TWI527687B - Production method of copper foil, copper clad laminate, printed wiring board, electronic machine, and printed wiring board - Google Patents

Description

Copper foil, copper clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method with carrier

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

In terms of the ease of wiring or the lightness, a small electronic device such as a smart phone or a tablet PC uses a flexible printed wiring board (hereinafter referred to as FPC). In recent years, the high functionality of these electronic devices has required the multilayering of FPCs or the miniaturization (fine pitching) of conductor patterns on printed wiring boards. With such a demand, it is more important to form a circuit plating on the wiring, and to perform processing with high precision at a specific position.

On the other hand, in order to reduce the pitch, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less has recently been required. However, such an extremely thin copper foil has low mechanical strength and is liable to be broken or wrinkled at the time of manufacturing a printed wiring board. Therefore, there has been a copper foil with a carrier obtained by plating a very thin copper layer through a peeling layer using a metal foil having a thickness as a carrier. After the surface of the ultra-thin copper layer is bonded to the insulating substrate and thermocompression bonded, the carrier is peeled off by the release layer. A method of etching an extremely thin copper layer by a sulfuric acid-hydrogen peroxide-based etchant by forming a circuit pattern using a resist on an exposed ultra-thin copper layer (MSAP: Modified-Semi-Additive-Process, modified semi-additive method) to form a fine circuit. For example, WO2004/005588 (Patent Document 1), JP-A-2007-007937 (Patent Document 2), and JP-A-2010- Japanese Patent Publication No. 006071 (Patent Document 3) and Japanese Patent Laid-Open No. 2009-004423 (Patent Document 4).

[Patent Document 1] WO2004/005588

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-007937

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-006071

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-004423

In the development of copper foil with a carrier, the center of gravity has hitherto been placed to ensure the peel strength of the ultra-thin copper layer and the resin substrate. Therefore, there has not been sufficient research on the micro-pitching, and there is still room for improvement in the technique for improving the processing precision thus produced. Accordingly, it is an object of the present invention to provide a copper foil with a carrier that achieves good processing accuracy.

The present inventors have repeatedly conducted diligent research, and as a result, have found that it is possible to provide a color difference ΔL based on JIS Z8730 by controlling the specific color difference of the extremely thin copper layer of the copper foil with the carrier, specifically, the surface of the extremely thin copper layer. A copper foil with a carrier that achieves good processing accuracy.

The invention completed based on the above findings is a copper foil with a carrier which has a carrier, an intermediate layer, and an extremely thin copper layer in sequence, and the above-mentioned ultra-thin copper layer table The color difference ΔL based on JISZ8730 is -40 or less.

In another aspect, the invention is a copper foil with a carrier, which has a carrier, an intermediate layer, and an ultra-thin copper layer, and the color difference ΔE*ab of the surface of the ultra-thin copper layer is based on JISZ8730. 45 or more.

In one embodiment of the copper foil with a carrier according to the present invention, the color difference Δa of the surface of the ultra-thin copper layer based on JIS Z8730 is 20 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the color difference Δb based on JIS Z8730 on the surface of the ultra-thin copper layer is 20 or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer contains Ni, and when the copper foil with the carrier is heated at 220 ° C for 2 hours, the ultra-thin copper layer is peeled off according to JIS C 6471, The Ni adhesion amount on the surface of the intermediate layer side of the ultra-thin copper layer is 5 μg/dm ² or more and 300 μg/dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the copper foil with the carrier is heated at 220 ° C for 2 hours, the intermediate layer side surface of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. the amount of deposition of Ni 5μg / dm ² or more 250μg / dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the copper foil with the carrier is heated at 220 ° C for 2 hours, the intermediate layer side surface of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. The Ni adhesion amount is 5 μg/dm ² or more and 200 μg/dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the copper foil with the carrier is heated at 220 ° C for 2 hours, the intermediate layer side surface of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. The Ni adhesion amount is 5 μg/dm ² or more and 150 μg/dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the copper foil with the carrier is heated at 220 ° C for 2 hours, the intermediate layer side surface of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. The Ni adhesion amount is 5 μg/dm ² or more and 100 μg/dm ² or less.

A copper foil with a carrier of the present invention in still another embodiment, Ni content of the intermediate layer is 100μg / dm ² or more 5000μg / dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an alloy selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, and the like. One or more of the group consisting of hydrates, oxides, and organic substances.

A copper foil with a carrier of the present invention in a further embodiment, when the intermediate layer comprises in the case of Cr, comprising Cr 5 ~ 100μg / dm ^2, in the case where Mo is contained, the containing Mo 50μg / dm ² or more 1000μg / When dm ² or less, when Zn is contained, Zn is 1 μg/dm ² or more and 120 μg/dm ² or less.

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

In another embodiment of the present invention, the organic material is an organic material comprising one or more selected from the group consisting of an organic compound containing nitrogen, an organic compound containing sulfur, and a carboxylic acid.

In still another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 It is 0.2 μm or more and 1.0 μm or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 0.6 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.6 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.4 μm or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the standard deviation of the surface roughness Rz is 0.2 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.1 μm or less.

In still another embodiment, the copper foil with a carrier of the present invention is attached to the side surface of the ultra-thin copper layer of the copper foil with the carrier under normal temperature and normal pressure, and/or by the atmosphere. After heating at 220 ° C for 2 hours under a pressure of 20 kgf / cm ² , the insulating substrate is thermocompression bonded to the side surface of the extremely thin copper layer of the copper foil with the carrier, and/or by the atmosphere at 20 kgf / cm after 220 ℃ × 2 hours under heating and ^pressure of the thermocompression bonding the insulating substrate to the side surface of the ultra-thin copper layer of a copper foil with a carrier described above, in a nitrogen atmosphere, 180 ℃ × two times at atmospheric pressure After heating for 1 hour, the peel strength at the time of peeling the above-mentioned ultra-thin copper layer according to JIS C 6471 was 2 to 100 N/m in the state of thermocompression bonding.

In still another embodiment of the copper foil with a carrier of the present invention, the peel strength is 2 to 50 N/m.

In still another embodiment of the copper foil with a carrier of the present invention, the peel strength is 2 to 20 N/m.

In still another embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultra-thin copper layer sequentially on both sides of the carrier.

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, the copper foil with a carrier of the present invention has a roughened layer on at least one surface or both surfaces of the ultra-thin copper layer and the carrier.

In still another embodiment of the copper foil with a carrier of the present invention, the roughening treatment layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A simple substance or a layer composed of any one or more alloys.

In still another embodiment, the copper foil with a carrier of the present invention has a surface 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. More than one layer.

In still another embodiment, the copper foil with a carrier of the present invention has at least one surface or both surfaces of the ultra-thin copper layer and the carrier selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling. One or more layers of the group consisting of the treatment layers.

In still another embodiment, the copper foil with a carrier of the present invention has a surface selected from the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate layer and the decane on one surface or both surfaces of the ultra-thin copper layer. One or more layers of the group consisting of the processing layers are coupled.

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

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

In still another embodiment, the copper foil with a carrier of the present invention has a resin 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. Floor.

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 still another aspect, the present invention is a printed wiring board manufactured using the copper foil with a carrier of the present invention.

In another aspect, the invention is an electronic machine manufactured using the printed wiring board of the invention.

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and stacking the copper foil with the carrier and the insulating substrate And after laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminate is formed by peeling off the copper foil carrier of the copper foil with the carrier, and then, by semi-additive method, subtraction The method of forming a circuit by any one of a method, a partial addition method, or a modified semi-additive method.

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier of the present invention; and burying the circuit a step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with the carrier; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; and Removing the above-mentioned ultra-thin copper after the above carrier The layer is formed by exposing a circuit buried in the resin layer on the side surface of the ultra-thin copper layer.

In a method of manufacturing a printed wiring board according to the present invention, in the step of forming a circuit on the resin layer, a copper foil with another carrier is bonded to the resin layer from the side of the ultra-thin copper layer, and the bonding is performed. The step of forming the above circuit on the copper foil with the carrier of the above resin layer.

In another embodiment, the copper foil attached to the resin layer of the present invention is a copper foil with a carrier of the present invention.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method is carried out.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the method further comprises the step of forming a substrate on the side of the carrier side of the copper foil with the carrier before peeling off the carrier.

According to the present invention, it is possible to provide a copper foil with a carrier which achieves good visibility and processing accuracy.

A to C of Fig. 1 is a schematic view showing a cross section of a wiring board in a step of removing a resist from a plating circuit and a specific example of a method for producing a printed wiring board of a copper foil with a carrier of the present invention.

D to F in Fig. 2 is a wiring in a step from the lamination of the resin and the copper foil of the second layer with the carrier to the laser opening in the specific example of the method for producing the printed wiring board of the copper foil with a carrier of the present invention. Schematic diagram of the plate section.

Fig. 3 is a schematic view showing a cross section of the wiring board in the step from the formation of the via filling to the removal of the carrier of the first layer, using a specific example of the method for producing a printed wiring board of the copper foil with a carrier of the present invention; .

Fig. 4 is a schematic view showing a cross section of the wiring board in the step of forming a bump or a copper pillar in a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 5 is a schematic view showing the transfer type of the drum type.

Fig. 6 is a schematic view showing the manner in which the hairpin bends the foil.

Fig. 7 is a graph showing the relationship between the etching time and the thickness which is reduced by etching.

Fig. 8 is a schematic view showing a measurement site of a sample piece in the evaluation of the carbon concentration depth profile obtained by XPS measurement.

<copper foil with carrier>

The copper foil of the present invention has a carrier, an intermediate layer, and an extremely thin copper layer in this order. The method of using the copper foil with the carrier itself is well known, for example, bonding the surface of the ultra-thin copper layer 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 resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film and other insulating substrates Then, after the thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer next to the insulating substrate is etched into the target conductor pattern, and finally the printed wiring board can be manufactured.

<carrier>

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

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, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, 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 No. C1020 or JIS H3510 alloy No. C1011), for example, Sn-doped copper or Ag-doped copper may be used. A copper alloy such as Cr, Zr or Mg or a copper alloy to which a Cassson copper alloy such as Ni or Si is added is added.

Further, the electrolytic copper foil can be produced by the following electrolyte composition and production conditions. When the electrolytic copper foil is produced by the following conditions, the TD of the surface of the copper foil (the direction (width direction) of the copper foil manufacturing apparatus which is perpendicular to the traveling direction of the copper foil) is small, and the Rz is small and 60 degrees of TD. Electrolytic copper foil with high gloss.

