TWI503454B - Method for manufacturing copper foil, attached copper foil, printed wiring board, printed circuit board, copper clad sheet, and printed wiring board - Google Patents

Description

Carrier copper foil, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper clad laminate, and printed wiring board manufacturing method

The present invention relates to a carrier-attached copper foil, a method of manufacturing a carrier-attached copper foil, a printed wiring board, a printed circuit board, a copper-clad laminate, and a method of manufacturing a printed wiring board, and more particularly to a printed wiring board for manufacturing a fine pattern A carrier copper foil to be used, a method for producing a copper foil with a carrier, a printed wiring board, a printed circuit board, a copper clad laminate, and a method for producing a printed wiring board.

Printed wiring boards have grown tremendously in the past half century and are now used in almost all electronic machines. In recent years, as the demand for miniaturization and high performance of electronic equipment has increased, the high-density mounting of components and the high-frequency of signals have been increasing, and the conductor pattern has been required to be miniaturized (micro-pitched). In the case where the IC chip is mounted on the printed wiring board, it is required to have a fine pitch of L (line) / S (gap) = 20 μm / 20 μm or less.

The printed wiring board is first produced by laminating a copper foil and an insulating substrate mainly composed of an epoxy glass substrate, a BT resin, a polyimide film, or the like. The bonding method is a method (lamination method) in which an insulating substrate and a copper foil are superposed and heated and pressurized, or A varnish of a precursor of an insulating substrate material is applied to a surface of a copper foil having a coating layer and heated to be cured (casting).

With the fine pitch, the thickness of the copper foil used for the copper clad laminate is also 9 μm, further 5 μm or less, and the thickness of the foil is gradually reduced. However, when the thickness of the foil is 9 μm or less, the workability in forming the copper clad laminate by the above-described lamination method or casting method is extremely deteriorated. Therefore, there has been a copper foil with a carrier on which a metal foil having a certain thickness is used as a carrier and an extremely thin copper layer is formed thereon via a peeling layer. A conventional method of using a carrier copper foil is to bond the surface of an ultra-thin copper layer to an insulating substrate and thermocompression bonding, and then peel the carrier through the release layer.

Conventionally, Patent Document 1 discloses that a diffusion preventing layer, a peeling layer, and an electroplated copper layer are sequentially formed on the surface of a carrier foil, and a Cr or Cr hydrated oxide layer is used as a peeling layer, and Ni, Co, Fe, Cr, Mo are used. A simple substance or alloy of Ta, Cu, Al, or P is used as a diffusion preventing layer, thereby maintaining a good peeling property after heating and pressurization.

Further, it is known that the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P or the alloys thereof or the hydrates thereof. Further, in Patent Documents 2 and 3, in order to stabilize the peeling property in a high-temperature use environment such as heating and pressurization, it is effective to provide Ni, Fe, or an alloy layer on the base of the peeling layer.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-022406

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-006071

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-007937

For the copper foil with a carrier, it is necessary to prevent the ultra-thin copper foil from being peeled off from the carrier before the step of laminating the insulating substrate, and on the other hand, the carrier is easily peeled off from the ultra-thin copper foil after the lamination step to the insulating substrate. Further, since the carrier is peeled off from the ultra-thin copper foil after lamination, the circuit is formed on the ultra-thin copper foil by the semi-additive method, so it is necessary to reduce the organic matter or the metal and metal oxide or metal hydrate oxide which are not easily etched. The amount is present to maintain good etchability.

In Patent Document 1, although the peeling property after heating and pressurization is good, the state of the surface of the ultra-thin copper foil is not mentioned.

Further, although the order of the diffusion preventing layer and the peeling layer is described in the patent document, the examples are described in the order of the carrier foil, the peeling layer, the diffusion preventing layer, and the copper plating layer, and the peeling layer is formed at the time of peeling/ The anti-diffusion layer interface is peeled off. If so, the diffusion preventing layer may remain on the surface of the electroplated copper layer (very thin copper layer), resulting in poor etching when the circuit is formed.

Regarding Patent Documents 2 and 3, it is not considered that the characteristics such as the peel strength between the carrier and the ultra-thin copper foil have been sufficiently studied, and there is still room for improvement.

Accordingly, an object of the present invention is to provide a copper foil with a carrier which has a high adhesion force between a carrier and an ultra-thin copper foil before the step of laminating to an insulating substrate, and on the other hand, a carrier and a carrier layer which are caused by a lamination step to an insulating substrate The extreme increase or decrease of the adhesion of the ultra-thin copper foil can be easily peeled off at the interface of the carrier/very thin copper foil, and the electron migration of the circuit formed on the surface can be more well suppressed, and the etching of the ultra-thin copper foil can be performed. Good sex.

In order to achieve the above object, the inventors have conducted intensive studies and found that the control of the insulating substrate is thermally bonded to the extremely thin copper layer under specific conditions, and the ultra-thin copper layer is attached. The amount of Ni on the peeling side surface of the ultra-thin copper layer at the time of peeling of the carrier copper foil is extremely effective for improving the peelability of the carrier/very thin copper foil interface and the etching property of the ultra-thin copper foil.

The invention is based on the above findings, and is a carrier copper foil with a carrier, an intermediate layer and an ultra-thin copper layer in sequence, and the above-mentioned ultra-thin copper is used according to JIS B0601-1982 by a contact type roughness meter. The average value of Rz obtained by measuring the surface of the layer is 1.5 μm or less, and the standard deviation of Rz is 0.1 μm or less. The intermediate layer contains Ni, and the insulating substrate is placed in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C. When the ultra-thin copper layer is peeled off by the above-mentioned ultra-thin copper layer under the condition of 2 hours, and the above-mentioned ultra-thin copper layer is peeled off according to JIS C 6471, the depth direction obtained by the depth direction analysis from the surface by XPS (x: unit nm) The atomic concentration (%) of chromium is set to e(x), the atomic concentration (%) of zinc is f(x), and the atomic concentration (%) of nickel is set to g(x), and the atom of copper is used. The concentration (%) is h (x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) When k(x) is set, ∫ g(x)dx/(∫ e(x)dx+ is within the interval [0, 1.0] of the depth direction analysis from the surface of the above-mentioned intermediate layer side of the ultra-thin copper layer. ∫ f(x)dx+∫ g(x ) dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 20.0% or less.

In another aspect, the invention is a copper foil with carrier, which has a carrier, an intermediate layer and an ultra-thin copper layer in sequence, and the Rt obtained by measuring the surface of the ultra-thin copper layer according to JIS B0601-2001 by a contact type roughness meter. The average value is 2.0 μm or less, and the standard deviation of Rt satisfies 0.1 μm or less. The intermediate layer contains Ni, and the insulating substrate is thermocompression-bonded in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. In the above-mentioned ultra-thin copper layer, when the ultra-thin copper layer is peeled off according to JIS C 6471, the atomic concentration of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS (%) ) is set to e(x), the atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is g(x), and the atomic concentration (%) of copper is h ( x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) is k (x).区间 g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g in the interval [0,1.0] of the depth direction analysis from the surface of the above-mentioned intermediate layer side of the ultra-thin copper layer (x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx +∫ k(x)dx) satisfies 20.0% or less.

According to still another aspect of the present invention, a copper foil with a carrier, which has a carrier, an intermediate layer, and an extremely thin copper layer, is obtained by measuring a surface of the ultra-thin copper layer according to JIS B0601-1982 by a contact type roughness meter. The average value is 0.2 μm or less, and the standard deviation of Ra satisfies 0.03 μm or less. The intermediate layer contains Ni, and the insulating substrate is thermocompression-bonded in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. In the above-mentioned ultra-thin copper layer, when the ultra-thin copper layer is peeled off according to JIS C 6471, the atomic concentration of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS (%) ) is set to e(x), the atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is g(x), and the atomic concentration (%) of copper is h ( x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) is k (x).区间 g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g in the interval [0,1.0] of the depth direction analysis from the surface of the above-mentioned intermediate layer side of the ultra-thin copper layer (x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)d x+∫ k(x)dx) satisfies 20.0% or less.

In one embodiment, the copper foil with a carrier of the present invention is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and is in accordance with JIS C. 6471, when the ultra-thin copper layer is peeled off, in the interval [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫e(x) Dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 10.0% or less.

In another embodiment, the copper foil with a carrier of the present invention has an average value of Rt measured by measuring the surface of the ultra-thin copper layer according to JIS B0601-2001 by a contact type roughness meter of 2.0 μm or less, and a standard deviation of Rt. It is 0.1 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the average value of Ra obtained by measuring the surface of the ultra-thin copper layer by a contact-type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or less, and the standard deviation of Ra It is 0.03 μm or less.

In still another embodiment, the copper foil with a carrier of the present invention has a roughened layer on the surface of the ultra-thin copper layer.

In still another embodiment, the copper foil with a carrier of the present invention is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and is based on JIS. When the ultra-thin copper layer is peeled off, C 6471 is in the interval [0, 1.0] in the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫ e( x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or more and 20.0% or less, and Within the interval [1.0, 4.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j( x) dx + ∫ k(x) dx) satisfies 1.0% or more and 10.0% or less.

In still another embodiment, the copper foil with a carrier of the present invention is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and is based on JIS. When the ultra-thin copper layer is peeled off by C 6471, in the interval [0, 1.0] of the depth direction analysis from the surface of the XPS on the intermediate layer side of the ultra-thin copper layer, ∫ e(x)dx/( ∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 3.0% or less.

In still another embodiment, the copper foil with a carrier of the present invention is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and is based on JIS. When the ultra-thin copper layer is peeled off, C 6471 is in the interval [0, 1.0] in the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫ e( x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 11.0% or less.

In still another embodiment, the copper foil with a carrier of the present invention is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and is based on JIS. C 6471, when the ultra-thin copper layer is peeled off, in the interval [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫ e( x) dx + ∫ f (x) dx + ∫ g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) satisfies 7.0% or less.

In still another embodiment of the copper foil with a carrier of the present invention, an average value of Rz of the surface of the ultra-thin copper layer is 1.0 μm or less.

In another embodiment of the copper foil with carrier of the present invention, the above ultra-thin copper layer table The average value of Rz of the surface is 0.5 μm or less.

In another embodiment, the copper foil with a carrier of the present invention has a depth direction (x: unit nm) obtained by depth direction analysis from the surface by XPS when the ultra-thin copper layer is peeled off in accordance with JIS C 6471. The atomic concentration (%) of chromium is set to e(x), which will be the atom of zinc. The concentration (%) is f(x), the atomic concentration (%) of nickel is set to g(x), the atomic concentration (%) of copper is h(x), and the atomic concentration (%) of total oxygen is used. When i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) is k (x), the intermediate layer side of the ultrathin copper layer is In the interval [0,1.0] of the depth direction analysis from the surface, ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) satisfies 5.0% or less.

In another embodiment, the copper foil with a carrier of the present invention has a depth direction (x: unit nm) obtained by depth direction analysis from the surface by XPS when the ultra-thin copper layer is peeled off in accordance with JIS C 6471. The atomic concentration (%) of chromium is set to e(x), the atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is set to g(x), and the atomic concentration of copper is determined. (%) is h(x), the total atomic concentration (%) of oxygen is i(x), the atomic concentration (%) of carbon is j(x), and the other atomic concentration (%) is set. k(x), in the interval [1.0, 4.0] of the depth direction analysis from the surface of the above-mentioned intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or less.

In still another embodiment, the copper foil with a carrier according to the present invention is a section for analyzing the depth direction from the surface of the intermediate layer side of the ultra-thin copper layer when the ultra-thin copper layer is peeled off according to JIS C 6471 [ Within 0,1.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+ ∫ k(x)dx) satisfies 0.1% or more and 5.0% or less, and within the interval [1.0, 4.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x Dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.1% or more and 1.0% or less.

In still another embodiment, the copper foil with a carrier according to the present invention is a section for analyzing the depth direction from the surface of the intermediate layer side of the ultra-thin copper layer when the ultra-thin copper layer is peeled off according to JIS C 6471 [ Within 0,1.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+ ∫ k(x)dx) satisfies 3.0% or less.

In still another embodiment of the copper foil with a carrier according to the present invention, when the ultra-thin copper layer is peeled off according to JIS C 6471, the depth direction of the surface of the ultra-thin copper layer on the intermediate layer side by the XPS is analyzed. Within the interval [0,1.0], ∫ e(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j( x) dx + ∫ k(x) dx) satisfies 2.0% or less.

In still another embodiment of the present invention, the intermediate layer is a layer in which nickel or a nickel-containing alloy is sequentially laminated on a carrier, and an oxide containing chromium, a chromium alloy or chromium is contained. Any one or more layers are formed.

In still another embodiment of the copper foil with a carrier according to the present invention, the layer containing at least one of chromium, a chromium alloy, and an oxide of chromium includes a chromate-treated layer.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains zinc.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer is formed by sequentially laminating a layer of any one of nickel, a nickel-zinc alloy, a nickel-phosphorus alloy, and a nickel-cobalt alloy on the carrier, and chromium. It is composed of any one of a zinc acid treatment layer, a pure chromate treatment layer, and a chromium plating layer.

In still another embodiment of the present invention, the intermediate layer is formed by sequentially laminating a nickel layer, a nickel-zinc alloy layer, and a zinc chromate treatment layer on the carrier, or sequentially laminating nickel-zinc. The alloy layer and the pure chromate treatment layer or the zinc chromate treatment layer are formed. The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , and the adhesion amount of chromium is 5 to 100 μg/dm ² . The amount is 1 to 70 μg/dm ² .

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer is formed by sequentially depositing a nickel layer on the carrier, and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. Further, the amount of nickel attached to the intermediate layer is 100 to 40000 μg/dm ² .

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer is formed by sequentially laminating an organic layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on the carrier. Further, the amount of nickel attached to the intermediate layer is 100 to 40000 μg/dm ² .

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an organic substance having a thickness of 25 nm or more and 80 nm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer is formed by sequentially depositing a nickel layer or an alloy layer containing nickel on the carrier, and a layer containing at least one of molybdenum, cobalt, and molybdenum cobalt alloy. Further, the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , and in the case of containing molybdenum, the adhesion amount of molybdenum is 10 to 1000 μg/dm ² , and in the case of containing cobalt, the adhesion amount of cobalt is 10~1000μg/dm ² .

In still another embodiment of the copper foil with a carrier of the present invention, the carrier is formed of an electrolytic copper foil or a rolled copper foil.

In still another embodiment of the present invention, the roughened layer is one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A single layer or a layer composed of an alloy selected from any one or more of the group.

In still another embodiment, the copper foil with a carrier of the present invention has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the roughened layer. Layer.

In still another embodiment, the copper foil with a carrier of the present invention has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the ultra-thin copper layer. Layer.

In still another embodiment, the copper foil with a carrier of the present invention is provided with a resin layer on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. .

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is provided on the roughened layer.

In still another embodiment of the copper foil with a carrier of the present invention, the ultra-thin copper layer is provided with a resin layer.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is a resin for subsequent use.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is a resin in a semi-hardened state.

In another aspect, the present invention provides a method for producing a copper foil with a carrier according to the present invention, which comprises the steps of forming a layer containing any one of nickel or an alloy containing nickel on a support to form a chromium or chromium alloy or Any one or more of the chromium oxides, at least one of the above nickel or an alloy containing nickel, or an oxide containing chromium, a chromium alloy or chromium An intermediate layer containing zinc is formed on any of the above layers; and an extremely thin copper layer is formed by electrolytic plating on the intermediate layer.

