KR101762049B1 - Copper foil with carrier, copper-clad laminate, printed wiring board, electronic device, and production method for printed wiring board - Google Patents

Abstract

A copper foil with a carrier realizing good visibility and processing accuracy is provided.
A copper foil with a carrier having a carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the color difference? L based on JIS Z8730 on the surface of the ultra-thin copper layer is -40 or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper foil with a carrier, a copper clad laminate, a printed wiring board, an electronic device, and a method for manufacturing a printed wiring board,

The present invention relates to a copper foil with a carrier, a copper clad laminate, a printed wiring board, an electronic apparatus, and a method for producing a printed wiring board.

Flexible printed wiring boards (hereinafter referred to as FPC) are employed in small electronic devices such as smart phones and tablet PCs due to their ease of wiring and light weight. In recent years, the electronic devices have become increasingly sophisticated, and conductor patterns have become finer (fine pitch) for multilayer FPCs and printed wiring boards. With this demand, it becomes more important to perform machining with high precision at a predetermined position as represented by the formation of circuit plating on the wiring.

On the other hand, a copper foil having a thickness of 9 占 퐉 or less, more specifically, a thickness of 5 占 퐉 or less has been required in recent years in response to the fine pitching. However, such a copper foil with a very thin foil has low mechanical strength, A copper foil with a carrier on which a very thin copper layer is electrodeposited with a release layer interposed therebetween has appeared. The surface of the ultra-thin copper layer is bonded to an insulating substrate, and after thermocompression bonding, the carrier is peeled off through the peeling layer. A microcircuit is formed by a modified method (MSAP: Modified-Semi-Additive-Process) in which a circuit pattern is formed on the exposed ultra-thin copper layer with a resist and then the ultra-thin copper layer is etched away with an etchant of sulfuric acid-hydrogen peroxide system. As a technique related to the copper foil with a carrier for such a fine circuit, for example, there are known a copper foil with a carrier as described in WO2004 / 005588 (Patent Document 1), JP-A 2007-007937 (Patent Document 2) 006071 (Patent Document 3) and JP-A-2009-004423 (Patent Document 4).

WO2004 / 005588 Japanese Patent Application Laid-Open No. 2007-007937 Japanese Laid-Open Patent Publication No. 2010-006071 Japanese Laid-Open Patent Publication No. 2009-004423

In the development of copper foil with a carrier, emphasis has been placed on securing the peeling strength between the ultra-thin copper layer and the resin substrate (base material) so far. Therefore, the fine pitching has not yet been sufficiently examined, and there is still room for improvement regarding the technique for improving the machining accuracy. Therefore, it is an object of the present invention to provide a copper foil with a carrier that realizes good processing accuracy.

As a result of intensive studies, the inventors of the present invention have found that, by controlling the predetermined color difference of the ultra-thin copper layer of the copper foil with a carrier, specifically, the color difference DELTA L based on JIS Z8730 on the surface of the ultra-thin copper layer, I found out that I could provide a night.

According to one aspect of the present invention, there is provided a copper foil with a carrier having a carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the color difference? L based on JIS Z8730 on the surface of the ultra- 40 or less.

According to another aspect of the present invention, there is provided a copper foil with a carrier having a carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the copper foil with a carrier having a color difference? E * ab of 45 or more based on JIS Z8730 on the surface of the ultra- to be.

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

In another embodiment of the copper foil with a carrier of the present invention, the color difference? B based on JIS Z8730 on the surface of the extremely thin copper layer is 20 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer contains Ni,

Wherein the ultra thin copper layer is peeled off according to JIS C 6471 after heating the copper foil with a carrier at 220 캜 for 2 hours and then the Ni deposition amount of the ultra thin copper layer on the side of the intermediate layer is not less than 5 쨉 g / Mu] g / dm2 or less.

The copper foil with a carrier according to another embodiment of the present invention is characterized in that when the copper foil with a carrier is heated at 220 캜 for 2 hours and then the ultra thin copper layer is peeled off, The deposition amount is not less than 5 占 퐂 / dm2 and not more than 250 占 퐂 / dm2.

The copper foil with a carrier according to another embodiment of the present invention is characterized in that when the copper foil with a carrier is heated at 220 캜 for 2 hours and then the ultra thin copper layer is peeled off, And the adhesion amount is not less than 5 占 퐂 / d㎡ and not more than 200 占 퐂 / d㎡.

The copper foil with a carrier according to another embodiment of the present invention is characterized in that when the copper foil with a carrier is heated at 220 캜 for 2 hours and then the ultra thin copper layer is peeled off, And the adhesion amount is not less than 5 占 퐂 / dm2 and not more than 150 占 퐂 / dm2.

The copper foil with a carrier according to another embodiment of the present invention is characterized in that when the copper foil with a carrier is heated at 220 캜 for 2 hours and then the ultra thin copper layer is peeled off, And the adhesion amount is not less than 5 占 퐂 / dm2 and not more than 100 占 퐂 / dm2.

In another embodiment of the copper foil with a carrier according to the present invention, the Ni content of the intermediate layer is 100 占 퐂 / dm2 or more and 5000 占 퐂 / dm2 or less.

In the copper foil with a carrier according to another embodiment of the present invention, the intermediate layer may be at least one selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, Oxides, and organic materials.

In the copper foil with a carrier according to another embodiment of the present invention, when the intermediate layer contains Cr, it contains 5 to 100 占 퐂 / dm2 of Cr, and when Mo contains 50 占 퐂 / dm2 or more and 1000 占 퐂 / dm2 or less, and when containing Zn, 1 占 퐂 / dm2 or more and 120 占 퐂 / dm2 or less of Zn.

In 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 copper foil with a carrier according to the present invention, the organic material is one or more organic materials selected from a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.

In 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 using a contact type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less.

In 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 using a contact-type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.0 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 0.6 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the standard deviation of the surface roughness Rz is 0.6 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the standard deviation of the surface roughness Rz is 0.4 占 퐉 or less.

In 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 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, the standard deviation of the surface roughness Rz is 0.1 占 퐉 or less.

In another embodiment of the copper foil with a carrier according to the present invention, after the insulating substrate is adhered to the surface of the ultra-thin copper layer side of the copper foil with a carrier under normal temperature and pressure, and /

The insulating substrate is thermally compressed in the atmosphere on the surface of the ultra thin copper layer side of the carrier with copper foil by heating at 220 캜 for 2 hours under a pressure of 20 kgf / cm 2, and /

The insulating substrate was thermally pressed on the surface of the copper foil with the carrier on the surface of the ultra-thin copper layer under the pressure of 20 kgf / cm 2 at 220 캜 for 2 hours. Thereafter, After heating for 1 hour twice and then thermocompression bonding,

The peel strength in peeling the extremely thin copper layer according to JIS C 6471 is 2 to 100 N / m.

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

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

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer and the ultra-thin copper layer are provided on both sides of the carrier in this order.

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

The copper foil with a carrier according to another embodiment 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.

The copper foil with a carrier according to another embodiment of the present invention is characterized in that the roughening treatment layer is made of any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, Or an alloy containing at least one of them.

In another embodiment of the copper foil with a carrier according to the present invention, the surface of the roughening treatment layer has at least one layer selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer.

In the copper foil with a carrier according to another embodiment of the present invention, at least one surface or both surfaces of the ultra-thin copper layer and the carrier are provided with a heat resistant layer, a rustproof layer, a chromate treatment layer and a silane coupling treatment layer And at least one layer selected from the group consisting of

The copper foil with a carrier according to another embodiment of the present invention is a copper foil with a carrier characterized in that a copper foil with a carrier is formed on one surface or both surfaces of the ultra-thin copper layer with a roughened layer, a heat resistant layer, a rustproof layer, a chromate treatment layer and a silane coupling treatment layer And at least one layer selected from the group consisting of

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

In another embodiment of the copper foil with a carrier according to the present invention, a resin layer is provided on the roughening treatment layer.

In another embodiment of the copper foil with a carrier according to the present invention, the resin layer is provided on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer.

The present invention is, in another aspect, a copper clad laminate produced by using the copper foil with a carrier of the present invention.

In another aspect, the present invention is a printed wiring board produced by using the copper foil with a carrier of the present invention.

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

According to another aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to the present invention; laminating the copper foil with the carrier and the insulating substrate; , And a step of peeling the copper foil carrier of the copper foil with a carrier to form a copper clad laminate. Thereafter, a copper clad laminate is formed by a semi-additive method, a subtractive method, a potato additive method or a modified semi- And forming a circuit by the method described above.

According to another aspect of the present invention, there is provided a method for manufacturing a copper foil with a carrier, comprising the steps of: forming a circuit on the ultra-thin copper layer side surface of the copper foil with a carrier of the present invention; A step of forming a circuit on the resin layer, a step of peeling the carrier after forming a circuit on the resin layer, and a step of removing the ultra-thin copper layer after peeling off the carrier, And a step of exposing a circuit embedded in the resin layer formed on the surface of the extremely thin copper layer side.

The method for producing a printed wiring board according to one embodiment of the present invention is characterized in that the step of forming a circuit on the resin layer is a step of bonding a copper foil with other carrier on the resin layer on the side of the ultra- And forming the circuit using the copper foil with the carrier.

In another embodiment of the method for producing a printed wiring board of the present invention, the copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier of the present invention.

In the method of manufacturing a printed wiring board according to another embodiment of the present invention, the step of forming a circuit on the resin layer may be a semi-additive method, a subtractive method, a patty additive method or a modified semi-additive method Or the like.

The method for manufacturing a printed wiring board of the present invention further includes a step of forming a substrate on a carrier-side surface of a copper foil with a carrier before peeling off the carrier, according to another embodiment.

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

Figs. 1A to 1C are schematic diagrams of a section of a wiring board in a process up to circuit plating and resist removal, relating to a concrete example of a production method of a printed wiring board using the copper foil with a carrier of the present invention. Fig.
Fig. 2D to Fig. 2D show cross-sectional views of the wiring board in cross-section (in the steps from resin laminate of copper foil with a carrier and laser hole formation to resin And the like.
3G to 3I are schematic diagrams of wiring section cross sections in a process from via-hole formation to carrier peeling of the first layer, relating to a specific example of a method for producing a printed wiring board using a copper foil with a carrier according to the present invention.
4A to 4K are schematic views of a wiring board section in a process from flash etching to bump-copper filler formation, according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier according to the present invention.
Fig. 5 is a schematic diagram showing a drum-type foil transportation system.
Fig. 6 is a schematic view showing a thin transportation mode of the phrase.
7 is a graph showing the relationship between the etching time and the thickness reduced by etching.
8 is a schematic diagram showing the measurement points of the sample sheet in the evaluation of the depth profile of the carbon concentration by the XPS measurement.

≪ Copper foil with carrier &

The copper foil with a carrier of the present invention has a carrier, an intermediate layer and an ultra-thin copper layer in this order. The method of using the copper foil with a carrier is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer may be coated with a paper substrate phenol resin, a paper base epoxy resin, a synthetic fiber cloth epoxy resin, Epoxy resin, glass cloth, glass nonwoven fabric composite base material epoxy resin and glass cloth base material is bonded to an insulating substrate such as an epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer film and a fluororesin film, And the ultra thin copper layer adhered to the insulating substrate is etched with a target conductor pattern to finally produce a printed wiring board.

<Carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, and examples thereof include a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, a steel foil, an iron alloy foil, a stainless steel foil, An insulating resin film, a polyimide film, and an LCD film.

