in the steady state peeling, and the peel strength after heating was measured. The evaluation of the peel strength was evaluated as: when the initial peel strength was 0.5 kg / cm or more and the peel strength after heating was 0.3 kg / cm or more, the initial peel strength was 0.5 kg / cm or less or the peel strength after heating was 0.3 kg / &Lt; / RTI &gt;

For the laminated resin described in Table 2, "LCP" is a liquid crystal polymer, "Low dielectric constant PI" is a low dielectric constant polyimide, and "PTFE" is polytetrafluoroethylene.

As the liquid crystal polymer, vecstor CT-Z manufactured by Kuraray Co., Ltd., a liquid crystal polymer resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester) was used.

For the low-dielectric polyimide, polyimide having a dielectric tangent value of 0.002 was used. In the present specification, a polyimide having a dielectric tangent value of 0.01 or less is referred to as a low dielectric polyimide. The dielectric tangent can be measured by the triple plate resonance technique described in JPCA-TM001-2007, "Permittivity and dielectric tangent of test method for copper clad laminate for printed circuit boards", Japan Electronics and Information Technology Association.

The heat press conditions of the above-described copper foil and resin substrate were as follows.

When the liquid crystal polymer is a resin substrate: pressure 3.5 MPa, heating temperature 300 DEG C, heating time 10 minutes

When the low-dielectric-constant polyimide is a resin substrate: pressure 4 MPa, heating temperature 360 DEG C, heating time 5 minutes

When polytetrafluoroethylene is used as the resin substrate: pressure 5 MPa, heating temperature 350 DEG C, heating time 30 minutes

The thickness of the above-mentioned resin base material is 50 mu m.

The production conditions and evaluation results are shown in Tables 1 to 4.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

(Evaluation results)

In all of Examples 1 to 16, the transmission loss was satisfactorily suppressed, and the peel strength was good.

In Comparative Examples 1 and 6, the adhesion amount of Zn in the surface treatment layer was less than 150 占 퐂 / dm2, the total adhesion amount of Zn and Mo in the surface treatment layer was less than 200 占 퐂 / dm2, and the peel strength was poor .

In Comparative Example 2, the transfer loss was inferior because the amount of Co deposited on the surface treated layer was more than 3000 占 퐂 / dm2.

In Comparative Examples 3 and 8, the transmission loss was poor because the 10-point average roughness (Rz) of the outermost surface treatment layer was more than 1.5 탆.

In Comparative Example 4, the primary particle layer and the secondary particle layer were not formed, and the peel strength was poor.

In Comparative Example 5, the adhesion amount of Zn in the surface treatment layer was less than 150 占 퐂 / dm2, the total deposition amount of Zn and Mo was less than 200 占 퐂 / dm2, and the 10 point average roughness Rz) was more than 1.5 占 퐉, the transmission loss and the peel strength were poor.

In Comparative Example 7, although the surface treatment layer contained Ni, the transmission loss was poor because the adhesion amount of Ni exceeded 800 占 퐂 / dm2.

Claims (36)

