JP2013001993A - Ultrathin copper foil with carrier foil and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultrathin copper foil with carrier foil, in which the ultrathin copper foil is surely tightly held on the carrier foil and the carrier foil after thermocompression bonding is easily peeled off, and to provide a method of manufacturing the same.SOLUTION: The ultrathin copper foil with carrier foil is made by providing the ultrathin copper foil onto the carrier foil of copper via a nickel layer or a nickel alloy layer, and a peeling layer. The peeling layer contains nickel oxyhydroxide, and the thickness of the layer is in a range of 20-60 nm, and variation of the thickness is 20% or less.

Description

  The present invention relates to an ultrathin copper foil with a carrier foil and a method for producing the same, and more particularly to an ultrathin copper foil with a peelable carrier foil suitable for forming a fine pattern on a printed wiring board and a method for producing the same.

In recent years, electronic devices are rapidly becoming lighter, thinner, and shorter, and various printed wiring boards used for these devices are required to have higher density, higher multilayer, and thinner thickness by forming fine patterns. For this reason, various package substrates on which electronic components such as ICs and LSIs are mounted are, of course, demanded for higher density, higher multi-layers, and thinner thickness on the motherboard as well.
At present, in the subtractive method, which is the mainstream in the production of printed wiring boards, there is a strong tendency to reduce the copper film thickness to be etched as much as possible in order to cope with the fine pitch. In this case, it is only necessary to reduce the thickness of the copper foil laminated on the surface of an insulator used for a printed wiring board or the like. For example, an ultrathin copper foil having a thickness of 9 μm or less has a low mechanical strength, and it is Is very difficult to handle. In order to solve this problem, a method of laminating a copper foil with a thickness of several tens of μm on the insulator surface and half-etching the copper foil to reduce the film thickness has been adopted. There was a problem that thickness control was difficult and complicated.

  In order to solve such a problem, a peelable type carrier using a copper foil having a thickness of about 18 to 35 μm as a carrier foil for holding a very thin copper foil having a thickness of 1 to 5 μm having a low mechanical strength. A method has been proposed and practiced in which an ultrathin copper foil with a foil is prepared and laminated by thermocompression bonding to the insulator surface, and then the carrier foil is peeled off to transfer the ultrathin copper foil to the insulator surface. However, in the thermocompression treatment by a press using such a peelable type ultrathin copper foil with a carrier foil, when the insulator is a glass epoxy prepreg (FR-4 grade), the insulator is at least 170 ° C. In the case of a high heat-resistant resin such as polyimide, since it is exposed for several tens of minutes at a high temperature of 300 ° C. or more, the thermal diffusion of copper occurs and it becomes difficult to peel off the carrier foil and the ultrathin copper foil was there.

  In order to solve such a problem and stably peel off the carrier foil and the ultrathin copper foil after the thermocompression treatment by the press machine, for example, an organic bonding interface layer is formed using carboxybenzotriazole on the carrier foil. On the carrier foil using one or more selected from among those formed and formed with an ultrathin copper foil (Patent Document 1), a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid A bonding interface layer is formed, and an ultrathin copper foil is formed thereon (Patent Document 2). A thermal diffusion prevention layer and a release layer are interposed between the carrier foil and the ultrathin copper foil, and the release layer is organic. An organic film formed by immersing in a solution containing a substance, or a metal oxide film formed by subjecting a Ni alloy layer to cathodic treatment, anodic oxidation, or oxidant immersion (Patent Document 3), carrier foil and Release layer between ultrathin copper foil Metal A (Mo, Ta, V, MN, W, Cr) that maintains the peelability and metal B (Fe, Co, Ni, Cr) that facilitates the formation of ultrathin copper foil plating. And a bonding interface layer that is a carbon layer or a composite layer composed of a metal layer and a carbon layer is formed on the carrier foil by physical vapor deposition on the carrier foil. An ultra-thin copper foil is formed thereon (Patent Document 5), and an organic agent layer made of a nitrogen-containing organic compound, which is a triazole compound, is formed as a bonding interface layer on a carrier foil, and a nickel layer and a nickel alloy layer are formed thereon. Various ultrathin copper foils with a carrier foil, such as those obtained by forming an ultrathin copper foil through a heat-resistant metal layer that is either a cobalt layer or a cobalt alloy layer (Patent Document 6), are provided.

JP 2001-89892 A JP 2001-140090 A JP 2002-292788 A JP 2007-186781 A JP 2007-307767 A JP 2010-222657 A

However, the ultrathin copper foil with carrier foil described in Patent Documents 1, 2, and 6 described above has an organic film as the bonding interface layer that contributes to the separation between the carrier foil and the ultrathin copper foil, and thus heat at high temperatures. There was a problem in the peelability after the crimping process. In addition, the ultrathin copper foil with a carrier foil described in Patent Document 3 has a problem in peelability after thermocompression treatment at a high temperature when the release layer is an organic film, and the release layer is a metal oxide film. In this case, there is a problem that the adhesion between the release layer formed on the carrier foil and the copper strike plating before the ultrathin copper foil formation is insufficient, and the ultrathin copper foil may fall off. . The ultra-thin copper foil with a carrier foil described in Patent Document 4 is expensive for the metal A, and requires strict control to set the ratio of the metal A and the metal B to a predetermined ratio. There was a limit to the reduction of manufacturing costs. Furthermore, since the ultrathin copper foil with a carrier foil described in Patent Document 5 forms a bonding interface layer by a physical vapor deposition method, there is a problem that the initial cost of equipment is extremely high and the running cost is also high.
The present invention has been made in view of the above circumstances, and is a carrier in which the ultrathin copper foil is securely adhered and held on the carrier foil and the carrier foil is easily peeled off after the thermocompression treatment. It aims at providing the ultrathin copper foil with foil, and the manufacturing method for manufacturing this.

In order to achieve such an object, the ultrathin copper foil with a carrier foil of the present invention comprises an ultrathin copper foil on a carrier foil via a nickel layer or a nickel alloy layer and a release layer, and the release The layer contained nickel oxyhydroxide, had a thickness in the range of 20 to 60 nm, and had a thickness variation of 20% or less.
As a preferred embodiment of the present invention, the release layer is configured to contain sulfur in the range of 0.5 to 4.5% by weight.
As a preferred embodiment of the present invention, the nickel alloy layer is a nickel-phosphorus alloy layer or a nickel-chromium alloy layer.
As a preferred embodiment of the present invention, a copper strike plating film is provided between the release layer and the ultrathin copper foil, and the total thickness of the ultrathin copper foil and the copper strike plating film is in the range of 1 to 5 μm. A certain configuration was adopted.

As a preferred aspect of the present invention, the ultrathin copper foil has a 10-point average roughness Rz in the range of 0.8 to 4 μm.
As a preferred embodiment of the present invention, the ultra-thin copper foil has any of a zinc plating layer, a zinc alloy plating layer, a tin plating layer, a tin alloy plating layer, a nickel plating layer, a composite layer of zinc plating and a chromate film on the surface. It was set as the structure which has.
As a preferred embodiment of the present invention, the ultrathin copper foil has a silane coupling agent layer on the surface.
As a preferred embodiment of the present invention, the ultrathin copper foil is configured to have a triazine thiol derivative layer on the surface.

  According to the method for producing an ultrathin copper foil with a carrier foil of the present invention, a nickel layer or a nickel alloy layer is formed on a carrier foil, and then immersed in an alkaline solution, whereby oxywater is formed on the nickel layer or the nickel alloy layer. A step of forming a release layer containing nickel oxide and having a thickness in the range of 20 to 60 nm, copper strike plating is performed on the release layer, and then an ultrathin copper foil is formed on the copper strike plating film The alkaline solution contains one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide in a range of 10 to 200 g / L, and the liquid temperature is 40 to 60 ° C. It was set as the structure which is a range.

  In addition, a method for producing an ultra-thin copper foil with a carrier foil comprises forming a nickel layer or a nickel alloy layer on a carrier foil and then immersing it in an alkaline solution to thereby form an oxyhydroxide on the nickel layer or the nickel alloy layer. A step of forming a release layer containing nickel and having a thickness in the range of 20 to 60 nm, a step of performing copper strike plating on the release layer, and then forming an ultrathin copper foil on the copper strike plating film The alkaline solution contains one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide in a range of 10 to 500 g / L, and sodium sulfide as a metal sulfide, One or more of potassium sulfide and lithium sulfide is contained in the range of 0.005 to 0.05% by weight, and the liquid temperature is in the range of 40 to 60 ° C. And the.