Carriers which can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment using a rolling roll. Examples of the copper foil material include high purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) A copper alloy to which Zr or Mg is added, and a copper alloy such as a Colson type copper alloy to which Ni and Si are added can be used.

The electrolytic copper foil can be produced by the following electrolytic solution composition and manufacturing conditions. In the case of producing an electrolytic copper foil under the following conditions, the Rz of the TD of the surface of the copper foil (the direction (width direction) perpendicular to the traveling direction of the copper foil in the copper foil production facility) is small, A highly electrolytic copper foil can be obtained.

In addition, the balance of the treatment liquid used in the production of copper foil, surface treatment of copper foil or plating of copper foil described in this specification is water unless otherwise specified.

<Electrolyte Composition>

Copper: 90 ~ 110 g / ℓ

Sulfuric acid: 90 to 110 g / l

Chlorine: 50 to 100 ppm

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

Leveling second (amine compound): 10 to 30 ppm

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

[Chemical Formula 1]

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

<Manufacturing Conditions>

Current density: 70 to 100 A / dm 2

Electrolyte temperature: 50 to 60 ° C

Electrolyte flux: 3 ~ 5 m / sec

Electrolysis time: 0.5 to 10 minutes

In the present specification, when the term &quot; copper foil &quot; is used alone, it also includes a copper alloy foil.

The thickness of the carrier that can be used in the present invention is not particularly limited, but may be suitably adjusted to a suitable thickness for fulfilling its role as a carrier, and may be, for example, 5 占 퐉 or more. However, if it is excessively thick, the production cost is increased, and therefore, it is generally preferable to be 35 mu m or less. Thus, the thickness of the carrier is typically from 8 to 70 microns, more typically from 12 to 70 microns, and more typically from 18 to 35 microns. From the viewpoint of reducing the raw material cost, it is preferable that the thickness of the carrier is small. Therefore, the thickness of the carrier is typically 5 mu m or more and 35 mu m or less, preferably 5 mu m or more and 18 mu m or less, preferably 5 mu m or more and 12 mu m or less, preferably 5 mu m or more and 11 mu m or less And preferably not less than 5 占 퐉 and not more than 10 占 퐉. Further, when the thickness of the carrier is small, folded wrinkles are likely to occur at the time of the passage of the carrier. It is effective to smooth the conveying roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the conveying roll and the next conveying roll in order to prevent the occurrence of folds. In addition, when a copper foil with a carrier is used in the embedding method (Embedded Process), which is one of the methods for producing a printed wiring board, it is necessary that the carrier has high rigidity. Therefore, when used in an embedding method, the carrier preferably has a thickness of 18 탆 or more and 300 탆 or less, preferably 25 탆 or more and 150 탆 or less, more preferably 35 탆 or more and 100 탆 or less, Or less.

<Middle layer>

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

For example, the intermediate layer may be a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, , Mo, Ti, W, P, Cu, Al and Zn to form a layer composed of a hydrate or an oxide of one or more elements selected from the group consisting of Mo, Ti, W, P, Cu, Al and Zn.

In addition, an intermediate layer containing Ni may be formed on one side or both sides of the carrier. It is preferable that the intermediate layer is formed by laminating a layer containing any one of nickel or nickel-containing alloy on the carrier and a layer containing at least one of chromium, chromium alloy and chromium oxide in this order . In addition, it is preferable that zinc is contained in the layer containing any one of nickel and nickel-containing alloys and / or any one or more of chromium, chromium alloy and chromium oxide. Here, the alloy containing nickel is an alloy containing at least one element selected from the group consisting of nickel, cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium It says. The nickel-containing alloy may be an alloy consisting of three or more elements. The chromium alloy refers to an alloy consisting of at least one element selected from the group consisting of chromium and cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium. The chromium alloy may be an alloy comprising three or more elements. The layer containing at least one of chromium, chromium alloy and chromium oxide may be a chromate treatment layer. Here, the chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromic acid or dichromate. The chromate treatment layer contains elements (metal, alloy, oxide, nitride, sulfide, and the like) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium You can. Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic acid anhydride or potassium dichromate is referred to as a pure chromate treatment layer. In the present invention, the chromate treatment layer treated with the treatment liquid containing chromic anhydride, potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

The intermediate layer may be formed by depositing on the carrier at least one layer selected from the group consisting of nickel, a nickel-zinc alloy, a nickel-phosphorus alloy and a nickel-cobalt alloy and a zinc chromate treatment layer, a pure chromate treatment layer and a chromium plating layer And the intermediate layer is preferably formed by stacking a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer on the carrier in this order, or a nickel-zinc alloy layer Layer, and a pure chromate treatment layer or a zinc chromate treatment layer are laminated in this order. Since the adhesive force between nickel and copper is higher than the adhesion between chromium and copper, when the ultra-thin copper layer is peeled off, it is peeled from the interface between the ultra-thin copper layer and the chromate treatment layer. In addition, a barrier effect for preventing the copper component from diffusing from the carrier into the ultra-thin copper layer is expected for nickel in the intermediate layer. It is also preferable to form a chromate treatment layer on the intermediate layer instead of chromium plating. Since the chromium plating forms a dense chromium oxide layer on the surface, when the extremely thin copper foil is formed by electroplating, the electrical resistance increases and pinholes are likely to be generated. Since the surface on which the chromate treatment layer is formed is less dense than the chromium plating, the chromium oxide layer is less likely to be resistant to electroplating and the pinhole can be reduced. Here, by forming the zinc chromate treatment layer as the chromate treatment layer, the resistance when the ultra-thin copper foil is formed by electroplating is lower than that of the conventional chromate treatment layer, and the occurrence of pinholes can be suppressed more.

When an electrolytic copper foil is used as the carrier, it is preferable to form an intermediate layer on the shiny side from the viewpoint of reducing pinholes.

The ultra-thin copper layer is not peeled off from the carrier before the step of laminating to the insulating substrate. On the other hand, after the laminating step to the insulating substrate, the ultra-thin copper layer is peeled off from the carrier It is preferable in obtaining a characteristic that it is possible. When the chromate treatment layer is present at the boundary between the carrier and the ultra-thin copper layer without forming a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the peelability is hardly improved, (For example, a nickel-zinc alloy layer) containing a nickel layer or nickel and an ultra-thin copper layer directly on a nickel layer or nickel alloy layer (for example, a nickel-zinc alloy layer The peel strength is too strong or too weak depending on the amount of nickel in the steel sheet, so that adequate peel strength can not be obtained.

When the chromate treatment layer is present at the boundary between the carrier and the nickel layer or the alloy layer containing nickel (for example, the nickel-zinc alloy layer), the intermediate layer is also adhered and peeled off at the peeling of the ultra-thin copper layer, And peeling occurs between the intermediate layer and the intermediate layer. This situation may occur not only when the chromate treatment layer is formed at the interface with the carrier but also when the chromate treatment layer is formed at the interface with the ultra-thin copper layer, if the amount of chromium is excessively large. This is because, since copper and nickel are easy to solid-solubilize, when they are in contact with each other, the adhesive force increases due to mutual diffusion and does not peel off easily. On the other hand, chromium and copper are not well- And at the interface between copper and copper, the adhesive force is weak, which is considered to be the cause of peeling. When the amount of nickel in the intermediate layer is insufficient, since there is only a trace amount of chromium between the carrier and the ultra-thin copper layer, they are closely adhered to each other and can not be separated easily.

The nickel layer of the intermediate layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer) can be formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV As shown in FIG. From the viewpoint of cost, electroplating is preferable. When 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.

The chromate treatment layer can be formed by, for example, electrolytic chromate or immersion chromate. However, since the chromium concentration can be increased and the peeling strength of the ultra-thin copper layer from the carrier is improved, .

It is also preferable that the adhesion amount of nickel in the intermediate layer is 100 to 40,000 占 퐂 / dm2, the adhesion amount of chromium is 5 to 100 占 퐂 / dm2, and the adhesion amount of zinc is 1 to 70 占 퐂 / dm2. As described above, in the copper foil with a carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil with the carrier is controlled. However, It is preferable that the intermediate layer includes a metal species (Cr, Zn) that reduces the amount of Ni adhered to the intermediate layer and inhibits diffusion of Ni to the ultra-thin copper layer side. From such a viewpoint, the Ni content of the intermediate layer is preferably 100 to 40,000 占 퐂 / dm 2, more preferably 200 占 퐂 / dm 2 to 20000 占 퐂 / dm 2, more preferably 500 占 퐂 / M &lt; 2 &gt; or less, more preferably 700 mu g / dm &lt; 2 &gt; The Cr content is preferably 5 to 100 μg / dm 2, more preferably 8 μg / dm 2 to 50 μg / dm 2, still more preferably 10 μg / dm 2 to 40 μg / dm 2 , And more preferably not less than 12 μg / dm 2 and not more than 30 μg / dm 2. The Zn content is preferably 1 to 70 占 퐂 / dm2, more preferably 3 占 퐂 / dm2 to 30 占 퐂 / dm2, and still more preferably 5 占 퐂 / dm2 to 20 占 퐂 / dm2.

The intermediate layer of the copper foil with a carrier of the present invention is formed by laminating a nickel layer and an organic material layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid in this order on the carrier, May be 100 to 40,000 占 퐂 / dm2. The intermediate layer of the copper foil with a carrier of the present invention is formed by laminating an organic material layer containing a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer in this order on a carrier, The adhesion amount of nickel may be 100 to 40,000 占 퐂 / dm2. As described above, in the copper foil with a carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil with the carrier is controlled. However, It is preferable that the intermediate layer contains an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid which reduces the amount of Ni adhered to the intermediate layer and inhibits diffusion of Ni to the ultra-thin copper layer side Do. From such a viewpoint, the Ni content of the intermediate layer is preferably 100 to 40,000 占 퐂 / dm 2, more preferably 200 占 퐂 / dm 2 to 20000 占 퐂 / dm 2, more preferably 300 占 퐂 / M &lt; 2 &gt; or less, more preferably 500 mu g / dm &lt; 2 &gt; Examples of the organic substance containing any of the nitrogen-containing organic compound, the sulfur-containing organic compound and the carboxylic acid include BTA (benzotriazole) and MBT (mercaptobenzothiazole).

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

As the sulfur-containing organic compound, mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid and 2-benzimidazole thiol are preferably used.

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

The above-mentioned organic materials preferably contain 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 contain a plurality of kinds (at least one) of the above-mentioned organic substances.

The thickness of the organic material can be measured in the following manner.

&Lt; Thickness of organic material in intermediate layer &

After the extremely thin copper layer of the copper foil with the carrier is peeled from the carrier, the surface of the intermediate layer side of the exposed ultra-thin copper layer and the surface of the intermediate layer side of the exposed carrier are measured by XPS to create a depth profile. The depth at which the carbon concentration first became 3 at% or less from the surface of the intermediate layer side of the ultra-thin copper layer was A (nm), and the depth at which the carbon concentration was 3 at% or less for the first time from the surface of the intermediate layer side of the carrier was B (Nm), and the sum of A and B can be set as the thickness (nm) of the organic material in the intermediate layer.

The operating conditions of the XPS are shown below.