In addition, the remainder of the treatment liquid used for the production of the copper foil, the surface treatment of the copper foil, the plating of the copper foil, and the like described in the present specification is water unless otherwise specified.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

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

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

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

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

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

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 suitable thickness in order to realize the action as a carrier, and may be, for example, 5 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Further, in terms of reducing the cost of raw materials, the thickness of the carrier is preferably small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less. It is preferably 5 μm or more and 12 μm or less, more preferably 5 μm or more and 11 μm or less, and still more preferably 5 μm or more and 10 μm or less. Furthermore, in the case where the thickness of the carrier is small, it is easy to cause bending when the carrier is passed through the foil. In order to prevent the occurrence of bending, for example, it is effective to smooth the conveying roller of the copper foil manufacturing apparatus with a carrier or to shorten the distance between the conveying roller and the next conveying roller. Further, in the case of using a copper foil with a carrier in an embedding method (Enbedded Process) which is one of the methods for producing a printed wiring board, the rigidity of the carrier must be high. Therefore, in the case of the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, more preferably 25 μm or more and 150 μm or less, further preferably 35 μm or more and 100 μm or less, and more preferably 35 μm or more and 70 μm or less.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as the electrode layer is not easily peeled off from the carrier before the step of laminating the copper foil with the carrier to the insulating substrate, and the step of laminating the insulating substrate is performed. The rear ultra-thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a hydrate selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like. One or more of the group consisting of such oxides and organic substances. Also, the intermediate layer may be a plurality of layers. Further, the intermediate layer may be disposed on both sides of the carrier.

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

Further, an intermediate layer containing Ni may be provided on one side or both sides of the carrier. The intermediate layer is preferably formed by sequentially laminating one layer of nickel or a nickel-containing alloy on the carrier, and one or more layers of chromium, a chromium alloy, and an oxide of chromium. Further, it is preferable that zinc is contained in any one of layers of nickel or a nickel-containing alloy and/or one or more layers containing chromium, a chromium alloy, and an oxide of chromium. 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 nickel-containing alloy 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 chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (may also be metals, alloys, oxides, nitrides, sulfides). Any form of matter). Specific examples of the chromate treatment layer include a pure chromate treatment layer or a zinc chromate treatment layer. 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 acid 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. And constituting any one of the layers of the chrome plating layer, wherein the intermediate layer is further preferably laminated on the carrier in sequence or The nickel-zinc alloy layer and the zinc chromate treatment layer are formed, or a nickel-zinc alloy layer, a pure chromate treatment layer or a zinc chromate treatment layer are sequentially laminated. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, it is peeled off at the interface between the ultra-thin copper layer and the chromate-treated layer. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer. Further, it is preferred that the intermediate layer is not subjected to chrome plating to form a chromate treatment layer. Since chromium plating forms a dense chromium oxide layer on the surface, when an extremely thin copper foil is formed by plating, the electric resistance rises and pinholes are likely to occur. The surface on which the chromate-treated layer is formed is formed with a chromium oxide layer which is not denser than chromium plating, so that it is less likely to be an electric 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 electric resistance when forming an extremely thin copper foil by electroplating is lower than that of the usual chromate treatment layer, and the occurrence of pinholes can be further suppressed.

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

When the chromate treatment layer in the intermediate layer is present thinly at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the lamination step to the insulating substrate, and on the other hand, it can be obtained on the insulating substrate. It is preferred that the ultra-thin copper layer is peeled off from the carrier after the lamination step. When the nickel layer or the nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is not provided and the chromate-treated layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and the chromic acid is not removed. When the salt layer is directly treated with a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) and an extremely thin copper layer, a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is used. The amount of nickel in the peeling strength is too strong or too weak to obtain a suitable peel strength.

Moreover, if the chromate treatment layer is present on the carrier and the nickel layer or the alloy layer containing nickel (for example) For example, at the boundary of the nickel-zinc alloy layer, the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, peeling occurs between the carrier and the intermediate layer, which is not preferable. Such a situation occurs not only when a chromate treatment layer is provided at the interface with the carrier, but also when the chromate treatment layer is provided at the interface with the ultra-thin copper layer. The reason for this is that copper and nickel are easily dissolved in a solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since chromium and copper are not easily dissolved, it is less likely to occur. Diffusion, so the interface between chromium and copper is weaker and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of chromium is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and become difficult to peel 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 dry plating such as sputtering, CVD, and PDV. Formed by 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 and PDV or wet plating such as electroless plating and immersion plating.

Further, the chromate treatment layer may be formed, for example, by electrolytic chromate or impregnated chromate. However, since the chromium concentration is increased and the peel strength of the ultra-thin copper layer from the carrier is improved, it is preferably electrolytic chromic acid. Salt formation.

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, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the copper foil of the self-supporting carrier is peeled off from the ultra-thin copper layer, in order to control the amount of Ni on the surface of the extremely thin copper layer after such peeling, It is preferable that the intermediate layer contains a metal species (Cr, Zn) which reduces the amount of Ni adhesion 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 20000μg / dm ² or less, and further preferably 500μg / dm ² or more 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, still more preferably 10 μg/dm ² or more and 40 μg/dm ² or less, and 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 30μg / dm ² or less, and further preferably 5μg / dm ² or more 20μg / dm ² or less.

The intermediate layer of the copper foil with a carrier of the present invention is formed by sequentially laminating a nickel layer on a carrier, and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and an intermediate layer. The amount of nickel attached may also be from 100 to 40000 μg/dm ² . Further, the intermediate layer of the copper foil with a carrier of the present invention is formed by sequentially laminating an organic layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on a carrier. The amount of nickel attached to the intermediate layer may also be from 100 to 40000 μg/dm ² . As described above, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the copper foil of the self-supporting carrier is peeled off from the ultra-thin copper layer, in order to control the amount of Ni on the surface of the extremely thin copper layer after such peeling, It is preferable that 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 extremely 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 20000μg / dm ² or less, and further preferably 300μg / dm ² or more 10000μg / dm ² or less, Further more preferably 500μg / dm ² or more 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.

Further, as the organic substance contained in the intermediate layer, it is preferred to use one selected from the group consisting of nitrogen One or more of the organic compound, the sulfur-containing organic compound, and the carboxylic acid. Among the nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. As the specific nitrogen-containing organic compound, it is preferred to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis(benzotriazole). 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, and the like are preferably used.

The organic substance preferably has a thickness of 25 nm or more and 80 nm or less, more preferably 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 substance can be measured as follows.

<intermediate layer organic matter thickness>

After the ultra-thin copper layer of the copper foil with the carrier was peeled off from the carrier, the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side surface of the exposed carrier were subjected to XPS measurement to prepare a depth profile. Then, the depth from the intermediate layer side surface of the ultra-thin copper layer to the carbon concentration of 3 at% or less is set to A (nm), and the depth from the intermediate layer side surface of the carrier to the carbon concentration is initially set to 3 at% or less. In the case of B (nm), the total of A and B is set as the thickness (nm) of the organic substance in 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 AlKα or non-monochromatic MgKα, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

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

Regarding the method of using the organic substance contained in the intermediate layer, the method of forming the intermediate layer on the carrier foil will be described below. The intermediate layer is formed on the carrier, and the organic substance is dissolved in a solvent and the carrier is immersed in the solvent, or the surface to be formed with the intermediate layer may be subjected to a shower method, a spray method, a dropping method, a plating method, or the like, without using A specially defined method. In this case, the concentration of the organic agent in the solvent is preferably in the range of 0.01 g/L to 30 g/L and the liquid temperature of 20 to 60 ° C in all of the above organic matters. The concentration of the organic substance is not particularly limited, and the original concentration is higher or lower without any problem. Further, there is a tendency that the higher the concentration of the organic substance, the longer the contact time of the carrier with the solvent for dissolving the organic substance, and the greater the thickness of the organic substance of the intermediate layer. Further, when the thickness of the organic material in the intermediate layer is thick, the effect of suppressing the diffusion of Ni to the extremely thin copper layer side tends to be large.

Further, the intermediate layer is preferably formed by sequentially laminating nickel, molybdenum or cobalt or a molybdenum-cobalt alloy on the carrier. The adhesion between nickel and copper is higher than that of molybdenum or cobalt and copper. Therefore, when the ultra-thin copper layer is peeled off, it is peeled off at the interface between the ultra-thin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely 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 one or more elements selected from the group consisting of molybdenum and a group selected from the group consisting of cobalt, iron, chromium, nickel, zinc, lanthanum, 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 also contain an element other than molybdenum or cobalt (for example, one selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium). The above elements).

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny side 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 lamination step to the insulating substrate, and on the other hand, It is preferable since the ultra-thin copper layer can be peeled off from the carrier after the lamination step of the insulating substrate. When the nickel layer is not provided and the molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and the molybdenum-free or cobalt-molybdenum-cobalt alloy layer is not present. When the nickel layer and the ultra-thin copper layer are directly laminated, there is a case where the peel strength of the nickel in the nickel layer is too strong or too weak, and the appropriate peel strength cannot be obtained.

Further, if a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the support and the nickel layer, there is a case where the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, peeling occurs between the carrier and the intermediate layer. Therefore, it is not good. This condition occurs not only when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the carrier, but also when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the ultra-thin copper layer. Too much will happen. This is considered to be because copper and nickel are easily dissolved in the solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since molybdenum or cobalt and copper are not easily dissolved, it is difficult to form. Interdiffusion occurs, so in molybdenum or cobalt or molybdenum - The interface between the cobalt alloy layer and the copper has a weak adhesion and is easily peeled off. Further, when the amount of nickel in the intermediate layer is insufficient, there is a case where 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 difficult to be 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 and PDV. From the viewpoint of cost, electroplating is preferred.

In the intermediate layer, it is preferable that 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, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the copper foil of the self-supporting carrier is peeled off from the ultra-thin copper layer, in order to control the amount of Ni on the surface of the extremely thin copper layer after such peeling, It is preferable that the intermediate layer contains a metal species (Co, Mo) which reduces the amount of Ni adhesion of 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 , more preferably from 200 to 20,000 μg/dm ² , still more preferably from 300 to 15,000 μg/dm ² , and even more preferably Set to 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 .} .

Further, 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 treatment for setting the molybdenum or cobalt or molybdenum-cobalt alloy layer is reduced, The current density below, slowing the carrier transport speed, the density of the molybdenum or cobalt or molybdenum-cobalt alloy layer becomes higher The tendency. 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.

In the case where the intermediate layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the surface opposite to the carrier. Further, in the case where the intermediate layer is provided by the chromate treatment or the zinc chromate treatment or the plating treatment, it is considered that a part of the metal to which the chromium or zinc adheres is a hydrate or an oxide.