As a preferred embodiment of the present invention, the immersion time in the alkaline solution is in the range of 30 to 180 seconds.
As a preferred embodiment of the present invention, the nickel layer or the nickel alloy layer is formed by forming the nickel layer or the nickel-phosphorus alloy layer by an electroless plating method or an electrolytic plating method.
As a preferred embodiment of the present invention, the nickel layer or the nickel alloy layer is formed by forming a nickel layer or a nickel-chromium alloy layer by a vacuum film forming method.

As a preferred embodiment of the present invention, the ultrathin copper foil is subjected to a roughening treatment so that a 10-point average roughness Rz is in a range of 0.8 to 4 μm, and then a step of performing a rust prevention treatment. It was.
As a preferred embodiment of the present invention, a configuration including a step of forming a silane coupling agent layer on the ultrathin copper foil is adopted.
As a preferred embodiment of the present invention, a configuration including a step of forming a triazine thiol derivative layer on the ultrathin copper foil is adopted.

The ultra-thin copper foil with a carrier foil of the present invention is reliable and excellent in handleability of the ultra-thin copper foil on the carrier foil before the thermo-compression treatment, and is, for example, thermo-compression treatment at a high temperature of 300 ° C. or higher. The later peelability is also good.
Moreover, the manufacturing method of the ultra-thin copper foil with a carrier foil of this invention contains nickel oxyhydroxide on a nickel layer or a nickel alloy layer by immersion in an alkaline solution, and the thickness is within a range of 20 to 60 nm. Since a certain release layer is formed, it is possible to produce an ultrathin copper foil with a carrier foil that has a well-balanced tradeoff between retention and peelability of the ultrathin copper foil formed on the release layer.

Next, an optimal embodiment of the present invention will be described.
[Ultra thin copper foil with carrier foil]
The ultra-thin copper foil with a carrier foil of the present invention includes an ultra-thin copper foil on a carrier foil via a nickel layer or a nickel alloy layer and a release layer.
The carrier foil constituting the ultrathin copper foil with the carrier foil of the present invention can be copper foil, copper alloy foil, stainless steel foil, iron alloy foil, titanium foil, titanium alloy foil, etc. A copper foil having the same thermal expansion coefficient is most suitable. Moreover, the thickness of carrier foil is not specifically limited, For example, it can set in the range of 7-35 micrometers. If the thickness of the carrier foil is less than 7 μm, the mechanical strength is low, and wrinkles and creases are likely to occur during lamination by thermocompression bonding to an insulator or the like, which is not preferable. In addition, if the thickness of the carrier foil exceeds 35 μm, problems such as tension control during the production of the ultrathin copper foil with the carrier foil and an increase in the weight of the coil wound with the ultrathin copper foil with the carrier foil may occur. It is not preferable. Furthermore, since the surface shape of the carrier foil on the side provided with the ultrathin copper foil affects the surface shape of the laminated ultrathin copper foil, the surface shape of the carrier foil is, for example, 10 The point average roughness Rz is preferably about 0.01 to 2 μm. In the present invention, the 10-point average roughness Rz is measured using a laser microscope VK-8700 manufactured by KEYENCE.

  The nickel layer or nickel alloy layer constituting the ultrathin copper foil with a carrier foil of the present invention serves as a base substrate for the release layer and serves to prevent thermal diffusion of copper. The nickel alloy layer can be a nickel-phosphorus alloy layer or a nickel-chromium alloy layer, and the nickel content in the nickel alloy layer is preferably 85% by weight or more. The thickness of such a nickel layer or nickel alloy layer can be appropriately set, for example, in the range of 0.001 to 0.5 μm, preferably 0.01 to 0.3 μm. When the thickness of the nickel layer or the nickel alloy layer is less than 0.001 μm, the effect of preventing copper thermal diffusion is insufficient, and when it exceeds 0.5 μm, the productivity may decrease and the manufacturing cost may increase. It is not preferable.

The release layer constituting the ultrathin copper foil with a carrier foil of the present invention contains nickel oxyhydroxide, and the content of nickel oxyhydroxide in the release layer is 50 to 100% by weight, preferably 60 to 60%. It is in the range of 100% by weight. Such a release layer has a thickness in the range of 20 to 60 nm, preferably 25 to 50 nm, and the variation in thickness is 20% or less, preferably 10% or less. The content of nickel oxyhydroxide in the release layer is measured using ESCA PHI Quantera SXM (manufactured by ULVAC-PHI). The thickness of the release layer and the variation in thickness are determined by the cross section of the release layer. was observed by ESCA PHI Quantera SXM (ULVAC-PHI, Inc.), the maximum thickness T _max, the minimum thickness T _min in the length 50 mm, measured an average thickness T _a, the average thickness T _a is the thickness of the peeling layer, the peeling The variation of the layers is calculated by (T _max −T _min ) / T _a × 100.

  When the content of the nickel oxyhydroxide in the release layer is less than 50% by weight, the peelability from the ultrathin copper foil is lowered, and in particular, the peelability after thermocompression treatment at a high temperature of 300 ° C. or higher is not good. It will be enough. Moreover, when the thickness of the release layer is less than 20 nm, the peelability from the ultrathin copper foil is lowered, and the peelability after the thermocompression treatment at a high temperature of 300 ° C. or higher is particularly insufficient. Further, when the thickness of the release layer exceeds 60 nm, the adhesion with the ultrathin copper foil is lowered, and in particular, when a copper strike plating film is interposed between the release layer and the ultrathin copper foil as described later. The peeling layer and the copper strike plating film are floated, and the ultrathin copper foil is likely to fall off, which is not preferable in terms of handling. On the other hand, when the variation in the thickness of the release layer exceeds 20%, the adhesion with the ultrathin copper foil is lowered and the film tends to fall off, which is not preferable from the viewpoint of handleability.

  In the present invention, it is preferable that the release layer contains sulfur in order to provide a well-balanced tradeoff between the retention and release properties of the ultrathin copper foil formed on the release layer. The sulfur in the release layer is uniformly dispersed as, for example, nickel sulfide, and the sulfur content in the release layer is, for example, in the range of 0.5 to 4.5% by weight, preferably 1 to 4% by weight. can do. If the sulfur content is less than 0.5% by weight, the effect due to the sulfur content cannot be obtained, and if it exceeds 4.5% by weight, the peelability after thermocompression treatment at a high temperature becomes insufficient. In the present invention, the sulfur content in the release layer is measured using ESCA PHI Quantera SXM (manufactured by ULVAC-PHI).

The ultrathin copper foil which comprises the ultrathin copper foil with a carrier foil of this invention is 9 micrometers or less in thickness, Preferably it is 1-5 micrometers, and is a copper foil of uniform thickness without a pinhole. Such a copper foil can be formed by, for example, copper plating. In the present invention, a copper strike plating film may be interposed between the release layer and the ultrathin copper foil. In this case, the total thickness of the ultrathin copper foil and the copper strike plating film is 9 μm or less, preferably It can be set to 1 to 5 μm.
Such an ultra-thin copper foil with a carrier foil of the present invention has excellent adhesion and excellent adhesion of the ultra-thin copper foil on the carrier foil before the thermocompression treatment, and is, for example, 300 ° C. or higher. The peelability between the release layer and the ultrathin copper foil after the thermocompression treatment at high temperature is good.

The above-mentioned embodiment is an illustration and the ultra-thin copper foil with a carrier foil of this invention is not limited to these. For example, in order to improve the adhesion to the insulator surface, the surface roughness of the ultrathin copper foil is such that the 10-point average roughness Rz is in the range of 0.8 to 4 μm, preferably 2.5 to 3.5 μm. Can be set to
In addition, for the purpose of rust prevention of ultra-thin copper foil, the surface of ultra-thin copper foil is coated with zinc plating layer, zinc alloy plating layer, tin plating layer, tin alloy plating layer, nickel plating layer, zinc plating and chromate film. It may have a rust prevention layer such as a composite layer. The thickness of such a rust prevention layer can be suitably set, for example in the range of 0.1-2 micrometers.