Device: XPS measuring device (NBP, type 5600MC)

• Approaching degree of vacuum: 3.8 × 10 ^-7 Pa

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

Ion line: ion species Ar ⁺ , accelerating voltage 3 kV, sweep area 3 mm 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )

The method of using the organic material contained in the intermediate layer will be described below while describing the method of forming the intermediate layer on the carrier foil. The formation of the intermediate layer on the carrier can be carried out by dissolving the organic substance described above in a solvent and immersing the carrier in the solvent or by using a showering, spraying, dropping, electrodeposition, or the like on the surface on which the intermediate layer is to be formed And there is no need to adopt a particularly limited technique. The concentration of the organic solvent in the solvent at this time is preferably in the range of 0.01 g / l to 30 g / l in concentration and 20 to 60 ° C in the liquid temperature in all of the above-described organic substances. The concentration of the organic substance is not particularly limited, and it may be low even if the concentration is originally high. Further, the longer the contact time of the carrier with the solvent in which the above-mentioned organic substance is dissolved, the greater the thickness of the organic substance in the intermediate layer tends to be, the higher the concentration of the organic substance is. When the thickness of the organic material in the intermediate layer is large, the effect of the organic material that suppresses the diffusion of Ni into the ultra-thin copper layer side tends to increase.

It is preferable that the intermediate layer is formed by stacking nickel, molybdenum or cobalt or molybdenum-cobalt alloy on the carrier in this order. Since the adhesive force between nickel and copper is higher than the adhesion force between molybdenum or cobalt and copper, when the ultra-thin copper layer is peeled, it is peeled from the interface between the ultra-thin copper layer and molybdenum or cobalt or molybdenum-cobalt alloy. It is also expected that a barrier effect for preventing diffusion of the copper component from the carrier into the ultra-thin copper layer is expected for nickel in the intermediate layer.

Further, the nickel described above may be an alloy containing nickel. Here, the alloy containing nickel is an alloy containing at least one element selected from the group consisting of nickel, cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium It says. The above-mentioned molybdenum may be an alloy containing molybdenum. The alloy containing molybdenum is an alloy containing molybdenum and at least one element selected from the group consisting of cobalt, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium It says. The above-mentioned cobalt may be an alloy containing cobalt. The alloy containing cobalt is an alloy containing at least one element selected from the group consisting of cobalt and molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium It says.

The molybdenum-cobalt alloy may be at least one element selected from the group consisting of molybdenum and elements other than cobalt (for example, at least one element selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, .

When an electrolytic copper foil is used as the carrier, it is preferable to form an intermediate layer on the shiny side from the viewpoint of reducing pinholes.

The molybdenum or cobalt or molybdenum-cobalt alloy layer of the intermediate layer is thinly present at the interface of the ultra-thin copper layer. The ultra-thin copper layer does not peel off from the carrier before the step of laminating to the insulating substrate, In order to obtain characteristics that the ultra-thin copper layer can be peeled off. When a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer without forming a nickel layer, the peelability may hardly be improved, and there may be a case where no molybdenum or cobalt or molybdenum- When the nickel layer and the ultra-thin copper layer are laminated directly, the peel strength may become too strong or too weak depending on the amount of nickel in the nickel layer, so that appropriate peel strength may not be obtained.

If the molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the interface between the carrier and the nickel layer, the intermediate layer may also be adhered to and peeled off during peeling of the ultra-thin copper layer, that is, peeling occurs between the carrier and the intermediate layer It may be undesirable. Such a situation is not only the case where a molybdenum or cobalt or molybdenum-cobalt alloy layer is formed at the interface with the carrier, but a molybdenum or cobalt or molybdenum-cobalt alloy layer is formed at the interface with the ultra-thin copper layer, If the amount is too large, it can occur. This is because, since copper and nickel are easy to be molten, when they are in contact with each other, the mutual diffusion increases the adhesive strength and does not easily peel off. On the other hand, molybdenum or cobalt and copper are not dissolved well, Or at the interface between the cobalt or molybdenum-cobalt alloy layer and the copper, the adhesive force is weak, which is considered to be the cause of peeling easily. When the amount of nickel in the intermediate layer is insufficient, since there is only a small amount of molybdenum or cobalt between the carrier and the ultra-thin copper layer, the molybdenum or cobalt may not adhere closely to the carrier and the ultra thin copper layer.

The nickel and cobalt or molybdenum-cobalt alloy of the intermediate layer can be formed by wet plating such as electroplating, electroless plating and immersion plating, or by dry plating such as sputtering, CVD and PDV. In addition, molybdenum can be formed only by dry plating such as CVD and PDV. From the viewpoint of cost, electroplating is preferable.

In the intermediate layer, the adhesion amount of nickel is 100 to 40,000 占 퐂 / dm2, the adhesion amount of molybdenum is 10 to 1000 占 퐂 / dm2, and the adhesion amount of cobalt is 10 to 1000 占 퐂 / dm2. As described above, in the copper foil with a carrier of the present invention, the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil with the carrier is controlled. However, It is preferable that the intermediate layer contains metal species (Co and Mo) that reduce the Ni deposition amount of the intermediate layer and inhibit diffusion of Ni to the ultra-thin copper layer side. From this viewpoint, it is preferable that the nickel adhesion amount is 100 to 40,000 占 퐂 / dm2, preferably 200 to 20,000 占 퐂 / dm2, more preferably 300 to 15,000 占 퐂 / dm2, More preferably 10000 占 퐂 / dm2. When molybdenum is contained in the intermediate layer, the molybdenum adhesion amount is preferably 10 to 1000 占 퐂 / dm2, and the molybdenum adhesion amount is preferably 20 to 600 占 퐂 / dm2, more preferably 30 to 400 占 퐂 / Is more preferable. When the intermediate layer contains cobalt, the cobalt adhesion amount is preferably 10 to 1000 占 퐂 / dm2, and the cobalt adhesion amount is preferably 20 to 600 占 퐂 / dm2, more preferably 30 to 400 占 퐂 / Is more preferable.

When the nickel, molybdenum, or cobalt or molybdenum-cobalt alloy is laminated in this order on the carrier as described above, the intermediate layer may be formed by a plating treatment for forming a molybdenum, cobalt or molybdenum-cobalt alloy layer The carrier density of the molybdenum or cobalt or molybdenum-cobalt alloy layer tends to increase. When the density of the layer containing molybdenum and / or cobalt is increased, nickel in the nickel layer is not diffused well, and the amount of Ni on the surface of the ultra-thin copper layer after peeling can be controlled.

When the intermediate layer is formed only on one side, it is preferable to form a rust prevention layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is formed by chromate treatment, zinc chromate treatment or plating treatment, it is considered that a part of the attached metal such as chromium or zinc may be a hydrate or an oxide.

When the intermediate copper layer of the present invention contains Ni in the intermediate layer, when the ultra-thin copper layer is peeled off according to JIS C 6471 after being heated at 220 占 폚 for 2 hours, And an adhesion amount of not less than 5 mu g / dm &lt; 2 &gt; and not more than 300 mu g / dm & Copper foil carrier is peeled off after thermocompression bonding, and the ultra-thin copper layer adhered to the insulating substrate is etched with a target conductor pattern. At this time, the surface of the ultra-thin copper layer On the surface opposite to the adhesion side of the copper foil) is too much, the ultra-thin copper layer is not well etched and it becomes difficult to form a fine pitch circuit. For this reason, the copper foil with a carrier of the present invention is controlled so that the Ni deposition amount on the surface of the ultra-thin copper layer after the peeling is 300 占 퐂 / dm2 or less. If the amount of Ni adhered exceeds 300 / / dm 2, the extremely thin copper layer is etched to form a fine wiring of L / S = 30 탆 / 30 탆, for example, a fine wiring of L / S = 25 탆 / It is difficult to form minute wirings of L / S = 20 mu m / 20 mu m, for example, fine wirings of L / S = 15 mu m / 15 mu m. The above &quot; heating at 220 占 폚 for 2 hours &quot; shows a typical heating condition in the case where copper foil with a carrier is bonded to an insulating substrate and thermocompression bonding is performed.

If the amount of Ni deposited on the surface of the extremely thin copper layer after the peeling is too small, Cu of the copper foil carrier may diffuse toward the ultra-thin copper layer. In such a case, the degree of bonding between the copper foil carrier and the ultra-thin copper layer becomes too strong, and pinholes are liable to be generated in the ultra-thin copper layer when the ultra-thin copper layer is peeled off. In addition, the adhesion between the resin and the copper foil may deteriorate. Therefore, the adhesion amount of Ni is controlled to be 5 占 퐂 / dm2 or more. The Ni adhesion amount is preferably 5 / / dm 2 to 250 / / dm 2, more preferably 5 / / dm 2 to 200 / / dm 2.

As described above, when the copper foil with a carrier is heated at 220 占 폚 for 2 hours and then the ultra-thin copper layer is peeled off, when the Ni deposition amount on the surface of the intermediate layer side of the ultra-thin copper layer becomes 300 占 퐂 / In order to control the amount of Ni deposited on the surface of the ultra-thin copper layer after peeling, it is necessary to reduce the Ni content of the intermediate layer and to prevent the diffusion of Ni (Cr, Mo, Zn, etc.) It is necessary to contain an intermediate layer. From such a viewpoint, the Ni content of the intermediate layer is preferably 100 占 퐂 / dm 2 to 5000 占 퐂 / dm 2, more preferably 200 占 퐂 / dm 2 to 4000 占 퐂 / dm 2, more preferably 300 占 퐂 / More preferably not more than 3000 μg / dm 2, and even more preferably not less than 400 μg / dm 2 and not more than 2000 μg / dm 2. The metal species contained in the intermediate layer is preferably one or more selected from the group consisting of Cr, Mo, and Zn. When Cr is contained, Cr is preferably contained in an amount of 5 to 100 占 퐂 / dm2, more preferably 5 占 퐂 / dm2 to 50 占 퐂 / dm2. When Mo is contained, Mo is preferably contained in an amount of 50 쨉 g / dm 2 or more and 1000 쨉 g / dm 2 or less, more preferably 70 쨉 g / dm 2 or more and 650 쨉 g / dm 2 or less. In the case of containing Zn, it is preferable that Zn be contained in an amount of 1 쨉 g / dm 2 or more and 120 쨉 g / dm 2 or less, more preferably 2 쨉 g / dm 2 or more and 70 쨉 g / M &lt; 2 &gt; and not more than 50 mu g / dm &lt; 2 &gt;

<Ultra-thin copper layer>

And an ultra-thin copper layer is formed on the intermediate layer. Another layer may be formed between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and a copper sulfate bath is preferable because a copper layer can be formed at a high current density. The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 占 퐉 or less. Typically from 0.5 to 12 占 퐉, more typically from 1 to 5 占 퐉, more typically from 1.5 to 5 占 퐉, and even more typically from 2 to 5 占 퐉. The ultra-thin copper layer may be formed on both sides of the carrier. It is also possible to form at least one layer selected from the group consisting of a roughened layer, a heat resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer on one surface or both surfaces of the ultra-thin copper layer And a surface treatment layer may be formed. The surface treatment layer may be at least one layer selected from the group consisting of a roughened treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer.

It is also preferable that the surface roughness Rz (10-point average roughness) of the surface of the ultra-thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less. When the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter according to JIS B0601-1982 is less than 0.2 탆, when the carrier is peeled from the copper foil after the copper foil with the carrier is laminated on the resin, There is a possibility that a problem of peeling from the resin is likely to occur. In addition, if the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter in accordance with JIS B0601-1982 is more than 1.5 탆, there is a possibility that a problem that the etching property is deteriorated may occur. More preferably, the surface roughness Rz is 0.2 mu m or more and 1.0 mu m or less, more preferably 0.2 mu m or more and 0.9 mu m or less, more preferably 0.25 mu m or more and 0.8 mu m or less, more preferably 0.28 mu m or more and 0.7 mu m or less, Mu m or less is more preferable.

