JP2016191086A - Copper foil with carrier, laminate, printed wiring board, electronic device, manufacturing method of copper foil with carrier and manufacturing method of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a carrier high in adhesion force between the carrier and an ultra thin copper foil before a laminating process to an insulation substrate and capable of achieving easy peeling at a carrier/ultra thin copper foil boundary without extreme increase or decrease of adhesiveness of the carrier and the ultra thin copper foil in the laminating process to the insulation substrate.SOLUTION: A copper foil with a carrier contains chromium and one or more element selected from a group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium in an intermediate layer, depth from a surface in an intermediate layer side of the carrier in terms of SiOtill atom concentration of chromium becomes 5 at% or less is 0.2 nm to 10 nm inclusive at 12 or more locations of 20 locations when peeling the carrier from the foil with the carrier according to JIS C6471 and conducting analysis of total 20 locations which are 10 locations with 20 mm interval in a width direction (TD direction) and 10 locations with 20 mm interval in a longer direction (MD direction) in the depth direction by AES from the intermediate side of the peeled carrier.SELECTED DRAWING: Figure 1

Description

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

  Printed wiring boards have made great progress over the last half century and are now used in almost all electronic devices. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  A printed wiring board is first manufactured as a copper clad laminate in which an insulating substrate mainly composed of a copper foil and a glass epoxy substrate, BT resin, polyimide film or the like is bonded. Bonding is performed by laminating an insulating substrate and a copper foil and applying heat and pressure (laminating method), or by applying a varnish that is a precursor of an insulating substrate material to a surface having a coating layer of copper foil, A heating / curing method (casting method) is used.

  Along with the fine pitch, the thickness of the copper foil used for the copper clad laminate is also 9 μm, and further, 5 μm or less. However, when the foil thickness is 9 μm or less, the handleability when forming a copper clad laminate by the above-described lamination method or casting method is extremely deteriorated. Therefore, a copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is formed on the metal foil via a release layer. It is a general method of using a copper foil with a carrier that the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded, and then the carrier is peeled off via the peeling layer.

  Conventionally, a diffusion prevention layer, a release layer, and an electrolytic copper plating are formed in this order on the surface of the carrier foil, and a Cr or Cr hydrated oxide layer is used as the release layer, and Ni, Co, Fe, Cr, Patent Document 1 discloses a method for maintaining good peelability after hot pressing by using a single element or alloy of Mo, Ta, Cu, Al, and P.

  Alternatively, it is known that the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P, alloys thereof, or hydrates thereof. Furthermore, it is described in Patent Documents 2 and 3 that it is effective to provide Ni, Fe or an alloy layer thereof on the base of the release layer in order to stabilize the peelability in a high temperature use environment such as a hot press. Has been.

Or a carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer, the intermediate layer containing nickel and chromium, When peeling between layers / ultra thin copper layers according to JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS e (x), the atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), The total atomic concentration (%) is i (x), the carbon atomic concentration (%) is j (x), and the other atomic concentration (%) is k (x). In the interval [0, 1.0] of the depth direction analysis, E (x) = ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + + h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) The standard deviation of E (x) when measuring E (x) at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction is σ _E, and the coefficient of variation of the chromium concentration is X _E = σ _{Assuming that E} × 100 / (20-point arithmetic average value of E (x)), X _E satisfies 40.0% or less, and 20-point arithmetic average value of E (x) satisfies 1-30%. A copper foil with a carrier is described in Patent Document 4.

JP 2006-022406 A JP 2010-006071 A JP 2007-007937 A JP 2014-195871 A

  In copper foil with carrier, the ultrathin copper foil must not be easily peeled off from the carrier before the lamination process on the insulating substrate, while the carrier from the ultrathin copper foil is easily peeled off after the lamination process on the insulation substrate. It is necessary to peel off.

  Regarding Patent Document 1, the peelability after hot pressing is good, but the state of the ultrathin copper foil surface is not mentioned. Further, in the same patent document, it is described that the order of the diffusion prevention layer and the release layer may be either, but the examples described are all in the order of carrier foil, release layer, diffusion prevention layer, electrolytic copper plating, At the time of peeling, the peeling layer / diffusion prevention layer interface may peel off. If it becomes so, a diffusion prevention layer will remain on the surface of electrolytic copper plating (ultra-thin copper layer), and it will lead to the etching failure at the time of forming a circuit.

  In Patent Documents 2 and 3, there is no description that can be considered that the properties such as the peel strength between the carrier and the ultrathin copper foil are sufficiently examined, and there is still room for improvement.