Further, the copper foil with a carrier of the present invention is preferably an intermediate layer side surface of an extremely thin copper layer when the ultra-thin copper layer is peeled according to JIS C 6471 after heating at 220 ° C for 2 hours in the case where the intermediate layer contains Ni. The Ni adhesion amount is 5 μg/dm ² or more and 300 μg/dm ² or less. After bonding the copper foil with the carrier to the insulating substrate and thermocompression bonding, the copper foil carrier is peeled off, and the ultra-thin copper layer next to the insulating substrate is etched into the target conductor pattern. At this time, if it is attached to the extremely thin copper layer When the amount of Ni on the surface (the surface on the side opposite to the side opposite to the insulating substrate) is large, it is difficult to etch the extremely thin copper layer, and it is difficult to form a fine pitch circuit. Therefore, the copper foil with a carrier of the present invention is controlled so that the Ni adhesion amount on the surface of the ultra-thin copper layer after peeling as described above is 300 μg/dm ² or less. When the Ni adhesion amount exceeds 300 μg/dm ² , it is difficult to etch an extremely thin copper layer to form a finer wiring of L/S=30 μm/30 μm, for example, a fine wiring of L/S=25 μm/25 μm, for example, L/S. A fine wiring of 20 μm/20 μm, for example, a fine wiring of L/S = 15 μm / 15 μm. In addition, the above-mentioned "heating at 220 ° C for 2 hours" is a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.

When the Ni adhesion amount on the surface of the ultra-thin copper layer after peeling is too small as described above, Cu of the copper foil carrier may diffuse toward the ultra-thin copper layer side. In this case, the degree of bonding between the copper foil carrier and the ultra-thin copper layer becomes too strong, and the ultra-thin copper layer is liable to generate pinholes when the ultra-thin copper layer is peeled off. Further, there is a case where the adhesion between the resin and the copper foil is deteriorated. Therefore, the Ni adhesion amount is controlled to be 5 μg/dm ² or more. Further, the Ni deposition amount is preferably 5μg / dm ² or more 250μg / dm ² or less, more preferably 5μg / dm ² or more 200μg / dm ² or less.

In addition, when the copper foil with a carrier is heated at 220 ° C for 2 hours, when the ultra-thin copper layer is peeled off, the Ni adhesion amount of the surface of the intermediate layer side of the ultra-thin copper layer is 300 μg / dm ² or less. In order to control the amount of Ni adhesion on the surface of the ultra-thin copper layer thus peeled off, the intermediate layer must contain a metal species (Cr, Mo, Zn, etc.) or an organic substance which reduces the Ni content 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 100μg / dm ² or more 5000μg / dm ² or less, more preferably 200μg / dm ² or more 4000μg / dm ² or less, and further preferably 300μg / dm ² or more 3000μg / dm ² or less, and more preferably 400μg / dm ² or more 2000μg / dm ² or less. Further, the metal species contained in the intermediate layer is preferably one or more selected from the group consisting of Cr, Mo, and Zn. In the case of containing Cr, it is preferable to contain Cr 5 to 100 μg/dm ² , and more preferably 5 μg/dm ² or more and 50 μg/dm ² or less. When the Mo containing case, preferably containing Mo 50μg / dm ² or more 1000μg / dm ² or less, more preferably containing 70μg / dm ² or more 650μg / dm ² or less. When containing the Zn case, preferably containing Zn 1μg / dm ² or more 120μg / dm ² or less, more preferably containing 2μg / dm ² or more 70μg / ² or less dm, further preferably 50μg containing 5μg / dm ² or more / Dm ² or less.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. 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 of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and is preferable in terms of forming a copper layer at a high current density. It is a copper sulfate bath. The thickness of the ultra-thin copper layer is not particularly limited and is usually thinner than the carrier, for example, 12 μm. under. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, and 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. Further, one or more selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer may be provided on one surface or both surfaces of the ultra-thin copper layer. The layer may also be provided with a surface treatment layer. The surface treatment layer may be one or more layers selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer.

Further, the surface roughness Rz (ten-point average roughness) of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is preferably 0.2 μm or more and 1.5 μm or less. When the surface roughness Rz of the surface of the ultra-thin copper layer measured by the stylus type roughness meter according to JIS B0601-1982 is less than 0.2 μm, the copper foil with the carrier is laminated on the resin, and the carrier is peeled off from the copper foil. The problem of peeling off the copper foil from the resin occurs. Further, when the surface roughness Rz of the surface of the ultra-thin copper layer measured by the stylus type roughness meter according to JIS B0601-1982 exceeds 1.5 μm, there is a problem that the etching property is deteriorated. The surface roughness Rz is preferably 0.2 μm or more and 1.0 μm or less, more preferably 0.2 μm or more and 0.9 μm or less, further preferably 0.25 μm or more and 0.8 μm or less, and more preferably 0.28 μm or more and 0.7 μm or less and 0.28 μm or more. 0.6 μm or less.

Furthermore, in order to lower Rz, it is effective to lower the Rz of the TD direction of the carrier and to increase the gloss of 60 degrees. Further, in the case where the surface of the ultra-thin copper layer is roughened, it is effective to increase the current density in the roughening treatment and to shorten the roughening treatment time.

The roughness (Rz) and gloss of the TD of the treated side surface of the carrier before the formation of the intermediate layer were controlled in the following manner. Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is preferably from 0.20 to 0.55 μm, more preferably from 0.20 to 0.42 μm. As such a copper foil, the oil film equivalent of the rolling oil can be adjusted to perform calendering (high gloss calendering) or to adjust the surface roughness of the calender roll. Calendering (for example, when measuring in a direction perpendicular to the circumferential direction of the roll, the arithmetic mean roughness Ra (JIS B0601) of the surface of the calender roll can be set to 0.01 to 0.25 μm; on the surface of the calender roll When the value of the arithmetic mean roughness Ra is large, the roughness (Rz) of the TD of the copper foil becomes large, and the gloss tends to decrease; and the value of the arithmetic mean roughness Ra of the surface of the calender roll is small. In some cases, the roughness (Rz) of the TD of the copper foil becomes small, and the gloss tends to increase), or it is produced by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, the surface roughness (Rz) and the surface area of the copper foil after the treatment can be easily controlled by setting the surface roughness (Rz) and the gloss of the TD of the copper foil before the treatment to the above range.

Further, the copper foil before the surface treatment is preferably a TD of 60 degrees Gloss of 300 to 910%, more preferably 500 to 810%, and still more preferably 500 to 710%. If the 60-degree gloss of the MD of the copper foil before the surface treatment is less than 300%, the transparency of the above-mentioned resin becomes poor as compared with the case of 300% or more, and if it exceeds 910%, it may change. It is difficult to carry out the problem of manufacturing.

Further, the high gloss rolling can be carried out by setting the oil film equivalent of the following formula to 10000 to 24,000 or less.

Oil film equivalent = {(calender oil viscosity [cSt]) × (passing plate speed [mpm] + roll circumferential speed [mpm])} / {(roller meshing angle [rad]) × (material's lodging stress [kg/mm] ^2])}

The rolling oil viscosity [cSt] is the dynamic viscosity at 40 °C.

In order to set the oil film equivalent to 10,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing the speed of the sheet can be used.

The chemical polishing is carried out for a long period of time using an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system at a lower concentration than usual.

Further, preferably, the surface of the extremely thin copper layer measured using the stylus type roughness meter The standard deviation of the surface roughness Rz is 0.6 μm or less. When the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured by the stylus type roughness meter according to JIS B0601-1982 exceeds 0.6 μm, there is a problem that unevenness in etching property is large. The standard deviation of the surface roughness Rz is preferably 0.5 μm or less, more preferably 0.4 μm or less, still more preferably 0.3 μm or less, still more preferably 0.25 μm or less, still more preferably 0.2 μm or less, and still more preferably 0.15 μm or less, and more preferably 0.1 μm or less. Further, the lower limit of the standard deviation is not particularly limited, and is, for example, 0.001 μm or more, for example, 0.005 μm or more, for example, 0.01 μm or more.

Further, in the present invention, the "very thin copper layer surface" regarding the surface roughness Rz of the surface of the ultra-thin copper layer and the standard deviation thereof means that a roughened layer is formed on the surface of the extremely thin copper layer and / The outermost surface of the surface treated layer in the case of a heat treatment layer and/or a rustproof layer and/or a chromate treatment layer and/or a surface treatment layer such as a decane coupling treatment layer.

Furthermore, when the surface treatment layer is formed on the surface of the ultra-thin copper layer, the surface can be reduced by keeping the distance between the copper foil of the carrier and the electrode (the distance between the electrodes) closer to a uniform state than before. Standard deviation of roughness Rz.

As a method of keeping the distance from the electrode (the distance between the electrodes) closer to the uniform state than before, a method is used in which the cathode drum is used for the cathode, or the distance between the transfer rollers (for example, 200 to 500 mm) is reduced and transported. The tension is higher than the previous one (for example, 3 kgf/mm ² or more) or the like.

In one aspect of the invention, the color difference ΔL based on JIS Z8730 on the surface of the ultra-thin copper layer is controlled to be -40 or less. If the color difference ΔL of the surface of the ultra-thin copper layer based on JISZ8730 is -50 or less, the contrast between the ultra-thin copper layer and the circuit becomes clear, for example, when a circuit is formed on the surface of the extremely thin copper layer of the copper foil with a carrier. As a result, the visibility becomes good, and the alignment of the circuit can be performed with high precision. The color difference ΔL based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably -45 or less, more preferably It is below -50.

The copper foil with a carrier of the present invention preferably has a color difference Δa based on JIS Z8730 on the surface of the ultra-thin copper layer of 20 or less. When the color difference Δa of the surface of the ultra-thin copper layer based on JISZ8730 is 20 or less, for example, when a circuit is formed on the surface of the ultra-thin copper layer of the copper foil with a carrier, the contrast between the ultra-thin copper layer and the circuit becomes clear, and as a result, the result is clear. The visibility becomes better, and the alignment of the circuit can be performed with high precision. The color difference Δa based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

The copper foil with a carrier of the present invention preferably has a color difference Δb based on JIS Z8730 on the surface of the ultra-thin copper layer of 20 or less. When the color difference Δb based on JIS Z8730 of the surface of the ultra-thin copper layer is 20 or less, for example, when a circuit is formed on the surface of the extremely thin copper layer of the copper foil with a carrier, the contrast between the ultra-thin copper layer and the circuit becomes clear, and as a result, the result is clear. The visibility becomes better, and the alignment of the circuit can be performed with high precision. The color difference Δb based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

In still another aspect of the invention, the color difference ΔE*ab based on JISZ8730 on the surface of the ultra-thin copper layer is controlled to be 45 or more. If the JIS Z8730-based color difference ΔE*ab is 45 or more on the surface of the ultra-thin copper layer, for example, when a circuit is formed on the surface of the extremely thin copper layer of the copper foil with a carrier, the contrast between the ultra-thin copper layer and the circuit becomes clear. As a result, the visibility is improved, and the alignment of the circuit can be performed with high precision. The color difference ΔE*ab based on JISZ8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more. Further, in the present invention, the "very thin copper layer surface" based on JIS Z8730 color difference ΔL, Δa, Δb, and ΔE*ab on the surface of the ultra-thin copper layer means extremely thin copper. When the surface of the layer forms a surface treated layer such as a roughened layer and/or a heat-resistant layer and/or a rust-proof layer and/or a chromate-treated layer and/or a decane coupling treatment layer, The outermost surface of the surface treatment layer.