Further, in order to lower the Rz, it is effective to lower the Rz of the carrier in the TD direction and increase the degree of 60-degree gloss. When the roughening treatment is performed on the surface of the ultra-thin copper layer, it is effective to increase the current density in the roughening treatment and shorten the roughening treatment time.

The illuminance (Rz) and gloss of TD on the surface of the carrier-processed surface before the formation of the intermediate layer are controlled as follows. Specifically, the surface roughness (Rz) of the TD of the copper foil before the surface treatment is preferably 0.20 to 0.55 mu m, more preferably 0.20 to 0.42 mu m. Such a copper foil may be rolled by adjusting the equivalent film amount of the rolling oil to perform rolling (high gloss rolling) or by adjusting the surface roughness of the rolling roll (for example, measuring in the direction perpendicular to the circumferential direction of the roll The arithmetic average roughness Ra (JIS B0601) of the surface of the rolled roll can be set to 0.01 to 0.25 mu m. When the arithmetic mean roughness Ra of the rolled roll surface is large, the roughness Rz of the TD of the copper foil is When the value of the arithmetic average roughness Ra of the surface of the rolled roll is small, the roughness Rz of the TD of the copper foil tends to be small and the glossiness tends to be high), or , Chemical polishing such as chemical etching, or electrolytic polishing in a phosphoric acid solution. By setting the surface roughness (Rz) and the gloss of the TD of the copper foil before the treatment to the above-mentioned range in this manner, the surface roughness (Rz) and the surface area of the copper foil after the treatment can be easily controlled.

The copper foil before surface treatment preferably has a 60 degree glossiness of TD of 300 to 910%, more preferably 500 to 810%, and further preferably 500 to 710%. If the 60 degree glossiness of the MD of the copper foil before the surface treatment is less than 300%, the transparency of the above-mentioned resin may be worse than that of 300% or more, and if it exceeds 910%, the problem that the production becomes difficult There is a concern.

The high gloss rolling can be carried out by setting the oil film equivalent as defined by the following formula to 10000 to 24000 or less.

(Yielding pressure [kg / mm &lt; 2 &gt;]) of the material = {(rolling oil viscosity [cSt]) x (passing speed [mpm] + roll main speed [mpm])} }

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

In order to make the oil film equivalent to 10000 to 24000, a known method may be used, such as using low-viscosity rolling oil or slowing the passing speed.

The chemical polishing is carried out for a long time by lowering the concentration by an etching solution such as a sulfuric acid-hydrogen peroxide-water system or an ammonia-hydrogen peroxide-water system.

It is also preferable that the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured by the contact-type roughness meter is 0.6 탆 or less. If the standard deviation of the surface roughness Rz of the surface of the ultra-thin copper layer measured using the contact-type roughness meter according to JIS B0601-1982 is more than 0.6 mu m, there is a possibility that the deviation of the etching property becomes large. The standard deviation of the surface roughness Rz is more preferably 0.5 mu m or less, more preferably 0.4 mu m or less, still more preferably 0.3 mu m or less, still more preferably 0.25 mu m or less, still more preferably 0.2 mu m or less, More preferably 0.15 mu m or less, and further preferably 0.1 mu m or less. The lower limit of the standard deviation is not particularly limited, but is, for example, 0.001 m or more, for example, 0.005 m or more, for example, 0.01 m or more.

The term &quot; ultra-thin copper layer surface &quot; relating to the surface roughness Rz of the surface of the ultra-thin copper layer and the standard deviation thereof in the present invention means that the surface of the ultra-thin copper layer is coated with the roughened layer and / Or a surface treatment layer such as a chromate treatment layer and / or a silane coupling treatment layer is formed, it means the outermost surface of the surface treatment layer.

In addition, when the surface treatment layer is formed on the surface of the ultra-thin copper layer, the standard deviation of the surface roughness Rz can be reduced by keeping the distance between the copper foil with the carrier (electrode distance) have.

As a method for maintaining the distance (distance between the electrodes) to the electrode uniformly closer to the conventional one, a negative electrode may be used for the negative electrode, or a distance between the transport rolls may be reduced (for example, 200 to 500 mm) (For example, 3 kgf / mm &lt; 2 &gt; or more) and the like.

In one aspect of the present invention, the color difference DELTA L based on JIS Z8730 on the surface of the ultra-thin copper layer is controlled to be -40 or less. When the color difference DELTA L based on JIS Z8730 on the surface of the ultra-thin copper layer is -50 or less as described above, 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 of the circuit with the ultra-thin copper layer becomes clear, As a result, the visibility is improved, and alignment of the circuit can be performed with good precision. The color difference DELTA L based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably -45 or less, more preferably -50 or less.

It is preferable that the color difference? A based on JIS Z8730 on the surface of the ultra-thin copper layer of the carrier copper foil of the present invention is controlled to 20 or less. When the color difference? A based on JIS Z8730 on the surface of the ultra-thin copper layer is 20 or less as described above, 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 of the circuit with the ultra- As a result, the visibility becomes better, and the alignment of the circuit can be performed with good precision. The color difference? A based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

It is preferable that the color difference? B based on JIS Z8730 on the surface of the ultra-thin copper layer of the carrier copper foil of the present invention is controlled to 20 or less. When the color difference &quot; b &quot; based on JIS Z8730 on the surface of the ultra-thin copper layer 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 of the circuit with the ultra- As a result, the visibility becomes better, and the alignment of the circuit can be performed with good precision. The color difference? B based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

In another aspect of the present invention, the color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is controlled to 45 or more. When the color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more as described above, 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 of the circuit with the ultra- As a result, visibility is improved, and alignment of the circuit can be performed with good precision. The color difference? E * ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more. In the present invention, the &quot; ultra-thin copper layer surface &quot; regarding the color differences DELTA L, DELTA a, DELTA b and DELTA E * ab based on JIS Z8730 on the surface of the ultra- Or a surface treatment layer such as a heat resistant layer and / or an anticorrosion layer and / or a chromate treatment layer and / or a silane coupling treatment layer is formed, it means the outermost surface of the surface treatment layer.

Here, the above-described color differences? L,? A, and? B are measured as colorimeters, and the composite indexes represented by using the L * a * b colorimetric system based on JIS Z8730 in addition to black / white / red / green / , ΔL is black and white, Δa is reddish, and Δb is white. ? E * ab is expressed by the following equation using these color differences.

The above-mentioned color difference can be adjusted by controlling the plating conditions for forming the ultra-thin copper layer or by adjusting the surface of the ultra-thin copper layer to form the roughened treatment layer.

In the case of adjusting the above-described color difference by controlling the plating conditions for forming the ultra-thin copper layer, electrolytic plating is used. In that case, the ultra-thin copper layer can be produced by the following electrolyte composition and manufacturing conditions. The above-mentioned color difference can be adjusted by increasing the current density at the time of forming the ultra-thin copper layer and / or decreasing the copper concentration in the plating liquid and / or increasing the linear flow rate of the plating liquid.

<Electrolyte Composition>

Copper: 90 ~ 110 g / ℓ

Sulfuric acid: 90 to 110 g / l

Chlorine: 50 to 100 ppm

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

Leveling second (amine compound): 10 to 30 ppm

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

(2)

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

<Manufacturing Conditions>

Current density: 70 to 100 A / dm 2

Electrolyte temperature: 50 to 60 ° C

Electrolyte flux: 3 ~ 5 m / sec

Electrolysis time: 0.5 to 10 minutes

On the other hand, when the above-described color difference is adjusted by applying a roughening treatment to the surface of the ultra-thin copper layer to form a roughened treatment layer, the roughening treatment can be carried out by forming roughened particles with, for example, copper or a copper alloy have. The harmonic treatment may be fine. The roughening treatment layer may be a layer made of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc or an alloy including at least one of them. It is also possible to carry out a harmonizing treatment for forming secondary particles or tertiary particles with nickel, cobalt, copper, zinc alone, or an alloy of nickel, cobalt, zinc, or the like after the roughening particles are formed of copper or a copper alloy.

The above-mentioned color difference can be obtained by using a plating solution containing at least one element selected from the group consisting of copper, nickel, cobalt, tungsten, molybdenum and phosphorus in the case of forming the roughened layer, (For example, 38 to 60 A / dm 2) and the treatment time is shortened (for example, 0.1 to 1.5 seconds).

For example, the copper-cobalt-nickel alloy plating as the roughening treatment for controlling the above-described color difference is preferably a copper-cobalt-nickel alloy plating having a coating amount of 15 to 40 mg / dm 2 of copper and 100 to 3000 쨉 g / A ternary alloy layer of nickel of -100 to 1500 占 퐂 / dm 2 can be formed.

An example of a plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:

Plating bath composition: 10 to 20 g / l of Cu, 1 to 10 g / l of Co, 1 to 10 g / l of Ni

pH: 1-4

Temperature: 30 ~ 50 ℃

Current density D _k : 38 to 55 A / dm 2

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

In the case of forming an alloy plating layer containing Ni (for example, Ni-W alloy plating, Ni-Co-P alloy plating, or Ni-Zn alloy plating) instead of roughening treatment as described above, The concentration of Ni is set to twice or more the concentration of other elements, the current density is reduced to 0.1 to 2 A / dm 2, and the plating time is made 20 seconds or longer (for example, 20 seconds to 40 seconds) Can be adjusted.

Further, the copper foil with the carrier having the carrier and the ultra-thin copper layer laminated on the carrier and laminated on the intermediate layer is provided with a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment Layer may be provided.

A heat resistant layer and a rustproof layer may be provided on the roughened layer, a chromate treated layer may be provided on the heat resistant layer and the rustproof layer, and a silane coupling treatment layer may be provided on the chromated layer.

The copper foil with a carrier may be provided with a resin layer on the extremely thin copper layer, on the roughened layer, or on the heat resistant layer, the rust prevention layer, the chromate treatment layer, or the silane coupling treatment layer. The resin layer may be an insulating resin layer.

The copper foil with a carrier may be provided with a roughened treatment layer on the carrier, and one or more layers selected from the group consisting of a roughened treatment layer, a heat resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer You can. The above-mentioned roughening treatment layer, heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer may be formed by a known method, or may be formed by the method described in the present specification, claims and drawings. The formation of at least one layer selected from the above-mentioned roughening treatment layer, heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer in the carrier means that the carrier is supported on a support such as a resin substrate It has an advantage that the carrier and support do not peel off easily.

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

The resin layer may include a thermosetting resin or a thermoplastic resin. 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 or the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP- , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, JP-A-2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A- 2004-82687, 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication No. 4178415, International Publication Japanese Patent Application Laid-Open Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207, Japanese Patent Application Laid-Open No. 2009-71817, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Patent Publication No. International Publication Nos. WO2008 / 114858, WO2009 / 008471, JP-A-2011-14727, WO009 / 001850, WO2009 / 145179, WO2011 / 068157, JP-A-2013-19056 (Resin, curing accelerator, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton, etc.) and / or a method of forming a resin layer and a forming apparatus .

The type of the resin layer is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleic acid resin, (Also referred to as polyether sulfone, polyether sulfone), polyether sulfone (also referred to as polyether sulfone, polyether sulfone) resin, aromatic polyamide resin, aromatic polyamide resin But are not limited to, resin polymers, rubber resins, polyamines, aromatic polyamines, polyamideimide resins, rubber modified epoxy resins, phenoxy resins, carboxyl group modified acrylonitrile-butadiene resins, polyphenylene oxides, bismaleimide triazine resins, A cyanate ester resin, a carboxylic acid (4-cyanatophenyl) propane, a phosphorus-containing phenol compound, a manganese naphthenate, a 2,2-bis (4-cyanatophenyl) propane, an anhydride, a polyhydric carboxylic acid anhydride, Modified polyamide-imide resin, cyanoester resin, phosphazene-based resin, rubber-modified polyamideimide resin, isoprene, hydrogenated poly (vinylidene fluoride) Resins containing at least one member selected from the group consisting of butadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerized polyimide resin and cyanoester resin can be exemplified .