Moreover, in order to improve adhesiveness with the insulator surface, a silane coupling agent layer may be provided on the surface of the ultrathin copper foil. Examples of the silane coupling agent used include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. , 3-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane and the like.
Furthermore, the surface of the ultrathin copper foil is smoothed (for example, 10-point average roughness Rz is 1.3 to 1.7 μm) for the purpose of high-speed signal transmission on a printed wiring board or the like (transmission on the conductor surface by the skin effect). In this case, an organic film may be provided on the smooth surface of the ultrathin copper foil in order to improve the adhesion between the ultrathin copper foil and the insulator surface. Examples of such an organic film include a triazine thiol derivative layer, and the thickness can be appropriately set within a range of 0.01 to 1 μm, preferably 0.1 to 0.5 μm.

[Method of manufacturing ultrathin copper foil with carrier foil]
In the method for producing an ultrathin copper foil with a carrier foil of the present invention, first, a nickel layer or a nickel alloy layer is formed on the carrier foil, and then immersed in an alkaline solution to thereby form an oxygen on the nickel layer or the nickel alloy layer. A release layer containing nickel hydroxide and having a thickness in the range of 20 to 60 nm, preferably 25 to 50 nm is formed.

  The carrier foil used in the present invention can be a copper foil, a copper alloy foil, a stainless steel foil, an iron alloy foil, a titanium foil, a titanium alloy foil, etc. Among them, a thermal expansion coefficient with an ultrathin copper foil Can be used suitably. Moreover, the thickness of carrier foil is not specifically limited, For example, it can set in the range of 7-35 micrometers. If the thickness of the carrier foil is less than 7 μm, the mechanical strength is low, and wrinkles and creases are likely to occur during lamination by thermocompression bonding to an insulator or the like, which is not preferable. In addition, if the thickness of the carrier foil exceeds 35 μm, problems such as tension control during the production of the ultrathin copper foil with the carrier foil and an increase in the weight of the coil wound with the ultrathin copper foil with the carrier foil may occur. It is not preferable. Furthermore, it is desirable that the surface shape of the carrier foil on the side provided with the ultrathin copper foil has a small surface roughness considering the fine pattern formation by the laminated ultrathin copper foil, for example, the 10-point average roughness Rz is 0. It is preferably about 0.01 to 2 μm.

The nickel layer or nickel alloy layer can be formed on the carrier foil by a wet method or a dry method. In the wet method, a nickel layer, a nickel-phosphorus alloy layer, or the like can be formed by an electroless plating method or an electrolytic plating method. Examples of plating baths used in the electroless plating method include Enplate NI-426 (Meltex Co., Ltd. low phosphorus type), Melplate NI-865 (Meltex Co., Ltd. medium phosphorus type), Melplate NI-875M (Meltex Co., Ltd. high phosphorus type) etc. can be mentioned. Examples of the nickel plating bath used in the electrolytic plating method include Elpilite GS-6 (manufactured by Meltex Co., Ltd.) and Elpilite GS-7 (manufactured by Meltex Co., Ltd.). Examples of the nickel-phosphorus alloy plating bath include a nickel citrate-phosphorus alloy plating bath and a watt-type nickel-phosphorus alloy plating bath.
In the dry method, for example, a nickel layer, a nickel-chromium alloy layer (nickel content: 85% by weight or less), and the like can be formed by a sputtering method.

  The thickness of the nickel layer or nickel alloy layer as described above can be appropriately set in the range of 0.001 to 0.5 μm, preferably 0.01 to 0.3 μm. If the thickness of the nickel layer or the nickel alloy layer is less than 0.001 μm, it will hinder the formation of a release layer, which will be described later, and the effect of preventing the thermal diffusion of copper may be insufficient. On the other hand, if the thickness exceeds 0.5 μm, the productivity is lowered and the production cost is increased, which is not preferable.

  The release layer containing nickel oxyhydroxide and having a thickness in the range of 20 to 60 nm, preferably 25 to 50 nm is obtained by placing a carrier foil having a nickel layer or a nickel alloy layer as described above in an alkaline solution. This is done by dipping. When the thickness of the release layer to be formed is less than 20 nm, the peelability from the ultrathin copper foil to be formed in the subsequent process is lowered, and in particular, the peelability after the thermocompression treatment at a high temperature of 300 ° C. or higher is lowered. On the other hand, if the thickness of the release layer exceeds 60 nm, the copper strike plating film to be formed in the subsequent process is floated and the ultrathin copper foil is likely to fall off, which is not preferable in terms of handling.

  The alkaline solution to be used contains one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide in the range of 20 to 200 g / L, preferably 50 to 200 g / L, and the liquid temperature is 40 to 60. It shall be in the range of ° C. When the above concentration is less than 20 g / L, the immersion time required to bring the thickness of the release layer containing nickel oxyhydroxide into the above range becomes longer, and when the concentration exceeds 200 g / L, the release The thickness variation of the layer tends to exceed 20%, and there is a possibility that the later-described copper strike plating film may float, which is not preferable. Moreover, when the liquid temperature of the alkaline solution is lower than 40 ° C., the immersion time required for setting the thickness of the release layer containing nickel oxyhydroxide to be in the above range becomes longer, and the liquid temperature exceeds 60 ° C. In addition, the variation in the thickness of the release layer tends to exceed 20%, which may cause the later-described copper strike plating film to float.

  Further, in the present invention, in order to further improve the trade-off characteristic balance between retention and peelability of the ultrathin copper foil formed on the release layer, sodium sulfide, potassium sulfide and sulfide as metal sulfides are added to the alkaline solution. What contains 1 type, or 2 or more types of lithium in 0.005-0.05 weight% can be used. By using an alkaline solution containing such a metal sulfide, a release layer in which sulfur is uniformly dispersed in nickel oxyhydroxide can be formed. If the content of the metal sulfide in the alkaline solution is less than 0.005% by weight, the effect of adding the metal sulfide cannot be obtained, and the content of the metal sulfide is 0.05% by weight. If it exceeds 1, the content of sulfur contained in the release layer is excessively increased, and the adhesion after the thermocompression treatment at a high temperature of 330 ° C. or higher of the copper strike plating film described later becomes too high.

Thus, when using an alkaline solution containing one or more of sodium sulfide, potassium sulfide and lithium sulfide within the above content range as the metal sulfide, sodium hydroxide contained in the alkaline solution, The concentration of one or more of potassium hydroxide and lithium hydroxide is 20 to 500 g / L, preferably 50 to 500 g / L. When the above concentration is less than 20 g / L, the immersion time required to bring the thickness of the release layer containing nickel oxyhydroxide into the above range becomes longer, and when the concentration exceeds 500 g / L, the release is peeled off. The thickness variation of the layer tends to exceed 20%, and there is a possibility that the later-described copper strike plating film may float, which is not preferable.
The immersion time in the alkaline solution as described above can be set in the range of 30 to 180 seconds, for example.

In the production method of the present invention, copper strike plating is performed on the release layer formed as described above, and then an ultrathin copper foil is formed on the copper strike plating film.
The formation of the copper strike plating film is effective in forming a copper foil having a uniform thickness without pinholes in the formation of an ultrathin copper foil in a later step. Although the thickness of the copper strike plating film to form is not specifically limited, It is preferable to set it as the range of 0.001-1 micrometer. Examples of the copper strike plating solution to be used include Mercapa CF-2120 (Meltex Co., Ltd.), Mercapa CF-2130 (Meltex Co., Ltd.), Mercapa CF-2140 (Meltex Co., Ltd.) Mercapa CF. -2170 (Meltex Co., Ltd.) etc. can be used.