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is used, and it is represented by an L*a*b color system based on JIS Z8730. Comprehensive index, and expressed as △ L: white black, △ a: red green, △ b: yellow blue. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration can be adjusted by controlling the plating conditions for forming an extremely thin copper layer, or can be adjusted by providing a roughening treatment by roughening the surface of the ultra-thin copper layer.

When the chromatic aberration is adjusted by controlling the plating conditions for forming an extremely thin copper layer, electrolytic plating is used. In this case, the ultra-thin copper layer can be produced by the following electrolyte composition and production conditions. The chromatic aberration can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, and/or decreasing the copper concentration in the plating solution, and/or increasing the linear flow rate of the plating solution.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

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

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

An amine compound of the following chemical formula can be used for the above amine compound.

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

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

On the other hand, when the roughening treatment layer is provided by roughening the surface of the ultra-thin copper layer to adjust the chromatic aberration, the roughening treatment can be performed by, for example, forming a roughened particle from copper or a copper alloy. get on. The roughening treatment can also be fine. The roughening treatment layer may be a simple substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer composed of any one or more alloys. . 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 from a simple substance such as nickel, cobalt, copper or zinc or an alloy.

In the case where the roughening layer is provided, the above color difference can be adjusted by using a plating solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, molybdenum and phosphorus, compared to the previous one. Increase the current density (for example, 38~60A/dm ² ) and shorten the processing time (for example, 0.1~1.5 seconds).

For example, copper-cobalt-nickel alloy plating as a roughening treatment for controlling the above chromatic aberration can be formed by electrolytic plating to form a cobalt-100-3000 μg/dm ² cobalt having an adhesion amount of 15 to 40 mg/dm ² . The method is carried out in the form of a ternary alloy layer of -100 to 1500 μg/dm ² of nickel.

One example of the plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating layer is as follows: plating bath composition: Cu 10-20 g/L, Co 1 10 g/L, Ni 1~ 10g/L

pH: 1~4

Temperature: 30~50°C

Current density D _k : 38~55A/dm ²

Plating time: 0.3~1.5 seconds, more preferably 0.3~1.3 seconds

Further, in the case where an alloy plating layer containing Ni (for example, Ni-W alloy plating, Ni-Co-P alloy plating, or Ni-Zn alloy plating) which is not roughened is provided, the above color difference can be obtained by Adjust as follows: the concentration of Ni in the plating solution is set to be twice or more the concentration of other elements, and the current density is set to be 0.1 to 2 A/dm ² lower than the previous one, and the plating time is set to be as long as 20 More than seconds (for example, 20 seconds to 40 seconds).

Further, the copper foil with a carrier and a carrier having an extremely thin copper layer laminated on the carrier and laminated on the intermediate layer may have one or more layers selected from the heat-resistant layer and the rust-proof layer on the roughened layer. a layer composed of a chromate treatment layer and a decane coupling treatment layer.

Further, the heat-treated layer and the rust-preventing layer may be provided on the roughened layer, and the chromate-treated layer may be provided on the heat-resistant layer or the rust-preventing layer, or a decane coupling layer may be provided on the chromate-treated layer. The management layer.

Further, the copper foil with the carrier may be provided with a resin layer on the ultra-thin copper layer or the roughened layer or the heat-resistant layer, the rust-preventing layer, the chromate-treated layer or the decane coupling treatment layer. The above resin layer may also be an insulating resin layer.

Further, the copper foil with a carrier may have a roughening treatment layer on the carrier, or may have one or more layers selected from the roughening treatment layer, the heat resistant layer, the rustproof layer, the chromate treatment layer, and the decane coupling treatment layer on the carrier. The layer in the group. The roughening layer, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be provided by a known method, or may be set by the method described in the specification, the patent application, and the drawings. . When the carrier is laminated on a surface of the resin substrate or the like from the surface side having the roughening layer or the like, one or more layers selected from the above-described roughening layer, heat-resistant layer, rust-proof layer, and chromate are disposed on the carrier. The layer or the layer in the decane coupling treatment layer has the advantage that the carrier and the support are not easily peeled off.

The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer is superimposed and stored even if the surface is touched with a finger, and the heat-treated reaction is caused by further heat treatment.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, a resin (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) can be used. And/or a method of forming a resin layer, forming a device The document is International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. 11-5828, Japanese Patent Laid-Open No. Hei 11-140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Special Japanese Patent No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Special Open 2009-67029, International Japanese Patent 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 Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

In addition, the type of the resin layer is not particularly limited, and examples thereof include a resin containing at least one selected from the group consisting of epoxy resins, polyimine resins, and polyfunctional cyanates. a compound, a maleimide compound, a polys-methyleneimine compound, a maleimide resin, an aromatic maleimide resin, a polyvinyl acetal resin, Urethane resin, polyether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber Resin, polyamine, aromatic polyamine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, di-n-butylene Imine three Resin, thermosetting polyphenylene ether resin, cyanate ester resin, acid anhydride, acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2- Bis(4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin , oxoxane modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, Phenoxy group, polymer epoxy resin, aromatic polyamine, fluororesin, bisphenol, block copolymer polyimine resin and cyanoester resin.

Further, the epoxy resin has two or more epoxy groups in its molecule, and can be used without any problem as long as it 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, one or two or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol may be used. AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac type epoxy resin, naphthalene ring Oxygen resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, epoxidized propylamine type epoxy resin, triglycidyl isocyanurate a ring of a glycidylamine such as N,N-diepoxypropylaniline or a diglycidyl tetrahydrophthalate Oxypropyl propyl ester compound, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or A hydrogenated body or a halogenated body of the above epoxy resin is used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin is preferably a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which has two or more epoxy groups in its molecule. The epoxy resin obtained in the form.

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

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

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

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

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 cellosolve, N-methyl-2-pyrrolidine A resin liquid (resin varnish) is prepared in a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and is applied to the resin liquid (resin varnish) by, for example, a roll coating method. The side surface of the extremely thin copper layer of the copper foil with the carrier is then heated and dried as necessary to remove the solvent to be in a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved in a solvent to form a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Resin solution. Further, from the viewpoint of the atmosphere, 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.

Moreover, it is preferable that the resin layer is a semi-hardened resin film in the range of 5% to 35% of the resin flow amount measured according to MIL-P-13949G in the MIL standard.

In the present specification, the amount of resin flow refers to four pieces of 10 cm square samples taken from a surface-treated copper foil with a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard, so that the four pieces are made. In the state in which the samples were overlapped (layered body), the bonding was carried out under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf/cm ² , and a pressing time of 10 minutes, and based on the result of measuring the resin outflow weight at this time, based on the number 1 And calculate the value.

The surface-treated copper foil (surface-treated copper foil with resin) provided with the above resin layer is used in such a manner that the resin layer is superposed on the substrate and then thermally bonded to the resin layer. Thermal hardening, and then in the case where the surface-treated copper foil is an extremely thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose an extremely thin copper layer (of course, the intermediate layer side surface of the extremely thin copper layer is exposed), The surface on the side opposite to the roughening side of the surface-treated copper foil forms a specific wiring pattern.

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

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, so that it is economically advantageous, and has the following advantages: only the prepreg is manufactured. The thickness of the multilayer printed wiring board of the thickness of the material is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

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

When the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesion is lowered, and it is difficult to ensure that the surface-treated copper foil with the resin is laminated on the substrate having the inner layer material without interposing the prepreg material. Interlayer insulation between the inner layer material and the circuit. On the other hand, when the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one coating step, and an unnecessary material cost and number of steps are required, so that it is economically disadvantageous. .

In the case where a surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, and more preferably When the thickness is from 1 μm to 5 μm, the thickness of the multilayer printed wiring board can be reduced, which is preferable.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" also includes a printing package equipped with electronic components. Wire boards and printed circuit boards and printed boards.

In addition, an electronic device can be produced by using the printed wiring board, and an electronic device can be produced by using a printed circuit board on which the electronic component is mounted, and an electronic device can be manufactured by using the printed circuit board on which the electronic component is mounted. Hereinafter, an example of a manufacturing procedure of a plurality of printed wiring boards using the copper foil with a carrier of the present invention will be described.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; and making the ultra-thin copper layer side After laminating the copper foil with the carrier and the insulating substrate opposite to the insulating substrate, the copper laminated plate is formed by peeling off the carrier of the copper foil with the carrier, and then, by a semi-additive method, The circuit is formed by any one of a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

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

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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. Completely removed; Providing a through hole or/and a blind hole in the resin exposed by removing the ultra-thin copper layer by etching; removing a region containing the through hole or/and the blind hole; and containing the resin and the above An electroless plating layer is disposed in a region of the through hole or/and the blind hole; a plating resist is disposed on the electroless plating layer; and the plating resist is exposed, and then the plating of the region where the circuit is formed is removed a resisting agent; an electrolytic plating layer disposed in the circuit-formed region from which the plating resist is removed; removing the plating resist; and removing an area other than the region in which the circuit is formed by rapid etching or the like Electroless plating layer.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 by peeling off the carrier and the insulating resin substrate are provided with through holes or/and blind holes; The area containing the through holes or/and the blind holes is subjected to desmear treatment; the extremely thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an acid or the like; Etching the above-mentioned resin and the through hole exposed by removing the ultra-thin copper layer Or / and the area of the blind hole is provided with an electroless plating layer; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resistance of the region where the circuit is formed is removed Providing an electrolytic plating layer in the circuit-formed region from which the plating resist is removed; removing the plating resist; and removing the region other than the region in which the circuit is formed by rapid etching or the like Electrolytic plating.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 by peeling off the carrier and the insulating resin substrate are provided with through holes or/and blind holes; The extremely thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; the desmear treatment is performed on the region containing the through hole or/and the blind hole; An electroless plating layer is provided in a region where the ultra-thin copper layer is removed by etching or the like, and the through hole or/and the blind hole are exposed; a plating resist is provided on the electroless plating layer; and the plating is performed on the electroless plating layer; The resist is exposed, and thereafter, the plating resist in the region where the circuit is formed is removed; Providing an electrolytic plating layer in the circuit-formed region from which the plating resist is removed; removing the plating resist; and removing electroless plating in a region other than the region in which the circuit is formed by rapid etching or the like Coating.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 extremely thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an acid or the like. Removing an electroless plating layer on the 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 Thereafter, the plating resist is removed from the region where the circuit is formed; the electrolytic plating layer is disposed in the region where the circuit is formed by removing the plating resist; the plating resist is removed; and the etching is removed by rapid etching or the like An electroless plating layer and an extremely thin copper layer located in a region other than the region in which the circuit is formed.