The above-mentioned epoxy resin can be used without particular problems, as long as it has two or more epoxy groups in the molecule and can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, Epoxy resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, canceled bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, Glycidyl amine compounds such as triglycidyl isocyanurate and N, N-diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl type epoxy Resin, biphenyl novolak type epoxy resin, trishydroxyphenyl methane type epoxy resin, and tetraphenyl ethane type epoxy resin It may may be used by mixing one or two or more, or using a hydrogenating chena halogenated product of the epoxy resin.

An epoxy resin containing phosphorus known as phosphorus-containing epoxy resin may be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule desirable.

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

The resin layer may include a dielectric (dielectric filler).

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

The dielectric (dielectric filler) may be in powder form. When the dielectric material (dielectric filler) is in the form of powder, it is preferable that the powder characteristic of the dielectric material (dielectric filler) has a particle diameter in the range of 0.01 mu m to 3.0 mu m, preferably 0.02 mu m to 2.0 mu m. Further, when a dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particles in the photograph, the length of the dielectric particles in the longest straight line crossing the dielectric particles is expressed by Diameter of the dielectric particles. Then, the average value of the diameters of the dielectric particles in the measurement field is taken as the diameter of the dielectric.

The resin and / or the resin composition and / or the compound contained in the resin layer described above may be dissolved in a solvent such as methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, , Ethanol, propylene glycol monomethyl ether, dimethyl formamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, (Resin varnish) by dissolving it in a solvent such as acetone or amide to form a resin solution (resin varnish), which is applied to the surface of the ultra-thin copper layer side of the copper foil with a carrier by a roll coating method or the like, And B stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved by using a solvent, and the resin solid content is 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 may be used. Further, it is most preferable to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone from the environmental viewpoint at the present stage. It is preferable to use a solvent having a boiling point in the range of 50 to 200 占 폚.

It is preferable that the resin layer is a semi-cured resin film having a resin flow in a range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.

In the present specification, the resin flow refers to four samples of 10 cm in length and 10 cm from a resin-coated surface-treated copper foil having a resin thickness of 55 탆 in accordance with MIL-P-13949G in the MIL standard, The sample was laminated in a stacked state under conditions of a press temperature of 171 DEG C, a press pressure of 14 kgf / cm &lt; 2 &gt;, and a press time of 10 minutes. From the result of measurement of the resin outflow weight at that time, Value.

The surface-treated copper foil having the resin layer (resin-coated surface-treated copper foil) is formed by superimposing the resin layer on the base material and thermally pressing the entire body to thermally cure the resin layer, In the case of an ultra-thin copper layer of a foil, the carrier is peeled to expose the ultra-thin copper layer (of course, the exposed surface is the surface of the intermediate layer side of the ultra-thin copper layer) To form a predetermined wiring pattern.

The use of this resin-coated surface-treated copper foil can reduce the number of prepreg materials used in the production of a multilayer printed wiring board. In addition, the copper clad laminate can be produced even if the thickness of the resin layer is set to a thickness sufficient for ensuring interlayer insulation or the prepreg material is not used at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is simplified, which is economically advantageous. Further, the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is It is possible to produce an ultra-thin multilayer printed circuit board having a thickness of 100 m or less in one layer.

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

When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered. When the resin-coated surface-treated copper foil is laminated on the substrate having the inner layer material without interposing the prepreg material, It may be difficult to ensure insulation. On the other hand, if the thickness of the resin layer is made larger than 120 占 퐉, it is difficult to form a resin layer having a desired thickness by one coating step, and economical disadvantage may be caused due to the extra material cost and the number of steps.

When the surface-treated copper foil having a resin layer is used for producing a very thin multilayered printed circuit board, the thickness of the resin layer is preferably 0.1 to 5 占 퐉, more preferably 0.5 to 5 占 퐉, The thickness of 1 mu m to 5 mu m is preferable in order to reduce the thickness of the multilayered printed circuit board.

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

An electronic apparatus may be manufactured using the printed wiring board, an electronic apparatus may be manufactured using a printed circuit board on which the electronic apparatus is mounted, or an electronic apparatus may be manufactured using the printed board on which the electronic apparatus is mounted . Hereinafter, several examples of the manufacturing process of the printed wiring board using the copper foil with a carrier according to the present invention are shown.

In one embodiment of the method for producing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to the present invention; laminating the copper foil with the carrier and the insulating substrate; And the insulating substrate are laminated so that the extremely thin copper layer side faces the insulating substrate and then the carrier of the copper foil with the carrier is peeled off to form a copper clad laminate. Thereafter, a semi-additive process, a modified semi-additive Method, a pattern additive method, and a subtractive method. It is also possible that the insulating substrate contains an inner layer circuit.

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

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

.

In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, a copper thickness is formed in the circuit forming portion by electrolytic plating, And a metal foil other than the circuit forming portion is removed by (flash) etching to form a circuit on the insulating layer.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

A step of removing the plating resist,

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

.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

A step of removing the ultra-thin copper layer in a region other than the region where the circuit is formed by flash etching or the like

.

In the present invention, the palladium additive method is a method in which a catalyst core is provided on a substrate on which conductor layers are formed and, if necessary, punched holes for through-holes or via holes, etched to form conductor circuits, A solder resist or a plating resist is formed if necessary, and thereafter the thickness is formed by electroless plating (through electrolytic plating, if necessary) on a through hole or a via hole on the conductor circuit to produce a printed wiring board Method.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

Removing the ultra-thin copper layer and the catalyst core by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit;

A step of removing the etching resist,

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

A step of forming an electroless plating layer in a region where the solder resist or the plating resist is not formed

.

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

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

A step of forming an electroplating layer on the surface of the electroless plating layer,

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

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

Removing the extremely thin copper layer, the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit,

A step of removing the etching resist

.

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

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

A step of peeling the carrier of the copper foil with the carrier after the lamination of the copper foil with the carrier and the insulating substrate,

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

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

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

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

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

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

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

Removing the extremely thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit,

A step of removing the etching resist

.

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

Here, specific examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings. Although the copper foil with a carrier having an ultra-thin copper layer formed with a roughened treatment layer is described here as an example, the copper foil with a carrier having an ultra-thin copper layer on which no roughened treatment layer is formed is not limited thereto. A manufacturing method of a printed wiring board can be carried out.

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

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

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

Next, as shown in Fig. 2-D, a resin layer is formed on the extremely thin copper layer so as to cover the circuit plating (so that the circuit plating is buried) to laminate the resin layers, ) From the ultra-thin copper layer side.

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

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

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

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

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

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

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

The copper foil with a carrier of the present invention may be used as the copper foil with the other carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, one or more layers may be additionally formed on the second layer circuit shown in FIG. 3-H. The circuit formation may be performed by a semi-additive method, a subtractive method, a pattern additive method, And a semi-additive method.

The copper foil with a carrier used in the first layer may have a substrate on the carrier-side surface of the copper foil with the carrier. By having such a substrate, copper foil with a carrier used for the first layer is supported, and wrinkles are not formed well, so that there is an advantage that productivity is improved. Further, all the substrates can be used as long as they have the effect of supporting the copper foil with a carrier used in the first layer. For example, the substrate may be 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, You can use pak.

The timing for forming the substrate on the carrier-side surface is not particularly limited, but it is necessary to form the carrier before peeling off. Particularly, it is preferable to form it before the step of forming the resin layer on the surface of the ultra thin copper layer side of the carrier-coated copper foil, and it is more preferable to form it before the step of forming the circuit on the ultra-thin copper layer side surface of the carrier- .

In the copper foil with a carrier according to the present invention, the color difference on the surface of the ultra-thin copper layer is controlled, so the contrast with the circuit plating is clear and the visibility is good. Therefore, for example, in the above-described printed wiring board, it is possible to form the circuit plating at a predetermined position with good precision in the manufacturing process as shown in Fig. 1-C. According to the above-described method for producing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in, for example, The circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of the fine circuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved and conduction of the circuit wiring is well suppressed. Therefore, formation of a fine circuit is facilitated. In addition, as shown in Figs. 4-J and 4-K, when the extremely thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes a depressed form from the resin layer, The copper filler is easily formed thereon, and the production efficiency is improved.

Known resins and prepregs can be used for the buried resin (resin). For example, glass cloth prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The embedding resin may include a thermosetting resin, or may be a thermoplastic resin. The embedding resin may include a thermoplastic resin. The type of the above-mentioned reclaimed resin is not particularly limited. For example, an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, a block copolymerized polyimide resin, Polyimide resin, etc. Paper base phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass nonwoven composite base material epoxy resin and glass cloth base Epoxy A resin, a polyester film, a polyimide film, a liquid crystal polymer film, a fluororesin film, and the like.

&Lt; Peel strength (N / m) &gt;

The copper foil with a carrier of the present invention is characterized in that an extremely thin copper layer side is formed on an insulating substrate at a temperature of 220 占 폚 at a pressure of 20 kgf / cm 2 in an atmosphere, (1) (3) heating at 220 캜 for 2 hours in air at a pressure of 20 kgf / cm 2, followed by thermocompression bonding, and then (2) The carrier side was pulled by a load cell after heating at 180 ° C for 1 hour under atmospheric pressure (that is, in a state where no pressure was applied and at atmospheric pressure) in a nitrogen atmosphere, and peeling the ultra-thin copper layer in accordance with JIS C 6471 , The peel strength is preferably 2 to 100 N / m. If the peel strength is less than 2 N / m, the extremely thin copper layer may peel off from the carrier during the production of the printed wiring board. If the peel strength is more than 100 N / m, unnecessary force may be applied at the time of peeling. For example, There is a risk of peeling off at the interface between the buried resin and the ultra-thin copper layer in one embedding method (Embedded Process). The peel strength is more preferably 2 to 50 N / m, and still more preferably 2 to 20 N / m.

Example

The following is a description based on examples and comparative examples. Note that this embodiment is merely an example, and is not limited to this example.

1. Preparation of copper foil with carrier

As the carrier, elongated electrolytic copper foils or rolled copper foils having the thicknesses shown in Tables 1, 3 and 4 were prepared.

Electrolytic copper foils were produced under the conditions described in Tables 1, 3 and 4, or using JTC foils manufactured by JX Nikkoseki Metal Co., Ltd.

The rolled copper foil was prepared as follows. A predetermined copper ingot was produced and subjected to hot rolling. Annealing and cold rolling of the continuous annealing line at 300 to 800 占 폚 were repeated to obtain a rolled plate having a thickness of 1 to 2 mm. The rolled sheet was subjected to annealing in a continuous annealing line at 300 to 800 캜, followed by recrystallization and final cold rolling to the thicknesses of Tables 1, 3 and 4 to obtain a copper foil. Tables 1, 3 and 4 show the rolling conditions (high gloss rolling or normal rolling, film equivalent) at this time. Quot; high gloss rolling &quot; and &quot; ordinary rolling &quot; mean that the final cold rolling (cold rolling after final recrystallization annealing) is carried out at the oil film equivalent values shown in Tables 1, 3 and 4, respectively. The "tough pitch copper" in Tables 1, 3 and 4 represents tough pitch copper specified in JIS H3100 C1100. &Quot; Anoxic copper &quot; in Tables 1, 3 and 4 indicates oxygen free copper specified in JIS H3100 C1020. &Quot; ppm &quot; of the additive elements described in Tables 1, 3, and 4 indicates ppm by mass. For example, &quot; tough pitch copper + Ag 180 ppm &quot; in the carrier type column in Tables 1, 3, and 4 means that 180 mass ppm of Ag is added to tough pitch copper.