In one embodiment, the method for producing a copper foil with a carrier according to the present invention comprises the steps of: forming a plating layer containing nickel and zinc on a carrier, forming a plating layer containing chromium or a chromate treatment layer, thereby forming An intermediate layer; and an extremely thin copper layer formed by electrolytic plating on the intermediate layer.

In another embodiment, the method for producing a copper foil with a carrier according to the present invention comprises the steps of: forming a plating layer containing nickel on a carrier to form a plating layer containing chromium and zinc or a zinc chromate treatment layer; Forming an intermediate layer; and forming an extremely thin copper layer by electrolytic plating on the intermediate layer.

In still another embodiment, the method for producing a copper foil with a carrier according to the present invention comprises the steps of: forming a plating layer containing nickel and zinc on a carrier, and forming a plating layer containing chromium and zinc or a zinc chromate treatment layer; Thereby, an intermediate layer is formed; and an extremely thin copper layer is formed by electrolytic plating on the intermediate layer.

In still another embodiment, the method for producing a copper foil with a carrier of the present invention comprises the steps of: forming a nickel plating layer on a carrier, forming a zinc chromate treatment layer by electrolytic chromate, thereby forming an intermediate layer, or After forming the nickel-zinc alloy plating layer, forming a pure chromate treatment layer or a zinc chromate treatment layer by electrolytic chromate, thereby forming an intermediate layer; and forming a pole on the intermediate layer by electrolytic plating The step of a thin copper layer.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the method further comprises the step of forming a roughened layer on the ultra-thin copper layer.

In another aspect, the invention is a printed wiring board which uses the invention Manufactured with a carrier copper foil.

In another aspect, the invention is a printed circuit board manufactured using the carrier-attached copper foil of the present invention.

In still another aspect, the present invention is a copper clad laminate which is produced using the copper foil with a carrier of the present invention.

In another aspect, the invention provides a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After laminating the foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then by semi-additive method, subtractive method, partial addition method or modified semi-additive method Either method forms a circuit.

According to the present invention, it is possible to provide a copper foil with a carrier which has a high adhesion force between the carrier and the ultra-thin copper foil before the lamination step to the insulating substrate, and on the other hand, has no carrier and extremely thin layer caused by the lamination step to the insulating substrate. The extreme increase or decrease in the adhesion of the copper foil can be easily peeled off at the interface of the carrier/very thin copper foil, and the electron migration of the circuit formed on the surface can be more satisfactorily suppressed, and the etching property of the ultra-thin copper foil is good. .

1A to 1C are schematic views showing a cross section of a wiring board in a step of plating a circuit and removing a resist, in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

2D to F are sectional views of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening using the specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention. Schematic diagram of the surface.

3G to 3 are schematic views showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier, in a specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

4J to K are schematic views showing a cross section of the wiring board in the step from the rapid etching to the step of forming the bumps and the copper pillars in the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

Fig. 5 is a schematic view showing a cross section in the width direction of the circuit pattern in the embodiment, and an outline of a calculation method using the etching factor (EF) of the schematic diagram.

Fig. 6 is a profile in the depth direction of the extremely thin copper surface (before the substrate is crimped) of Example 5.

Fig. 7 is a distribution diagram in the depth direction of the extremely thin copper surface of Example 5 (after the substrate is crimped).

Fig. 8 is a distribution diagram in the depth direction of the extremely thin copper surface of Example 14 (after the substrate is crimped).

Fig. 9 is a distribution diagram in the depth direction of the extremely thin copper surface (before the substrate is pressed) of Comparative Example 5.

Fig. 10 is a schematic view showing the manner of transporting a foil using a drum.

Fig. 11 is a schematic view showing the manner in which the foil is conveyed by bending.

Fig. 12 is a schematic view for explaining an integration method of atomic concentration.

Fig. 13 is a schematic view showing the measurement site of the sample sheet in the example.

<With carrier copper foil>

The copper foil with carrier of the present invention has a carrier, an intermediate layer and an extremely thin copper layer in this order. The method of using the carrier copper foil itself is well known to the manufacturer, for example, the surface of the ultra-thin copper layer can be attached to the paper. Substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy An insulating substrate such as a resin, a polyester film, or a polyimide film is peeled off by thermocompression bonding, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern to finally produce a printed wiring board, a printed circuit board, or Copper clad laminates, etc.

After the insulating substrate is thermally bonded to the ultra-thin copper layer, when the ultra-thin copper layer is peeled off from the carrier copper foil, if the amount of Ni remaining on the surface of the intermediate layer side of the ultra-thin copper layer is large, the ultra-thin copper is The layer is not easily etched, making it difficult to form a micro-pitch circuit. Therefore, the copper foil with a carrier of the present invention is thermocompression bonded to an extremely thin copper layer under the conditions of atmospheric pressure, pressure: 20 kgf/cm ² , 220 ° C × 2 hours, and ultra-thin copper according to JIS C 6471. When the layer is peeled off, if the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is e(x), the atomic concentration (%) of zinc is set. For f(x), the atomic concentration (%) of nickel is set to g(x), the atomic concentration (%) of copper is h(x), and the atomic concentration (%) of oxygen is set to i (x). ), the carbon atom concentration (%) is set to j (x), and the other atomic concentration (%) is k (x), and the depth direction of the ultra-thin copper layer from the surface of the intermediate layer side is analyzed. Within the interval [0,1.0], ∫ .g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) is controlled to be 20.0% or less, preferably controlled to be 18.0% or less, preferably controlled to be 16.0% or less, preferably controlled to be 14.1% or less, preferably controlled to 12.0% or less is preferably controlled to be 11.0% or less, preferably controlled to be 10.0% or less, and preferably controlled to be 5.0% or less. After attaching the carrier copper foil to the insulating substrate and thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer on the insulating substrate is etched into a target conductor pattern. At this time, if it remains on the middle layer side of the ultra-thin copper layer When the amount of Ni on the surface is large, the extremely thin copper layer is not easily etched, and it is difficult to form a micro-pitch circuit. Therefore, the amount of Ni on the surface of the ultra-thin copper layer after peeling as described above in the copper foil with carrier of the present invention is controlled. If the Ni amount is within the interval [0, 1.0], let ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x When dx+∫ j(x)dx+∫ k(x)dx) exceeds 20.0%, it is difficult to form an ultra-thin copper layer to form a finer wiring of L/S=20 μm/20 μm, for example, L/S=15 μm. In the case of a fine wiring of /15 μm, there is a possibility that the etching property of an extremely thin copper foil may become poor. In addition, the above-mentioned "thermocompression bonding under conditions of 220 ° C × 2 hours" indicates typical heating conditions in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.

The copper foil with a carrier of the present invention is thermocompression bonded to an extremely thin copper layer under the conditions of atmospheric pressure, pressure: 20 kgf/cm ² , 220 ° C × 2 hours, and the ultra-thin copper layer is stripped according to JIS C 6471. When the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface of XPS is e(x), the atomic concentration (%) of zinc is set to f. (x), the atomic concentration (%) of nickel is set to g(x), the atomic concentration (%) of copper is h(x), and the atomic concentration (%) of oxygen is set to i(x). When the atomic concentration (%) of carbon is j (x) and the other atomic concentration (%) is k (x), it is preferable to have a depth from the surface of the ultra-thin copper layer from the intermediate layer side. In the interval [1.0, 4.0] of the direction analysis, let ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+ ∫ j(x)dx+∫ k(x)dx) is controlled so as to satisfy 10.0% or less, preferably more preferably 8.0% or less, more preferably 7.0% or less, still more preferably 6.0% or less, and even more preferably The control is performed in a manner of 5.0% or less, more preferably 4.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less. According to such a configuration, the etching property can be further improved.

If the ultra-thin copper layer is peeled off from the thermocompression-attached carrier copper foil as described above When the amount of Ni on the surface of the extremely thin copper layer is too small, the carrier Cu may diffuse toward the very thin copper layer side. In this case, the degree of bonding between the carrier and the ultra-thin copper layer is too strong, and pinholes are easily generated in the extremely thin copper layer when the ultra-thin copper layer is peeled off. Therefore, the amount of Ni is preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+ in the interval [0,1.0] ∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or more and 20.0% or less, and/or makes ∫ g(x)dx/(∫ e in the interval [1.0, 4.0] (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or more and 10.0% or less Way to control. Moreover, the Ni amount is more preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+ in the interval [0,1.0] ∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 2.0% or more and 18.0% or less, and/or makes ∫ g(x)dx/(∫ e in the interval [1.0, 4.0] (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 2.0% or more and 8.0% or less Way to control. Further, the amount of Ni is more preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+ in the interval [0,1.0] ∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 3.0% or more and 15.0% or less, and/or makes ∫ g(x)dx/(∫ e in the interval [1.0, 4.0] (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 3.0% or more and 7.0% or less Way to control. Further, the amount of Ni is preferably within the interval [0, 1.0] such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x) Dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 11.0% or less, and/or within the interval [1.0, 4.0], such that ∫ g(x)dx/(∫ e(x ) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) is controlled so as to satisfy 7.0% or less.

Further, when the insulating substrate is thermally bonded to the ultra-thin copper layer under the conditions of a pressure of 20 kgf/cm ² and 220 ° C for 2 hours in the atmosphere, and the ultra-thin copper layer is peeled off in accordance with JIS C 6471,区间 e(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ in the interval [0,1.0] of the above-mentioned intermediate layer side of the ultra-thin copper layer using the XPS from the surface depth direction analysis g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) preferably satisfies 3.0% or less, more preferably satisfies 2.0% or less, and further preferably Meet below 1.0%. Further, when the amount of Cr on the surface of the ultra-thin copper layer is too small, the surface of the ultra-thin copper foil is oxidized and discolored. Therefore, the insulating substrate is placed in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. Under the condition that the ultra-thin copper layer is thermally bonded under the condition, and the ultra-thin copper layer is peeled off according to JIS C 6471, the interval of the depth direction analysis from the surface of the XPS on the intermediate layer side of the ultra-thin copper layer [0, 1.0 ], ∫ e(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k( More preferably, x) dx) satisfies 0.1% or more and 2.0% or less, and more preferably 0.2% or more and 1.5% or less.

Further, in the copper foil with a carrier of the present invention, when the ultra-thin copper layer is directly peeled off in accordance with JIS C 6471 without being thermally bonded to the insulating substrate as described above, the depth direction analysis by the surface from the surface using XPS is obtained. The atomic concentration (%) of chromium in the depth direction (x: unit nm) is set to e(x), the atomic concentration (%) of zinc is set to f(x), and the atomic concentration (%) of nickel is set to g. (x), the atomic concentration (%) of copper is h (x), the total atomic concentration (%) of oxygen is i (x), and the atomic concentration (%) of carbon is j (x). When the other atomic concentration (%) is k (x), it is preferable to make ∫ g in the interval [0, 1.0] in the depth direction analysis from the surface of the above-mentioned intermediate layer side of the ultra-thin copper layer. (x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) 5.0% or less Take control. If the Ni amount is within the interval [0, 1.0], let ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x) When dx+∫ j(x)dx+∫ k(x)dx) exceeds 5.0%, it is difficult to form an ultra-thin copper layer to form a finer wiring L/S=20 μm/20 μm, for example, L/S=15 μm/ In the case of a fine wiring of 15 μm, the etching property of an extremely thin copper foil is deteriorated. Further, it is preferable to make ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i in the interval [0,1.0] x) dx + ∫ j (x) dx + ∫ k (x) dx) is controlled so as to satisfy 3.0% or less. With such a configuration, the etching property is further improved.

The copper foil with a carrier of the present invention is preferably a section for analyzing the depth direction from the surface of the intermediate layer side of the ultra-thin copper layer when the ultra-thin copper layer is peeled off according to JIS C 6471 [1.0, 4.0] Inside, let ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k( x) dx) Controls in a manner that satisfies 1.0% or less. With such a configuration, the etching property is further improved.

When the amount of Ni on the surface of the ultra-thin copper layer from which the ultra-thin copper layer is peeled off from the copper foil is too small as described above, the carrier Cu may diffuse toward the ultra-thin copper layer side. In this case, the degree of bonding between the carrier and the ultra-thin copper layer is too strong, and pinholes are easily generated in the extremely thin copper layer when the ultra-thin copper layer is peeled off. Therefore, the amount of Ni is preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+ in the interval [0,1.0] ∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.1% or more and 5.0% or less, and/or makes ∫ g(x)dx/(∫ e in the interval [1.0, 4.0] (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.1% or more and 1.0% or less Way to control. Further, the amount of Ni is more preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f is within the interval [0, 1.0] (x) dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.2% or more and 4.0% or less, and/or in the interval [ 1.0, 4.0] makes ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+ ∫ k(x)dx) is controlled so as to satisfy 0.2% or more and 0.8% or less. Further, the amount of Ni is more preferably such that ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+ in the interval [0,1.0] ∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.5% or more and 3.0% or less, and/or makes ∫ g(x)dx/(∫ e in the interval [1.0, 4.0] (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.3% or more and 0.7% or less Way to control.

Further, when the ultra-thin copper layer is peeled off in accordance with JIS C 6471, if the amount of Cr on the surface of the ultra-thin copper layer is too small, oxidative discoloration occurs on the surface of the ultra-thin copper foil. Preferably, in the interval [0, 1.0] of the depth direction analysis from the surface of the XPS on the intermediate layer side of the ultra-thin copper layer, ∫ e(x)dx/(∫ e(x)dx+∫ f(x Dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 2.0% or less. Further, when the ultra-thin copper layer is peeled off in accordance with JIS C 6471, ∫ e(x)dx is in the interval [0, 1.0] of the depth direction analysis from the surface of the XPS on the intermediate layer side of the ultra-thin copper layer. /(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) is better to satisfy 0.1 % or more and 2.0% or less, and more preferably 0.2% or more and 1.0% or less.

Furthermore, the integral value of the concentration of each of the above elements is obtained by a trapezoidal formula.

Hereinafter, an integration method using the concentration of the trapezoidal formula will be described. Here, a case where the atomic concentration of nickel is integrated in the section [0.0, 4.0] in the depth direction analysis from the surface of the intermediate layer will be described as an example. Also, in order to simplify the description, it is listed in the interval [0.0, 4.0]. The case of the point is explained as an example. Fig. 12 is a schematic view showing an integration method for explaining atomic concentration.

Fig. 12 is a diagram in which the horizontal axis represents the depth x (nm) from the surface of the intermediate layer, and the vertical axis represents the nickel atom concentration (at%). Points a, b, c, d, e, and f represent the measurement results of the nickel atom concentration at the depths l, k, j, i, h, g (nm) from the surface of the intermediate layer, respectively.

As shown in Fig. 12, the atomic concentration of nickel was measured by a specific depth (1 to g) of several points in the interval [0.0, 4.0] in the depth direction analysis from the surface of the intermediate layer by XPS.

Then, the area S1 of the trapezoid abk1, the area S2 of the trapezoidal bcjk, the area S3 of the trapezoidal cdij, the area S4 of the trapezoid dehi, and the area S5 of the trapezoid efgh are obtained. Then, the value of the total area of S1 to S5 is the integral value 镍 g(x)dx of the atomic concentration of nickel in the section [0.0, 4.0] in the depth direction analysis from the surface of the intermediate layer. That is, ∫ g(x)dx=S1+S2+S3+S4+S5 in the section [0.0, 4.0] of the depth direction analysis from the surface of the intermediate layer is calculated.

Here, for example, the area S1 of the trapezoid abk1 is represented by {(the atomic concentration of nickel of point a (at%)) + (the atomic concentration of nickel of point b (at%))}× (depth between points a and b) It is obtained by x1 (nm))/2. In the same manner, the area S2 of the trapezoidal bcjk, the area S3 of the trapezoidal cdij, the area S4 of the trapezoid dehi, and the area S5 of the trapezoid efgh are obtained.