More specifically, the bath composition of Mercapa CF-2120 is preferably set within the following range.
(Mercapar CF-2120 bath composition)
-Mercapa CF-2120A ... 60-80mL / L
-Mercapa CF-2120B ... 360-400mL / L

If the CF-2120A concentration is less than the above range, burns are likely to occur, and if it exceeds the above range, the adhesion to the release layer tends to decrease and the ultrathin copper foil is likely to fall off, which is preferable in terms of handleability. Absent. In addition, when the CF-2120B concentration is less than the above range, the adhesion to the release layer is reduced and the ultrathin copper foil is liable to fall off, which is not preferable in terms of handleability. May cause bath turbidity and precipitation. The pH of the bath can be set in the range of 8.4 to 10, but the pH is preferably 9.0 to 9.5 in order to suppress copper substitution. Moreover, although bath temperature can be set in the range of 20-40 degreeC, it is preferable to set in the range of 35-40 degreeC with a low internal stress of a plating film. The cathode current density in copper strike plating can be in the range of 0.3 to 1.0 A / dm ² , and OFHC, SUS304, SUS316, or the like can be used for the anode. In addition, the agitation of the bath is performed by continuous filtration using air agitation.

Moreover, it is preferable that the bath composition of Mercapa CF-2130 be in the following range.
(Mercapar CF-2130 bath composition)
・ Mercapa CF-2130A: 200 to 240 mL / L
-Mercapa CF-2130B: 440-560 mL / L

If the CF-2130A concentration is less than the above range, burns are likely to occur, and if it exceeds the above range, adhesion to the release layer tends to decrease and the ultrathin copper foil is likely to fall off, which is preferable in terms of handling. Absent. In addition, when the CF-2130B concentration is less than the above range, the adhesion to the release layer is reduced and the ultrathin copper foil is likely to drop off, which is not preferable in terms of handling properties, and exceeds the above range. May cause bath turbidity and precipitation. The pH of the bath can be set in the range of 8.3 to 10, but the pH is preferably 9.0 to 9.5 in order to suppress copper substitution. Moreover, although bath temperature can be set in the range of 20-40 degreeC, it is preferable to set in the range of 35-40 degreeC with a low internal stress of a plating film. The cathode current density in the copper strike plating can be in the range of 0.3 to 1.0 A / dm ² , and OFHC, electrolytic copper, or the like can be used for the anode. In addition, the agitation of the bath is performed by continuous filtration using air agitation.

In addition, the bath composition of Mercapa CF-2140 is preferably in the following range.
(Mercapar CF-2140 bath composition)
-Mercapa CF-2140A ... 150-190mL / L
-Mercapa CF-2140B: 340 to 420 mL / L

If the CF-2140A concentration is less than the above range, burns are likely to occur, and if it exceeds the above range, adhesion to the release layer tends to decrease and the ultrathin copper foil tends to fall off, which is preferable in terms of handling. Absent. In addition, when the CF-2140B concentration is less than the above range, the adhesion to the release layer is reduced and the ultrathin copper foil is likely to drop off, which is not preferable in terms of handling properties, and exceeds the above range. May cause bath turbidity and precipitation. The pH of the bath can be set in the range of 8.4 to 10, but the pH is preferably 9.0 to 9.5 in order to suppress copper substitution. Moreover, although bath temperature can be set in the range of 20-40 degreeC, it is preferable to set in the range of 35-40 degreeC with a low internal stress of a plating film. The cathode current density in the copper strike plating can be in the range of 0.3 to 1.0 A / dm ² , and OFHC, electrolytic copper, or the like can be used for the anode. In addition, the agitation of the bath is performed by continuous filtration using air agitation.

Moreover, it is preferable that the bath composition of Mercapa CF-2170 be in the following range.
(Mercapar CF-2170 bath composition)
-Mercapa CF-2170A ... 170-270 mL / L
・ Mercapa CF-2170B ... 420-580mL / L
・ Mercaper CF-2170C: 30 g / L

If the CF-2170A concentration is less than the above range, burns are likely to occur, and if it exceeds the above range, adhesion to the release layer tends to decrease and the ultrathin copper foil tends to fall off, which is preferable in terms of handling. Absent. In addition, when the CF-2170B concentration is less than the above range, the adhesion to the release layer tends to decrease, and the ultrathin copper foil is liable to fall off, which is not preferable in terms of handling properties. May cause bath turbidity and precipitation. The pH of the bath can be set in the range of 8.4 to 9.4, but the pH is preferably 9.0 to 9.4 in order to suppress copper substitution. Moreover, although bath temperature can be set in 25-55 degreeC, it is preferable to set in 35-45 degreeC with a low internal stress of a plating film. The cathode current density in copper strike plating can be in the range of 1 to 3 A / dm ² , and OFHC, electrolytic copper, or the like can be used for the anode. In addition, the agitation of the bath is performed by continuous filtration using air agitation.

Copper sulfate plating can be used to form an ultrathin copper foil on the copper strike plating film. For example, a commercially available copper sulfate plating additive can be added to a basic bath having the following composition.
(Basic bath composition)
・ Copper sulfate / pentahydrate: 30-220 g / L
・ Sulfuric acid: 70 to 300 g / L
・ Chloride ion: 30-75mg / L

The bath temperature of copper sulfate plating can be set in the range of 20 to 40 ° C., but is preferably set in the range of 22 to 28 ° C. where the internal stress of the plating film is low. The cathode current density may be in the range of 0.5~15A / dm ^2, it is preferably in the range of 2~6A / dm ² taking into account the internal stress of the plating film. For the anode, phosphorous copper, an insoluble anode (for example, an electrode in which iridium oxide is coated on titanium) or the like can be used. In addition, the agitation of the bath is performed by continuous filtration using air agitation or jet flow.
Further, Mercapa CF-2170 (Meltex Co., Ltd.), which is a non-cyanic alkaline copper strike bath used for the above copper strike plating, can also be used for forming an ultrathin copper foil.
The thickness of the ultrathin copper foil to be formed can be set so that the total thickness with the copper strike plating film is 9 μm or less, preferably in the range of 1 to 5 μm.

The manufacturing method of the ultrathin copper foil with a carrier foil of the present invention as described above is such that the thickness containing nickel oxyhydroxide is within a range of 20 to 55 nm on the nickel layer or nickel alloy layer by immersion in an alkaline solution. Therefore, it is possible to produce an ultrathin copper foil with a carrier foil that has a well-balanced tradeoff between retention and peelability of an ultrathin copper foil formed on the release layer.
Moreover, in the manufacturing method of the ultra-thin copper foil with a carrier foil of the present invention, the above-mentioned ultra-thin copper foil surface is covered with a copper fine particle forming plating for improving the adhesion to the insulator surface and the copper fine particle fixing. A series of roughening treatments including plating and beard plating may be performed. By such a roughening treatment, the surface roughness of the ultrathin copper foil can be in a range of 10-point average roughness Rz of 0.8 to 4 μm, preferably 2.5 to 3.5 μm.

The copper fine particle forming plating is to form a finely divided copper electrodeposit on the surface of an ultrathin copper foil. For example, a copper fine particle forming plating bath having the following composition can be used.
(Cu fine particle forming plating bath composition)
・ Copper sulfate / pentahydrate: 30-200 g / L
・ Sulfuric acid: 50 to 300 g / L
・ Chloride ion: 30-80mg / L
The bath temperature of the copper fine particle forming plating bath may be 20 to 40 ° C., the cathode current density may be 1 to 50 A / dm ² , and the plating time may be 5 to 15 seconds. For the anode, phosphorous copper, an insoluble anode (for example, an electrode in which iridium oxide is coated on titanium) or the like can be used. In addition, the agitation of the bath is performed by continuous filtration using air agitation or jet flow.

The covering plating for fixing copper fine particles is to deposit copper fine particles by depositing on the fine particles formed on the surface of the ultrathin copper foil as described above. For example, a covering plating bath having the following composition should be used. Can do.
(Cover plating bath composition)
・ Copper sulfate / pentahydrate: 100 to 300 g / L
・ Sulfuric acid: 50 to 150 g / L
・ Chloride ion: 30-80mg / L
Further, the bath temperature of the covering plating bath can be 40 to 60 ° C., the cathode current density can be 5 to 50 A / dm ² , and the plating time can be 5 to 15 seconds. For the anode, phosphorous copper, an insoluble anode (for example, an electrode in which iridium oxide is coated on titanium) or the like can be used. In addition, the agitation of the bath is performed by continuous filtration using air agitation or jet flow.