A surface treatment layer on at least one side,
Wherein the surface treatment layer has a primary particle layer or a primary particle layer and a secondary particle layer,
The adhesion amount of Zn in the surface treatment layer is 150 占 퐂 / dm2 or more,
The surface treatment layer does not contain Ni or the adhesion amount of Ni is 800 占 퐂 / dm2 or less,
Wherein the surface treatment layer does not contain Co, or the coating amount of Co is 3000 占 퐂 / dm2 or less,
Wherein the 10-point average roughness (Rz) of the outermost surface of the surface treatment layer is 1.5 占 퐉 or less. A surface treatment layer on at least one side,
Wherein the surface treatment layer has a primary particle layer or a primary particle layer and a secondary particle layer,
Wherein the surface treatment layer comprises Zn and Mo,
The total deposition amount of Zn and Mo in the surface treatment layer is 200 占 퐂 / dm2 or more,
The surface treatment layer does not contain Ni, or the adhesion amount of Ni is 800 占 퐂 / dm2 or less,
The surface treatment layer does not contain Co, or the amount of deposited Co is 3000 占 퐂 / dm2 or less,
Wherein the 10-point average roughness (Rz) of the outermost surface of the surface treatment layer is 1.5 占 퐉 or less. 3. The method according to claim 1 or 2,
Wherein the amount of Zn deposited on the surface treatment layer is 165 占 퐂 / dm2 or more. 3. The method according to claim 1 or 2,
Wherein the adhesion amount of Zn in the surface treatment layer is 180 占 퐂 / dm2 or more. 3. The method according to claim 1 or 2,
Wherein the amount of Zn deposited on the surface treatment layer is 200 占 퐂 / dm2 or more. 3. The method according to claim 1 or 2,
Wherein the adhesion amount of Zn in the surface treatment layer is 250 占 퐂 / dm2 or more. 3. The method according to claim 1 or 2,
Wherein the adhesion amount of Ni in the surface treatment layer is 750 占 퐂 / dm2 or less. 3. The method according to claim 1 or 2,
Wherein the amount of Co deposited in the surface treatment layer is 2790 占 퐂 / dm2 or less. 3. The method according to claim 1 or 2,
Wherein a 10-point average roughness (Rz) of the outermost surface of the surface treatment layer is 1.0 占 퐉 or less. 3. The method of claim 2,
Wherein the total deposition amount of Zn and Mo in the surface treatment layer is 340 占 퐂 / dm2 or more. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer comprises Co. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer comprises Ni. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer comprises Co and Ni,
Wherein the total deposition amount of Co and Ni in the surface treatment layer is 3500 占 퐂 / dm2 or less. 3. The method according to claim 1 or 2,
A surface-treated copper foil having the surface treatment layer on both sides. 3. The method according to claim 1 or 2,
A surface-treated copper foil satisfying any one or two or three or four or five or six or seven or eight of the following (D) to (K).
(D) The adhesion amount of Zn in the surface treatment layer satisfies any one of the following,
· Greater than or equal to 165 μg / dm 2
≥ 180 μg / dm 2
More than 200 μg / dm 2
≥ 250 μg / dm 2
· Greater than 270 μg / dm 2
≥ 280 μg / dm 2
· Greater than 290 μg / dm 2
(E) the surface treatment layer contains Zn and Mo, and the total deposition amount of Zn and Mo in the surface treatment layer satisfies any one of the following:
More than 340 μg / dm 2
· Greater than 360 μg / dm 2
More than 400 μg / dm 2
· More than 420 μg / dm 2
More than 460 μg / dm 2
More than 500 μg / dm 2
(F) The adhesion amount of Ni in the surface treatment layer is 750 占 퐂 / dm2 or less,
(G) The adhesion amount of Co in the surface treatment layer is 2790 占 퐂 / dm2 or less,
(H) The 10-point average roughness (Rz) of the outermost surface of the surface treatment layer is 1.0 탆 or less
(I) The surface treatment layer includes Co
(J) the surface treatment layer contains Ni
(K) the surface treatment layer comprises Co and Ni,
The total deposition amount of Co and Ni in the surface treatment layer is 3500 占 퐂 / dm2 or less 3. The method according to claim 1 or 2,
Treating the surface-treated copper foil with a resin from the surface-treated layer side, etching the surface-treated copper foil to prepare a circuit having a width of 10 mm, and then peeling the circuit from the resin in the 90 占 direction, cm,
The conditions of the resin and the lamination are any one, two or three of the following (1) to (3), the surface-treated copper foil.
(1) Resin: liquid crystal polymer resin which is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 m
Lamination conditions: pressure 3.5 MPa, heating temperature 300 DEG C, heating time 10 minutes
(2) Resin: low dielectric polyimide resin, thickness 50 m
Lamination conditions: pressure 4 MPa, heating temperature 360 DEG C, heating time 5 minutes
(3) Resin: polytetrafluoroethylene, thickness 50 탆
Lamination conditions: pressure 5 MPa, heating temperature 350 DEG C, heating time 30 minutes 17. The method of claim 16,
Wherein the peel strength is 0.7 kg / cm or more. 3. The method according to claim 1 or 2,
Treating the surface-treated copper foil with a resin from the surface-treated layer side, etching the surface-treated copper foil to prepare a circuit having a width of 10 mm, heating the circuit at 180 占 폚 for 10 days in the atmosphere, The peel strength when peeling in the 90 占 direction is 0.4 kg / cm or more,
The conditions of the resin and the lamination are any one, two or three of the following (1) to (3), the surface-treated copper foil.
(1) Resin: liquid crystal polymer resin which is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 m
Lamination conditions: pressure 3.5 MPa, heating temperature 300 DEG C, heating time 10 minutes
(2) Resin: low dielectric polyimide resin, thickness 50 m
Lamination conditions: pressure 4 MPa, heating temperature 360 DEG C, heating time 5 minutes
(3) Resin: polytetrafluoroethylene, thickness 50 탆
Lamination conditions: pressure 5 MPa, heating temperature 350 DEG C, heating time 30 minutes 19. The method of claim 18,