Further, the point a is the measurement result of the nickel atom concentration which is closest to the depth 1 of the depth of 0.0 nm from the surface of the intermediate layer, and the point f is the nickel atom concentration of the depth g which is closest to the depth of 4.0 nm from the surface of the intermediate layer. The measurement results.

The measurement interval of each point (x1, x2, x3, x4, x5 in Fig. 12) is preferably 0.10 to 0.30 nm (in terms of SiO ₂ ).

Therefore, in the case of the interval [0.0, 4.0], it means that the depth at which the integration starts is 0.0 nm (in terms of SiO ₂ ) (that is, the surface of the analysis object), and the depth of the integration integral is 4.0 nm (in terms of SiO ₂ ) (from The surface is at a depth of 4.0 nm). Similarly, in the case of the interval [4.0, 12.0], it means that the depth at which integration is started is 4.0 nm (in terms of SiO ₂ ) (depth of 4.0 nm from the surface), and the depth of integration is 12.0 nm (in terms of SiO ₂ ). (depth from 12.0 nm from the surface).

<carrier>

The carrier usable in the present invention is typically a metal foil or a resin film, for example, a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, an insulating resin film, A form of a polyimide film or an LCD film is provided.

The carrier which can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy No. C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, copper to which Sn is added may be used. A copper alloy containing Ag is added, a copper alloy such as Cr, Zr or Mg is added, and a copper alloy such as a Cason copper alloy such as Ni or Si is added. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

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

<intermediate layer>

An intermediate layer containing Ni is provided on one or both sides of the carrier. Furthermore, it can also be in the carrier and Set other layers between the layers.

The intermediate layer is preferably formed by sequentially laminating a layer of nickel or a nickel-containing alloy on the carrier, and a layer containing at least one of chromium, a chromium alloy, and an oxide of chromium. Further, it is preferable that a layer of any one of nickel or an alloy containing nickel and/or a layer containing at least one of chromium, a chromium alloy, and an oxide of chromium contains zinc. Here, the alloy containing nickel means one or more elements selected from the group consisting of nickel and cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. The alloy containing nickel may be an alloy composed of three or more elements. Further, the term "chromium alloy" means an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. . The chromium alloy may also be an alloy composed of three or more elements. Further, the layer containing at least one of chromium, a chromium alloy, and an oxide of chromium may be a chromate-treated layer. Here, the chromate treatment layer means a layer treated with a liquid containing chromate or dichromate. The chromate treatment layer may also contain metals such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, the chromate treatment layer treated with the treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

Further, the intermediate layer is preferably a layer of any one of nickel, a nickel-zinc alloy, a nickel-phosphorus alloy, and a nickel-cobalt alloy, and a zinc chromate treatment layer and a pure chromate treatment layer, which are sequentially laminated on the carrier. The chrome layer is formed of any one of the layers, and the intermediate layer is preferably formed by sequentially laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer on the carrier, or sequentially laminating a nickel-zinc alloy layer, and It is composed of a pure chromate treatment layer or a zinc chromate treatment layer. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, peeling occurs at the interface between the ultra-thin copper layer and the chromate-treated layer when the ultra-thin copper layer is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer. Further, it is preferred to form a chromate treatment layer instead of a chrome plating layer in the intermediate layer. Since the chromium plating layer forms a dense chromium oxide layer on the surface, the resistance is increased when an extremely thin copper foil is formed by plating, and pinholes are likely to occur. Since the surface on which the chromate-treated layer is formed forms a chromium oxide layer which is not denser than the chrome-plated layer, it is less likely to be a resistance when forming an extremely thin copper foil by electroplating, and pinholes can be reduced. Here, by forming the zinc chromate treatment layer as the chromate treatment layer, the resistance when forming an extremely thin copper foil by electroplating can be made lower than that of the usual chromate treatment layer, thereby further suppressing the occurrence of pinholes.

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the polishing surface from the viewpoint of reducing pinholes.

When the chromate-treated layer in the intermediate layer is thinly present at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the step of laminating to the insulating substrate, and on the other hand, the step of laminating to the insulating substrate The characteristics of the extremely thin copper layer peeled off from the carrier can be preferably obtained. When a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is not provided and a chromate-treated layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property hardly increases, and the chromium-free layer is formed. When the acid salt treatment layer directly laminates a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) and an extremely thin copper layer, the peel strength is based on a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer). The amount of nickel in the ) is too strong or too weak to obtain proper peel strength.

Moreover, if the chromate treatment layer is present at the boundary between the support and the nickel layer or the alloy layer containing nickel (for example, a nickel-zinc alloy layer), the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, the carrier Peeling occurs with the intermediate layer, so it is not good. This is not the case where a chromate-treated layer is provided at the interface with the carrier, and even if a chromate-treated layer is provided at the interface with the ultra-thin copper layer, this may occur if the amount of chromium is excessive. I think the reason is that copper and nickel are easy Since it is solid-solved, if the contact occurs, the force will increase due to mutual diffusion and will not be easily peeled off. On the other hand, chromium and copper are not easily dissolved, and mutual diffusion is less likely to occur. Therefore, the interface between chromium and copper is weak. It is easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of chromium exists between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and are not easily peeled off.

The nickel layer of the intermediate layer or the alloy layer containing nickel (for example, a nickel-zinc alloy layer) may be, for example, wet plating such as electroplating, electroless plating, and immersion plating, or sputtering, CVD, PDV, or the like. Formed by dry plating. From the viewpoint of cost, electroplating is preferred. Further, in the case where the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD or PDV or wet plating such as electroless plating or immersion plating.

Further, the chromate treatment layer may be formed of, for example, electrolytic chromate or impregnated chromate, but is preferably formed of electrolytic chromate because the chromium concentration can be increased and the peel strength of the ultra-thin copper layer from the carrier can be increased. Becomes good.

Further, it is preferable that the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , the adhesion amount of chromium is 5 to 100 μg/dm ² , and the adhesion amount of zinc is 1 to 70 μg/dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer from which the ultra-thin copper layer is peeled off from the carrier copper foil is controlled, so that Ni in order to control the surface of the extremely thin copper layer after peeling is controlled. The amount of the intermediate layer is preferably a metal species (Cr, Zn) which reduces the amount of Ni deposited in the intermediate layer and suppresses diffusion of Ni to the ultra-thin copper layer side. On such viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm ^2, more preferably 200μg / dm ² or more and 20000μg / dm ² or less, more preferably 500μg / dm ² or more and 10000μg / dm ² or less More preferably, it is 700 μg/dm ² or more and 5000 μg/dm ² or less. Further, Cr preferably contains 5 to 100 μg/dm ² , more preferably 8 μg/dm ² or more and 50 μg/dm ² or less, more preferably 10 μg/dm ² or more and 40 μg/dm ² or less, still more preferably 12 μg/dm. ² or more and 30 μg/dm ² or less. Zn preferably contains 1 ~ 70μg / dm ^2, more preferably 3μg / dm ² or more and 30μg / dm ² or less, more preferably 5μg / dm ² or more and 20μg / dm ² or less.

The intermediate layer of the copper foil with carrier of the present invention may also be formed by sequentially laminating a nickel layer on the carrier and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and the intermediate layer The adhesion amount of nickel is 100 to 40000 μg/dm ² . Further, the intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating an organic layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on the carrier, and the intermediate layer. The adhesion amount of nickel in the range is 100 to 40000 μg/dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer from which the ultra-thin copper layer is peeled off from the carrier copper foil is controlled, so that Ni in order to control the surface of the extremely thin copper layer after peeling is controlled. The amount of the intermediate layer contains an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, which reduces the Ni adhesion amount of the intermediate layer and suppresses diffusion of Ni to the ultra-thin copper layer side. On such viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm ^2, more preferably 200μg / dm ² or more and 20000μg / dm ² or less, more preferably 300μg / dm ² or more and 10000μg / dm ² or less , more preferably 500μg / dm ² or more and 5000μg / dm ² or less. In addition, examples of the organic substance containing the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid include BTA (benzotriazole), MBT (mercaptobenzothiazole), and the like.

Moreover, as the organic substance contained in the intermediate layer, it is preferred to use one or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. Among the nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, the nitrogen-containing organic compound contains a nitrogen-containing organic compound having a substituent. As the specific nitrogen-containing organic compound, it is preferred to use 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis(benzotriazole) as a triazole compound having a substituent. Methyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole and the like.

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

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

The organic substance preferably contains 25 nm or more and 80 nm or less in thickness, and more preferably contains 30 nm or more and 70 nm or less. The intermediate layer may also contain a plurality of (one or more) of the above organic substances.

Further, the thickness of the organic matter can be measured in the following manner.

<intermediate layer organic matter thickness>

After the ultra-thin copper layer with the carrier copper foil was peeled off from the carrier, the surface on the intermediate layer side of the exposed ultra-thin copper layer and the surface on the intermediate layer side of the exposed carrier were subjected to XPS measurement to obtain a depth profile. In addition, the surface of the ultra-thin copper layer from the surface of the intermediate layer side may have a depth of 3 at% or less of A (nm), and the surface of the carrier from the surface of the intermediate layer may have a carbon concentration of 3 at% or less. The depth is set to B (nm), and the total of A and B is set as the thickness (nm) of the organic substance of the intermediate layer.

The operating conditions of XPS are shown below.

‧Device: XPS measuring device (ULVAC-PHI, model 5600MC)

‧ ultimate vacuum: 3.8 × 10 ^-7 Pa

‧X-ray: Monochromatic AlK α or non-monochromatic MgK α, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

‧Ion beam: ion species Ar ⁺ , accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

Hereinafter, a method of forming the intermediate layer on the carrier foil will be described, and a method of using the organic substance contained in the intermediate layer will be described. The shape of the middle layer on the carrier The organic substance may be dissolved in a solvent and impregnated with the carrier in the solvent, or by a spray method, a spray method, a dropping method, a plating method, or the like for the surface on which the intermediate layer is to be formed, and a method which is not particularly limited is not required. The concentration of the organic-based agent in the solvent at this time is preferably in the range of 0.01 g/L to 30 g/L and the liquid temperature of 20 to 60 ° C in the entire organic material. The concentration of the organic substance is not particularly limited, and the original concentration has no problem regardless of the height. Further, the higher the concentration of the organic substance, the longer the contact time between the carrier and the solvent in which the organic substance is dissolved, and the greater the thickness of the organic substance in the intermediate layer. Further, when the thickness of the organic material in the intermediate layer is thick, the effect of suppressing the organic matter in which Ni diffuses toward the ultra-thin copper layer side tends to increase.

Further, the intermediate layer is preferably formed by sequentially laminating nickel, molybdenum or cobalt or a molybdenum-cobalt alloy on the carrier. Since the adhesion between nickel and copper is higher than the adhesion of molybdenum or cobalt to copper, peeling occurs at the interface between the ultra-thin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy when the ultra-thin copper layer is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer.

Further, the nickel may be an alloy containing nickel. Here, the alloy containing nickel means one or more elements selected from the group consisting of nickel and cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. Further, the molybdenum may be an alloy containing molybdenum. Here, the alloy containing molybdenum refers to an element selected from the group consisting of molybdenum and a group selected from the group consisting of cobalt, iron, chromium, nickel, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. Further, the cobalt may be an alloy containing cobalt. Here, the alloy containing cobalt means one or more elements selected from the group consisting of cobalt and molybdenum, iron, chromium, nickel, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed.

The molybdenum-cobalt alloy may further contain an element other than molybdenum or cobalt (for example, one or more selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium). element).

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the polishing surface from the viewpoint of reducing pinholes.

When the molybdenum or cobalt or molybdenum-cobalt alloy layer in the intermediate layer is thinly present at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the step of laminating to the insulating substrate, and on the other hand, the insulating layer is insulated. It is preferable that the ultra-thin copper layer is peeled off from the carrier after the lamination step of the substrate. When a nickel layer is not provided and a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer, there is almost no improvement in peelability, and no molybdenum or cobalt or molybdenum-cobalt alloy layer is present. In the case where the nickel layer and the ultra-thin copper layer are directly laminated, the peel strength is too strong or too weak depending on the amount of nickel in the nickel layer, so that appropriate peel strength cannot be obtained.

Moreover, if a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the support and the nickel layer, the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, between the carrier and the intermediate layer. Peeling occurs, so it is not good. In addition to the case where a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the carrier, and even if a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the ultra-thin copper layer, if the amount of molybdenum or cobalt is excessive, This may also happen. The reason is considered to be that copper and nickel are easily dissolved in a solid solution. Therefore, if such contact occurs, the bonding force is increased due to mutual diffusion, and the separation is not easy. On the other hand, molybdenum or cobalt and copper are not easily dissolved, and it is difficult to generate mutual Diffusion, so the interface between the molybdenum or cobalt or molybdenum-cobalt alloy layer and copper is weak and easily peeled off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of molybdenum or cobalt is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and are not easily peeled off.

The intermediate layer of nickel and cobalt or molybdenum-cobalt alloy can be formed, for example, by wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Further, molybdenum can be formed only by dry plating such as CVD or PDV. In terms of cost, it is preferably electricity plating.

In the intermediate layer, the adhesion amount of nickel is 100 to 40000 μg/dm ² , the adhesion amount of molybdenum is 10 to 1000 μg/dm ² , and the adhesion amount of cobalt is 10 to 1000 μg/dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer from which the ultra-thin copper layer is peeled off from the carrier copper foil is controlled, so that Ni in order to control the surface of the extremely thin copper layer after peeling is controlled. The amount of the intermediate layer is preferably a metal species (Co, Mo) which reduces the amount of Ni deposited in the intermediate layer and suppresses diffusion of Ni to the ultra-thin copper layer side. From such a viewpoint, the nickel adhesion amount is preferably from 100 to 40,000 μg/dm ² , preferably from 200 to 20,000 μg/dm ² , more preferably from 300 to 15,000 μg/dm ² , and even more preferably 300~10000μg/dm ² . When the intermediate layer contains molybdenum, the molybdenum adhesion amount is preferably set to 10 to 1000 μg/dm ² , and the molybdenum adhesion amount is preferably set to 20 to 600 μg/dm ² , more preferably 30 to 400 μg/dm ^{2 .} . When the intermediate layer contains cobalt, the cobalt adhesion amount is preferably 10 to 1000 μg/dm ² , and the cobalt adhesion amount is preferably 20 to 600 μg/dm ² , more preferably 30 to 400 μg/dm ^{2 .} .

Furthermore, in the case where the intermediate layer is sequentially laminated with nickel and molybdenum or cobalt or a molybdenum-cobalt alloy as described above, if the plating process for setting the molybdenum or cobalt or molybdenum-cobalt alloy layer is lowered, The current density tends to lower the density of the carrier, and the density of the molybdenum or cobalt or molybdenum-cobalt alloy layer tends to be high. When the density of the layer containing molybdenum and/or cobalt is increased, the nickel of the nickel layer is less likely to diffuse, and the amount of Ni on the surface of the extremely thin copper layer after peeling can be controlled. Furthermore, the release layer can also be disposed on both sides of the carrier.

<Bottom plating>

An extremely thin copper layer is provided on the intermediate layer. Prior to this, a copper-phosphorus alloy strike plating may be used to reduce pinholes of the ultra-thin copper layer. Bottom plating can be cited as copper pyrophosphate plating Apply liquid and so on.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Furthermore, other layers 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 sulfonate or copper cyanide, and is used in a conventional electrolytic copper foil and can form a copper foil at a high current density. In other words, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically it is 0.5 to 12 μm, more typically 1.5 to 5 μm, and more typically 2 to 5 μm. Furthermore, an extremely thin copper layer may be provided on both sides of the carrier.