The shiny side (shiny side) of the copper foil was electroplated with a roll, a roll and a continuous plating line under the following conditions to form an intermediate layer.

&Quot; Ni &quot;: Nickel plating

(Liquid composition) Nickel sulfate: 270 to 280 g / l, nickel chloride: 35 to 45 g / l, nickel acetate: 10 to 20 g / l, boric acid: 15 to 25 g / 5 to 15 ppm, sodium dodecyl sulfate: 55 to 75 ppm

(pH) 4 to 6

(Liquid temperature) 55 to 65 ° C

(Current density) 1 to 11 A / dm &lt; 2 &gt;

(Energization time) 1 to 20 seconds

· "Ni-Zn": Nickel zinc alloy plating

In the formation condition of the nickel plating, zinc in the form of zinc sulfate (ZnSO ₄ ) was added to the nickel plating solution and adjusted to a zinc concentration of 0.05 to 5 g / l to form a nickel zinc alloy plating.

"Cr": Chrome plating

(Liquid composition) CrO ₃ : 200 to 400 g / l, H ₂ SO ₄ : 1.5 to 4 g / l

(pH) 1 to 4

(Liquid temperature) 45 to 60 DEG C

(Current density) 10 to 40 A / dm 2

(Energization time) 1 to 20 seconds

· "Chromate": electrolytic pure chromate treatment

(Liquid composition) Potassium dichromate: 1 to 10 g / l, zinc: 0 g / l

(pH) 7 to 10

(Liquid temperature) 40 to 60 DEG C

(Current density) 0.1 to 2.6 A / d &lt;

(Coulomb amount) 0.5 to 90 As / dm 2

(Energization time) 1 to 30 seconds

· "Zn-chromate": Zinc chromate treatment

The electrolytic chromate treatment was carried out by adding zinc in the form of zinc sulfate (ZnSO ₄ ) to the solution and adjusting the zinc concentration to a range of 0.05 to 5 g / l.

· "Ni-Mo": Nickel molybdenum alloy plating

(Liquid composition) Ni sulfate hexahydrate: 50 g / dm 3, sodium molybdate dihydrate: 60 g / dm 3, sodium citrate: 90 g / d 3

(Liquid temperature) 30 DEG C

(Current density) 1 to 4 A / dm 2

(Energization time) 3 to 25 seconds

&Quot; Organic &quot;: Organic layer formation treatment

And spraying an aqueous solution containing a carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / l at a liquid temperature of 40 DEG C and a pH of 5 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 / d 3

(Liquid temperature) 30 DEG C

(Current density) 1 to 4 A / dm 2

(Energization time) 3 to 25 seconds

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

(Liquid composition) Ni: 30 to 70 g / l, P: 0.2 to 1.2 g / l

(pH) 1.5 to 2.5

(Liquid temperature) 30 to 40 DEG C

(Current density) 1.0 to 10.0 A / d &lt;

(Energization time) 0.5 to 30 seconds

Subsequently, on the roll-to-roll type continuous plating line, an ultra-thin copper layer having a thickness described in Tables 1, 3 and 4 was formed on the intermediate layer by electroplating under the conditions shown in the table to prepare a copper foil with a carrier.

The surface of the above-mentioned ultra-thin copper layer was subjected to surface treatment under the surface treatment conditions (surface treatments 1 to 3) shown in Tables 2, 5 and 6. Here, FIG. 5 shows a schematic view of the electrolytic plating process using the thin foil conveying method with respect to the surface treatment method. Fig. 6 shows a schematic diagram of an electrolytic plating process using a foil conveying method by phrase binding. In Examples and Comparative Examples described as &quot; drums &quot; for the surface treatment method, the surface treatments 1 to 3 were each treated with a &quot; drum &quot;. Similarly, in the examples and comparative examples described as &quot; phrase chapters &quot;, the surface treatments 1 to 3 were each subjected to "phrase chapters".

For the copper foil with a carrier of Examples 3, 5, 7, and 10 to 18, heat treatment, chromate treatment and silane coupling treatment as described below were performed on the surface treatment layer.

In Example 20, only heat-resistant treatment was carried out. In Example 22, only a chromate treatment was carried out. For Example 24, only silane coupling treatment was performed. For Examples 1 and 26, chromate treatment and silane coupling treatment were carried out in this order.

· Heat treatment (forming heat resistant layer)

Liquid composition: nickel 5 to 20 g / l, cobalt 1 to 8 g / l

pH: 2-3

Solution temperature: 40 to 60 ° C

Current density: 5 to 20 A / dm 2

Coulomb amount: 10 ~ 20 As / d㎡

Chromate treatment (forming a chromate treatment layer)

Liquid composition: Potassium dichromate 1 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0 to 2 A / dm 2 (for immersion chromate treatment)

Coulomb amount: 0 to 2 As / dm 2 (for immersion chromate treatment)

Silane coupling treatment (forming a silane coupling treatment layer)

A silane coupling agent coating treatment was carried out by spraying an aqueous solution of pH 7 to 8 and 60 DEG C containing 0.2 to 2 mass% of alkoxysilane.

Table 7 shows the plating bath of the surface treatment and Table 8 shows the plating bath of the ultra-thin copper layer formation.

2. Evaluation of copper foil with carrier

Various evaluations were carried out for each of the samples prepared as described above and the comparative example as follows.

Measurement of surface color difference;

When the surface of the ultra-thin copper layer of the copper foil with a carrier (heat-resistant treatment, chromate treatment, and silane coupling treatment is performed using a color difference system MiniScan XE Plus manufactured by HunterLab Co., Ltd., according to JIS Z8730, , The color differences DELTA L, DELTA a, DELTA b and DELTA E * ab of white color were measured. In the above-mentioned color difference meter, the color difference is calibrated by setting the measurement value when the measurement value of the white plate is covered with the black encapsulation of DELTA E * ab = 0 and the measurement value in the dark place is DELTA E * ab = 90. Among them,? E * ab was measured on the basis of the following formula as? L: black and white,? A: red color, and? B: white color using the L * a * b color system. Here, the color difference [Delta] E * ab is defined as zero for white and 90 for black;

The color differences DELTA L, DELTA a, DELTA b, and DELTA E * ab based on JIS Z8730 of a micro area such as a copper circuit surface can be measured by using a micro face spectrophotometer (model: VSS400) manufactured by Nippon Seimei Kogyo Co., The measurement can be carried out by using a known measuring device such as a microscopic-surface-side spectrophotometer (type: SC-50 占 or the like).

The amount of metal deposited in the middle layer;

The nickel deposition amount was measured by ICP emission spectrometry using an ICP emission spectrochemical analyzer (model: SPS3100) manufactured by SII, and the sample was dissolved in nitric acid at a concentration of 20 mass% Phosphoric acid concentration of 7% by mass, and subjected to quantitative analysis by atomic absorption spectrometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by Varian Co. The amount of molybdenum deposition was measured by mixing the sample in a mixed solution of nitric acid and hydrochloric acid (Concentration of nitric acid: 20% by mass, concentration of hydrochloric acid: 12% by mass) and quantitatively analyzed by atomic absorption spectrometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. The nickel, zinc, chromium, and molybdenum adhesion amounts were measured as follows. First, after peeling the ultra-thin copper layer from the copper foil with a carrier, only the vicinity of the surface of the ultra-thin copper layer on the intermediate layer side was dissolved (when the thickness of the ultra-thin copper layer was 1.4 mu m or more, And when the thickness of the ultra-thin copper layer is less than 1.4 m, only 20% of the thickness of the ultra-thin copper layer is dissolved from the surface of the ultra-thin copper layer on the side of the intermediate layer) . After the extremely thin copper layer is peeled off, only the vicinity of the surface of the carrier on the intermediate layer side is dissolved (only 0.5 탆 thickness from the surface is dissolved), and the adhesion amount of the surface of the carrier on the intermediate layer side is measured. The value obtained by adding together the adhesion amount of the surface of the extremely thin copper layer on the intermediate layer side and the adhesion amount of the surface of the carrier on the intermediate layer side was regarded as the metal adhesion amount of the intermediate layer.

When the sample is not well dissolved in the nitric acid having the concentration of 20% by mass or the hydrochloric acid having the concentration of 7% by mass, the sample is mixed with a mixture of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% After dissolution, the adhesion amount of nickel, zinc, and chromium can be measured by the above-described method.

The &quot; metal adhesion amount &quot; refers to the metal adhesion amount (mass) per unit area of the sample (1 dm 2).

· Organic matter thickness in the middle layer

After the extremely thin copper layer of the copper foil with a carrier was peeled from the carrier, the surface of the intermediate layer side of the exposed ultra-thin copper layer and the surface of the intermediate layer side of the exposed carrier were measured by XPS to prepare a depth profile. The depth at which the carbon concentration first became 3 at% or less from the surface of the intermediate layer side of the ultra-thin copper layer was A (nm), and the depth at which the carbon concentration was 3 at% or less for the first time from the surface of the intermediate layer side of the carrier was B (Nm), and the sum of A and B is defined as the thickness (nm) of the organic material in the intermediate layer.

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 this embodiment, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (in terms of SiO ₂ ) (the sputtering time was measured at 0.1 minute intervals).

The depth profile of the carbon concentration by the XPS measurement was obtained by measuring the depth profile of the carbon concentration from the both ends to the surface of the intermediate layer side of the exposed ultra thin copper layer and the surface of the intermediate layer side of the exposed carrier, The surface on the intermediate layer side of the exposed ultra thin copper layer, and the surface on the intermediate layer side of the exposed carrier in total, three points in total of one point in the area of 50 mm x 50 mm in the center part, So that a total of six points were created. Fig. 8 shows measurement points at three points on the surface of the intermediate layer side of the exposed ultra-thin copper layer and on the surface of the intermediate layer side of the exposed carrier. Subsequently, from the depth profile created for the surface of the intermediate layer side of the exposed ultra-thin copper layer and the area of each of the three points on the exposed intermediate layer side of the carrier, The depth A (nm) at which the concentration is 3 at% or less and the depth B (nm) at which the carbon concentration is first made to be 3 at% or less from the surface of the intermediate layer side of the carrier are calculated and the arithmetic average value of A The sum of the arithmetic average values of B (nm) was defined as the thickness (nm) of the organic matter in the intermediate layer.

When the size of the sample is small, the area within 50 mm from both ends and the area of 50 mm x 50 mm at the center may be overlapped.

The operating conditions of the XPS are shown below.

Device: XPS measuring device (NBP, type 5600MC)

• Approaching degree of vacuum: 3.8 × 10 ^-7 Pa

· X-ray: monochromatic AlKα or non-tinted MgKα, x-ray output 300 W, detection area 800 μm φ, angle between sample and detector 45 °

Ion line: ion species Ar ⁺ , accelerating voltage 3 kV, sweep area 3 mm 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )

XPS means X-ray photoelectron spectroscopy. In the present invention, it is premised to use an XPS measuring apparatus (model 5600MC or equivalent measurement apparatus manufactured and sold by ULVAC FIBER) of ULVACPY Co., Ltd. However, when such a measuring apparatus can not be obtained, Other XPS measurement apparatuses may be used when the measurement interval of the concentration is 0.10 to 0.30 nm (in terms of SiO ₂ ) and the sputtering rate is 1.0 to 3.0 nm / min (in terms of SiO ₂ ).