Patent Document 4 has been studied based on information obtained from depth analysis from the surface by XPS, but the detection area of XPS is 800 μmΦ, and the amount of chromium deposited is 5 to 100 μg / cm ² . In order to grasp the structure of the intermediate layer, there is a problem that the detection area is wide. As a result, even the copper foil with a carrier described in Patent Document 4 has a strong or weak peel strength between the carrier and the ultrathin copper layer.

  Therefore, the present invention has a high adhesion between the carrier and the ultrathin copper foil before the lamination process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper foil is extremely increased due to the lamination process to the insulation substrate. It is an object of the present invention to provide a carrier-attached copper foil that does not deteriorate and can be easily peeled off at the carrier / ultra-thin copper foil interface.

In order to achieve the above-mentioned object, the present inventor has made extensive studies and formed an intermediate layer containing chromium as an essential component, and peeled off the intermediate layer / ultra-thin copper layer by a predetermined method. When analyzing in the depth direction from the side surface in the depth direction by AES, the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less is within a predetermined range. It discovered that the copper foil with a carrier which can solve the said subject can be provided by controlling so that it may become.

The present invention has been completed based on the above knowledge, and in one aspect, a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the intermediate layer is nickel, cobalt, iron, tungsten Including one or more elements selected from the group consisting of molybdenum and vanadium, and chromium, and the carrier is peeled from the carrier-attached copper foil in accordance with JIS C 6471, and the intermediate layer side of the peeled carrier When the analysis in the depth direction by AES was performed on the total of 20 places, 10 places at intervals of 20 mm in the width direction (TD direction) and 10 places at intervals of 20 mm in the longitudinal direction (MD direction) from the surface, At 12 or more locations, the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less is 0. It is a copper foil with a carrier which is 2 nm or more and 10 nm or less.

In still another embodiment of the carrier-attached copper foil of the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 16 or more of the 20 locations. The depth from is not less than 0.2 nm and not more than 10 nm.

In yet another embodiment, the carrier-attached copper foil of the present invention is the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 18 or more of the 20 locations. The depth from is not less than 0.2 nm and not more than 10 nm.

In yet another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in all 20 of the 20 locations. The depth from is not less than 0.2 nm and not more than 10 nm.

In still another embodiment of the carrier-attached copper foil of the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 12 or more of the 20 locations. Is from 0.5 nm to 9 nm.

In still another embodiment of the carrier-attached copper foil of the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 12 or more of the 20 locations. The depth from is 1 nm or more and 9 nm or less.

In still another embodiment of the carrier-attached copper foil of the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 12 or more of the 20 locations. Is from 1.5 nm to 8 nm.

In still another embodiment of the carrier-attached copper foil of the present invention, the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 12 or more of the 20 locations. The depth from is 2 nm or more and 5 nm or less.

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

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

  In yet another embodiment of the copper foil with a carrier of the present invention, the carrier is peeled from the copper foil with a carrier in accordance with JIS C 6471, and the intermediate layer side surface of the carrier is used in the depth direction by AES. When the analysis was performed, the atomic concentration of copper (at%) <chromium in a range from the intermediate layer side surface to a depth where the total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum and vanadium is 70 at% or less. It has a portion with atomic concentration (at%).

In still another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer is thermocompression bonded under pressure of 20 kgf / cm ² and 220 ° C. for 2 hours in the atmosphere with the insulating substrate. The carrier is peeled off from the copper foil in accordance with JIS C 6471, and from the surface on the intermediate layer side of the carrier, 10 places at intervals of 20 mm in the width direction (TD direction) and 10 places at intervals of 20 mm in the longitudinal direction (MD direction). When the analysis in the depth direction by AES was performed for a total of 20 locations, the depth from the surface in terms of SiO ₂ until the atomic concentration of chromium became 5 at% or less in 12 or more of the 20 locations. It is 0.2 nm or more and 10 nm or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer is thermocompression bonded under pressure of 20 kgf / cm ² and 220 ° C. for 2 hours in the atmosphere with the insulating substrate. When the carrier was peeled from the copper foil in accordance with JIS C 6471 and analyzed in the depth direction by AES from the intermediate layer side surface of the carrier, nickel, cobalt, iron, tungsten from the intermediate layer side surface was analyzed. In the range up to a depth where the total atomic concentration of molybdenum and vanadium is 70 at% or less, there is a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%).