<Coarsening treatment>

For example, in order to improve the adhesion to the insulating substrate, the roughened layer may be provided by roughening the surface of the ultra-thin copper layer. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening treatment can also be fine. The roughening treatment layer may be a simple substance selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing any one or more selected from the group. The layer of composition, etc. Further, after the roughened particles are formed of copper or a copper alloy, a roughening treatment of secondary particles or tertiary particles may be further carried out using a simple substance such as nickel, cobalt, copper or zinc or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of a simple substance such as nickel, cobalt, copper or zinc, or an alloy, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventive layer may be formed of a simple substance such as nickel, cobalt, copper or zinc or an alloy without performing a roughening treatment, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be formed on the surface of the ultra-thin copper layer. The surface is formed into one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. Further, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, or the like). Moreover, these surface treatments hardly affect the surface roughness of the extremely thin copper layer.

The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. From the viewpoint of the formation of the fine pitch, the roughened layer is preferably composed of fine particles. Regarding the plating conditions in the case of forming the roughened particles, if the current density is increased, the concentration of copper in the plating solution is lowered, or the amount of coulomb is increased, the particles tend to be fine.

In terms of improving the in-plane uniformity of the surface roughness of the surface-treated surface, it is effective to keep the anode-cathode distance constant when the roughened layer is formed. Although it is not limited, from the viewpoint of industrial production, it is effective to secure the distance between the electrodes by means of a foil which is a supporting medium such as a drum. Fig. 10 is a schematic view showing the manner of transporting the foil. The carrier copper foil conveyed by the conveyance roller is supported by a roller, and a roughened particle layer is formed by electrolytic plating on the surface of the ultra-thin copper layer. The treated surface of the carrier copper foil supported by the drum also serves as a cathode, and each electrolytic plating is performed in the plating solution between the roller and the anode provided to face the roller. On the other hand, Fig. 11 is a schematic view showing a conventional foil transfer method using bending. In this method, there is a problem that it is difficult to fix the distance between the anode and the cathode due to the influence of the electrolyte solution and the tension of the foil. Further, in order to keep the distance between the anode and the cathode at the time of forming the roughened layer by the use of the bending foil, it is effective to increase the tension for transporting the foil and shorten the distance between the transport rollers.

As shown in Fig. 10, the foil transfer method can be used not only for the roughening treatment but also for the formation of the peeling layer and the formation of an extremely thin copper layer. The reason is By using the foil transfer method, the thickness accuracy of the peeling layer or the ultra-thin copper layer can be improved. Furthermore, in order to keep the distance between the anode and the cathode when the peeling layer or the ultra-thin copper layer is formed by using the foil transfer method, it is effective to increase the tension for transporting the foil and shorten the transfer roller. The distance.

The distance between the electrodes is not limited. However, if the length is too long, the production cost becomes high. On the other hand, if the surface unevenness is too short, the surface unevenness is likely to increase. Therefore, it is usually preferably 3 to 100 mm, more preferably 5 to 80 mm.

The surface of the ultra-thin copper layer (also referred to as "surface-treated surface") after various surface treatments such as roughening treatment is performed by using a contact type roughness meter according to JIS B0601-1982, by Rz (ten point average) The average value of the roughness is set to 1.5 μm or less, and the generation of electron migration in the circuit formed on the surface can be satisfactorily suppressed, which is extremely advantageous from the viewpoint of formation of fine pitch. The average value of Rz is preferably 1.4 μm or less, more preferably 1.3 μm or less, still more preferably 1.2 μm or less, still more preferably 1.0 μm or less, still more preferably 0.8 μm or less. However, when the average value of Rz is too small, the adhesion to the resin is lowered. Therefore, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and most preferably 0.5 μm or more. In the present invention, the average value of Rz is the average value of each Rz obtained when the standard deviation of Rz is obtained by the method described below.

In the present invention, by setting the standard deviation of Rz of the surface-treated surface to 0.1 μm or less, generation of electron migration in the circuit formed on the surface can be more satisfactorily suppressed, which is extremely advantageous from the viewpoint of formation of fine pitch. The standard deviation of Rz can be preferably set to 0.05 μm or less, and can be, for example, 0.01 to 0.7 μm. The standard deviation of Rz of the surface treated surface was determined from the in-plane measurement data of 100 points. In addition, the measurement data of 100 points in the plane can be obtained by dividing the 550 mm square sheet into 10 sections in the longitudinal direction and the lateral direction, and measuring the central portions of the 100 divided regions. This method uses this method in order to maintain in-plane uniformity, but the verifier The law is not limited to this. For example, a sample of a size such as 550 mm × 440 mm to 400 mm × 200 mm which is usually used is divided into 100 parts in the plane (divided into 10 parts in the vertical and horizontal directions), and the same information is taken.

In addition, when the surface-treated surface is measured by JIS B0601-2001 using a contact-type roughness meter, the average value of Rt (maximum cross-sectional height) is 2.0 μm or less, and the circuit formed on the surface can be satisfactorily suppressed. The generation of electron migration is extremely advantageous from the viewpoint of micro-pitch formation. The average value of Rt is preferably 1.8 μm or less, preferably 1.5 μm or less, preferably 1.3 μm or less, or preferably 1.1 μm or less from the viewpoint of formation of fine pitch. However, when the average value of Rt is too small, the adhesion to the resin is lowered, so that it is preferably 0.5 μm or more, more preferably 0.6 μm or more, and still more preferably 0.8 μm or more. In the present invention, the average value of Rt is the average value of each Rt obtained when the standard deviation of Rt is obtained by the method described below.

In the present invention, by setting the standard deviation of Rt of the surface-treated surface to 0.1 μm or less, generation of electron migration in the circuit formed on the surface can be more satisfactorily suppressed, which is extremely advantageous from the viewpoint of formation of fine pitch. The standard deviation of Rt can be preferably set to 0.05 μm or less, and can be, for example, 0.01 to 0.6 μm. The standard deviation of Rt of the surface-treated surface was determined in the same manner as Rz based on the measurement data of 100 points in the plane.

In addition, when the surface-treated surface is measured by JIS B0601-1982 using a contact-type roughness meter, the average value of Ra (arithmetic mean roughness) is 0.2 μm or less, and formation on the surface can be satisfactorily suppressed. The generation of electron mobility of the circuit is ideal from the viewpoint of micro-pitch formation. The average value of Ra is more preferably 0.18 μm or less, and is preferably 0.15 μm or less. However, if the average value of Ra is too small, the adhesion to the resin is lowered, so It is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.12 μm or more, and most preferably 0.13 μm or more. In the present invention, the average value of Ra is used as an average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

In the present invention, by setting the standard deviation of Ra of the surface-treated surface to 0.03 μm or less, generation of electron migration in the circuit formed on the surface can be more satisfactorily suppressed, which is extremely advantageous from the viewpoint of formation of fine pitch. The standard deviation of Ra can be preferably 0.02 μm or less, and can be, for example, 0.001 to 00.3 μm. The standard deviation of Ra of the surface-treated surface was determined in the same manner as Rz based on the measurement data of 100 points in the plane.

Further, in the present invention, in the case where the ultra-thin copper layer is subjected to surface treatment, the surface roughness of the ultra-thin copper layer indicates the roughness of the surface of the surface-treated side. In the case where an insulating substrate such as a resin is adhered to the surface of the ultra-thin copper layer such as a printed wiring board or a copper-clad laminate, the surface roughness of the copper circuit or the copper foil surface can be measured by dissolving and removing the insulating substrate. Degree (Ra, Rt, Rz).

<Printed wiring board, printed circuit board and copper clad laminate>

The copper clad laminate can be produced by attaching a copper foil with a carrier to the insulating resin plate from the side of the ultra-thin copper layer, performing thermocompression bonding, and peeling off the carrier. Further, the ultra-thin copper layer portion is etched thereafter, whereby a copper circuit of a printed wiring board or a printed circuit board can be formed. The insulating resin sheet used herein is not particularly limited as long as it has characteristics applicable to a printed wiring board or a printed circuit board. For example, a paper substrate phenol resin or a paper substrate epoxy resin can be used for rigid PWB applications. Synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., polyester film can be used for FPC use or Polyimine film and the like. Printed wiring boards, printed circuit boards, and copper-clad laminates produced in this way can be mounted on We are looking for various electronic parts that are mounted on high-density parts.

Further, a copper foil-attached carrier having a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer may have a roughened layer on the ultra-thin copper layer, or may be provided The roughening layer is provided with one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer.

Further, the ultra-thin copper layer may be provided with a roughened layer, or a heat-resistant layer or a rust-preventing layer may be provided on the roughened layer, or a chromate-treated layer may be provided on the heat-resistant layer or the rust-proof layer. Further, a decane coupling treatment layer may be provided on the chromate treatment layer.

Further, the copper foil with a carrier may have a resin layer on the ultra-thin copper layer or the roughened layer or the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the decane coupling treatment layer. .

The resin layer may be a resin, that is, an adhesive, or an insulating resin layer in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a non-adhesive feeling even when the surface is touched by a finger, and the insulating resin layer can be stacked and stored, and if subjected to heat treatment, a state of hardening reaction is caused.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. Further, as the resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. No. 3184485, International Public No. WO97/02728, Japanese Patent No. 3676375, Japanese Special Japanese Patent No. 2000-43188, Japanese Patent No. 3 612 594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japan Patent No. 4, 136, 509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open Japanese Patent No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Application No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007 /105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International The materials described in WO2009/145179, International Publication No. WO2011/068157, and JP-A-2013-19056 (resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymerization) The method of forming a material, a prepreg, a skeleton, or the like and/or a resin layer, and forming a device.

Further, the type of the resin layer is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polybutene.醯imino compound, maleimide-based resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin, polyether oxime, polyether oxime resin, aromatic Polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified propylene Nitrile-butadiene resin, polyphenylene ether, di-n-butylene diimide Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic acid anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional groups, polyphenylene ether resin, 2,2-dual ( 4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin, helium oxygen Alkyl modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, One or more resins selected from the group consisting of a phenoxy group, a polymer epoxide, an aromatic polyamine, a fluororesin, a bisphenol, a block copolymerized polyimide resin, and a cyanoester resin are preferred.

In addition, the epoxy resin can be used without any problem as long as it has two or more epoxy groups in the molecule and can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. Further, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AD type epoxy resin, a novolac type epoxy resin, or a cresol novolac type may be used. Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolak epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac Epoxy resin, rubber modified bisphenol A epoxy resin, epoxy propyl amine epoxy resin, triglycidyl isocyanurate, N, N-diepoxypropyl aniline and other epoxy propyl groups Amine compound, glycidyl ester compound such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl novolac type epoxy resin, trihydroxyphenylmethane type One type of the epoxy resin or the tetraphenylethane type epoxy resin may be used in combination of two or more kinds, or a hydrogenated body or a halogenated body of the above epoxy resin may be used.

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

The epoxy resin obtained in the form of a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a naphthoquinone or hydroquinone with 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is reacted to form a compound represented by the following 1 (HCA-NQ) or 2 (HCA-HQ), and then the epoxy resin is A portion of the OH group reacts to form a phosphorus-containing epoxy resin.

The phosphorus-containing epoxy resin which is obtained by using the above-mentioned compound as the above-mentioned component E is preferably one of or a mixture of two types of compounds having the following composition: a compound of the formula. This is because the stability of the resin quality in the semi-hardened state is excellent, and the flame retardancy effect is high.

Further, as the brominated epoxy resin, a known brominated epoxy resin can be used. For example, the brominated epoxy resin is preferably used in the form of one or a mixture of two kinds of derivatives derived from tetrabromobisphenol A having two or more epoxy groups in the molecule. The brominated epoxy resin of the structural formula shown by the formula 6 has a brominated epoxy resin having the structural formula shown by the following formula 7.

As the maleimide-based resin or the aromatic maleimide resin or the maleimide compound or the poly-n-butylene imide compound, a known butylene can be used. A quinone imine resin or an aromatic maleimide resin or a maleimide compound or a poly-n-butylene imine compound. For example, as a maleimide-based resin or an aromatic maleimide resin or a maleimide compound or a poly-n-butylene imide compound, 4, 4'-two can be used. Phenyl methane bis-m-butylene iminoimide, polyphenylmethane maleimide, m-phenyl bis-succinimide, bisphenol A diphenyl ether, bis-succinimide, 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-n-butylene diimide, 4-methyl-1,3-phenylene bis-bis Butylene diimide, 4,4'-diphenyl ether bis-n-butylene imide, 4,4'-diphenylfluorene bis-s-butylene diimide, 1,3-double (3- a maleimide phenoxy)benzene, a 1,3-bis(4-maleoximine phenoxy)benzene, a polymer obtained by polymerizing the above compound with the above compound or other compound, etc. . Further, the maleimide-based resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may be present in the molecule. A polymerized adduct obtained by polymerizing two or more maleimide-imide-based aromatic maleimide resins with a polyamine or an aromatic polyamine.

As the polyamine or aromatic polyamine, a known polyamine or an aromatic polyamine can be used. For example, as the polyamine or aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6 can be used. -diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4' -diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl Base, bis(4-aminophenyl)phenylamine, m-phenylenediamine, p-phenylenediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4 '-Diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenyl Methane, 2,2',5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2 , 2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl 4-aminophenyl)phenylethane, ethylidene diamine and hexamethylenediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane and A polymer obtained by polymerizing a compound with the above compound or other compound. Further, one or two or more kinds of known polyamines and/or aromatic polyamines or the above polyamines or aromatic polyamines may be used.

As the phenoxy resin, a known phenoxy resin can be used. Further, as the phenoxy resin, a combination of a reaction of a bisphenol and a divalent epoxy resin can be used. As the epoxy resin, a known epoxy resin and/or the above epoxy resin can be used.

As the bisphenol, a known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, and HCA (9, 10) can be used. -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide) and terpenoids such as hydroquinone or naphthoquinone Bisphenol or the like obtained in the form of an adduct.

As the above linear polymer having a crosslinkable functional group, it is known to have a crosslinkable A linear polymer of a functional group. For example, the linear polymer having a crosslinkable functional group preferably has a functional group such as a hydroxyl group or a carboxyl group which contributes to the hardening reaction of the epoxy resin. Further, the linear polymer having a crosslinkable functional group is preferably an organic solvent which is soluble in a boiling point of from 50 ° C to 200 ° C. Specific examples of the linear polymer having a functional group herein include a polyvinyl acetal resin, a phenoxy resin, a polyether oxime resin, a polyamidoximine resin, and the like.

The above resin layer may also contain a crosslinking agent. As the crosslinking agent, a known crosslinking agent can be used. As the crosslinking agent, for example, an amine ester-based resin can be used.

A well-known rubber resin can be used for the said rubber-type resin. For example, the above-mentioned rubber resin is described by the concept including natural rubber and synthetic rubber, and the latter synthetic rubber is styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile-butyl. Diene rubber, acrylic rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, and the like. Further, in order to secure the heat resistance of the formed resin layer, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. In order to produce a copolymer by reacting these rubber-based resins with an aromatic polyamide resin or a polyamide amine imide resin, it is preferred to have various functional groups at both ends. It is especially useful to use CTBN (butadienyl nitrile with a carboxyl group at the end). Further, in the acrylonitrile-butadiene rubber, when it is a carboxyl group-modified body, a crosslinked structure is formed with the epoxy resin, and the flexibility of the resin layer after curing can be improved. As the carboxyl group-modified body, a nitrile-butadiene rubber (CTBN) having a carboxyl group at the end, a butadiene rubber (CTB) having a carboxyl group at the end, and a carboxyl-modified nitrile-butadiene rubber (C-NBR) can be used.