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

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 through hole or/and the blind hole are formed on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; Desmear treatment is performed on the region containing the through hole or/and the blind hole; an electroless plating layer is disposed in the region including the through hole or/and the blind hole; and the surface of the extremely thin copper layer exposed by peeling off the carrier is disposed a plating 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.

Another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 a plating resist is disposed on the extremely thin copper layer exposed by peeling off the carrier; Exposing the plating resist to the above, and then removing the plating resist in the region where the circuit is formed; and providing an electrolytic plating layer in the region where the circuit is formed by removing the plating resist; removing the plating resistance And removing an extremely thin copper layer located in a region other than the region in which the circuit is formed by rapid etching or the like.

In the present invention, the partial addition method refers to a substrate in which a conductor layer is provided, a catalyst core is provided on a substrate formed by passing through a via hole or an auxiliary hole, and etching is performed to form a conductor circuit. After a solder resist or a plating resist is required, the via hole or the auxiliary hole or the like is thickened by electroless plating treatment (electrolytic plating treatment if necessary) on the conductor circuit to manufacture a printed wiring board. Methods.

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using a partial addition method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; 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 through hole or/and the blind hole are provided on the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; The area containing the through hole or/and the blind hole is subjected to desmear treatment; the catalyst core is provided in the above-mentioned region containing the through hole or/and the blind hole; and the etching resist is provided on the surface of the extremely thin copper layer exposed by peeling off the carrier And exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer by using etching or plasma etching using an acid or the like a catalyst core is formed to form a circuit; the etching resist is removed; and 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 acid or the like is provided, and a solder resist is disposed. Or plating a resist; and providing an electroless plating layer in a region where the above-mentioned solder resist or plating resist is not provided.

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

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

Another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and laminating the copper foil with the carrier and the insulating substrate; After the copper foil with the carrier is laminated with the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier are provided with through holes or/and blind holes; The area of the through hole or/and the blind hole is subjected to desmear treatment; the electroless plating layer is disposed in the area containing the through hole or/and the blind hole; the mask is formed on the surface of the electroless plating layer; An electroless plating layer is disposed on a surface of the electroless plating layer of the mask; an etching resist is disposed on a surface of the electroplating layer or/and the ultra-thin copper layer; and the etching resist is exposed to form a circuit pattern; The ultra-thin copper layer and the electroless plating layer are removed by etching or plasma etching using an etching solution such as an acid to form a circuit; and the etching resist is removed.

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

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. Here, a copper foil having a carrier having an extremely thin copper layer on which a roughened layer is formed will be described as an example, but it is not limited thereto, and an extremely thin copper layer having no roughened layer is used. The copper foil with a carrier can also be similarly printed with the following printed wiring board Manufacturing method.

First, as shown in Fig. 1-A, a copper foil (first layer) with a carrier having an extremely thin copper layer having a roughened layer formed thereon is prepared.

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

Next, as shown in FIG. 1-C, a circuit plating of a specific shape is formed by forming a plating layer for a circuit and removing the resist.

Next, as shown in FIG. 2-D, a resin layer is embedded on the ultra-thin copper layer by coating the circuit layer (in the form of a buried circuit plating layer), and then a resin layer is laminated on the side of the ultra-thin copper layer. Copper foil of the carrier (layer 2).

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

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

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

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

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

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

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. A printed wiring board using the copper foil with the carrier of the present invention was produced in this manner.

The copper foil (the second layer) of the other carrier may be used as the carrier of the present invention. For the copper foil, the copper foil with the previous carrier can be used, and a usual copper foil can also be used. Further, a layer 1 or a plurality of layers may be further formed on the second layer circuit shown in FIG. 3-H, and may be a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method forms the circuits.

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

The time at which the substrate is formed on the side surface of the carrier is not particularly limited, but it must be formed before the carrier is peeled off. In particular, it is preferably formed before the step of forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with the carrier, and more preferably to form a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier. Formed before the steps.

The copper foil with the carrier of the present invention controls the chromatic aberration of the surface of the ultra-thin copper layer, so that the contrast with the circuit plating layer is clear and the visibility is good. Therefore, in the manufacturing steps shown in, for example, FIG. 1-C of the printed wiring board as described above, the circuit plating layer can be formed at a specific position with high precision. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating layer is buried in the resin layer, when the ultra-thin copper layer is removed by rapid etching as shown in, for example, FIG. 4-J, the resin is used. The layer protection circuit is plated to maintain its shape, whereby it becomes easy to form a fine circuit. Moreover, since the circuit layer is protected by the resin layer, the electron mobility resistance is improved, and the wiring of the circuit is satisfactorily suppressed. Therefore, it becomes easy to form a fine circuit. Also, as shown in Figure 4-J and Figure 4-K When the ultra-thin copper layer is removed by rapid etching, the exposed surface of the circuit plating layer is formed into a shape recessed from the resin layer, so that it is easy to form bumps on the circuit plating layer, thereby forming a copper pillar thereon, and the manufacturing efficiency is improved. .

Further, a well-known resin or prepreg can be used as the resin. For example, BT (bis-non-butenylene diimide III can be used A resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, the embedded resin may contain a thermosetting resin or a thermoplastic resin. Further, the embedded resin may contain a thermoplastic resin. The type of the embedded resin is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and polyethylene. a resin such as an acetal resin, an amine ester resin, a block copolymerized polyimine resin, a block copolymerized polyimide resin, or a paper base material phenol resin or 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 resin, polyester film, polyimide film, A liquid crystal polymer film, a fluororesin film, or the like.

<Peel strength (N/m)>

The copper foil (1) of the carrier of the present invention is attached to the insulating substrate on the side of the normal temperature and normal pressure (normal state), and/or (2) by atmospheric pressure, pressure: 20 kgf/cm ² After heating at 220 ° C for 2 hours, the ultra-thin copper layer is thermocompression bonded and attached to the insulating substrate, and/or (3) heated at 220 ° C for 2 hours by atmospheric pressure at a pressure of 20 kgf/cm ² After the ultra-thin copper layer side is thermocompression-bonded and attached to the insulating substrate, after heating at 180 ° C for 1 hour under normal pressure (that is, in a state where no pressure is applied and atmospheric pressure) in a nitrogen atmosphere, When the carrier side is stretched by the load cell, the peel strength at the time of peeling off the ultra-thin copper layer according to JIS C 6471 is preferably 2 to 100 N/m. When the peeling strength is less than 2 N/m, the extremely thin copper layer is peeled off from the carrier during the production of the printed wiring board, and if it exceeds 100 N/m, excessive force is applied during peeling, for example, the above-described embedding method. (Enbedded Process) The peeling of the interface between the embedded resin and the ultra-thin copper layer occurs. The peel strength is more preferably 2 to 50 N/m, and still more preferably 2 to 20 N/m.

[Examples]

Hereinafter, description will be made based on examples and comparative examples. Furthermore, this embodiment is merely an example and is not limited to this example.

1. Manufacture of copper foil with carrier

As the carrier, a long-length electrolytic copper foil or a rolled copper foil having the thicknesses described in Tables 1, 3, and 4 was prepared.

The electrolytic copper foil was produced under the conditions described in Tables 1, 3, and 4, or JTC foil manufactured by JX Nippon Mining & Metals Co., Ltd. was used.

The rolled copper foil was produced in the following manner. A specific copper ingot is produced, and after hot rolling, annealing and cold rolling of a continuous annealing line of 300 to 800 ° C are repeated to obtain a rolled sheet of 1 to 2 mm thick. The rolled sheet was annealed by a continuous annealing line at 300 to 800 ° C to be recrystallized, and finally cold rolled to a thickness of Tables 1, 3 and 4 to obtain a copper foil. The rolling conditions (high gloss rolling or normal rolling, oil film equivalent) at this time are shown in Tables 1, 3 and 4. "High gloss rolling" and "normal rolling" mean that the final cold rolling (cold rolling after final recrystallization annealing) is performed using the values of the oil film equivalents described in Tables 1, 3, and 4, respectively. The "fine copper" of Tables 1, 3 and 4 indicates the refined copper standardized by JIS H3100 C1100. "Oxygen-free copper" in Tables 1, 3 and 4 indicates oxygen-free copper standardized by JIS H3100 C1020. The "ppm" of the additive elements described in Tables 1, 3, and 4 indicates the mass ppm. Further, for example, "fine copper + Ag 180 ppm" in the carrier type column of Tables 1, 3, and 4 is expressed in the addition of refined copper. Ag 180 mass ppm.

The intermediate layer was formed by electroplating the shiny side of the copper foil by a roll-to-roll type continuous plating line under the following conditions.

"Ni": nickel plating

(Liquid composition) Nickel sulfate: 270~280g/L, nickel chloride: 35~45g/L, nickel acetate: 10~20g/L, boric acid: 15~25g/L, brightener: saccharin, butynediol: 5~15ppm, sodium lauryl 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-described nickel plating, zinc in the form of zinc sulfate (ZnSO ₄ ) was added to the nickel plating solution, and the nickel zinc-zinc plating layer was formed by adjusting the zinc concentration in the range of 0.05 to 5 g/L.

. "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) 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

. "Zn-chromate": zinc chromate treatment

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

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

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

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

. "Organic": organic layer formation treatment

The aqueous solution containing carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L and a liquid temperature of 40 ° C and a pH of 5 was showered and sprayed for 20 to 120 seconds.

. "Co-Mo": Cobalt-molybdenum alloy plating

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

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

. "Ni-P": nickel-phosphorus alloy plating

(liquid composition) Ni: 30~70g/L, P: 0.2~1.2g/L

(pH) 1.5~2.5

(liquid temperature) 30~40°C

(current density) 1.0~10.0A/dm ²

(Power-on time) 0.5~30 seconds

Then, on a roll-to-roll type continuous plating line, an extremely thin copper layer of the thickness described in Tables 1, 3, and 4 is formed on the intermediate layer by the conditions shown in the table, thereby producing a copper foil with a carrier. .