In another embodiment of the copper foil with a carrier of the present invention, the intermediate layer has a total deposition amount of nickel, cobalt, iron, tungsten, molybdenum, and vanadium of 1000 to 40000 μg / dm ² , and a deposition amount of chromium of 5. -200 [mu] g / dm < ² > is satisfied.

  In still another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is formed on a carrier with nickel, cobalt, iron, tungsten, molybdenum, vanadium, or nickel, cobalt, iron, tungsten, molybdenum and vanadium. Any one layer of an alloy containing one or more elements selected from the group consisting of, and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium are provided in this order.

  In yet another embodiment of the copper foil with a carrier of the present invention, the layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium includes a chromate treatment layer.

  In another embodiment of the copper foil with a carrier according to the present invention, the carrier further has an intermediate layer and an ultrathin copper layer in this order on the surface opposite to the surface having the ultrathin copper layer. .

  In still 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.

  In still another embodiment, the carrier-attached copper foil according to the present invention has a roughened layer on one or both of the ultrathin copper layer surface and the carrier surface.

  In still another embodiment of the copper foil with a carrier according to the present invention, the roughening treatment layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is the layer which consists of an alloy containing any one simple substance or any 1 type or more.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. Has more than seed layers.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. Has more than seed layers.

  In yet another embodiment, the carrier-attached copper foil according to the present invention comprises a resin layer on the ultrathin copper layer.

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

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a resin on one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the silane coupling-treated layer. With layers.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the resin layer is an adhesive resin.

  In still another embodiment of the copper foil with a carrier according to the present invention, the resin layer is a semi-cured resin.

  In another aspect, the present invention is a laminate manufactured using the copper foil with a carrier of the present invention.

  Another aspect of the present invention is a laminate including the copper foil with a carrier according to the present invention and a resin, wherein the end face of the copper foil with a carrier is partly or entirely covered with the resin. is there.

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

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

  In another aspect of the present invention, there is provided a laminate in which one copper foil with a carrier according to the present invention is laminated from the carrier side to the carrier side of another copper foil with a carrier according to the present invention.

  In one embodiment, the laminate of the present invention is configured by directly laminating the carrier of the one copper foil with a carrier and the carrier of the other copper foil with a carrier through an adhesive as necessary. ing.

  In another embodiment of the laminate of the present invention, the carrier of the one copper foil with carrier and the carrier of the other copper foil with carrier are joined.

  According to another aspect of the present invention, there are provided a step of providing two layers of a resin layer and a circuit at least once on the surface of the laminate according to any one of the present invention, and 2 of the resin layer and the circuit. It is a manufacturing method of a printed wiring board including the process of peeling the ultra-thin copper layer from the copper foil with a carrier of the layered product after forming a layer at least once.

  In yet another aspect, the present invention is a method for producing a printed wiring board using the laminate of the present invention.

  In one embodiment of the method for producing a copper foil with a carrier according to the present invention, after forming a plating layer containing nickel on the carrier, the intermediate layer is formed by forming a plating layer containing chromium or a chromate treatment layer. And a step of forming the ultrathin copper layer on the intermediate layer by electrolytic plating.

  The manufacturing method of the copper foil with a carrier of this invention in another one Embodiment further includes the process of forming a roughening process layer on the said ultra-thin copper layer.

  In yet another aspect of the present invention, the step of preparing the copper foil with carrier and the insulating substrate of the present invention, the step of laminating the copper foil with carrier and the insulating substrate, and the copper foil with carrier and the insulating substrate And then forming a copper-clad laminate through a step of peeling the carrier of the copper foil with carrier, and then by any one of the semi-additive method, subtractive method, partly additive method or modified semi-additive method A method of manufacturing a printed wiring board including a step of forming a circuit.

  In yet another aspect of the present invention, the step of forming a circuit on the surface of the ultrathin copper layer or the surface of the carrier of the copper foil with a carrier of the present invention, the copper foil with a carrier so that the circuit is buried. The step of forming a resin layer on the surface of the ultrathin copper layer or the surface of the carrier, the step of forming a circuit on the resin layer, the circuit on the resin layer, the carrier or the ultrathin copper layer And after removing the carrier or the ultrathin copper layer, the ultrathin copper layer or the carrier is removed to form the ultrathin copper layer side surface or the carrier side surface. And a method of manufacturing a printed wiring board including a step of exposing a circuit buried in the resin layer.