The beard plating is performed to further improve the adhesion to the insulator on the surface on which the covering plating is performed. For example, a beard plating bath having the following composition can be used.
(Beard plating bath composition)
・ Copper sulfate / pentahydrate 30 to 150 g / L
・ Sulfuric acid: 30-100 g / L
・ Chloride ion: 30-80mg / L
Further, the bath temperature of the beard plating bath may be 20 to 30 ° C., the cathode current density may be 5 to 40 A / dm ² , and the plating time may be 5 to 15 seconds. For the anode, phosphorous copper, an insoluble anode (for example, an electrode in which iridium oxide is coated on titanium) or the like can be used. In addition, the agitation of the bath is performed by continuous filtration using air agitation or jet flow.

  Moreover, in the manufacturing method of the ultra-thin copper foil with a carrier foil of this invention, you may give an antirust plating process to the surface which gave said series of roughening processes. Such a roughening treatment is to form a metal plating layer and an alloy plating layer having a rust prevention effect and a heat resistance effect. For example, a galvanization layer, a tin plating layer, a nickel plating layer, or these metals An alloy plating layer, for example, a tin-zinc alloy plating layer, a tin-nickel alloy plating layer, or a zinc-nickel alloy plating layer can be formed. For forming the galvanized layer, for example, Melzinc 2400 (Meltex Co., Ltd.) or the like can be used. For forming the tin plating layer, for example, a sulfuric acid bath, an alkanesulfonic acid bath, an alkanolsulfonic acid bath, or the like can be used. Moreover, for the formation of the nickel plating layer, for example, Elpilite GS-6 (Meltex Co., Ltd.), Elpilite GS-7 (Meltex Co., Ltd.) or the like can be used.

  Further, a chromate treatment may be applied to further enhance the rust prevention effect. Chromate treatment can be performed using, for example, Splendor Blue TC-1580 (Meltex Co., Ltd.), Splendor Blue TC-1581 (Meltex Co., Ltd.) using trivalent chromium.

  Moreover, in the manufacturing method of the ultra-thin copper foil with carrier foil of this invention, in order to improve the adhesiveness of ultra-thin copper foil and an insulator surface, a silane coupling agent can be apply | coated to the ultra-thin copper foil surface. . Examples of the silane coupling agent used include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. , 3-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane and the like. As a method for applying such a silane coupling agent to the surface of the ultrathin copper foil, dipping or spraying can be used.

  Furthermore, in the manufacturing method of the ultrathin copper foil with a carrier foil of the present invention, the organic film is directly applied to the smooth surface of the ultrathin copper foil without performing the roughening treatment and the rust prevention treatment as described above on the ultrathin copper foil. By forming, a no-profile copper foil (for example, 10-point average roughness Rz of 1.3 to 1.7 μm) required for high-speed transmission can be produced. As a signal processed by a printed wiring board or the like increases in speed and frequency, signal transmission is performed on the conductor surface due to the skin effect. Therefore, the conventional roughening process for improving the adhesion between the copper foil and the insulator delays signal transmission, and the copper foil has a smooth surface with better adhesion. It is requested.

In order to meet such requirements, an organic film, for example, a triazine thiol derivative layer can be formed on the smooth surface of the ultrathin copper foil. The triazine thiol derivative layer is obtained by, for example, dissolving sun thiol N-1 (manufactured by Sankyo Kasei Co., Ltd.) in a solvent, performing anodization in this solution, performing electrolytic polymerization, washing with water, and drying. Can be formed. In this case, the concentration of sunthiol N-1 is 0.1 to 15 g / L, the liquid temperature is 20 to 50 ° C., the electrolytic polymerization potential is 0.1 to 2 V, and the electrolytic polymerization time is 0.1 to 10 minutes, preferably It can be about 0.5 to 2 minutes.
The above-mentioned embodiment is an illustration and the manufacturing method of the ultra-thin copper foil with a carrier foil of this invention is not limited to these.

Next, an Example is shown and this invention is demonstrated further in detail.
[Example 1]
<Preparation of Sample 1-1>
An electrolytic copper foil having a thickness of 35 μm and a 10-point average roughness Rz of 0.04 μm on a shiny surface (surface on which an ultrathin copper foil was laminated) was prepared as a carrier foil. The 10-point average roughness Rz was measured using a laser microscope VK-8700 manufactured by KEYENCE.
The carrier foil was subjected to cathodic electrolysis at 70 ° C. and 5 V for 1 minute using an alkaline electrolytic degreasing bath (Meltex Co., Ltd. cleaner 160), sufficiently washed with water and neutralized with 10% sulfuric acid.
Using a nickel electrolytic plating bath (Mertex Co., Ltd. Elpilite GS-6) on the shiny surface of the carrier foil, plating was performed at a bath temperature of 35 ° C. and a current density of 0.5 A / dm ^{2 for} 1 minute. A nickel layer having a thickness of 0.05 μm was formed and then thoroughly washed.

Next, a 100 g / L sodium hydroxide aqueous solution was prepared as an alkaline solution, and the carrier foil on which the nickel layer was formed was immersed in the alkaline solution having a liquid temperature of 50 ° C. for 60 seconds, and then sufficiently washed. This formed the peeling layer which consists of a nickel oxyhydroxide membrane | film | coat. The composition and thickness of the formed release layer were measured using ESCA PHI Quantera SXM (manufactured by ULVAC-PHI) and are shown in Table 1 below. The maximum thickness T _max, the minimum thickness T _min in the length 50mm in the release layer, was measured an average thickness T _a, the average thickness T _a is the thickness of the release _{layer, (T max -T min) /} T a × 100 The thickness variation of the release layer was calculated from the results shown in Table 1 below.
Next, as a copper strike plating bath, Mercapa CF-2120 (Mercapa CF-2120A: 70 mL / L, Mercapa CF-2120B: 100 mL / L) manufactured by Meltex Co., Ltd., bath temperature 35 ° C., current density 1 A Plating was performed at / dm ^{2 for} 30 seconds, and after sufficient washing, it was immersed in 1% sulfuric acid at room temperature for 10 seconds. Next, after thorough cleaning, plating is performed for 4 minutes at a bath temperature of 25 ° C. and a current density of 3 A / dm ² using a commercially available copper sulfate plating bath to which a copper sulfate plating additive is added. Formed. In addition, the thickness of ultra-thin copper foil is a total thickness with a copper strike plating film | membrane, and it measured using the fluorescent X-ray minute film thickness meter FISHER SCOPE X-ray System XDL (made by FISHER).

Next, a series of roughening treatments including copper fine particle forming plating, covering plating, and whisker plating for improving the adhesion to the insulator were performed on the surface of the ultrathin copper foil. This roughening treatment uses each bath within the range of the above-described copper fine particle forming plating bath composition, the range of the covering plating bath composition, and the range of the mustache plating bath composition, and the range of the above-mentioned conditions regarding each treatment. Went in.
Furthermore, using a zinc plating bath (Meltex 2400, Melzinc 2400), plating was performed at a bath temperature of 25 ° C. and a current density of 5 A / dm ^{2 for} 30 seconds to form a galvanized layer to obtain a rust preventive layer. Then, it is immersed in Splendor Blue TC-1581 (manufactured by Meltex Co., Ltd.) with a liquid temperature of 25 ° C. for 10 seconds, subjected to chromate treatment, washed with water and dried, and an ultrathin copper foil with a carrier foil (Sample 1-1) Got.

<Preparation of Sample 1-2>
An ultrathin copper foil with a carrier foil (sample 1-2) was prepared in the same manner as in the preparation of sample 1-1 except that a 100 g / L potassium hydroxide aqueous solution was used as the alkaline solution.
<Preparation of Sample 1-3>
An ultrathin copper foil with a carrier foil (sample 1-3) was prepared in the same manner as in the preparation of sample 1-1 except that a 100 g / L lithium hydroxide aqueous solution was used as the alkaline solution.
<Preparation of Sample 1-4>
As the alkaline solution, except that a mixed solution of 50 g / L sodium hydroxide aqueous solution and 50 g / L potassium hydroxide aqueous solution was used, an ultrathin copper foil with a carrier foil (sample 1-4) was produced.