Treating the surface-treated copper foil with a resin from the surface-treated layer side, etching the surface-treated copper foil to prepare a circuit having a width of 10 mm, heating the circuit at 180 占 폚 for 10 days in the atmosphere, And the peel strength when peeled in the 90 占 direction is 0.5 kg / cm or more. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer is formed on the primary particle layer or the secondary particle layer,
(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti,
(B) a chromate treatment layer
, Or both of them. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer is formed on the primary particle layer or the secondary particle layer,
A surface-treated copper foil having one or both of (A) and (B) below, and (C).
(A) an alloy layer comprising Ni and at least one element selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn,
(B) a chromate treatment layer
(C) Silane coupling treatment layer 3. The method according to claim 1 or 2,
Wherein the surface treatment layer is formed on the primary particle layer or the secondary particle layer,
A Ni-Zn alloy layer, and a chromate treatment layer. 3. The method according to claim 1 or 2,
Wherein the surface treatment layer is formed on the primary particle layer or the secondary particle layer,
At least one or both of a Ni-Zn alloy layer and a chromate treatment layer, and a silane coupling treatment layer. 3. The method according to claim 1 or 2,
Surface treated copper foil used for high frequency circuit boards. A resin-coated surface-treated copper foil having a resin layer on a surface of the surface-treated layer of the surface-treated copper foil according to claim 1 or 2. An intermediate layer and a very thin copper layer on at least one side of the carrier,
Wherein the ultra-thin copper layer is a surface-treated copper foil according to any one of claims 1 to 3 or a surface-treated copper foil with a resin layer having a resin layer on the surface of the surface treatment layer of the surface- Copper with a carrier. A laminate having a surface-treated copper foil according to claim 1 or 2, or a surface-treated copper foil with a resin layer having a resin layer on a surface of the surface-treated layer of the surface-treated copper foil according to any one of claims 1 to 3. A laminate having the copper foil with a carrier according to claim 26. A resin composition comprising the copper foil with a carrier according to claim 26 and a resin,
And a part or all of an end surface of the carrier-coated copper foil is covered with the resin. 26. A laminate having the two copper foils with a carrier according to claim 26. A method for producing a printed wiring board using any one of (L) to (N) below.
(L) The surface-treated copper foil according to any one of claims 1 to 3,
(M) A resin-coated surface-treated copper foil having a resin layer on the surface of the surface-treated layer of the surface-treated copper foil according to any one of claims 1 to 3,
Treated copper foil according to any one of claims 1 to 3, or an intermediate layer and an ultra-thin copper layer on at least one surface of a carrier (N) A resin-coated copper foil having a resin layer on the surface of a surface treatment layer, (L) to (N) below, a step of preparing an insulating substrate,
(L) The surface-treated copper foil according to any one of claims 1 to 3,
(M) A resin-coated surface-treated copper foil having a resin layer on the surface of the surface-treated layer of the surface-treated copper foil according to any one of claims 1 to 3,
Treated copper foil according to any one of claims 1 to 3, or an intermediate layer and an ultra-thin copper layer on at least one surface of a carrier (N) A resin-coated copper foil having a resin layer on the surface of a surface treatment layer,
A process for producing a copper clad laminate comprising any one of the following (1) to (3)
(1) a step of laminating the surface-treated copper foil and the insulating substrate,
(2) a step of laminating the resin-layer-adhered surface-treated copper foil and the insulating substrate,
(3) a step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,
And
A step of forming a circuit using the copper clad laminate according to any one of the semi-additive method, the subtractive method, the partial additive method, and the modified semi additive method
Wherein the step of forming the printed wiring board comprises the steps of: A method for producing a copper foil, comprising the steps of: forming a circuit on the surface-treated layer side surface of the surface-treated copper foil according to claim 1 or 2; or a step of forming a circuit, an intermediate layer, Forming a circuit on the ultra thin copper layer side surface or the carrier side surface of the copper foil with a carrier, which is the surface treated copper foil according to claim 2,
Forming a resin layer on the surface treatment layer side surface of the surface treated copper foil or on the surface of the ultra thin copper layer side or the carrier side surface of the copper foil with a carrier so that the circuit is buried,
A step of exposing a circuit buried in the resin layer by removing the surface treated copper foil after forming the resin layer or removing the ultra thin copper layer or the carrier after peeling the carrier or the ultra thin copper layer,
Wherein the step of forming the printed wiring board comprises the steps of: A step of laminating the carrier side surface of the copper foil with a carrier according to claim 26 or the surface of the ultra thin copper layer side and the resin substrate,
A step of providing a resin layer and a circuit on the surface of the carrier-coated copper foil opposite to the side laminated with the resin substrate,
A step of peeling the carrier or the ultra-thin copper layer from the carrier-adhered copper foil after the resin layer and the circuit are formed
Wherein the step of forming the printed wiring board comprises the steps of: A step of providing a resin layer and a circuit in the laminate according to claim 28,
After the resin layer and the circuit are formed, a step of peeling the carrier or the ultra-thin copper layer from the copper-clad with a carrier constituting the laminate
Wherein the step of forming the printed wiring board comprises the steps of: A manufacturing method of an electronic device using a printed wiring board manufactured by the method according to claim 31.

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