Ni deposition amount on the surface of the ultra-thin copper layer;

The copper foil with the carrier was attached to a BT resin (triazine-bismaleimide-based resin, Mitsubishi Gas Chemical Co., Ltd.) on the ultra-thin copper layer side and heat-pressed at 220 캜 for 2 hours. Thereafter, the extremely thin copper layer was peeled from the copper foil carrier in accordance with JIS C 6471 (Method A). Subsequently, the Ni deposition amount on the surface of the intermediate layer side of the ultra-thin copper layer was measured by dissolving the sample with nitric acid having a concentration of 20 mass% and ICP emission spectrometry (model: SPS3100) manufactured by SII to perform ICP emission analysis. When the surface of the ultra-thin copper layer on the side opposite to the surface on the intermediate layer side is subjected to a surface treatment containing Ni, only the vicinity of the surface on the intermediate layer side of the ultra-thin copper layer is dissolved (the thickness of the ultra-thin copper layer is 1.4 占 퐉 or more Only the thickness of 0.5 탆 is melted from the surface of the intermediate layer side of the ultra-thin copper layer, and when the thickness of the ultra-thin copper layer is less than 1.4 탆, only 20% of the thickness of the ultra-thin copper layer is dissolved from the surface of the ultra- , It is possible to measure the amount of Ni deposited on the surface of the intermediate layer side of the extremely thin copper layer.

Etching properties;

The obtained copper foil with a carrier and a substrate (GHPL-832 NX-A, manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.05 mm x 4 sheets) were laminated and heated and pressed at 220 캜 for 2 hours. Then, the copper foil carrier was peeled off, So that the sample size was 250 x 250 mm &lt; 2 &gt;. The amount of each thickness of the ultra-thin copper layer was adjusted with an aqueous sulfuric acid-peroxide solution (SE07, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the entire surface was etched using a small etching machine (small half etching apparatus No. K-07003 manufactured by Nippon Respectively. Then, the etchability of the copper foil with a carrier was evaluated by the number of times of etching required until the resin was exposed on the entire surface. The etching conditions at this time are shown below.

 (Etching condition)

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

The temperature of the etching solution was controlled at 35 占 占 폚.

Spray pressure: 0.1 MPa (Spraying was performed so that the etching solution reached perpendicularly to the copper layer to be etched.)

Etching rate (etching equivalent): 0.3 占 퐉 / times (30 seconds per one etching machine)

The above-mentioned sulfuric acid-peroxygenated aqueous solution: an amount capable of etching each thickness to the ultra-thin copper layer by SE-07 manufactured by Mitsubishi Gas Chemical Company was previously measured with a total of electrolytic copper foil JTC (thickness: 35 m) manufactured by JX Nikkoseki Petroleum Metals & The relationship between the etching amount (reduction amount of the copper layer thickness) measured by the weight method of the electrolytic copper foil JTC when the surface was etched and the etching time at that time was obtained with the graph shown in FIG. 7, And the etching amount (reduction amount of the copper layer thickness) was estimated by the etching time actually taken.

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

Etching amount (decrease amount of the copper layer thickness) (㎛) = (weight before etching (g)) - (weight after etching (g)) / (etching area (㎛ ²⁾ Density (g / ㎛ ³⁾ of copper ×)

Density of copper = 8.96 g / cm 3 = 8.96 × 10 ^-12 g / μm ³ .

Concretely, the relationship between the equivalent thickness of the extremely thin copper layer removed by etching B = the etching time (seconds) x coefficient (= 0.0336) was obtained, and accordingly, the equivalent thickness B of the extremely thin copper layer removed by etching from the etching time was obtained . That is, for example, the equivalent thickness B of the extremely thin copper layer removed by etching means 5 占 퐉 / case where etching is performed for 5 占 퐉 / coefficient? (= 0.0336) = 148.8 seconds.

In this manner, the number of times of etching, the average number of times of etching, and the maximum value and the minimum value of the number of times of etching were measured. Table 10 shows the criterion of the number of times of etching with respect to the thickness of the ultra-thin copper layer and the criterion of the variation of the number of times of etching.

Evaluation of visibility;

A plating resist was coated on the extremely thin copper layer of the copper foil with a carrier of Examples and Comparative Examples, and then electrolytic plating was performed to form a copper plating portion having a size of 20 占 퐉 占 20 占 퐉. Thereafter, after removing the plating resist, an attempt was made to detect the copper plating portion with a CCD camera. Quot ;, &quot;? &Quot;, &quot;? &Quot;, &quot;? &Quot;, &quot; And &quot; x &quot; when it was detected five times or less.

Evaluation of surface roughness;

(1) Surface roughness Rz (10-point average roughness) of the ultra-thin copper layer surface

The surface roughness Rz (stylus) (10 point average roughness) of the surface of the ultra-thin copper layer was measured using a contact roughness tester, Surfcorder SE-3C, manufactured by Kosaka Laboratory Co., Ltd., according to JIS B0601-1982. Rz (stylus) was arbitrarily measured at 10 points, and the average value of Rz (stylus) was taken as the value of Rz (stylus). In addition, the standard deviation of 10 point values was calculated for Rz (stylus).

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

The surface roughness Rz (stylus) of the carrier in the TD direction on the surface of the intermediate layer forming side was measured using a contact roughness meter Surfcorder SE-3C contact type roughness meter manufactured by Kosaka Laboratory Co., Ltd. in accordance with JIS B0601-1982. Rz (stylus) was arbitrarily measured at 10 points, and the average value of Rz (stylus) was taken as the value of Rz (stylus).

The adhesion of the ultra-thin copper layer and the buried resin;

A resist was coated on the roughened layer of the ultra-thin copper layer of the copper foil with a carrier, and exposure and development were carried out, and the resist was etched in a line. Next, Cu plating for the circuit was formed, and then the resist was removed to form circuit plating on the line. Next, a buried resin (BT resin manufactured by Mitsubishi Gas Chemical Co., Ltd. (bismaleimide triazine resin)) was formed on the ultra-thin copper layer so that the circuit plating was buried, and the resin layer was laminated. Subsequently, attempts were made to peel the carrier from the interface with the ultra-thin copper layer, and the number of times of peeling at the interface between the resin layer and the ultra-thin copper layer was measured. Quot ;, &quot; &amp; cir &amp; &quot;, and &quot; &amp; cir &amp; &quot;, respectively, when the number of peels at the interface between the resin layer and the ultra-thin copper layer is 0 in 10 times, &Quot; DELTA &quot; in the case of 4 to 5 times out of 10 times, and &quot; x &quot; in the case of 6 or more out of 10 times.

(%) Of the carrier on the intermediate layer forming side surface in the TD direction

(TD) perpendicular to the rolling direction (the direction of progress of the copper foil at the time of rolling, that is, the width direction) by using a gloss gauge handy gloss meter PG-1 manufactured by Nippon Seisin Kogyo K.K. based on JIS Z8741 ) At an incident angle of 60 degrees was measured. For the electrolytic copper foil, the degree of gloss (%) was measured with respect to the mat surface at an incident angle of 60 degrees in the direction perpendicular to the copper foil transportation direction during the electrolytic treatment (i.e., in the width direction) TD.

Peel strength (N / m)

The copper foil with the carrier was hot-pressed to a BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on the ultra-thin copper layer side under the conditions of 20 kgf / It was a verb. Subsequently, the carrier side was pulled with a tensile tester, and the peel strength was measured when the ultra-thin copper layer was peeled off in accordance with JIS C 6471. (The value is shown in the column of &quot; 220 DEG C, 2 h after baking (N / m) &quot; in Table 9).

Further, after heating at 220 占 폚 for 2 hours, the sample was peeled off under the same conditions except that heating was conducted twice at 180 占 폚 for 1 hour in a nitrogen atmosphere without applying pressure (under normal pressure, i.e., at atmospheric pressure) The strength was measured. (The value is shown in the column of &quot; 180 占 폚, 1 h 占 2 times after baking (N / m) &quot; in Table 9).

Also, for each sample before and after the heat press bonding with the resin (at normal temperature and atmospheric pressure, that is, in the state of the state, the carrier side was pulled with a tensile tester after the adhesive tape was affixed to the resin substrate from the ultra-thin copper layer side, and according to JIS C 6471 The peeling strength when peeling the ultra-thin copper layer was measured (the value is shown in the column "state (N / m)" in Table 9).

(Evaluation results)

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

In Comparative Examples 1 to 9, the color difference DELTA L of the surface of the ultra-thin copper layer was more than -40, the color difference DELTA E * ab of the surface of the ultra-thin copper layer was less than 45, and at least the visibility was poor.

Claims (78)