As the above polyamidoximine resin, a known polyamidimide resin can be used. Further, as the polyimine amide resin, for example, benzenetricarboxylic anhydride, benzophenonetetracarboxylic anhydride, and tolylene diisocyanate can be used in N-methyl-2-pyrrole. a resin obtained by heating in a solvent such as ketone or / and N,N-dimethylacetamide, or by using phthalic anhydride, diphenylmethane diisocyanate and carboxy acrylonitrile-butadiene The rubber is obtained by heating in a solvent such as N-methyl-2-pyrrolidone or / and N,N-dimethylacetamide.

As the rubber-modified polyamidoximine resin, a known rubber-modified polyamidoximine resin can be used. The rubber-modified polyamidoximine resin is obtained by reacting a polyamide amine imide resin with a rubber resin. In order to increase the flexibility of the polyamidoximine resin itself, the polyamidoximine resin is reacted with a rubber resin and used. In other words, the polyamidoximine resin is reacted with a rubber resin to partially replace one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin with a rubber component. As the polyamidoximine resin, a known polyamidoximine resin can be used. Further, as the rubber resin, a known rubber resin or the above rubber resin can be used. When the rubber modified polyamidoximine resin is polymerized, the solvent used for dissolving the polyamidoximine resin and the rubber resin is preferably dimethylformamide or dimethylacetamide. N-methyl-2-pyrrolidone, dimethyl hydrazine, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, etc. Two or more types are used in combination.

As the phosphazene-based resin, a known phosphazene-based resin can be used. The phosphazene-based resin is a resin containing a phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene-based resin can drastically improve the flame retardancy by the synergistic effect of nitrogen and phosphorus in the molecule. Further, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it is possible to obtain an effect of stably presenting in the resin and preventing generation of electron migration.

As the fluororesin, a known fluororesin can be used. Further, as the fluororesin, for example, PTFE (polytetrafluoroethylene (4 fluorinated)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and FEP (tetrafluoroethylene-hexafluoropropylene copolymer) can be used. (4.6 fluorination)), ETFE (tetrafluoroethylene-B Ene copolymer), PVDF (polyvinylidene fluoride (2 fluorinated)), PCTFE (polychlorotrifluoroethylene (3 fluorinated)), selected from polyallyl fluorene, aromatic polythioether and aromatic A fluororesin composed of at least one of a thermoplastic resin and a fluororesin.

Further, the resin layer may contain a resin curing agent. As the resin curing agent, a known resin curing agent can be used. For example, as the resin curing agent, an amine such as dicyandiamide, an imidazole or an aromatic amine, a phenol such as bisphenol A or brominated bisphenol A, a novolac such as a phenol novolak resin or a cresol novolak resin can be used. An acid anhydride such as phthalic anhydride, a biphenyl type phenol resin, or a phenol aralkyl type phenol resin. Further, the resin layer may contain one or more of the above-mentioned resin curing agents. These hardeners are especially effective for epoxy resins.

A specific example of the above biphenyl type phenol resin is shown in Chemical Formula 8.

Further, a specific example of the above phenol aralkyl type phenol resin is shown in Chemical Formula 9.

As the imidazole, a known one can be used, and for example, 2-undecylimidazole, 2-71 Imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole or the like, these may be used singly or in combination.

Further, among them, an imidazole having a structural formula represented by the following formula 10 is preferably used. By using the imidazole of the structural formula shown by the chemical formula 10, the hygroscopicity of the semi-hardened resin layer can be remarkably improved, and the long-term storage stability is excellent. The reason for this is that the imidazole acts as a catalyst for curing the epoxy resin, and functions as a reaction initiator for causing self-polymerization of the epoxy resin in the initial stage of the curing reaction.

As the resin curing agent for the above amines, a known amine can be used. Further, as the resin curing agent for the amine, for example, the above polyamine or aromatic polyamine may be used, or an aromatic polyamine or a polyamine may be used, and the epoxy resin or the polycarboxylic acid may be used. One or more of a group of amine adducts obtained by acid polymerization or condensation. Further, as the resin hardener of the above amine, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, and 4,4-diaminodiphenylmethane are preferably used. Any one or more of 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(4-aminophenoxy)phenyl]anthracene.

The resin layer may also contain a hardening accelerator. As the hardening accelerator, a known hardening accelerator can be used. For example, as the hardening accelerator, a tertiary amine, an imidazole, a urea-based hardening accelerator, or the like can be used.

The above resin layer may also contain a reaction catalyst. As the reaction catalyst, a known reaction catalyst can be used. For example, as the reaction catalyst, finely pulverized ceria, antimony trioxide or the like can be used.

The anhydride of the polyvalent carboxylic acid is preferably a component that functions as a curing agent for the epoxy resin. Further, the anhydride of the polyvalent carboxylic acid is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, tetrahydroxyphthalic anhydride, or hexahydroxy neighbor. Phthalic anhydride, methyl hexahydroxyphthalic anhydride, Nadic anhydride, methyl acid anhydride.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.

The polyvinyl acetal resin may have a functional group other than an acid group or a hydroxyl group which is polymerizable with an epoxy resin or a maleimide compound. Further, the polyvinyl acetal resin may be one having a carboxyl group, an amine group or an unsaturated double bond introduced into the molecule.

The aromatic polyamine resin polymer is obtained by reacting an aromatic polyamide resin with a rubber resin. Here, the aromatic polyamine resin refers to a compound which is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. In this case, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl hydrazine, m-phenylenediamine, 3,3'-oxydiphenylamine, etc. are used for the aromatic diamine. . Further, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.

A well-known rubber resin or the above-mentioned rubber resin can be used for the above rubbery resin which reacts with the above-mentioned aromatic polyamide resin.

The aromatic polyamide resin polymer is used for etching a copper foil processed into a copper clad laminate without being damaged by under etching due to the etching liquid.

Further, the resin layer may be formed with a hardened resin layer (so-called "hardened resin layer", meaning a hardened resin layer) from the side of the copper foil (that is, the side of the extremely thin copper layer of the carrier copper foil). A resin layer of a semi-hardened resin layer. The hardened resin layer may be composed of any of a resin component having a thermal expansion coefficient of 0 ppm/° C. to 25 ppm/° C., a polyamidimide resin, and a composite resin.

Further, a semi-hardened resin layer having a thermal expansion coefficient after curing of from 0 ppm/° C. to 50 ppm/° C. may be provided on the cured resin layer. Moreover, the thermal expansion coefficient of the entire resin layer after the hardened resin layer and the semi-hardened resin layer are cured may be 40 ppm/° C. or less. The glass transition temperature of the above-mentioned cured resin layer may be 300 ° C or more. Further, the semi-cured resin layer may be formed by using a maleimide-based resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably contains a maleimide-based resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. As the epoxy resin, a known epoxy resin or an epoxy resin described in the present specification can be used. Further, as the maleimide-based resin, the aromatic maleimide resin, and the linear polymer having a crosslinkable functional group, a known maleimide-based resin can be used. An aromatic maleimide resin, a linear polymer having a crosslinkable functional group or the above-described maleimide-based resin, an aromatic maleimide resin, and crosslinkable a functional linear polymer.

Further, in the case of providing a carrier-attached copper foil having a resin layer suitable for the production of a three-dimensionally formed printed wiring board, the cured resin layer is preferably a cured polymer polymer layer which is flexible. The above polymer layer is preferably transferred from a glass having a temperature of 150 ° C or higher. The temperature is composed of a resin capable of withstanding the solder mounting step. The polymer layer is preferably composed of a polyamide resin, a polyether oxime resin, a polyarylamine resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, or a polyamide amide resin. Any one or two or more kinds of mixed resins. Further, the thickness of the polymer layer is preferably from 3 μm to 10 μm.

Further, the polymer layer preferably contains any one or two or more of an epoxy resin, a maleimide-based resin, a phenol resin, and an amine ester resin. Further, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Further, the epoxy resin composition preferably contains the following components of the components A to E.

Component A: Epoxy resin consisting of a group of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins selected from the group consisting of epoxy equivalents of 200 or less and liquid at room temperature. One or two or more of them.

Component B: High heat resistant epoxy resin.

Component C: a phosphorus-containing flame retardant resin which is any one of a phosphorus-containing epoxy resin and a phosphazene-based resin or a mixture thereof.

Component D: A rubber-modified polyamidoximine resin which is modified by a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C.

Component E: Resin hardener.

The component B is a "high heat resistant epoxy resin" having a high glass transition point Tg. The "high heat resistant epoxy resin" referred to herein is preferably a polyfunctional epoxy resin such as a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin. .

As the phosphorus-containing epoxy resin as the component C, the above-mentioned phosphorus-containing epoxy resin can be used. Moreover, as the phosphazene-based resin as the component C, the above-described phosphazene-based resin can be used.

As the rubber-modified polyamidoximine resin of the component D, the above-mentioned rubber-modified polyamidoximine resin can be used. As the resin curing agent of the component E, the above-mentioned resin curing agent can be used.

A solvent is added to the resin composition shown above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board. The resin varnish may be added to the above resin composition to prepare a resin solid content in a range of 30% by weight to 70% by weight to form a resin overflow according to MIL-P-13949G in the MIL standard (resin Flow) A semi-hardened resin film in the range of 5% to 35%. As the solvent, a known solvent or a solvent as described above can be used.

The resin layer may be a resin layer having a first thermosetting resin layer and a second thermosetting resin layer on the surface of the first thermosetting resin layer, and a first curable resin. The layer is a resin component formed of a chemical which is not dissolved in the desmear treatment in the wiring board manufacturing process, and the second thermosetting resin layer is a chemical used in the desmear treatment which is dissolved in the wiring board manufacturing process Resin formed by washing and removing. The first thermosetting resin layer may be formed by using any one of a polyimine resin, a polyether oxime, and a polyphenylene ether, or a resin component obtained by mixing two or more kinds thereof. The second thermosetting resin layer may be formed by using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is preferably such that the roughened surface roughness of the copper foil with a carrier is Rz (μm), and the thickness of the second thermosetting resin layer is set to In the case of t2 (μm), t1 is a thickness satisfying the condition of Rz < t1 < t2.

The resin layer may be a prepreg obtained by impregnating a resin with a skeleton. The resin impregnated with the above-mentioned skeleton material is preferably a thermosetting resin. The above prepreg may also be a well-known pre-preg Prepreg used in the manufacture of dip or printed wiring boards.

The above framing material may also comprise polyarmine fibers or glass fibers or wholly aromatic polyester fibers. The above-mentioned skeleton material is preferably a non-woven fabric or a woven fabric of polyarsenamide fibers or glass fibers or wholly aromatic polyester fibers. Further, the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C or higher refers to a fiber produced by using a resin called a so-called liquid crystal polymer which is based on 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid. The polymer is the main component. Since the wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, it has excellent performance as a constituent material of the electrical insulating layer, and can be used in the same manner as glass fibers and polyarmine fibers.

Further, the fibers constituting the nonwoven fabric and the woven fabric are preferably treated with a decane coupling agent to improve the wettability of the surface and the resin. In the decane coupling agent at this time, a known decane coupling agent such as an amine group or an epoxy group or the above decane coupling agent may be used depending on the purpose of use.

Further, the prepreg may be a frame material obtained by impregnating a thermosetting resin with a non-woven fabric of polyaramide or glass fiber having a nominal thickness of 70 μm or less, or a glass cloth having a nominal thickness of 30 μm or less. Prepreg.

(In the case where the resin layer contains a dielectric (dielectric filler))

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

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

The dielectric (dielectric filler) may also be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder property of the dielectric (dielectric filler) must first be from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0. The range of μm. In the particle diameter referred to herein, since the particles form a fixed secondary aggregation state, the measurement of the average particle size is measured by measurement values such as laser diffraction scattering particle size distribution measurement or BET method. Since the precision is inferior and therefore cannot be used, it is an average particle diameter obtained by directly observing a dielectric (dielectric filler) by a scanning electron microscope (SEM) and performing image analysis on the SEM image. In the present specification, the particle size at this time is expressed as DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed by the scanning electron microscope (SEM) in the present specification is carried out using IP-1000PC manufactured by Asahi Engineering Co., Ltd. The threshold value is 10 and the degree of overlap is 20, and circular particle analysis is performed to obtain an average particle diameter DIA.

According to the above embodiment, a copper foil with a carrier having a resin layer for dielectric layer and an inner layer circuit surface of the inner core material and a dielectric containing body can be provided. The adhesiveness of the resin layer is improved, and a capacitor circuit layer having a low dielectric loss tangent is formed.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N -methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cyproterone, N-methyl-2-pyrrole A solvent (resin varnish) is prepared by a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and is coated by, for example, a roll coating method. The solvent is removed and the B-stage state is removed on the ultra-thin copper layer or the heat-resistant layer, the rust-preventive layer, or the chromate-treated layer or the decane coupling agent layer, followed by heat drying as necessary. Drying, for example, using a hot air drying oven, drying temperature The degree is preferably 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved by using a solvent to obtain a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt%. 40% by weight of resin solution. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Further, the resin layer is preferably a semi-hardened resin film having a resin overflow flow rate of 5% to 35% in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the term "resin overflow" refers to sampling 4 pieces of 10 cm square samples from a resin-coated copper foil having a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard, so that the four pieces are made. The state in which the samples were overlapped (layered body) was bonded under the conditions of a pressurization temperature of 171 ° C, a pressurization pressure of 14 kgf/cm ² , and a pressurization time of 10 minutes, and the resin outflow weight at this time was measured, and the result was based on the number 1 Calculate the value.

The carrier-attached copper foil (resin-attached copper foil with resin) provided with the resin layer is used in such a manner that the resin layer is superposed on the substrate, and the whole is thermocompression bonded, and the resin layer is thermally hardened, and then the resin layer is thermally cured. The carrier is peeled off to expose an extremely thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the copper foil with a carrier with a resin is used, the number of sheets of the prepreg used in the manufacture of the multilayer printed wiring board can be reduced. Further, the copper clad laminate can be produced even if the thickness of the resin layer is such that the thickness of the interlayer insulation can be ensured or the prepreg is not used at all. Again, this It is also possible to undercoat the insulating resin on the surface of the substrate to further improve the smoothness of the surface.

Furthermore, when the prepreg is not used, the material cost of the prepreg can be saved, and the lamination step becomes simple, so that it is economically advantageous, and the thickness and pre-production of the multilayer printed wiring substrate are manufactured. The thickness of the dip material is correspondingly thinned, and the advantage of one layer of a very thin multilayer printed wiring board having a thickness of 100 μm or less can be produced.

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

When the thickness of the resin layer is made thinner than 0.1 μm, the adhesion is lowered, and when the resin-attached copper foil with a resin is laminated on the substrate having the inner layer without interposing the prepreg, it is difficult to secure the inner layer. The case of interlayer insulation between the material and the circuit. On the other hand, when the thickness of the resin layer is made thicker than 120 μm, it is difficult to form the resin layer of the target thickness by the coating step once, and the excess material cost and the number of steps are required, which is economically disadvantageous.

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

Further, in the case where the resin layer contains a dielectric, the thickness of the resin layer is preferably from 0.1 to 50 μm, preferably from 0.5 μm to 25 μm, more preferably from 1.0 μm to 15 μm.