<Preparation of Sample 1-5>
As the alkaline solution, except that a mixed solution of 50 g / L sodium hydroxide aqueous solution and 50 g / L lithium hydroxide aqueous solution was used, an ultrathin copper foil with a carrier foil (sample 1-5) was produced.
<Preparation of Sample 1-6>
Preparation of Sample 1-1 above except that an electrolytic copper foil having a thickness of 35 μm and a 10-point average roughness Rz of 0.2 μm on a shiny surface (surface on which an ultrathin copper foil is laminated) is used as a carrier foil. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 1-6) was produced.
<Preparation of Sample 1-7>
Preparation of Sample 1-1 above, except that as the carrier foil, an electrolytic copper foil having a thickness of 18 μm and a 10-point average roughness Rz of a shiny surface (surface on which ultrathin copper foil is laminated) is 0.04 μm is used. In the same manner as above, an ultrathin copper foil with a carrier foil (Sample 1-7) was produced.

<Preparation of Sample 1-8>
Preparation of Sample 1-1 above, except that as the carrier foil, an electrolytic copper foil having a thickness of 18 μm and a 10-point average roughness Rz of a shiny surface (surface on which an ultrathin copper foil is laminated) is 0.2 μm is used. In the same manner as above, an ultrathin copper foil with a carrier foil (Sample 1-8) was produced.
<Preparation of Sample 1-9>
An ultrathin copper foil with a carrier foil (Sample 1-9) was produced in the same manner as in the production of Sample 1-1 except that the immersion in an alkaline solution was not performed.

<Preparation of Sample 1-10 to Sample 1-14>
The electrode with a carrier foil was prepared in the same manner as in the preparation of Sample 1-1 to Sample 1-5 except that the release layer was formed by anodic electrolysis at 1.5 V for 60 seconds in a state immersed in an alkaline solution. Thin copper foils (Sample 1-10 to Sample 1-14) were prepared. The formed release layer was a release layer composed of a nickel oxyhydroxide film, and the thickness and variation of the release layer were measured in the same manner as in Sample 1-1.

<Preparation of Sample 1-15>
The same carrier foil as that used to prepare Sample 1-1 was added to an organic agent-containing dilute sulfuric acid aqueous solution (liquid temperature 30 ° C.) containing 150 g / L of sulfuric acid, 10 g / L of copper, and 800 ppm of carboxybenzotriazole. It was immersed for 30 seconds, and carboxybenzotriazole was adsorbed on the surface of the carrier foil to form an organic agent layer to obtain a bonding interface layer.
Next, using a Watt bath of 330 g / L of nickel sulfate, 45 g / L of nickel chloride, 35 g / L of boric acid, pH 3 and plating at a bath temperature of 45 ° C. and a current density of 2.5 A / dm ² . A nickel layer having a thickness of 0.01 μm was formed on the organic agent layer, and then thoroughly washed.
Next, using a copper sulfate plating bath having a copper concentration of 65 g / L and a sulfuric acid concentration of 150 g / L, plating was performed at a bath temperature of 45 ° C. and a current density of 15 A / dm ² , and a thickness of 3 μm was formed on the nickel layer. An ultrathin copper foil was formed.
Then, similarly to preparation of Sample 1-1, roughening treatment, galvanized layer formation, and chromate treatment were performed, washed with water, and dried to obtain an ultrathin copper foil with a carrier foil (Sample 1-15).

<Evaluation of ultra-thin copper foil with carrier foil>
The ultrathin copper foils with the carrier foil (Sample 1-1 to Sample 1-15) produced as described above were evaluated and measured for peelability and peel strength after heating at 330 ° C. under the following conditions. It showed in Table 1.
(Evaluation method of peelability after heating at 330 ° C.)
Polyimide film as an insulator (UPILEX-VT manufactured by Ube Industries)
Was prepared, and an ultrathin copper foil with a carrier foil was crimped to this insulator at 330 ° C. (pressure: 50
kg / cm ² ), allowed to cool to room temperature, and then observed the state when the carrier foil was peeled from the insulator and evaluated according to the following criteria.
(Evaluation criteria)
○: Ultra-thin copper foil in the thermocompression bonding area is laminated on the insulator surface,
No remaining ultrathin copper foil
Δ: Part of the ultrathin copper foil in the thermocompression bonding region remains on the peeled carrier foil
×: Exfoliation between the ultrathin copper foil and the carrier foil in the thermocompression bonding area is impossible

(Measurement method of peel strength)
The produced ultrathin copper foil with carrier foil was peeled off according to JIS C6511, the peel strength was measured three times, and the average value was obtained.

[Example 2]
<Preparation of Sample 2-1>
An ultrathin copper foil with a carrier foil (Sample 2-1) was produced in the same manner as in the production of Sample 1-1 in Example 1, except that a 10 g / L aqueous sodium hydroxide solution was used as the alkaline solution.
<Preparation of Sample 2-2>
An ultrathin copper foil with a carrier foil (Sample 2-2) was produced in the same manner as in the production of Sample 1-1 of Example 1, except that a 20 g / L aqueous sodium hydroxide solution was used as the alkaline solution.
<Preparation of Sample 2-3>
An ultrathin copper foil with a carrier foil (Sample 2-3) was produced in the same manner as in the production of Sample 1-1 of Example 1 except that a 200 g / L aqueous sodium hydroxide solution was used as the alkaline solution.

<Preparation of Sample 2-4>
An ultrathin copper foil with a carrier foil (sample 2-4) was produced in the same manner as in the production of sample 1-1 in Example 1 except that a 300 g / L aqueous sodium hydroxide solution was used as the alkaline solution.
<Preparation of Sample 2-5>
An ultrathin copper foil with a carrier foil (Sample 2-5) was produced in the same manner as in the production of Sample 1-1 of Example 1, except that the temperature of the alkaline solution was 30 ° C.
<Preparation of Sample 2-6>
An ultrathin copper foil with a carrier foil (Sample 2-6) was produced in the same manner as in the production of Sample 1-1 of Example 1, except that the temperature of the alkaline solution was 40 ° C.

<Preparation of Sample 2-7>
An ultrathin copper foil with a carrier foil (Sample 2-7) was produced in the same manner as in the production of Sample 1-1 in Example 1, except that the temperature of the alkaline solution was 60 ° C.
<Preparation of Sample 2-8>
An ultrathin copper foil with a carrier foil (sample 2-8) was produced in the same manner as in the production of sample 1-1 in Example 1, except that the temperature of the alkaline solution was 80 ° C.

<Evaluation of ultra-thin copper foil with carrier foil>
About the ultra-thin copper foil with a carrier foil produced as described above (Sample 2-1 to Sample 2-8), the peelability and peel strength after heating at 330 ° C. were evaluated and measured in the same manner as in Example 1. The results are shown in Table 2 below.

[Example 3]
<Preparation of Sample 3-1>
An ultrathin copper foil with a carrier foil (Sample 3-1) was produced in the same manner as in the production of Sample 1-1 in Example 1.
The produced ultrathin copper foil with a carrier foil was a layer (nickel oxyhydroxide content: 100% by weight) in which the release layer was made of nickel oxyhydroxide. The content of nickel oxyhydroxide in the release layer was measured using ESCA PHI Quantera SXM (manufactured by ULVAC-PHI).

<Preparation of Sample 3-2>
Instead of forming a nickel layer using a nickel electrolytic plating bath (Mertex Co., Ltd. Elpilite GS-6), using a nickel-phosphorus alloy plating bath (Meltex Co., Ltd. Melbright NC-57), The plating was performed at a bath temperature of 55 ° C. and a current density of 0.5 A / dm ^{2 for} 30 seconds to form a 0.05 μm thick nickel-phosphorus (Ni—P) alloy layer (nickel content 88 wt%). An ultrathin copper foil with a carrier foil (Sample 3-2) was produced in the same manner as in the production of Sample 3-1.
The produced ultrathin copper foil with carrier foil is a layer in which the release layer contains 69% by weight of nickel oxyhydroxide. The thickness and variation of the thickness of this release layer were measured in the same manner as in Example 1 and It is shown in Table 3.