The surface of the above ultra-thin copper layer was subjected to surface treatment under the surface treatment conditions (surface treatment 1 to 3) shown in Tables 2, 5 and 6. Here, regarding the surface treatment method, a schematic diagram of an electrolytic plating step using a foil transfer method using a rotary drum is shown in FIG. 5. Further, a schematic view of an electrolytic plating step using a foil transfer method using a hairpin bend is shown in Fig. 6. Further, regarding the surface treatment method, the examples described in the "drum" and the comparative example surface treatments 1 to 3 were all processed by the "drum". Similarly, the examples described in the "hairpin bend" and the comparative example surface treatments 1 to 3 were all treated by "hairpin bend".

Further, the copper foil with the carrier of Examples 3, 5, 7, and 10 to 18 was subjected to the following heat treatment, chromate treatment, and decane coupling treatment on the surface treatment layer.

Further, Example 20 was only subjected to heat treatment. Example 22 was only subjected to chromate treatment. Example 24 was only subjected to a decane coupling treatment. Examples 1 and 26 were subjected to chromate treatment and decane coupling treatment in sequence.

. Heat-resistant treatment (formation of heat-resistant layer)

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 (formation of chromate treatment layer)

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 (for impregnation chromate treatment)

Coulomb amount: 0~2As/dm ² (for impregnation chromate treatment)

. Decane coupling treatment (formation of decane coupling treatment layer)

The decane coupling agent coating treatment was carried out by spraying an aqueous solution of 60 ° C containing 0.2 to 2% by mass of alkoxysilane and having a pH of 7 to 8.

Further, the above-described surface-treated plating bath is shown in Table 7, and the plating bath in which an extremely thin copper layer was formed is shown in Table 8.

2. Evaluation of copper foil with carrier

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

. Surface color difference measurement: using a color difference meter MiniScan XE Plus manufactured by HunterLab Co., Ltd., according to JIS Z8730, a surface-treated surface of a very thin copper layer of a copper foil with a carrier (for heat treatment, chromate treatment, decane coupling treatment) In the case, it is measured after the last processing) with the color difference ΔL, Δa, Δb, ΔE*ab of white. Further, in the color difference meter, the measured value of the white plate is ΔE*ab=0, and the measured value when the measurement is performed in the dark place by the black bag is ΔE*ab=90, thereby correcting the chromatic aberration. Among them, ΔE*ab was measured using the L*a*b color system, and was set to ΔL: white black, Δa: red green, Δb: yellow blue, and was measured based on the following formula. Here, the color difference ΔE*ab defines white with zero and black with 90:

Further, a color difference ΔL, Δa, Δb, ΔE*ab based on JIS Z8730 in a minute region such as a copper circuit surface can be, for example, a micro-surface spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd. (model: VSS400, etc.) It is measured by a known measuring device such as a micro-surface spectrophotometer (model: SC-50μ, etc.) manufactured by Suga Test Instruments Co., Ltd.

. Metal adhesion amount of the intermediate layer: Nickel adhesion amount was dissolved in a nitric acid having a concentration of 20% by mass, and was measured by ICP emission spectrometry using an ICP emission spectrometer (Model: SPS3100) manufactured by SII Corporation; zinc and chromium adhesion amount system The sample was dissolved by using a hydrochloric acid having a temperature of 100 ° C and a concentration of 7 mass %, and was determined by atomic absorption spectrophotometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN Co., Ltd.; A mixed solution of hydrochloric acid (concentration of nitric acid: 20% by mass, concentration of hydrochloric acid: 12% by mass) was dissolved, and the sample was measured by atomic absorption spectrophotometry using an atomic absorption spectrophotometer (Model: AA240FS) manufactured by VARIAN Co., Ltd. Further, the measurement of the adhesion amount of the above nickel, zinc, chromium, and molybdenum was carried out as follows. First, after the copper foil of the self-supporting carrier is peeled off from the ultra-thin copper layer, only the side surface of the intermediate layer of the extremely thin copper layer is dissolved. Nearly (when the thickness of the ultra-thin copper layer is 1.4 μm or more, the surface of the intermediate layer from the ultra-thin copper layer is only 0.5 μm thick, and when the thickness of the ultra-thin copper layer is less than 1.4 μm, the self-polarity The side surface of the intermediate layer of the thin copper layer dissolves only 20% of the thickness of the extremely thin copper layer, and the amount of adhesion of the side surface of the intermediate layer of the extremely thin copper layer is measured. Further, after the ultra-thin copper layer was peeled off, only the vicinity of the intermediate layer side surface of the carrier (dissolved only 0.5 μm thick from the surface) was dissolved, and the amount of adhesion of the intermediate layer side surface of the carrier was measured. Then, the total value of the adhesion amount of the intermediate layer side surface of the ultra-thin copper layer and the adhesion amount of the intermediate layer side surface of the carrier is the metal adhesion amount of the intermediate layer.

Further, when the sample is not easily dissolved in the above-described concentration of 20% by mass of nitric acid or the above-mentioned concentration of 7 mass% of hydrochloric acid, a mixed solution of nitric acid and hydrochloric acid (nitrogen concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) is used. After dissolving the sample, the adhesion amount of nickel, zinc, and chromium can be measured by the above method.

In addition, the "metal adhesion amount" means the metal adhesion amount (mass) per unit area (1 dm ² ) of the sample.

. Intermediate layer organic thickness

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

Further, the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) may be 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present example, 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 minute in the sputtering time).

Furthermore, the depth profile of the carbon concentration obtained by the XPS measurement is for the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side surface of the exposed carrier, respectively for the longitudinal direction of each sample piece. a total of three parts in one area in the area of 50 mm or less and 50 mm × 50 mm in the center, that is, the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side of the exposed carrier It is made by combining six parts on the surface. The measurement site of the three portions of the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side surface of the exposed carrier is shown in Fig. 8 . Then, the intermediate layer side surface of the self-exact thin copper layer is calculated from the depth profile formed on the intermediate layer side surface of the exposed ultra-thin copper layer and the three intermediate portions of the exposed carrier. The depth A (nm) at which the carbon concentration initially becomes 3 at% or less, and the depth B (nm) from the intermediate layer side surface of the carrier to the carbon concentration initially 3 at% or less, and the arithmetic mean of A (nm) and B (() The sum of the arithmetic mean values of nm) is set to the thickness (nm) of the organic matter of the intermediate layer.

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

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 AlKα or non-monochromatic MgKα, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

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

Furthermore, XPS means X-ray photoelectron spectroscopy. In the present invention, it is premised on the use of an XPS measuring device (model 5600MC or ULVAC-PHI company-sold equivalent measuring device) manufactured by ULVAC-PHI Co., Ltd., in the case where such a measuring device cannot be obtained, as long as the depth direction is interval to determine the elemental concentrations of 0.10 ~ 0.30nm (SiO ₂ basis), the rate of sputtering is set to 1.0 ~ 3.0nm / min (SiO ₂ equivalent), the measurement device may also be other XPS.

. Ni adhesion on the surface of the extremely thin copper layer: attaching the very thin copper layer side of the copper foil with the carrier to the BT resin (three Bis-butylene diimide-based resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was heated and pressure-bonded at 220 ° C for 2 hours. Thereafter, the ultra-thin copper layer was peeled off from the copper foil carrier in accordance with JIS C 6471 (Method A). Then, the sample was dissolved in nitric acid having a concentration of 20% by mass, and the amount of Ni adhesion on the surface of the intermediate layer side of the ultra-thin copper layer was measured by ICP emission analysis using an ICP emission spectrometer (Model: SPS3100) manufactured by SII Corporation. Further, in the case where the surface of the side opposite to the side surface of the intermediate layer of the ultra-thin copper layer is subjected to surface treatment with Ni, only the vicinity of the side surface of the intermediate layer of the extremely thin copper layer is dissolved (in the case of the extremely thin copper layer) When the thickness is 1.4 μm or more, the surface of the intermediate layer from the ultra-thin copper layer is only 0.5 μm thick, and when the thickness of the ultra-thin copper layer is less than 1.4 μm, the intermediate layer side of the ultra-thin copper layer The surface only dissolves 20% of the thickness of the extremely thin copper layer, and the amount of Ni adhesion on the side surface of the intermediate layer of the extremely thin copper layer can be measured.

. Etching property: The prepared copper foil with a carrier was laminated with a substrate (manufactured by Mitsubishi Gas Chemical Co., Ltd.: GHPL-832NX-A, 0.05 mm × 4 sheets), and heat-bonded at 220 ° C for 2 hours, and then the copper foil carrier was peeled off. The ultra-thin copper layer was exposed to form a sample having a size of 250 × 250 mm ² . The thickness of each of the ultra-thin copper layers can be etched by using a sulfuric acid-peroxidation aqueous solution (SE07 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the entire etching machine (small half etching apparatus No. K-07003 manufactured by Ninomiya System) is used. Surface etching. Then, the etching property of the copper foil with a carrier was evaluated by the number of etchings required until the resin was exposed on the entire surface. The etching conditions at this time are shown below.

(etching conditions)

. As the etching solution, a sulfuric acid-peroxidation aqueous solution: SE-07 20 vol% manufactured by Mitsubishi Gas Chemical (diluted 5 times with water and copper concentration of 18 g/L) was used.

. The temperature of the etching solution was managed to be 35 ± 2 °C.

. Spray pressure: 0.1 MPa (spray is performed by spraying an etching solution perpendicularly to the copper layer of the object to be etched)

. Etching speed (corresponding to the amount of etching): 0.3 μm / time (the etching machine is 30 seconds per pass)

The amount of etching of the ultra-thin copper layer by the above-mentioned sulfuric acid-peroxidation aqueous solution: SE-07 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be measured by the gravimetric method of electrolytic copper foil JTC at the time of etching by JX Nippon Mining & Metals Co., Ltd. The relationship between the etching amount (the amount of reduction in the thickness of the copper layer) obtained by the entire surface of the electrolytic copper foil JTC (thickness 35 μm) and the etching time at this time was obtained as shown in the graph of FIG. 7, and according to the example In the comparative example, the etching time actually consumed was calculated by estimating the etching amount (the amount of decrease in the thickness of the copper layer).

The measurement method of the etching amount (the amount of reduction in the thickness of the copper layer) was obtained by the following formula.