Further, the total resin layer thickness of the cured resin layer and the semi-hardened resin layer is preferably from 0.1 μm to 120 μm, preferably from 5 μm to 120 μm, preferably from 10 μm to 120 μm, more preferably from 10 μm to 60 μm. Further, the thickness of the cured resin layer is preferably from 2 μm to 30 μm, preferably from 3 μm to 30 μm, more preferably from 5 to 20 μm. Further, the thickness of the semi-hardened resin layer is preferably from 3 μm to 55 μm, preferably from 7 μm to 55 μm, more preferably from 15 to 115 μm. The reason is that if the total resin layer is thick When the degree is more than 120 μm, it is difficult to manufacture a multilayer printed wiring board having a small thickness. If the thickness is less than 5 μm, there is a tendency that a multilayer printed wiring board having a small thickness is easily formed, but the circuit between the inner layers is used. The resin layer of the insulating layer becomes too thin, and the insulation between the circuits of the inner layer becomes unstable. Further, when the thickness of the cured resin layer is less than 2 μm, the surface roughness of the roughened surface of the copper foil must be considered. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect of using the cured resin layer is not particularly improved, and the total insulating layer thickness is increased.

Further, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with a carrier, it is preferable to provide a heat-resistant layer and/or rust prevention on the ultra-thin copper layer. After the layer and/or the chromate treatment layer and/or the decane coupling treatment layer, a resin layer is formed on the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer.

In addition, the thickness of the above-mentioned resin layer means the average value of the thickness measured by the cross-sectional observation at arbitrary 10 points.

Further, as another form of the resin-attached copper foil with a resin, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the decane coupling treatment may be applied to the ultra-thin copper layer. The layer was coated with a resin layer to form a semi-hardened state, and then the carrier was peeled off, and was produced in the form of a resin-attached copper foil in which no carrier was present.

Further, as another form of the resin-attached copper foil with a resin, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the decane coupling treatment may be applied to the ultra-thin copper layer. The layer was coated with a resin layer to form a semi-hardened state, and then the carrier was peeled off, and was produced in the form of a resin-attached copper foil in which no carrier was present.

<Method of Manufacturing Printed Wiring Board>

In one embodiment of the method for manufacturing a printed wiring board of the present invention, the following steps are included: The copper foil and the insulating substrate with a carrier of the present invention are provided; the copper foil with the carrier is laminated with the insulating substrate; and the copper foil and the insulating substrate with the carrier are laminated so that the ultra-thin copper layer side faces the insulating substrate. The copper clad laminate is formed by stripping the carrier with the carrier copper foil, and then the circuit is formed by any one of a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate can also be made to have an inner layer circuit embedded therein.

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

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier by etching or plasma etching using an acid or the like is used. Removing all; the resin exposed by removing the ultra-thin copper layer by etching is provided with a pair of perforations or/and blind holes; and the desmear treatment is performed on the region including the perforation or/and the blind holes; An electroless plating layer is disposed on the resin and the region of the perforation or/and the blind hole; a plating resist is disposed on the electroless plating layer; and the plating resist is exposed, and then formed The plating resist is removed in the region of the circuit; and the electrolytic plating layer is disposed in the region where the circuit forming the resisting agent is formed; The plating resist is removed; the electroless plating layer located in the region outside the region where the circuit is formed is removed by rapid etching or the like.

In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is removed by etching or plasma etching using an acid or the like. Removing an electroless plating layer on a surface of the resin exposed by removing the ultra-thin copper layer by etching; providing a plating resist on the electroless plating layer; and exposing the plating resist And then removing the plating resist in the region where the circuit is formed; providing an electrolytic plating layer in the region where the circuit forming the above-mentioned plating resist is removed; removing the plating resist; and being located by rapid etching or the like The electroless plating layer and the ultra-thin copper layer in the region other than the region where the circuit is formed are removed.

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

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

In another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; a plating resist is provided on the extremely thin copper layer exposed by peeling the carrier; and the plating resist is exposed. And thereafter removing the plating resist in the region where the circuit is formed; and disposing the electrolytic plating layer in the region where the circuit forming the resisting agent is formed; The plating resist is removed; the electroless plating layer and the ultra-thin copper layer in the region outside the region where the circuit is formed are removed by rapid etching or the like.

In the present invention, the partial addition method refers to a method in which a catalyst core is provided on a substrate on which a conductor layer is provided, and a catalyst core is inserted through a hole for a through hole or a through hole, and is etched to form a conductor. In the circuit, if a solder resist or a plating resist is provided as needed, the conductor circuit, the via holes, the via holes, and the like are thickened by electroless plating to form a printed wiring board.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a partial addition method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer exposed to the carrier is peeled off and the insulating substrate is provided with a perforation or/and a blind hole; Performing desmear treatment on the region of the perforation or/and the blind hole; imparting a catalyst core to the region including the above-mentioned perforation or/and blind via; and providing an etching resist on the surface of the extremely thin copper layer exposed by peeling off the carrier; The etching resist is exposed to form a circuit pattern; the ultra-thin copper layer and the catalyst core are removed by etching or plasma etching using an acid or the like to form a circuit; and the etching resist is removed; Providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an etching solution such as an acid; Or an electroless plating layer is provided in the region where the resist is applied.

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

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

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; And laminating the copper foil with the carrier and the insulating substrate; after laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer and the insulating substrate are exposed to the carrier a perforated or/and blind hole; a desmear treatment for the region including the perforation or/and the blind hole; an electroless plating layer for the region including the perforation or/and the blind hole; and the electroless plating described above Forming a mask on the surface of the layer; providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; and providing an etching resist on the surface of the electrolytic plating layer or/and the ultra-thin copper layer Exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the electroless plating layer by using etching or plasma etching of an acid or the like to form a circuit; Remove the agent.

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

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings.

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

Next, as shown in Fig. 1-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a specific shape.

Next, as shown in Fig. 1-C, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit coating of a specific shape.

Next, as shown in FIG. 2-D, a resin layer is laminated on the ultra-thin copper layer by covering the circuit plating layer (in a manner of burying the circuit plating layer), and then another carrier copper foil is attached. Layer 2) is followed by a very thin copper layer.

Next, as shown in Fig. 2-E, the carrier was peeled off from the carrier copper foil of the second layer.

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

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

Next, as shown in FIG. 3-H, a circuit plating layer is formed on the via fill in the manner as shown in FIGS. 1-B and 1-C described above.

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

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

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

The above-mentioned other carrier copper foil (second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil with a carrier may be used, and a usual copper foil may be used. Further, in the circuit of the second layer shown in FIG. 3-H, one or more layers of circuits may be further formed, which may be performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method performs such circuit formation.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples of the invention, but the invention should not be construed as limited.

1. Manufacture of carrier copper foil

As a carrier, a strip of electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metal Co., Ltd.) and a rolled copper foil (manufactured by JX Nippon Mining & Metal Co., Ltd., fine copper foil JIS H3100 alloy No. C1100) having a thickness of 35 μm are prepared. An intermediate layer is formed on the surface. The formation of the intermediate layer is carried out by the processing sequence described in the item "Intermediate layer forming method" of the table. In other words, for example, "Ni/zinc chromate" means that the treatment of "Ni" is performed first, and then "zinc chromate" is performed. In the item of "intermediate layer", "Ni" means pure nickel plating, and "Ni-Zn" means nickel-zinc alloy plating, and it is called "Mo-Co". Refers to the molybdenum-cobalt alloy plating, which is referred to as "sputter Ni" means that the Ni plating layer is formed by sputtering, and the "chromate" is referred to as pure chromate treatment, which is referred to as "zinc chromate. The person who refers to the treatment of zinc chromate is referred to as "sputtering Cr" means that the Cr plating layer is formed by sputtering, and the "BTA treatment" means that the rust prevention treatment using benzotriazole is described as " The MBT treatment means the rust-preventing treatment using mercaptobenzotriazole. The respective processing conditions are shown below. Further, when the adhesion amount of Ni, Zn, Cr, Mo, or Co is increased, the high current density is set, and/or the long plating time is set, and/or the concentration of each element in the plating solution is increased. Further, when the adhesion amount of Ni, Zn, Cr, Mo, or Co is reduced, the low current density is set, and/or the short plating time is set, and/or the concentration of each element in the plating solution is lowered. Further, the remainder of the liquid composition of the plating solution or the like is water.

‧"Ni": nickel plating

(liquid composition) nickel sulfate: 270 ~ 280g / L, nickel chloride: 35 ~ 45g / L, nickel acetate: 10 ~20g / L, trisodium citrate: 15 ~ 25g / L, brightener: saccharin, butynediol, etc., sodium dodecyl sulfate: 55 ~ 75ppm

(pH) 4~6

(liquid temperature) 55~65°C

(current density) 1~11A/dm ²

(Power-on time) 1~20 seconds

‧"Ni-Zn": nickel-zinc alloy plating

Under the conditions of the above nickel plating, zinc in the form of zinc sulphate (ZnSO ₄ ) was added to the nickel plating solution, and the zinc concentration was adjusted in the range of 0.05 to 5 g/L to form a nickel-zinc alloy plating layer.

‧"Ni-Mo": nickel-molybdenum alloy plating

Under the conditions of the above nickel plating, molybdenum in the form of sodium molybdate was added to the nickel plating solution, and the nickel molybdenum alloy plating layer was formed by adjusting the molybdenum concentration: 0.1 to 10 g/L.

‧"Ni-Co": nickel-cobalt alloy plating

Under the conditions of the above-described nickel plating, cobalt in the form of cobalt sulfate was added to the nickel plating solution, and the nickel-cobalt alloy plating layer was formed by adjusting the cobalt concentration in the range of 0.1 to 10 g/L.

‧"Ni-W": nickel-tungsten alloy plating

Under the conditions of the above nickel plating, tungsten in the form of sodium tungstate was added to the nickel plating solution, and the nickel tungsten alloy plating layer was formed by adjusting the tungsten concentration in the range of 0.1 to 10 g/L.

‧"Ni-Sn": Nickel-tin alloy plating

Under the conditions of the above nickel plating, tin in the form of sodium stannate was added to the nickel plating solution, and the tin concentration was adjusted to a range of 0.1 to 10 g/L to form a nickel-tin alloy plating layer.

‧"Cr": chrome plating

(liquid composition) CrO ₃ : 200~400g/L, H ₂ SO ₄ : 1.5~4g/L

(pH) 1~4

(liquid temperature) 45~60°C

(current density) 10~40A/dm ²

(Power-on time) 1~20 seconds

‧ "Chromate": electrolytic pure chromate treatment

(liquid composition) potassium dichromate: 1~10g/L, zinc: 0g/L

(pH) 2~4, 7~10

(liquid temperature) 40~60°C

(current density) 0.1~2.6A/dm ²

(Coulomb: amount) 0.5~90As/dm ²

(Power-on time) 1~30 seconds

‧"Zinc Chromate": Zinc Chromate Treatment

Under the above-mentioned electrolytic pure chromate treatment conditions, zinc in the form of zinc sulphate (ZnSO ₄ ) is added to the liquid, and the zinc chromate treatment is carried out by adjusting the zinc concentration in the range of 0.05 to 5 g/L.

‧BTA treatment: anti-rust treatment with benzotriazole

(liquid composition) benzotriazole: 0.1~20g/L

(pH) 2~5

(liquid temperature) 20~40°C

(immersion time) 5~30s

‧MBT treatment: anti-rust treatment with mercaptobenzothiazole

(liquid composition) 2-mercaptobenzothiazole sodium: 0.1~20g/L

(pH) 7~10

(liquid temperature) 40~60°C

(voltage) 1~5V

(Power-on time) 1~30 seconds

‧ "Sputtered Ni": Ni plating using sputtering

Ni: A nickel layer was formed using a sputtering target of a composition of 99 mass%.

Target: Ni: 99mass%

Device: Sputtering device manufactured by Aifa Co., Ltd.

Output: DC50W

Argon pressure: 0.2Pa

‧ "Sputtered Cr": Cr plating using sputtering

Cr: a chromium layer is formed using a sputtering target of 99 mass%

Target: Cr: 99mass%

Device: Sputtering device manufactured by Aifa Co., Ltd.

Output: DC50W

Argon pressure: 0.2Pa

‧"Mo-Co": molybdenum-cobalt alloy plating

(Liquid composition) Cobalt sulfate: 10~200g/L, sodium molybdate: 5~200g/L, sodium citrate: 2~240g/L

(pH) 2~5

(liquid temperature) 10~70°C

(current density) 0.5~10A/dm ²

(Power-on time) 1~20 seconds

After the formation of the intermediate layer, an ultra-thin copper layer having a thickness of 1 to 10 μm was formed by electroplating on the intermediate layer under the following conditions to produce a copper foil with a carrier.

‧ very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20~120g/L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

Next, the surface of the ultra-thin copper layer is subjected to any of the roughening treatments A, B, C, and D shown below, and in each of the treatments A to D, the roughening treatment and the roughening treatment are sequentially performed. Anti-rust treatment, chromate treatment, and decane coupling treatment. Further, in Examples 2 and 9, and Comparative Example 2, the roughening treatment 1 and the roughening treatment 2 were not performed.

<Coarsening treatment A>

(liquid composition 1)

Cu: 10~30g/L

_{H 2 SO 4: 10 ~ 150g} / L

W: 0~50mg/L

Sodium dodecyl sulfate: 0~50mg/L

As: 0~200mg/L

(plating condition 1)

Temperature: 30~70°C

Current density: 25~110A/dm ²

Coarse coulomb amount: 50~500As/dm ²

Plating time: 0.5~20 seconds

‧Coarse processing 2

(liquid composition 2)

Cu: 20~80g/L

H ₂ SO ₄ : 50~200g/L

(plating condition 2)

Temperature: 30~70°C

Current density: 5~50A/dm ²

Coarse coulomb amount: 50~300As/dm ²

Plating time: 1~60 seconds

‧Anti-rust treatment

(liquid composition)

NaOH: 40~200g/L

NaCN: 70~250g/L

CuCN: 50~200g/L

Zn(CN) ₂ : 2~100g/L

As ₂ O ₃ : 0.01~1g/L

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

‧Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnOH or ZnSO ₄ ‧7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

‧decane coupling treatment

After spraying 0.1 vol% to 0.3 vol% of an aqueous solution of 3-glycidoxypropyltrimethoxydecane, it is dried in air at 100 to 200 ° C for 0.1 to 10 seconds.