<Preparation of Sample 3-3>
Sample 3 above except that a nickel (Ni) layer having a thickness of 0.05 μm was formed by sputtering instead of forming a nickel layer using a nickel electroplating bath (Mertex Co., Ltd. Elpilite GS-6). In the same manner as in preparation of -1, an ultrathin copper foil with a carrier foil (sample 3-3) was prepared.
The produced ultrathin copper foil with carrier foil is a layer in which the release layer is made of nickel oxyhydroxide, and the thickness and variation in thickness of the release layer are measured in the same manner as in Example 1 and shown in Table 3 below. It was.

<Preparation of Sample 3-4>
Instead of forming a nickel layer using a nickel electroplating bath (Mertex Co., Ltd. Elpilite GS-6), a 0.05 μm thick nickel-chromium (Ni—Cr) alloy layer (nickel content 90) was formed by sputtering. The ultrathin copper foil with a carrier foil (Sample 3-4) was produced in the same manner as in the production of Sample 3-1, except that (% by weight) was formed.
The produced ultrathin copper foil with a carrier foil is a layer in which the release layer contains 75% by weight of nickel oxyhydroxide. The thickness and variation in thickness of the release layer were measured in the same manner as in Example 1, and the following It is shown in Table 3.

<Preparation of Sample 3-5>
Instead of forming a nickel layer using a nickel electroplating bath (Mertex Co., Ltd. Elpilite GS-6), an electroless nickel-phosphorous plating bath (Meltex Co., Ltd. Melplate NI-865) is used. The sample 3-1 was prepared except that plating was performed at a bath temperature of 85 ° C. for 1 minute to form a nickel-phosphorus (Ni—P) alloy layer (nickel content 92% by weight) having a thickness of 0.3 μm. In the same manner as above, an ultrathin copper foil with a carrier foil (Sample 3-5) was produced.
The produced ultrathin copper foil with carrier foil is a layer in which the release layer contains 68% by weight of nickel oxyhydroxide. The thickness and variation in thickness of this release layer were measured in the same manner as in Example 1, and the following It is shown in Table 3.

<Preparation of Sample 3-6>
Instead of forming a nickel layer using a nickel electrolytic plating bath (Mertex Co., Ltd. Elpilite GS-6), an electroless nickel-phosphorous plating bath (Meltex Co., Ltd. Enplate NI-426) is used. The sample 3-1 was prepared except that plating was performed at a bath temperature of 80 ° C. for 1 minute to form a nickel-phosphorus (Ni—P) alloy layer (nickel content 89 wt%) having a thickness of 0.3 μm. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 3-6) was produced.
The produced ultrathin copper foil with carrier foil is a layer in which the release layer contains 60% by weight of nickel oxyhydroxide, and the thickness and variation of the thickness of the release layer are measured in the same manner as in Example 1 and It is shown in Table 3.

<Preparation of Sample 3-7>
Instead of forming a nickel layer using a nickel electroplating bath (Mertex Co., Ltd. Elpilite GS-6), an electroless nickel-phosphorous plating bath (Meltex Co., Ltd. Melplate NI-865) is used. Sample 3-1 was prepared except that plating was performed at a bath temperature of 85 ° C. for 1 minute to form a 0.3 μm-thick nickel-phosphorus (Ni—P) alloy layer (nickel content: 85 wt%). In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 3-7) was produced.
The produced ultra-thin copper foil with carrier foil is a layer in which the release layer contains 50% by weight of nickel oxyhydroxide. The thickness and variation of the thickness of the release layer were measured in the same manner as in Example 1 and It is shown in Table 3.

<Preparation of Sample 3-8>
Instead of forming a nickel layer using a nickel electrolytic plating bath (Mertex Co., Ltd. Elpilite GS-6), an electroless nickel-phosphorous plating bath (Meltex Co., Ltd. Melplate NI-875) is used. The sample 3-1 was prepared except that plating was performed at a bath temperature of 90 ° C. for 1 minute to form a nickel-phosphorus (Ni—P) alloy layer (nickel content 80 wt%) having a thickness of 0.3 μm. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 3-8) was produced.
The produced ultrathin copper foil with a carrier foil is a layer in which the release layer contains 40% by weight of nickel oxyhydroxide. The thickness and thickness variation of the release layer were measured in the same manner as in Example 1, and the following It is shown in Table 3.

<Preparation of Sample 3-9>
Instead of forming a nickel layer using a nickel electroplating bath (Mertex Co., Ltd. Elpilite GS-6), a cobalt strike bath having the following composition was used at a bath temperature of 25 ° C. and a current density of 10 A / dm ² . An ultrathin copper foil with a carrier foil (Sample 3-9) was prepared in the same manner as Sample 3-1 above, except that a cobalt (Co) layer having a thickness of 0.05 μm was formed by plating for 1 minute. did.
(Cobalt strike bath composition)
・ Cobalt sulfate: 200 g / L
・ Sulfuric acid: 80 g / L
The produced ultrathin copper foil with a carrier foil is a layer in which the release layer is made of cobalt oxide. The thickness and variation in thickness of the release layer were measured in the same manner as in Example 1 and are shown in Table 2 below.

<Preparation of Sample 3-10>
Instead of forming a nickel layer using a nickel electrolytic plating bath (Mertex Co., Ltd. Elpilite GS-6), an iron strike bath having the following composition was used, with a bath temperature of 60 ° C. and a current density of 10 A / dm ² . An ultra-thin copper foil with a carrier foil (Sample 3-10) was prepared in the same manner as Sample 3-1 above, except that plating was performed for 30 seconds to form an iron (Fe) layer having a thickness of 0.05 μm. did.
(Composition of iron strike bath)
・ Ferrous sulfate and heptahydrate: 400 g / L
・ Ammonium sulfate: 50 g / L
・ Urea ... 80g / L
The produced ultrathin copper foil with a carrier foil is a layer in which the release layer is made of iron oxide. The thickness and variation in thickness of the release layer were measured in the same manner as in Example 1 and are shown in Table 3 below.

<Evaluation of ultra-thin copper foil with carrier foil>
About the ultra-thin copper foil with a carrier foil (Sample 3-1 to Sample 3-10) produced as described above, the peelability and peel strength after heating at 330 ° C. were evaluated and measured in the same manner as in Example 1. The results are shown in Table 3 below.

[Example 4]
<Preparation of Sample 4-1>
Sample 1-1 of Example 1 was used except that an alkaline solution (lithium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of lithium sulfide to a 100 g / L sodium hydroxide aqueous solution was used as the alkaline solution. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 4-1) was prepared.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 2.8% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below. Note that ESCA PHI Quantera SXM (manufactured by ULVAC-PHI) was used to confirm the dispersion state of sulfur in the release layer and to measure the content of sulfur in the release layer.