A carrier-coated copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer (except for the ultra-thin copper layer for a plasma display panel)
Wherein at least one surface layer selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, or an alloy containing any one or more selected from the group consisting of copper, And,
Wherein the color difference DELTA L based on JIS Z8730 on the surface of the ultra thin copper layer is -40 or less. The method according to claim 1,
1. A copper foil with a carrier having a carrier, an intermediate layer and an ultra-thin copper layer in this order,
Wherein the color difference? E * ab based on JIS Z8730 on the surface of the ultra thin copper layer is 45 or more. A carrier-coated copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer (except for the ultra-thin copper layer for a plasma display panel)
Wherein at least one surface layer selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, or an alloy containing any one or more selected from the group consisting of copper, And,
Wherein the color difference? E * ab based on JIS Z8730 on the surface of the ultra thin copper layer is 45 or more. The method according to claim 1,
Wherein the color difference? A based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. 3. The method of claim 2,
Wherein the color difference? A based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. The method of claim 3,
Wherein the color difference? A based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. The method according to claim 1,
Wherein the color difference? B based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. 3. The method of claim 2,
Wherein the color difference? B based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. The method of claim 3,
Wherein the color difference? B based on JIS Z8730 on the surface of the ultra thin copper layer is 20 or less. The method according to claim 1,
Wherein the intermediate layer contains Ni,
Wherein the ultra thin copper layer is peeled off according to JIS C 6471 after heating the copper foil with a carrier at 220 캜 for 2 hours and then the Ni deposition amount of the ultra thin copper layer on the side of the intermediate layer is not less than 5 쨉 g / Mu] g / d &lt; 2 &gt; or less. 3. The method of claim 2,
Wherein the intermediate layer contains Ni,
Wherein the ultra thin copper layer is peeled off according to JIS C 6471 after heating the copper foil with a carrier at 220 캜 for 2 hours and then the Ni deposition amount of the ultra thin copper layer on the side of the intermediate layer is not less than 5 쨉 g / Mu] g / d &lt; 2 &gt; or less. The method of claim 3,
Wherein the intermediate layer contains Ni,
Wherein the ultra thin copper layer is peeled off according to JIS C 6471 after heating the copper foil with a carrier at 220 캜 for 2 hours and then the Ni deposition amount of the ultra thin copper layer on the side of the intermediate layer is not less than 5 쨉 g / Mu] g / d &lt; 2 &gt; or less. 10. The method according to any one of claims 1 to 9,
Wherein the intermediate layer contains Ni,
Wherein the ultra thin copper layer is peeled off according to JIS C 6471 after heating the copper foil with a carrier at 220 캜 for 2 hours and then the Ni deposition amount of the ultra thin copper layer on the side of the intermediate layer is not less than 5 쨉 g / Mu] g / d &lt; 2 &gt; or less. 11. The method of claim 10,
Wherein said ultra thin copper layer has an Ni deposition amount of not less than 5 쨉 g / dm 2 and not more than 250 쨉 g / dm 2 on said intermediate layer side surface of said ultra-thin copper layer when said copper foil with a carrier is heated at 220 캜 for 2 hours, Copper foil with carrier. 15. The method of claim 14,
Wherein the ultra-thin copper layer has an Ni deposition amount of not less than 5 mu g / dm2 and not more than 200 mu g / dm2 on the surface of the intermediate layer side of the ultra-thin copper layer, after heating the copper foil with the carrier at 220 DEG C for 2 hours, Copper foil with carrier. 16. The method of claim 15,
Wherein the ultra thin copper layer has an Ni deposition amount of not less than 5 占 / / dm2 and not more than 150 占 / / dm2 on the surface of the intermediate layer side of the ultra-thin copper layer, after heating the copper foil with the carrier at 220 占 폚 for 2 hours, Copper foil with carrier. 17. The method of claim 16,
Wherein the ultra-thin copper layer has an Ni deposition amount of not less than 5 mu g / dm 2 and not more than 100 mu g / dm 2 on the surface of the intermediate layer side of the ultra-thin copper layer, after heating the copper foil with the carrier at 220 DEG C for 2 hours, Copper foil with carrier. The method according to claim 1,
Wherein the Ni content of the intermediate layer is 100 占 퐂 / dm2 or more and 5000 占 퐂 / dm2 or less. The method according to claim 1,
Wherein the intermediate layer is one or two kinds selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, Copper foil with a carrier. 20. The method of claim 19,
Wherein the intermediate layer contains 5 to 100 占 퐂 / dm2 of Cr when containing Cr and not less than 50 占 퐂 / dm2 and not more than 1000 占 퐂 / dm2 of Mo when containing Mo; , The copper foil with a carrier containing Zn at not less than 1 占 퐂 / dm2 and not more than 120 占 퐂 / dm2. 20. The method of claim 19,
Wherein the intermediate layer contains an organic substance in a thickness of 25 nm or more and 80 nm or less. 20. The method of claim 19,
Wherein the organic material is one or more organic materials selected from a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. The method according to claim 1,
And the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less. 3. The method of claim 2,
And the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less. The method of claim 3,
And the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less. 23. The method according to any one of claims 1 to 12 and 14 to 22,
And the surface roughness Rz of the surface of the ultra-thin copper layer measured using a contact-type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.5 占 퐉 or less. 24. The method of claim 23,
And the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.2 占 퐉 or more and 1.0 占 퐉 or less. 28. The method of claim 27,
And the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is not less than 0.2 占 퐉 and not more than 0.6 占 퐉. The method according to claim 1,
And the standard deviation of the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.6 占 퐉 or less. 3. The method of claim 2,
And the standard deviation of the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.6 占 퐉 or less. The method of claim 3,
And the standard deviation of the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.6 占 퐉 or less. 29. The method according to any one of claims 1 to 12, 14 to 25, 27 and 28,
And the standard deviation of the surface roughness Rz of the surface of the extremely thin copper layer measured using a contact type roughness meter according to JIS B0601-1982 is 0.6 占 퐉 or less. 24. The method of claim 23,
And the standard deviation of the surface roughness Rz is 0.6 占 퐉 or less. 34. The method of claim 33,
And the standard deviation of the surface roughness Rz is 0.4 占 퐉 or less. 35. The method of claim 34,
And the standard deviation of the surface roughness Rz is 0.2 占 퐉 or less. 36. The method of claim 35,
And the standard deviation of the surface roughness Rz is 0.1 占 퐉 or less. The method according to claim 1,
After the insulating substrate is adhered to the surface of the ultra-thin copper layer side of the copper foil with the carrier under normal temperature and pressure, and /
The insulating substrate is thermally compressed in the atmosphere on the surface of the ultra thin copper layer side of the carrier with copper foil by heating at 220 캜 for 2 hours under a pressure of 20 kgf / cm 2, and /
The insulating substrate was thermally pressed on the surface of the copper foil with the carrier on the surface of the ultra-thin copper layer under the pressure of 20 kgf / cm 2 at 220 캜 for 2 hours. Thereafter, After heating for 1 hour twice and then thermocompression bonding,
And a peel strength of 2 to 100 N / m when the extremely thin copper layer is peeled in accordance with JIS C 6471. 3. The method of claim 2,
After the insulating substrate is bonded to the surface of the ultra-thin copper layer side of the copper foil with a carrier under normal temperature and pressure, and /
The insulating substrate is thermally compressed in the atmosphere on the surface of the ultra thin copper layer side of the carrier with copper foil by heating at 220 캜 for 2 hours under a pressure of 20 kgf / cm 2, and /
The insulating substrate was thermally pressed on the surface of the copper foil with the carrier on the surface of the ultra-thin copper layer under the pressure of 20 kgf / cm 2 at 220 캜 for 2 hours. Thereafter, After heating for 1 hour twice and then thermocompression bonding,
And a peel strength of 2 to 100 N / m when the extremely thin copper layer is peeled in accordance with JIS C 6471. The method of claim 3,
After the insulating substrate is bonded to the surface of the ultra-thin copper layer side of the copper foil with a carrier under normal temperature and pressure, and /
The insulating substrate is thermally compressed in the atmosphere on the surface of the ultra thin copper layer side of the carrier with copper foil by heating at 220 캜 for 2 hours under a pressure of 20 kgf / cm 2, and /
The insulating substrate was thermally pressed on the surface of the copper foil with the carrier on the surface of the ultra-thin copper layer under the pressure of 20 kgf / cm 2 at 220 캜 for 2 hours. Thereafter, After heating for 1 hour twice and then thermocompression bonding,
And a peel strength of 2 to 100 N / m when the extremely thin copper layer is peeled in accordance with JIS C 6471. 36. The method according to any one of claims 1 to 12, 14 to 25, 27 to 31 and 33 to 36,
After the insulating substrate is bonded to the surface of the ultra-thin copper layer side of the copper foil with a carrier under normal temperature and pressure, and /
The insulating substrate is thermally compressed in the atmosphere on the surface of the ultra thin copper layer side of the carrier with copper foil by heating at 220 캜 for 2 hours under a pressure of 20 kgf / cm 2, and /
The insulating substrate was thermally pressed on the surface of the copper foil with the carrier on the surface of the ultra-thin copper layer under the pressure of 20 kgf / cm 2 at 220 캜 for 2 hours. Thereafter, After heating for 1 hour twice and then thermocompression bonding,
And a peel strength of 2 to 100 N / m when the extremely thin copper layer is peeled in accordance with JIS C 6471. 39. The method of claim 37,
And the peel strength is 2 to 50 N / m. 42. The method of claim 41,
Wherein the peel strength is 2 to 20 N / m. The method according to claim 1,
And the intermediate layer and the ultra-thin copper layer in this order on both sides of the carrier. 3. The method of claim 2,
And the intermediate layer and the ultra-thin copper layer in this order on both sides of the carrier. The method of claim 3,
And the intermediate layer and the ultra-thin copper layer in this order on both sides of the carrier. The method according to any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 and 42,
And the intermediate layer and the ultra-thin copper layer in this order on both sides of the carrier. The method according to claim 1,
Wherein the copper foil has a roughened treatment layer on at least one surface or both surfaces of the ultra-thin copper layer and the carrier. 3. The method of claim 2,
Wherein the copper foil has a roughened treatment layer on at least one surface or both surfaces of the ultra-thin copper layer and the carrier. The method of claim 3,
Wherein the copper foil has a roughened treatment layer on at least one surface or both surfaces of the ultra-thin copper layer and the carrier. The method according to any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, and 41 to 45,
Wherein the copper foil has a roughened treatment layer on at least one surface or both surfaces of the ultra-thin copper layer and the carrier. 49. The method of claim 47,
Wherein the roughening treatment layer is a layer made of a single or any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, Copper foil. 49. The method of claim 47,
And at least one layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer is provided on the surface of the roughened treatment layer. 51. The method of claim 50,
And at least one layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer is provided on the surface of the roughened treatment layer. The method according to claim 1,
And at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer is provided on at least one surface or both surfaces of the extremely thin copper layer and the carrier. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, and 47 to 49 &Lt;
And at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer is provided on at least one surface or both surfaces of the extremely thin copper layer and the carrier. 44. The method of claim 43,
Wherein at least one layer selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer is provided on one surface or both surfaces of the extremely thin copper layer. 47. The method of claim 46,
Wherein at least one layer selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer is provided on one surface or both surfaces of the extremely thin copper layer. The method according to claim 1,
And a resin layer on the extremely thin copper layer. 3. The method of claim 2,
And a resin layer on the extremely thin copper layer. The method of claim 3,
And a resin layer on the extremely thin copper layer. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, 47 to 49, 51 56. The method according to any one of claims 52, 54 and 56,
And a resin layer on the extremely thin copper layer. 49. The method of claim 47,
And a resin layer on the roughening treatment layer. 49. The method of claim 48,
And a resin layer on the roughening treatment layer. 50. The method of claim 49,
And a resin layer on the roughening treatment layer. 51. The method of claim 50,
And a resin layer on the roughening treatment layer. 53. The method of claim 52,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. 55. The method of claim 54,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. 56. The method of claim 55,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. 58. The method of claim 57,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, 47 to 49, 51 , The copper foil with a carrier according to any one of claims 52, 54, 56, 58 to 60, 62 to 64, 66 and 67, Copper clad laminate produced. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, 47 to 49, 51 , The copper foil with a carrier according to any one of claims 52, 54, 56, 58 to 60, 62 to 64, 66 and 67, A printed wiring board manufactured. An electronic device manufactured using the printed wiring board according to claim 71. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, 47 to 49, 51 The copper foil with a carrier according to any one of claims 52, 54, 56, 58 to 60, 62 to 64, 66 and 67, ,
A step of laminating the copper foil with a carrier and an insulating substrate,
A step of peeling the copper foil carrier of the copper foil with a carrier to form a copper clad laminate after laminating the copper foil with the carrier and the insulating substrate,
And then forming a circuit by any one of a semi-additive method, a subtractive method, a pattern additive method, and a modified semi-additive method. The method of any one of claims 1 to 12, 14 to 25, 27 to 31, 33 to 39, 41 to 45, 47 to 49, 51 The copper foil with a carrier according to any one of claims 52, 54, 56, 58 to 60, 62 to 64, 66 and 67, A step of forming a circuit on the copper layer side surface,
A step of forming a resin layer on the surface of the extremely thin copper layer side of the copper foil with a carrier so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
A step of exposing a circuit buried in the resin layer formed on the surface of the extremely thin copper layer side by removing the extremely thin copper layer after peeling the carrier,
And a step of forming the printed circuit board. 75. The method of claim 74,
Wherein the step of forming a circuit on the resin layer comprises a step of forming a resin layer on the resin layer by bonding another copper foil with a carrier on the resin layer and bonding the resin layer to the resin layer, Wherein the step of forming the printed wiring board comprises the steps of: 78. The method of claim 75,
And another copper foil with a carrier to be laminated on the resin layer is formed below the resin layer. 75. The method of claim 74,
Wherein a step of forming a circuit on the resin layer is carried out by any one of a semiadditive method, a subtractive method, a palladium additive method, and a modified semi additive method. 75. The method of claim 74,
Further comprising a step of forming a substrate on a carrier-side surface of the copper foil with a carrier before peeling off the carrier.

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