<Coarsening B>

‧Coarse processing 1

Liquid composition: copper 10~20g/L, sulfuric acid 50~100g/L

Liquid temperature: 25~50°C

Current density: 1~58A/dm ²

Coulomb amount: 4~81As/dm ²

‧Coarse processing 2

Liquid composition: copper 10~20g/L, nickel 5~15g/L, cobalt 5~15g/L

pH: 2~3

Liquid temperature: 30~50°C

Current density: 24~50A/dm ²

Coulomb amount: 34~48As/dm ²

‧Anti-rust treatment

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

‧Chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (can also be applied without electrolysis for impregnation of chromate)

Coulomb amount: 0~2As/dm ² (can also be carried out without electrolysis for impregnation of chromate treatment) ‧ decane coupling treatment

Coating of diamino decane aqueous solution (diamine decane concentration: 0.1 to 0.5 wt%)

<Coarsening C>

‧Coarse processing 1

Liquid composition: copper 10~20g/L, nickel 2~20g/L, cobalt 2~20g/L

pH: 2~4

Liquid temperature: 30~50°C

Current density: 24~50A/dm ²

Coulomb amount: 30~48As/dm ²

‧Anti-rust treatment

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

‧Chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (can also be applied without electrolysis for impregnation of chromate)

Coulomb amount: 0~2As/dm ² (can also be carried out without electrolysis for impregnation of chromate treatment) ‧ decane coupling treatment

Coating of diamino decane aqueous solution (diamine decane concentration: 0.1 to 0.5 wt%)

<Coarsening D>

‧Coarse processing 1

(liquid composition 1)

Cu: 31~45g/L

_{H 2 SO 4: 10 ~ 150g} / L

As: 0.1~200mg/L

(plating condition 1)

Temperature: 30~70°C

Current density: 25~110A/dm ²

Coarse coulomb amount: 50~500As/dm ²

Plating time: 0.5~20 seconds

‧Coarse processing 2

(liquid composition 2)

Cu: 20~80g/L

H ₂ SO ₄ : 50~200g/L

(plating condition 2)

Temperature: 30~70°C

Current density: 5~50A/dm ²

Coarse coulomb amount: 50~300As/dm ²

Plating time: 1~60 seconds

‧Anti-rust treatment

(liquid composition)

NaOH: 40~200g/L

NaCN: 70~250g/L

CuCN: 50~200g/L

Zn(CN) ₂ : 2~100g/L

As ₂ O ₃ : 0.01~1g/L

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

‧Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnOH or ZnSO ₄ ‧7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

‧decane coupling treatment

After spraying 0.1 vol% to 0.3 vol% of an aqueous solution of 3-glycidoxypropyltrimethoxydecane, it is dried in air at 100 to 200 ° C for 0.1 to 10 seconds.

2. Evaluation of carrier copper foil

Each evaluation was carried out on the copper foil with a carrier obtained as described above by the following method.

<Metal adhesion amount of the intermediate layer>

The adhesion amount of nickel, zinc, chromium, molybdenum and cobalt was dissolved in a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass), and an ICP emission spectroscopic analyzer manufactured by SII Corporation was used (model number) : SPS3100) was determined by ICP luminescence analysis. In the case where the adhesion amount of any of nickel, zinc, chromium, molybdenum, and cobalt is less than 50 μg/dm ² , the atomic absorption spectrophotometer manufactured by VARIAN Co., Ltd. is used for the element having an adhesion amount of 50 μg/dm ² or less. The meter (model: AA240FS) was analyzed by atomic absorption. The measurement conditions are the conditions recommended for each measurement device. Further, the measurement of the adhesion amount of the above nickel, zinc, chromium, molybdenum, and cobalt was carried out as follows. First, after the ultra-thin copper layer is peeled off from the carrier copper foil, only the vicinity of the surface of the intermediate layer side of the ultra-thin copper layer is dissolved (only 0.5 μm thick from the surface is dissolved. That is, as shown in the table below, regarding the extremely thin Examples 5 and 10 and Comparative Examples 1, 6, 11, and 14 having a copper layer having a thickness of 10 μm dissolve 5% of the thickness of the ultra-thin copper layer. Further, Example 6 in which the thickness of the ultra-thin copper layer is 5 μm. 9, 16 and Comparative Examples 4, 5, and 7, 10% of the thickness of the extremely thin copper layer was dissolved. Further, Examples 1, 4, 11, 12, 13, 15, and 17 of the thickness of the extremely thin copper layer were 3 μm. And Comparative Examples 3, 8 to 10, 13, and 15, dissolving 16.7% of the thickness of the ultra-thin copper layer. Further, Examples 2, 3, 7, 8, and 14 and the comparative examples in which the thickness of the ultra-thin copper layer was 2 μm. 2, 12, 25% of the thickness of the extremely thin copper layer was dissolved, and the adhesion amount of the surface of the intermediate layer side of the ultra-thin copper layer was measured. Further, after the ultra-thin copper layer was peeled off, only the vicinity of the surface of the intermediate layer side of the carrier (only 0.5 μm thick from the surface) was dissolved, and the amount of adhesion on the surface of the intermediate layer side of the carrier was measured. Then, the value obtained by adding the adhesion amount of the surface of the intermediate layer side of the ultra-thin copper layer to the surface of the intermediate layer side of the carrier is the metal adhesion amount of the intermediate layer.

<surface roughness>

Copper foils (550 mm × 550 mm squares) each with a carrier were drawn in a vertical and horizontal line at a pitch of 55 mm, and were divided into 100 squares each having a square of 55 mm × 55 mm. A contact roughness measuring machine (Surfcorder SE-3C manufactured by Kosaka Research Institute Co., Ltd.) was used for each area, and the following were based on JIS B0601-1982 (Ra, Rz) and JIS B0601-2001 (Rt). The surface roughness (Ra, Rt, Rz) of the ultra-thin copper layer was measured under the measurement conditions, and the average value and standard deviation were measured.

(measurement conditions)

Cutoff value: 0.25mm

Base length: 0.8mm

Determination of ambient temperature: 23~25°C

<Amount of Ni and Cr (concentration) on the surface of the intermediate layer side of the ultra-thin copper layer (measured by XPS)>

The ultra-thin copper layer with the carrier copper foil is thermocompression bonded to the BT resin under the conditions of pressure: 20 kgf/cm ² and 220 ° C for 2 hours (three barrier-bis-butylene diimide-based resin) , manufactured by Mitsubishi Gas Chemical Co., Ltd.) and attached. Thereafter, the ultra-thin copper layer was peeled off from the carrier in accordance with JIS C 6471 (Method A). Then, the atomic concentration of the metal in the depth direction (x: unit nm) was measured on the surface of the intermediate layer side of the ultra-thin copper layer by the depth direction analysis from the surface by XPS under the following conditions. Further, in each of the samples before the heating and pressure bonding with the above resin, the atomic concentration of the metal in the depth direction (x: unit nm) was measured in the same manner by the depth direction analysis from the surface by XPS. Furthermore, it means that the larger the value of x, the deeper (further) the measurement position of the atomic concentration of the metal is from the surface. In addition, the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction is measured at intervals of 0.28 nm (in terms of SiO ₂ ) (measured every 0.1 minutes in terms of sputtering time).

In addition, for each of the three parts of the area of 50 mm × 50 mm in the central portion from the both ends in the longitudinal direction of each sample sheet, a total of three parts are used. The depth profile of the concentration of each metal obtained by the above XPS measurement. The measurement sites of the three sites are shown in Fig. 13 . Then, according to the depth profile made for the region of the three portions, the interval [0, 1.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer is respectively determined. Then g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x) Dx) and ∫ e(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k( x) The value of dx) and the interval [1.0, 4.0] of the depth direction analysis of the surface of the ultra-thin copper layer from the intermediate layer side g(x)dx/(∫ e(x)dx+∫ f(x The value of dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx), and the arithmetic mean of these is obtained.

Further, in the case where the size of the sample is small, the region within 50 mm from the both ends and the region of 50 mm × 50 mm at the center portion may overlap.

Furthermore, XPS means X-ray photoelectron spectroscopy. The above measurement and the measurement of the thickness of the organic substance in the intermediate layer described later were carried out using an XPS measuring device (Model 5600MC) of ULVAC-PHI Corporation. In the present invention, it is premised on the use of an XPS measuring device (model 5600MC or equivalent measuring device manufactured and sold by ULVAC-PHI Co., Ltd.) of ULVAC-PHI Co., Ltd., but if the measuring device cannot be obtained, the depth is as long as The measurement interval of each element concentration in the direction is 0.10 to 0.30 nm (in terms of SiO ₂ ), and the sputtering rate is 1.0 to 3.0 nm/min (in terms of SiO ₂ ), and other XPS measuring devices can be used.

(XPS analysis conditions)

‧Device: XPS measuring device (ULVAC-PHI, model 5600MC)

‧ ultimate vacuum: 3.8 × 10 ^-7 Pa

‧X-ray: Monochromatic AlK α or non-monochromatic MgK α, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

‧Ion beam: ion species Ar ⁺ , accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

<peel strength>

The extremely thin copper layer with the carrier copper foil is thermocompression bonded to the BT resin under the conditions of pressure: 20 kgf/cm ² and 220 ° C × 2 hours. - Bis-butylene diimide-based resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and attached. Then, the carrier side was stretched by a load cell, and the peel strength was measured in accordance with a 90° peeling method (JIS C 6471 8.1). Further, the peel strength was measured in advance in the same manner for each sample before the above-described heating and pressure bonding of the resin.

<etching property>

The copper foil with a carrier was attached to the polyimide substrate and heat-bonded at 220 ° C for 2 hours, after which the ultra-thin copper layer was peeled off from the carrier. Then, after applying a photosensitive resist on the surface of the ultra-thin copper layer on the polyimide substrate, 50 circuits of L/S=5 μm/5 μm width were printed by an exposure step, and copper was sprayed under the following spray etching conditions. An etch process that removes unwanted portions of the layer.

(spray etching conditions)

Etching solution: aqueous solution of ferric chloride (Pomet: 40 degrees)

Liquid temperature: 60 ° C

Spray pressure: 2.0MPa

The etching was continued, and the width of the tip of the circuit was measured to be 4 μm, and the width of the bottom of the circuit (the length of the bottom side X) and the etching factor were evaluated. Regarding the etching factor, the distance from the length of the burr from the intersection of the perpendicular line from the upper surface of the copper foil and the resin substrate is set to a in the case where the end is excessively etched (in the case where burrs are generated), and the case where the circuit is vertically etched is assumed. In this case, the ratio of the thickness b of the a to the copper foil: b/a means that the larger the value, the larger the inclination angle, the less the etching residue remains, and the burrs become smaller. Fig. 5 is a schematic view showing a cross section of the circuit pattern in the width direction and an outline of a calculation method of the etching factor using the schematic diagram. This X-ray was measured by SEM observation from the top of the circuit, and the etching factor (EF=b/a) was calculated. Furthermore, calculation was performed using a = (X (μm) - 4 (μm))/2. The etch factor is obtained by measuring 12 points in the measurement circuit and averaging them. Thereby, it is possible to easily determine whether or not the etchability is good. Further, by calculating the standard deviation of the etching factor of 12 o'clock, the linearity of the circuit formed by etching can be determined.

In the present invention, an etching factor of 5 or more is evaluated as etchability: ○, and 2.5 or more and less than 5 are evaluated as etchability: Δ, and a circuit which is less than 2.5 or cannot be calculated or cannot be formed is evaluated as etchability: ×, Will not be peeled off and evaluated as etch:-. Moreover, the smaller the standard deviation of the etching factor, the better the linearity of the circuit. The standard deviation of the etching factor was less than 0.5 and it was judged as linearity: ○, 0.5 to less than 1.0 was judged to be linear: Δ, and 1.0 or more was judged to be linear: ×.

<intermediate layer organic matter thickness>

For each sample before the thermocompression bonding with the resin, the extremely thin copper layer of the copper foil with the carrier is peeled off from the carrier, and the surface of the intermediate layer side of the exposed ultra-thin copper layer and the intermediate layer side of the exposed carrier are The surface was subjected to XPS measurement to prepare a depth profile. In addition, the depth of the surface of the ultra-thin copper layer from the surface of the intermediate layer to the carbon concentration of 3 at% or less is set to A (nm), and the surface of the carrier from the surface of the intermediate layer has a carbon concentration of 3 at% or less. Let B (nm) and the total of A and B be the thickness (nm) of the organic substance of the intermediate layer. Furthermore, it means that the larger the value of x, the deeper (further) the measurement position of the atomic concentration of the metal from the surface. In addition, the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present application, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (in terms of SiO ₂ ) (measured every 0.1 minutes in terms of sputtering time).

Furthermore, the above-mentioned depth profile of the carbon concentration measured by XPS is a very thin copper exposed. The surface on the intermediate layer side of the layer and the surface on the intermediate layer side of the exposed carrier are each 50 mm in the region within 50 mm from both ends in the longitudinal direction of each sample sheet, and 50 mm in the center portion. A total of three parts of one portion in the region of 50 mm, that is, the surface on the intermediate layer side of the exposed ultra-thin copper layer and the surface on the intermediate layer side of the exposed carrier are combined to form a total of six portions. The measurement sites of the three portions of the surface on the intermediate layer side of the exposed ultra-thin copper layer and the three portions of the surface on the intermediate layer side of the exposed carrier are shown in Fig. 13 . Then, based on the depth profile formed on the surface of the intermediate layer side of the exposed ultra-thin copper layer and the three portions of the intermediate layer side of the exposed carrier, the above-mentioned ultra-thin copper layer is calculated from the intermediate layer. The surface of the side has a depth A (nm) at which the carbon concentration is initially 3 at% or less and a depth B (nm) at which the carbon concentration initially becomes 3 at% or less from the surface of the intermediate layer side, and the arithmetic mean of A (nm) The sum of the arithmetic mean values of B (nm) is the thickness (nm) of the organic matter of the intermediate layer.

The operating conditions of XPS are shown below.

‧Device: XPS measuring device (ULVAC-PHI, model 5600MC)

‧ ultimate vacuum: 3.8 × 10 ^-7 Pa

‧X-ray: Monochromatic AlK α or non-monochromatic MgK α, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

‧Ion beam: ion species Ar, accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

As described above, the organic material thickness of the intermediate layer was measured, and as a result, the organic layer thickness of the intermediate layer of Example 6 was 39 nm, the organic layer thickness of the intermediate layer of Example 7 was 40 nm, and the organic layer thickness of the intermediate layer of Example 14 was 30 nm. The organic layer of the intermediate layer of 17 has a thickness of 35 nm, and the organic layer of the intermediate layer of Comparative Example 11 has a thickness of 16 nm, and the organic layer of the intermediate layer of Comparative Example 12 has a thickness of 35 nm. It is 11 nm.

<Electronic Migration>

Each of the carrier-attached copper foils (squares of 550 mm × 550 mm) before the formation of the resin layer was attached to a lanthanide resin, and then the carrier foil was peeled off. The thickness of the exposed ultra-thin copper layer was 1.5 μm by soft etching. Thereafter, after washing and drying, DF (manufactured by Hitachi Chemical Co., Ltd., trade name RY-3625) was laminated on an ultra-thin copper layer. Exposure was carried out under conditions of 15 mJ/cm ² , and liquid ejection was carried out at 38 ° C for 1 minute using a developing solution (sodium carbonate) and shaken. A resist pattern was formed with a line and space (L/S) = 15 μm / 15 μm. Next, after forming a 15 μm plating layer using a copper sulfate plating solution (CUBRITE 21 manufactured by 荏原优莱特), the DF was peeled off by a peeling liquid (sodium hydroxide). Thereafter, the ultra-thin copper layer was etched away by a sulfuric acid-hydrogen peroxide-based etchant to form a wiring of L/S = 15 μm / 15 μm. From the obtained wiring board, the wiring board was cut into 100 pieces in a size of 55 mm × 55 mm each.

The presence or absence of insulation deterioration between wiring patterns was evaluated for each of the obtained wiring substrates using the electron mobility measuring machine (IMV-9000, manufactured by IMV) under the following measurement conditions. The number of substrates on which electron migration occurred was evaluated on 100 wiring substrates.