<Preparation of Sample 4-2>
Sample 1-1 of Example 1 was used except that an alkaline solution (sodium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of sodium sulfide to a 100 g / L sodium hydroxide aqueous solution was used as the alkaline solution. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 4-2) was prepared.
The release layer of the ultra-thin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 2.5% by weight). The thickness of this release layer The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-3>
Sample 1-1 of Example 1 was used except that an alkaline solution (potassium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of potassium sulfide to a 100 g / L sodium hydroxide aqueous solution was used as the alkaline solution. In the same manner as in the above, an ultrathin copper foil with a carrier foil (Sample 4-3) was prepared.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 4.1% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-4>
Sample 1-2 of Example 1 was used except that an alkaline solution (sodium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of sodium sulfide to a 100 g / L potassium hydroxide aqueous solution was used as the alkaline solution. In the same manner as described above, an ultrathin copper foil with a carrier foil (Sample 4-4) was prepared.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 3.2% by weight). The thickness of the release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-5>
Sample 1-3 of Example 1 except that an alkaline solution (sodium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of sodium sulfide to a 100 g / L lithium hydroxide aqueous solution was used as the alkaline solution. In the same manner as described above, an ultrathin copper foil (sample 4-5) with a carrier foil was prepared.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 3.5% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-6>
As an alkaline solution, an alkaline solution (sodium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of sodium sulfide to a mixed solution of 50 g / L sodium hydroxide aqueous solution and 50 g / L potassium hydroxide aqueous solution was used. Others were carried out similarly to preparation of the sample 1-4 of Example 1, and produced the ultra-thin copper foil (sample 4-6) with a carrier foil.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 3.0% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-7>
As the alkaline solution, an alkaline solution (sodium sulfide content: 0.01% by weight) obtained by adding 0.1 g / L of sodium sulfide to a mixed solution of 50 g / L aqueous sodium hydroxide solution and 50 g / L lithium hydroxide aqueous solution was used. Others were carried out similarly to preparation of the sample 1-5 of Example 1, and produced the ultra-thin copper foil (sample 4-7) with a carrier foil.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 2.8% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-8>
An ultrathin copper foil with a carrier foil (Sample 4-8) was prepared in the same manner as in Sample 4-1, except that the amount of lithium sulfide in the alkaline solution was 0.05 g / L (0.005 wt%). Produced.
The peeling layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the peeling layer is 0.5% by weight). The thickness of this peeling layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-9>
Except that the amount of lithium sulfide in the alkaline solution was 0.08 g / L (0.008 wt%), an ultrathin copper foil with a carrier foil (Sample 4-9) was prepared in the same manner as in Sample 4-1. Produced.
The release layer of the produced ultrathin copper foil with a carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 1.6% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-10>
An ultrathin copper foil with a carrier foil (Sample 4-10) was prepared in the same manner as in Sample 4-1, except that the amount of lithium sulfide in the alkaline solution was 0.5 g / L (0.05% by weight). Produced.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 4.5% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-11>
An ultrathin copper foil with a carrier foil (Sample 4-11) was prepared in the same manner as in Sample 4-1, except that the amount of lithium sulfide in the alkaline solution was 0.7 g / L (0.07% by weight). Produced.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 5.2% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Preparation of Sample 4-12>
An ultrathin copper foil with a carrier foil (Sample 4-12) was prepared in the same manner as Sample 4-1, except that the amount of lithium sulfide in the alkaline solution was 1.0 g / L (0.1% by weight). Produced.
The release layer of the produced ultrathin copper foil with carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide (the sulfur content in the release layer is 6.4% by weight). The thickness of this release layer, The thickness variation was measured in the same manner as in Example 1 and shown in Table 4 below.

<Evaluation of ultra-thin copper foil with carrier foil>
About the ultra-thin copper foil with a carrier foil produced as described above (Sample 4-1 to Sample 4-12), the peelability and peel strength after heating at 330 ° C. were evaluated and measured in the same manner as in Example 1. The results are shown in Table 4 below.

[Example 5]
<Preparation of Sample 5-1 to Sample 5-5>
As an alkaline solution, 0.1 g / L (0.01% by weight) of lithium sulfide was added to each sodium hydroxide aqueous solution of five concentrations (10 g / L, 20 g / L, 200 g / L, 500 g / L, 800 g / L). ) An ultrathin copper foil with a carrier foil (Sample 5-1 to Sample 5-5) was produced in the same manner as in the production of Sample 4-1 of Example 4 except that the added one was used.
The peeled layer of the produced ultrathin copper foil with a carrier foil is a layer in which sulfur is uniformly dispersed in nickel oxyhydroxide, and the thickness and variation in thickness of each peeled layer are measured in the same manner as in Example 1. The results are shown in Table 5 below.

<Preparation of Sample 5-6 to Sample 5-9>
Except for setting the liquid temperature of the alkaline solution to 4 types (30 ° C., 40 ° C., 60 ° C., 80 ° C.), in the same manner as in the preparation of Sample 4-1 of Example 4, Samples 5-6 to 5-9) were prepared.
The peeled layer of each ultrathin copper foil with a carrier foil was a layer in which sulfur was uniformly dispersed in nickel oxyhydroxide. The thickness and thickness variation of each peeled layer were measured in the same manner as in Example 1. The results are shown in Table 5 below.

<Evaluation of ultra-thin copper foil with carrier foil>
About the ultra-thin copper foil with a carrier foil produced as described above (Sample 5-1 to Sample 5-9), the peelability and peel strength after heating at 330 ° C. were evaluated and measured in the same manner as in Example 1. The results are shown in Table 5 below.

  It is useful for producing various substrates having ultrathin copper foil on the surface and for producing various products using such substrates.

Claims (16)

  On the carrier foil, a nickel layer or nickel alloy layer, and an ultrathin copper foil through a release layer, the release layer contains nickel oxyhydroxide and has a thickness in the range of 20 to 60 nm, An ultrathin copper foil with a carrier foil, wherein the thickness variation is 20% or less.   2. The ultrathin copper foil with a carrier foil according to claim 1, wherein the release layer contains sulfur in a range of 0.5 to 4.5 wt%.   The ultrathin copper foil with a carrier foil according to claim 1 or 2, wherein the nickel alloy layer is a nickel-phosphorus alloy layer or a nickel-chromium alloy layer.   It has a copper strike plating film between the said peeling layer and the said ultra-thin copper foil, The total thickness of the said ultra-thin copper foil and the said copper strike plating film is the range of 1-5 micrometers, It is characterized by the above-mentioned. The ultra-thin copper foil with a carrier foil in any one of Claims 1 thru | or 3.   The ultrathin copper foil with a carrier foil according to any one of claims 1 to 4, wherein the ultrathin copper foil has a 10-point average roughness Rz in a range of 0.8 to 4 µm.   The ultra-thin copper foil has a zinc plating layer, a zinc alloy plating layer, a tin plating layer, a tin alloy plating layer, a nickel plating layer, or a composite layer of zinc plating and chromate film on the surface. The ultrathin copper foil with a carrier foil according to claim 5.   The ultrathin copper foil with a carrier foil according to any one of claims 1 to 4, wherein the ultrathin copper foil has a silane coupling agent layer on a surface thereof.   The ultrathin copper foil with a carrier foil according to any one of claims 1 to 4, wherein the ultrathin copper foil has a triazine thiol derivative layer on a surface thereof. After forming a nickel layer or a nickel alloy layer on the carrier foil, it is immersed in an alkaline solution to contain nickel oxyhydroxide on the nickel layer or the nickel alloy layer, and the thickness is within a range of 20 to 60 nm. Forming a release layer;
Performing copper strike plating on the release layer, and then forming an ultrathin copper foil on the copper strike plating film,
The alkaline solution contains one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide in the range of 10 to 200 g / L, and the liquid temperature is in the range of 40 to 60 ° C. To produce ultrathin copper foil with carrier foil. After forming a nickel layer or a nickel alloy layer on the carrier foil, it is immersed in an alkaline solution to contain nickel oxyhydroxide on the nickel layer or the nickel alloy layer, and the thickness is within a range of 20 to 60 nm. Forming a release layer;
Performing copper strike plating on the release layer, and then forming an ultrathin copper foil on the copper strike plating film,
The alkaline solution contains one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide in a range of 10 to 500 g / L, and includes sodium sulfide, potassium sulfide and lithium sulfide as metal sulfides. The manufacturing method of the ultra-thin copper foil with a carrier foil characterized by containing 1 type (s) or 2 or more types in the range of 0.005-0.05 weight%, and liquid temperature being the range of 40-60 degreeC.   The method for producing an ultrathin copper foil with a carrier foil according to claim 9 or 10, wherein the immersion time in the alkaline solution is in the range of 30 to 180 seconds.   The carrier according to any one of claims 9 to 11, wherein in the formation of the nickel layer or the nickel alloy layer, the nickel layer or the nickel-phosphorus alloy layer is formed by an electroless plating method or an electrolytic plating method. Manufacturing method of ultra-thin copper foil with foil.   12. The ultrathin with a carrier foil according to claim 9, wherein the nickel layer or the nickel alloy layer is formed by forming a nickel layer or a nickel-chromium alloy layer by a vacuum film forming method. A method for producing copper foil.   The ultrathin copper foil is subjected to a roughening treatment so that a 10-point average roughness Rz is in a range of 0.8 to 4 µm, and then a rust prevention treatment is performed. Item 14. A method for producing an ultrathin copper foil with a carrier foil according to any one of Items13.   The method for producing an ultrathin copper foil with a carrier foil according to any one of claims 9 to 13, further comprising a step of forming a silane coupling agent layer on the ultrathin copper foil.   The method for producing an ultrathin copper foil with a carrier foil according to any one of claims 9 to 13, further comprising a step of forming a triazine thiol derivative layer on the ultrathin copper foil.