Etching amount (reduction in thickness of copper layer) (μm) = (weight (g) before etching) - (weight (g) after etching) / (etched area (μm ² ) × density of copper (g / μm ³ ))

The density of copper was set to 8.96 g/cm ³ = 8.96 × 10 ^-12 g / μm ³ .

Specifically, a relationship is obtained between the thickness B of the ultra-thin copper layer removed by etching and the etching time (second) × coefficient α (=0.0336), thereby obtaining an extremely thin copper equivalent to removal by etching according to the etching time. The thickness B of the layer. That is, for example, it is equivalent to an extremely thin copper layer which is removed by etching. The thickness B = 5 μm means a case where etching is performed with a 5 μm ÷ coefficient α (=0.0336) = 148.8 seconds.

Thus, the number of etchings, the average of the number of etchings, and the maximum value to the minimum value of the number of etchings were measured. The criteria for determining the number of etching times with respect to the thickness of the ultra-thin copper layer and the criteria for determining the variation in the number of etching times are shown in Table 10.

. Evaluation of visibility: A plating resist was applied onto the ultra-thin copper layer of the copper foil with the carrier of the examples and the comparative examples, and then electrolytic plating was performed to form a copper plating portion of 20 μm × 20 μm square. Thereafter, an attempt was made to detect the copper plating portion by a CCD camera after removing the plating resist. The case where 10 times is detected 10 times is set to "◎ ◎", the case where 9 times or more is detected 10 times or more is set to "◎", and the case where 7 to 8 times is detected is set to "○", and When the number of detections is 6 times, it is set to "△", and the case where 5 or less times can be detected is set to "X".

. Evaluation of surface roughness:

(1) Surface roughness Rz (ten-point average roughness) of the surface of an extremely thin copper layer

According to JIS B0601-1982, the surface roughness Rz (contact pin) of the surface of the ultra-thin copper layer was measured using a contact roughness meter Surfcorder SE-3C stylus type roughness meter manufactured by Kosaka Research Institute Co., Ltd. (10-point average roughness) ). Rz (stylus) of 10 parts was arbitrarily measured, and the average value of this Rz (stylus) was set to the value of Rz (stylus). Further, the standard deviation of the values of the ten parts was calculated for Rz (stylus).

(2) Surface roughness of the carrier forming the side surface of the intermediate layer

Surface roughness Rz (stylus) in the TD direction of the carrier forming the side surface of the intermediate layer was measured using a contact roughness meter Surfcorder SE-3C stylus type roughness meter manufactured by Kosaka Research Institute Co., Ltd. in accordance with JIS B0601-1982 . Arbitrarily measure Rz (stylus) of 10 parts, The average value of Rz (stylus) is set to the value of Rz (stylus).

. Adhesion between the ultra-thin copper layer and the embedded resin: a resist is applied onto the roughened layer of the ultra-thin copper layer of the copper foil with the carrier, and exposure and development are performed to etch the resist into a linear shape. Next, a linear circuit plating layer is formed by removing the resist by forming a Cu plating layer for the circuit. Secondly, a buried resin is placed on the ultra-thin copper layer by burying the circuit plating (BT resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) Resin)) and a resin layer is laminated. Then, an attempt was made to peel the carrier from the interface with the extremely thin copper layer, and the number of times of peeling at the interface between the resin layer and the extremely thin copper layer was measured. In the case where the number of times of peeling off the interface between the resin layer and the ultra-thin copper layer is 0 in 10 times, it is set to "◎ ◎", and the case where 1 time is 10 times is "◎", and 2 out of 10 times is 2 The case of ~3 times is set to "○", the case of 4 to 5 times of 10 times is set to "△", and the case of 6 times or more of 10 times is set to "x".

. The TD direction gloss of the carrier forming the side surface of the intermediate layer (%)

According to JIS Z8741, a gloss meter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. is used, and the rolled copper foil is oriented at right angles to the rolling direction (the traveling direction of the copper foil to be delayed, that is, the width direction). The incident angle of TD) was measured at 60 degrees to measure the gloss (%). Further, the gloss (%) of the matte surface was measured for the electrolytic copper foil at an incident angle of 60 degrees in a direction perpendicular to the direction in which the copper foil was transported during the electrolytic treatment (i.e., the width direction) (TD).

. Peel strength (N/m)

The aluminum alloy side of the copper foil with the carrier is thermocompression bonded to the BT resin in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours. Bis-m-butylene imino-based resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then, the carrier side was stretched by a tensile tester, and the peel strength at the time of peeling off the ultra-thin copper layer was measured in accordance with JIS C 6471. (This value is indicated in the column after "2 hours of baking at 220 °C (N/m)" in Table 9)

Furthermore, after heating at 220 ° C for 2 hours, the pressure was again applied to the nitrogen atmosphere (at atmospheric pressure, that is, at atmospheric pressure), and heating was performed twice at 180 ° C for 1 hour, except for the same conditions. The peel strength of each sample was measured. (This value is indicated in the column of "1h × 2 times (N/m) after baking at 180 ° C) in Table 9.

Further, each of the samples before the resin is pressure-bonded (normal state at normal temperature and normal state) is attached to the resin substrate from the ultra-thin copper layer side, and then the carrier side is stretched by a tensile tester according to JIS. C 6471 measures the peel strength when the ultra-thin copper layer is peeled off. (This value is indicated in the "Normal (N/m)" column of Table 9)

(Evaluation results)

In Examples 1 to 36, the color difference ΔL on the surface of the ultra-thin copper layer was -40 or less, and the color difference ΔE*ab on the surface of the ultra-thin copper layer was 45 or more, and at least the visibility was good.

In Comparative Examples 1 to 9, the color difference ΔL on the surface of the extremely thin copper layer exceeded -40, and the color difference ΔE*ab on the surface of the extremely thin copper layer was less than 45, which was at least poor in visibility.

Claims (78)

A copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order, and a color difference ΔL based on JIS Z8730 of the surface of the ultra-thin copper layer is -40 or less. The copper foil with a carrier according to the first aspect of the patent application, which has a carrier, an intermediate layer, and an extremely thin copper layer, and the color difference ΔE*ab based on JISZ8730 is 45 or more on the surface of the ultra-thin copper layer. . A copper foil with a carrier according to the first aspect of the invention, wherein the surface of the ultra-thin copper layer has a color difference Δa of 20 or less based on JIS Z8730. A copper foil with a carrier according to the second aspect of the invention, wherein the surface of the ultra-thin copper layer has a color difference Δa of JISZ8730 of 20 or less. The copper foil with a carrier according to the first aspect of the invention, wherein the surface of the ultra-thin copper layer has a color difference Δb of JISZ8730 of 20 or less. A copper foil with a carrier according to the second aspect of the invention, wherein the surface of the ultra-thin copper layer has a color difference Δb of JISZ8730 of 20 or less. The copper foil with a carrier according to the first aspect of the invention, wherein the intermediate layer contains Ni, and the copper foil of the carrier is heated at 220 ° C for 2 hours, and then the ultra-thin copper layer is peeled off according to JIS C 6471. The Ni adhesion amount on the surface of the intermediate layer side of the ultra-thin copper layer is 5 μg/dm ² or more and 300 μg/dm ² or less. The copper foil with a carrier according to the second aspect of the invention, wherein the intermediate layer contains Ni, and the copper foil of the carrier is heated at 220 ° C for 2 hours, and then the ultra-thin copper layer is peeled off according to JIS C 6471. The Ni adhesion amount on the surface of the intermediate layer side of the ultra-thin copper layer is 5 μg/dm ² or more and 300 μg/dm ² or less. The copper foil with a carrier according to the seventh aspect of the invention, wherein the copper foil with the carrier is heated at 220 ° C for 2 hours, and the intermediate layer side of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off Ni deposition amount of the surface of 5μg / dm ² or more 250μg / dm ² or less. The copper foil with a carrier according to claim 9 wherein the copper foil with the carrier is heated at 220 ° C for 2 hours, and the intermediate layer side of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. The Ni adhesion amount on the surface is 5 μg/dm ² or more and 200 μg/dm ² or less. The copper foil with a carrier according to claim 10, wherein the intermediate layer side of the ultra-thin copper layer is peeled off after the copper foil of the carrier is heated at 220 ° C for 2 hours. The Ni adhesion amount on the surface is 5 μg/dm ² or more and 150 μg/dm ² or less. The copper foil with a carrier according to claim 11 wherein the copper foil with the carrier is heated at 220 ° C for 2 hours, and the intermediate layer side of the ultra-thin copper layer is peeled off when the ultra-thin copper layer is peeled off. The Ni adhesion amount on the surface is 5 μg/dm ² or more and 100 μg/dm ² or less. The patentable scope of application of the copper foil with a carrier, Paragraph 1, wherein, Ni content of the intermediate layer is 100μg / dm ² or more 5000μg / dm ² or less. The copper foil with a carrier according to claim 1, wherein the intermediate layer contains an alloy selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, etc. One or more of a group consisting of a hydrate, such an oxide or an organic substance. The copper foil with a carrier according to claim 14 of the invention, wherein the intermediate layer contains Cr, and contains Cr 5 to 100 μg/dm ² , and when Mo is contained, contains 50 μg/dm ² or more and 1000 μg of Mo. /dm ² or less, when Zn is contained, Zn is 1 μg/dm ² or more and 120 μg/dm ² or less. The copper foil with a carrier according to claim 14, wherein the intermediate layer contains an organic material having a thickness of 25 nm or more and 80 nm or less. The copper foil with a carrier of the invention of claim 14, wherein the organic substance is an organic substance composed of one or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. A copper foil with a carrier according to the first aspect of the invention, wherein the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less. A copper foil with a carrier according to the second aspect of the invention, wherein the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less. A copper foil with a carrier according to claim 18, wherein the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 1.0 μm or less. The copper foil with a carrier according to claim 20, wherein the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 0.6 μm or less. The copper foil with a carrier according to the first aspect of the invention, wherein the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.6 μm or less. A copper foil with a carrier as claimed in claim 2, wherein the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 It is 0.6 μm or less. A copper foil with a carrier as claimed in claim 18, wherein the standard deviation of the surface roughness Rz is 0.6 μm or less. A copper foil with a carrier as claimed in claim 24, wherein the standard deviation of the surface roughness Rz is 0.4 μm or less. A copper foil with a carrier as claimed in claim 25, wherein the standard deviation of the surface roughness Rz is 0.2 μm or less. A copper foil with a carrier as claimed in claim 26, wherein the standard deviation of the surface roughness Rz is 0.1 μm or less. The copper foil with a carrier according to the first aspect of the invention, wherein the insulating substrate is attached to the side surface of the ultra-thin copper layer of the copper foil of the carrier under normal temperature and pressure, and/or by the atmosphere, After heating at 220 ° C for 2 hours under a pressure of 20 kgf / cm ² , the insulating substrate is thermocompression bonded to the side surface of the very thin copper layer of the copper foil with the carrier, and / or by the atmosphere, at 20 kgf / After heating at 220 ° C for 2 hours under a pressure of cm ² , the insulating substrate was thermocompression bonded to the side surface of the extremely thin copper layer of the copper foil with the carrier, and then subjected to two times at normal pressure under a nitrogen atmosphere at 180 ° C. After heating for 1 hour, the peel strength of the ultra-thin copper layer was 2 to 100 N/m when the ultra-thin copper layer was peeled off in accordance with JIS C 6471 under the condition of thermocompression bonding. The copper foil with a carrier according to claim 2, wherein the insulating substrate is attached to the side surface of the extremely thin copper layer of the copper foil of the carrier under normal temperature and pressure, and/or by the atmosphere, After heating at 220 ° C for 2 hours under a pressure of 20 kgf / cm ² , the insulating substrate is thermocompression bonded to the side surface of the very thin copper layer of the copper foil with the carrier, and / or by the atmosphere, at 20 kgf / After heating at 220 ° C for 2 hours under a pressure of cm ² , the insulating substrate was thermocompression bonded to the side surface of the extremely thin copper layer of the copper foil with the carrier, and then subjected to two times at normal pressure under a nitrogen atmosphere at 180 ° C. After heating for 1 hour, the peel strength of the ultra-thin copper layer was 2 to 100 N/m when the ultra-thin copper layer was peeled off in accordance with JIS C 6471 under the condition of thermocompression bonding. A copper foil with a carrier as claimed in claim 28, wherein the peel strength is 2 to 50 N/m. A copper foil with a carrier as claimed in claim 30, wherein the peel strength is 2 to 20 N/m. A copper foil with a carrier as claimed in claim 1, which has the intermediate layer and the ultra-thin copper layer sequentially on both sides of the carrier. A copper foil with a carrier as claimed in claim 2, which has the intermediate layer and the ultra-thin copper layer sequentially on both sides of the carrier. A copper foil with a carrier as claimed in claim 1, which has a roughened layer on the ultra-thin copper layer and at least one surface or both surfaces of the carrier. A copper foil with a carrier as claimed in claim 2, which has a roughened layer on the ultra-thin copper layer and at least one surface or both surfaces of the carrier. The copper foil with a carrier according to claim 34, wherein the roughening layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. A simple substance or a layer composed of any one or more alloys. A copper foil with a carrier according to claim 34, which has a surface selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treated layer and a decane coupling treatment layer on the surface of the roughened layer. More than one layer. A copper foil with a carrier as claimed in claim 1 in the ultra-thin copper layer and the carrier The at least one surface or both surfaces have 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. A copper foil with a carrier as claimed in claim 32, which has a surface selected from a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane on one surface or both surfaces of the ultra-thin copper layer. One or more layers of the group consisting of the processing layers are coupled. A copper foil with a carrier as claimed in claim 1 which has a resin layer on the ultra-thin copper layer. A copper foil with a carrier as claimed in claim 2, which is provided with a resin layer on the ultra-thin copper layer. A copper foil with a carrier as claimed in claim 34, which is provided with a resin layer on the roughened layer. A copper foil with a carrier as claimed in claim 35, which is provided with a resin layer on the roughened layer. A copper foil with a carrier according to claim 37, which is provided with a resin 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. Floor. A copper foil with a carrier according to claim 38, which is provided with a resin 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. Floor. A copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order, and a color difference ΔE*ab based on JISZ8730 of the surface of the ultra-thin copper layer is 45 or more. A copper foil with a carrier according to claim 46, wherein the surface of the ultra-thin copper layer has a color difference Δa of JISZ8730 of 20 or less. The copper foil with a carrier according to claim 46, wherein the surface of the ultra-thin copper layer has a color difference Δb of JISZ8730 of 20 or less. The copper foil with a carrier according to claim 46, wherein the intermediate layer contains Ni, and the copper foil of the carrier is heated at 220 ° C for 2 hours, and then the ultra-thin copper layer is peeled off according to JIS C 6471. The Ni adhesion amount on the surface of the intermediate layer side of the ultra-thin copper layer is 5 μg/dm ² or more and 300 μg/dm ² or less. The copper foil with a carrier according to any one of claims 3 to 6, 47, 48, wherein the intermediate layer contains Ni, and the copper foil of the carrier is heated at 220 ° C for 2 hours, according to JIS C When the ultra-thin copper layer is peeled off by 6471, the Ni adhesion amount on the surface of the intermediate layer side of the ultra-thin copper layer is 5 μg/dm ² or more and 300 μg/dm ² or less. A copper foil with a carrier according to claim 46, wherein the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less. The copper foil with a carrier according to any one of claims 3 to 17, 47 to 49, wherein the surface roughness of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 Rz is 0.2 μm or more and 1.5 μm or less. A copper foil with a carrier according to claim 46, wherein the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured by a stylus type roughness meter according to JIS B0601-1982 is 0.6 μm or less. A copper foil with a carrier according to any one of claims 3 to 21, 47 to 49, and 51, wherein the surface of the surface of the ultra-thin copper layer is measured by a stylus type roughness meter according to JIS B0601-1982 The standard deviation of the roughness Rz is 0.6 μm or less. The copper foil with a carrier according to claim 46, wherein the insulating substrate is attached to the side surface of the ultra-thin copper layer of the copper foil of the carrier under normal temperature and pressure, and/or by the atmosphere, After heating at 220 ° C for 2 hours under a pressure of 20 kgf / cm ² , the insulating substrate is thermocompression bonded to the side surface of the very thin copper layer of the copper foil with the carrier, and / or by the atmosphere, at 20 kgf / After heating at 220 ° C for 2 hours under a pressure of cm ² , the insulating substrate was thermocompression bonded to the side surface of the extremely thin copper layer of the copper foil with the carrier, and then subjected to two times at normal pressure under a nitrogen atmosphere at 180 ° C. After heating for 1 hour, the peel strength of the ultra-thin copper layer was 2 to 100 N/m when the ultra-thin copper layer was peeled off in accordance with JIS C 6471 under the condition of thermocompression bonding. A copper foil with a carrier according to any one of claims 3 to 27, 47 to 49, 51, and 53, wherein the insulating substrate is attached to the copper foil of the carrier at a normal temperature and a normal pressure After the copper layer side surface, and/or by heating in the atmosphere at a pressure of 20 kgf/cm ² at 220 ° C for 2 hours, the insulating substrate is thermocompression bonded to the very thin copper layer side of the copper foil of the carrier. After the surface, and/or by heat-treating the insulating substrate to the side surface of the extremely thin copper layer of the copper foil of the carrier by heating at 220 ° C for 2 hours in the atmosphere at a pressure of 20 kgf / cm ² , After being heated at 180 ° C for 1 hour under normal pressure in a nitrogen atmosphere, the peel strength after peeling the ultra-thin copper layer according to JIS C 6471 is 2 to 100 N/m in the state of thermocompression bonding. . A copper foil with a carrier as claimed in claim 46, which has the intermediate layer and the ultra-thin copper layer sequentially on both sides of the carrier. A copper foil with a carrier according to any one of claims 3 to 31, 47 to 49, 51, 53 and 55, which has the intermediate layer and the ultra-thin copper layer sequentially on both sides of the carrier . A copper foil with a carrier as claimed in claim 46, which has a roughened layer on the ultra-thin copper layer and at least one surface or both surfaces of the carrier. A copper foil with a carrier according to any one of claims 3 to 33, 47 to 49, 51, 53, 55, 57, on the extremely thin copper layer and at least one surface or both surfaces of the carrier Has a roughening layer. A copper foil with a carrier as claimed in claim 60, which has a surface selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer and a decane coupling treatment layer on the surface of the roughened layer. More than one layer. A copper foil with a carrier according to any one of claims 2 to 35, 46 to 49, 51, 53, 55, 57, 59, on the extremely thin copper layer and at least one surface or both of the carrier Each of the surfaces has 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. A copper foil with a carrier as claimed in claim 58 which has a surface selected from a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane on one surface or both surfaces of the ultra-thin copper layer. One or more layers of the group consisting of the processing layers are coupled. A copper foil with a carrier as claimed in claim 46, which has a resin layer on the ultra-thin copper layer. A copper foil with a carrier according to any one of claims 3 to 39, 47 to 49, 51, 53, 55, 57, 59, which is provided with a resin layer on the ultra-thin copper layer. A copper foil with a carrier as claimed in claim 59, which has a tree on the roughened layer Lipid layer. A copper foil with a carrier as claimed in claim 60, which is provided with a resin layer on the roughened layer. A copper foil with a carrier according to claim 62, which is provided with a resin 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. Floor. A copper foil with a carrier according to claim 63, which is provided with a resin 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. Floor. A copper-clad laminate produced by using a copper foil with a carrier according to any one of claims 1 to 69. A printed wiring board manufactured by using a copper foil with a carrier according to any one of claims 1 to 69. An electronic machine manufactured using the printed wiring board of claim 71. A method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier according to any one of claims 1 to 69; and laminating the copper foil of the carrier with an insulating substrate And forming a copper-clad laminate after the copper foil with the carrier is laminated with the insulating substrate, and then removing the copper foil carrier of the copper foil with the carrier, and then, by semi-additive method, subtracting A method of forming a circuit by any one of a method of forming, a partial addition, or a modified semi-additive. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier according to any one of claims 1 to 69; a step of forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with the carrier; a step of forming a circuit on the resin layer; a step of peeling off the carrier after forming a circuit on the resin layer; After the carrier is peeled off, the ultra-thin copper layer is removed, and a circuit buried on the side surface of the ultra-thin copper layer is exposed. The manufacturing method of the printed wiring board of claim 74, wherein the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, using The step of forming the circuit by bonding a copper foil with a carrier of the resin layer. The manufacturing method of the printed wiring board of claim 75, wherein the copper foil attached to the resin layer is a copper of the carrier of any one of claims 1 to 69. Foil. The method of manufacturing a printed wiring board according to any one of claims 74 to 76, wherein the step of forming a circuit on the resin layer is by a semi-additive method, a subtractive method, a partial addition method or an improvement It is carried out by any one of the semi-additive methods. The method for producing a printed wiring board according to any one of claims 74 to 76, further comprising the step of forming a substrate on a carrier side surface of the copper foil with a carrier before peeling off the carrier.