Further, with respect to Example 3, wirings having a line-to-gap distance of 20 μm (L/S = 8 μm / 12 μm, L/S = 10 μm / 10 μm, L/S = 12 μm / 8 μm) were formed, and the above-mentioned electrons were performed. Evaluation of the migration. Further, in Example 17, the interval between the line and the gap was further 20 μm (L/S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm), and the line-to-gap distance was 15 μm ( Wiring of L/S = 5 μm/10 μm, L/S = 8 μm / 7 μm), and the above-described electron migration evaluation was performed. Further, in the case where the distance between the line and the gap is 15 μm, the thickness of the plating layer to be formed is set to 10 μm. The result is When the wiring of L/S=8 μm/12 μm, L/S=10 μm/10 μm, and L/S=12 μm/8 μm was formed using the copper foil with a carrier of Example 3, the in-plane electron mobility generation rate was 2/100, respectively. , 2/100, 3/100. Further, L-S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm, L / S = 5 μm / 10 μm, L / S = 8 μm were formed using the copper foil with a carrier of Example 17. In the case of /7 μm wiring, the in-plane electron mobility generation rates were 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

<Measurement conditions>

Threshold: initial resistance reduced to 60%

Measurement time: 1000h

Voltage: 60V

Temperature: 85 ° C

Relative humidity: 85% RH

The results are shown in Tables 1 to 5.

In Examples 1 to 17, the insulating substrate was thermocompression bonded to an extremely thin copper layer in the atmosphere of a copper foil with a pressure of 20 kgf/cm ² and 220 ° C for 2 hours in accordance with JIS C 6471 (method). A) When the ultra-thin copper layer is peeled off, the amount of Ni on the surface of the intermediate layer side of the ultra-thin copper layer is 20.0% or less in the interval [0, 1.0], so that the peeling property and the etching property of the ultra-thin copper layer are good.

In Comparative Examples 1 and 2, since the intermediate layer was not formed, it was not peeled off after the pressure bonding. In Comparative Examples 3 and 4, since Ni was not present in the intermediate layer, the ultra-thin copper layer could not be peeled off. In Comparative Example 5, since the intermediate layer was only Ni, it could not be peeled off after the pressure bonding. In Comparative Examples 6 and 8, since the adhesion amount of Cr in the intermediate layer was small, peeling could not be performed after the thermocompression bonding. In Comparative Example 9, since the amount of Zn adhered to the intermediate layer was too large, peeling could not be performed after the pressure bonding. In Comparative Examples 7 and 10 to 13, the concentration of Ni in the ultra-thin copper layer after the heat-compression bonding was high, and if the etching was performed after the heating and pressure bonding, the linearity of the circuit was deteriorated. In Comparative Examples 8, 11, 14, and 15, since the average value or standard deviation of the Rz of the surface of the ultra-thin copper layer was large, the etching factor and the linearity of the circuit were inferior.

Fig. 6 is a view showing the distribution in the depth direction of the extremely thin copper surface (before the substrate is bonded) of the fifth embodiment. Fig. 7 is a view showing the distribution in the depth direction of the extremely thin copper surface of Example 5 (after the substrate is pressure-bonded). Fig. 8 is a view showing the distribution in the depth direction of the extremely thin copper surface of Example 14 (after the substrate is pressure-bonded). Fig. 9 is a view showing the distribution in the depth direction of the extremely thin copper surface (before the substrate is pressed) of Comparative Example 5.

Claims (46)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer in this order, and an average value of Rz obtained by measuring the surface of the ultra-thin copper layer according to JIS B0601-1982 by a contact type roughness meter is 1.5 μm or less And the standard deviation of Rz satisfies 0.1 μm or less, and the intermediate layer contains Ni, and the insulating substrate is thermocompression-bonded to the ultra-thin copper layer under the conditions of pressure: 20 kgf/cm ² and 220 ° C × 2 hours. When the ultra-thin copper layer is peeled off in accordance with JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is defined as e(x). The atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is set to g(x), and the atomic concentration (%) of copper is h(x), and the total amount of oxygen is used. The atomic concentration (%) is i(x), the atomic concentration (%) of carbon is set to j(x), and the other atomic concentration (%) is k(x). The surface of the intermediate layer side is within the interval [0, 1.0] of the depth direction analysis, ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h( x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 20.0% or less. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer in this order, and an average value of Rt obtained by measuring the surface of the ultra-thin copper layer according to JIS B0601-2001 by a contact type roughness meter is 2.0 μm or less. And the standard deviation of Rt satisfies 0.1 μm or less, the intermediate layer contains Ni, and the insulating substrate is thermocompression bonded to the ultra-thin copper layer under the conditions of pressure: 20 kgf/cm ² and 220 ° C × 2 hours. When the ultra-thin copper layer is peeled off according to JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is e(x), The atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is set to g(x), and the atomic concentration (%) of copper is h(x), and the total atom of oxygen is added. The concentration (%) is assumed to be i(x), the atomic concentration (%) of carbon is set to j(x), and the other atomic concentration (%) is k(x), from the ultra-thin copper layer. The surface of the intermediate layer side is within the interval [0, 1.0] of the depth direction analysis, ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x ) dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 20.0% or less. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer in this order, and an average value of Ra obtained by measuring the surface of the ultra-thin copper layer by a contact-type roughness meter according to JIS B0601-1982 is 0.2 μm or less. And the standard deviation of Ra satisfies 0.03 μm or less, and the intermediate layer contains Ni, and the insulating substrate is thermocompression bonded to the extremely thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. When the ultra-thin copper layer is peeled off according to JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is e(x), The atomic concentration (%) of zinc is f(x), the atomic concentration (%) of nickel is set to g(x), and the atomic concentration (%) of copper is h(x), and the total atom of oxygen is added. The concentration (%) is assumed to be i(x), the atomic concentration (%) of carbon is set to j(x), and the other atomic concentration (%) is k(x), from the ultra-thin copper layer. The surface of the intermediate layer side is within the interval [0, 1.0] of the depth direction analysis, ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x ) dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 20.0% or less. The copper foil with a carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and JIS C 6471, when the ultra-thin copper layer is peeled off, in the interval [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫e (x) dx + ∫ f (x) dx + ∫ g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) satisfies 10.0% or less. The carrier-attached copper foil according to the first aspect of the invention, wherein the average value of Rt obtained by measuring the surface of the ultra-thin copper layer by a contact-type roughness meter according to JIS B0601-2001 is 2.0 μm or less, and the standard of Rt The deviation is 0.1 μm or less. The carrier-attached copper foil according to the first aspect of the invention, wherein the average value of Ra obtained by measuring the surface of the ultra-thin copper layer by a contact-type roughness meter according to JIS B0601-1982 is 0.2 μm or less, and the standard of Ra The deviation is 0.03 μm or less. The carrier-attached copper foil according to claim 1, wherein the surface of the ultra-thin copper layer has a roughened layer. The copper foil with a carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and JIS C 6471, when the ultra-thin copper layer is peeled off, ∫ g(x)dx/(∫e) in the interval [0, 1.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or more and 20.0% or less, And within the interval [1.0, 4.0], ∫ g(x)dx/ (∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j (x) dx + ∫ k (x) dx) satisfies 1.0% or more and 10.0% or less. The copper foil with a carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and JIS C 6471, when the ultra-thin copper layer is peeled off, in the interval [0, 1.0] of the depth direction analysis from the surface of the XPS on the intermediate layer side of the ultra-thin copper layer, ∫ e(x)dx/ (∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 3.0% or less. The copper foil with a carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and JIS C 6471, when the ultra-thin copper layer is peeled off, ∫ g(x)dx/(∫e) in the interval [0, 1.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer (x) dx + ∫ f (x) dx + ∫ g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) satisfies 11.0% or less. The copper foil with a carrier of the first aspect of the patent application, wherein the insulating substrate is thermocompression bonded to the ultra-thin copper layer in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours, and JIS C 6471, when the ultra-thin copper layer is peeled off, in the interval [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer, ∫ g(x)dx/(∫e (x) dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 7.0% or less. The carrier copper foil according to claim 1, wherein an average value of Rz of the surface of the ultra-thin copper layer is 1.0 μm or less. The carrier copper foil according to claim 12, wherein an average value of Rz of the surface of the ultra-thin copper layer is 0.5 μm or less. The carrier-attached copper foil according to the first aspect of the invention, wherein, when the ultra-thin copper layer is peeled off according to JIS C 6471, a depth direction obtained by depth direction analysis from the surface using XPS (x: unit nm) The atomic concentration (%) of chromium is set to e(x), the atomic concentration (%) of zinc is f(x), and the atomic concentration (%) of nickel is set to g(x), and the atom of copper is used. The concentration (%) is h (x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) When k(x) is set, ∫ g(x)dx/(∫ e(x)dx+ is within the interval [0, 1.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer. ∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 5.0% or less. The carrier-attached copper foil according to the first aspect of the invention, wherein, when the ultra-thin copper layer is peeled off according to JIS C 6471, a depth direction obtained by depth direction analysis from the surface using XPS (x: unit nm) The atomic concentration (%) of chromium is set to e(x), the atomic concentration (%) of zinc is f(x), and the atomic concentration (%) of nickel is set to g(x), and the atom of copper is used. The concentration (%) is h (x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) When k(x) is set, ∫ g(x)dx/(∫ e(x)dx+ is within the interval [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultra-thin copper layer. ∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 1.0% or less. The carrier-attached copper foil according to claim 1, wherein the depth direction is analyzed from the surface of the intermediate layer side of the ultra-thin copper layer when the ultra-thin copper layer is peeled off according to JIS C 6471 Within the interval [0,1.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j( x)dx+∫ k(x)dx) satisfies 0.1% or more and 5.0% or less, and within the interval [1.0, 4.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x)dx+∫ k(x)dx) satisfies 0.1% or more and 1.0% or less. The carrier-attached copper foil according to the first aspect of the invention, wherein, when the ultra-thin copper layer is peeled off according to JIS C 6471, a section for analyzing the depth direction from the surface of the intermediate layer side of the ultra-thin copper layer Within [0,1.0], ∫ g(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j(x) Dx+∫ k(x)dx) satisfies 3.0% or less. The carrier copper foil according to claim 1, wherein when the ultra-thin copper layer is peeled off according to JIS C 6471, the depth direction from the surface of the XPS is used on the intermediate layer side of the ultra-thin copper layer. Within the interval [0,1.0] of the analysis, ∫ e(x)dx/(∫ e(x)dx+∫ f(x)dx+∫ g(x)dx+∫ h(x)dx+∫ i(x)dx+∫ j (x) dx + ∫ k(x) dx) satisfies 2.0% or less. The copper foil with carrier according to claim 1, wherein the intermediate layer is a layer of nickel or a nickel-containing alloy sequentially laminated on the carrier, and an oxide containing chromium, a chromium alloy or chromium. Any one or more layers are formed. The copper foil with a carrier of claim 19, wherein the layer containing at least one of chromium, a chromium alloy, and an oxide of chromium contains a chromate treatment layer. The carrier copper foil according to claim 1, wherein the intermediate layer contains zinc. The carrier-attached copper foil according to claim 1, wherein the intermediate layer is formed by sequentially laminating a layer of any one of nickel, a nickel-zinc alloy, a nickel-phosphorus alloy, and a nickel-cobalt alloy, and It is composed of any one of a zinc chromate treatment layer, a pure chromate treatment layer, and a chromium plating layer. The copper foil with a carrier according to the first aspect of the invention, wherein the intermediate layer is formed by sequentially laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer on the carrier, or sequentially laminating nickel- The zinc alloy layer and the pure chromate treatment layer or the zinc chromate treatment layer are formed. The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , and the adhesion amount of chromium is 5 to 100 μg/dm ² , and zinc is used. The amount of adhesion is 1 to 70 μg/dm ² . The carrier copper foil according to claim 1, wherein the intermediate layer is formed by sequentially depositing a nickel layer on the carrier, and an organic substance containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. The layer is composed of a layer, and the amount of nickel attached to the intermediate layer is 100 to 40000 μg/dm ² . The carrier-attached copper foil according to claim 1, wherein the intermediate layer is formed by sequentially laminating an organic layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and nickel. The layer is composed of a layer, and the amount of nickel attached to the intermediate layer is 100 to 40000 μg/dm ² . The carrier-attached copper foil according to claim 1, wherein the intermediate layer contains an organic substance having a thickness of 25 nm or more and 80 nm or less. The carrier copper foil according to claim 1, wherein the intermediate layer is formed by sequentially laminating a nickel layer or an alloy layer containing nickel, and containing at least one of molybdenum, cobalt, molybdenum and cobalt alloys. It is composed of layers, the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , and in the case of containing molybdenum, the adhesion amount of molybdenum is 10 to 1000 μg/dm ² , and in the case of containing cobalt, the adhesion amount of cobalt is It is 10~1000μg/dm ² . The carrier copper foil according to claim 1, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil. The carrier-attached copper foil according to claim 7, wherein the roughened layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A single layer or a layer composed of an alloy selected from any one or more of the group. The carrier-attached copper foil according to claim 7, wherein the surface of the roughened layer has one selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Above layer. The carrier copper foil according to claim 1, wherein the surface of the ultra-thin copper layer has one selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Above layer. The carrier-attached copper foil according to claim 30, wherein the resin is one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Floor. The carrier-attached copper foil according to claim 7, wherein the roughened layer is provided with a resin layer. The carrier copper foil according to claim 1, wherein the ultra-thin copper layer is provided with a resin layer. The carrier copper foil of claim 32, wherein the resin layer is a resin for subsequent use. The carrier copper foil according to claim 32, wherein the resin layer is a resin in a semi-hardened state. A method for producing a copper foil with a carrier according to any one of claims 1 to 36, which comprises the steps of forming a layer containing any one of nickel or an alloy containing nickel on a support to form chromium and chromium. Any one or more of the alloy or the chromium oxide, at least one of the nickel or the alloy containing nickel, or a layer containing at least one of chromium, chromium alloy or chromium oxide An intermediate layer containing zinc is formed on one of the layers; and an extremely thin copper layer is formed on the intermediate layer by electrolytic plating. A method for producing a copper foil with a carrier according to any one of claims 1 to 36, which comprises the steps of: forming a plating layer containing nickel and zinc on a carrier to form a plating layer containing chromium or chromium The acid salt treatment layer forms an intermediate layer; and an extremely thin copper layer is formed by electrolytic plating on the intermediate layer. A method for producing a copper foil with a carrier according to any one of claims 1 to 36, which comprises the steps of forming a plating layer containing nickel on a carrier to form a plating layer or chromium containing chromium and zinc. The zinc oxide treatment layer forms an intermediate layer; and an extremely thin copper layer is formed by electrolytic plating on the intermediate layer. A method for producing a copper foil with a carrier according to any one of claims 1 to 36, which comprises the steps of forming a plating layer containing nickel and zinc on a carrier to form a plating layer containing chromium and zinc. Or treating the layer with zinc chromate, thereby forming an intermediate layer; and forming an extremely thin copper layer by electrolytic plating on the intermediate layer. A method for producing a copper foil with a carrier according to any one of claims 1 to 36, which comprises the steps of: forming a zinc chromate layer by electrolytic chromate after forming a nickel plating layer on the carrier, Thereby forming an intermediate layer, or forming a pure chromate treatment layer or a zinc chromate treatment layer by electrolytic chromate after forming a nickel-zinc alloy plating layer, thereby forming an intermediate layer; Electrolytic plating is applied to the intermediate layer to form an extremely thin copper layer. The method for producing a copper foil with a carrier according to claim 37, further comprising the step of forming a roughened layer on the ultra-thin copper layer. A printed wiring board manufactured by using the carrier-attached copper foil according to any one of claims 1 to 36. A printed circuit board manufactured by using the carrier copper foil of any one of claims 1 to 36. A copper-clad laminate produced by using the carrier-attached copper foil according to any one of claims 1 to 36. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate and an insulating substrate according to any one of claims 1 to 36; laminating the copper foil with the insulating substrate; After the carrier copper foil is laminated with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then by semi-additive method, subtractive method, partial addition method or modified semi-additive Any of the methods forms a circuit.