  In another aspect of the present invention, the step of laminating the carrier-attached copper foil of the present invention on the resin substrate from the carrier side, the circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil A step of forming, a step of forming a resin layer on the surface of the ultrathin copper layer or the carrier side of the copper foil with carrier so that the circuit is buried, a step of forming a circuit on the resin layer, the resin After forming a circuit on the layer, the step of peeling the carrier or the ultrathin copper layer, and removing the ultrathin copper layer or the carrier after peeling the carrier or the ultrathin copper layer The method of manufacturing a printed wiring board including a step of exposing a circuit embedded in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface.

  In yet another aspect of the present invention, the step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention and the resin substrate, laminating with the resin substrate of the copper foil with carrier. A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer opposite to the side or the carrier side surface, and after forming the two layers of the resin layer and the circuit, It is a manufacturing method of a printed wiring board including the process of exfoliating the career or the ultra-thin copper layer from copper foil with a carrier.

  In yet another aspect of the present invention, the step of laminating the carrier-side surface of the copper foil with a carrier and a resin substrate of the present invention, the ultrathin side opposite to the side of the copper foil with carrier and laminating the resin substrate A step of providing at least once a resin layer and a circuit on the copper layer side surface, and a step of peeling the carrier from the carrier-attached copper foil after forming the resin layer and the circuit two layers. It is a manufacturing method of a printed wiring board.

  According to the present invention, the adhesion between the carrier and the ultrathin copper foil is high before the laminating process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper foil due to the laminating process to the insulating substrate is extremely increased. It is possible to provide a copper foil with a carrier that is not lowered and can be easily peeled off at the carrier / ultra-thin copper foil interface.

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. It is the AES analysis result of the depth direction before the board | substrate bonding of the intermediate layer side surface of the partial sample of Example 2. FIG.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCD film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials 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), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.
In addition, you may provide a roughening process layer in the surface on the opposite side to the surface in the side which provides the ultra-thin copper layer of a carrier. The said roughening process layer may be provided using a well-known method, and may be provided by the below-mentioned roughening process. Providing a roughened layer on the surface opposite to the surface on which the ultrathin copper layer of the carrier is provided, when laminating the carrier from the surface side having the roughened layer to a support such as a resin substrate, There is an advantage that the carrier and the resin substrate are hardly separated.

Below, an example of manufacturing conditions in the case of using electrolytic copper foil as a carrier is shown.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.
The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.

(In the above chemical formula, 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.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention contains one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum, and vanadium, and chromium. Since the electrical conductivity is good, it is easy to provide an ultrathin copper layer and other layers on the intermediate layer, so that one or more selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium It is preferable that some or all of the elements are metals. The intermediate layer is made of nickel, cobalt, iron, tungsten, molybdenum, vanadium, or an alloy containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum, and vanadium on the carrier. You may have in this order the 1 type layer and the layer containing any 1 or more types selected from the group which consists of chromium, a chromium alloy, and the oxide of chromium. It is preferable that the intermediate layer further contains copper. When the intermediate layer contains copper, the peel strength at the carrier / ultra thin copper layer interface can be easily adjusted. The intermediate layer preferably further contains zinc. When the intermediate layer contains zinc, it becomes easier to adjust the peel strength at the carrier / ultra thin copper layer interface. When zinc is added to the chromate solution, it is easy to control the intermediate layer. Note that the layer containing any one or more selected from the group consisting of chromium, a chromium alloy, and a chromium oxide is preferably a chromate-treated layer because the peel strength can be easily controlled to an appropriate value.

  Here, the alloy containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium is selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium. One or more elements and one or more elements selected from the group consisting of nickel, cobalt, tungsten, molybdenum, vanadium, iron, chromium, zinc, tantalum, copper, aluminum, phosphorus, tin, arsenic, and titanium An alloy. The alloy including one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum, and vanadium may be an alloy including three or more elements. The chromium alloy is composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, vanadium, and titanium. An alloy. The chromium alloy may be an alloy composed of three or more elements. The layer containing any one or more selected from the group consisting of chromium, a chromium alloy and a 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, chromate or dichromate. The chromate treatment layer is made of elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, vanadium and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

  Since the adhesion between nickel, cobalt, iron, tungsten, molybdenum and vanadium and copper is higher than that of chromium and copper, when peeling the ultrathin copper layer, the ultrathin copper layer and chromium, chromium alloy and chromium It peels at the interface with a layer (for example, chromate treatment layer) containing any one or more selected from the group consisting of oxides. Further, nickel, cobalt, iron, tungsten, molybdenum, and vanadium in the intermediate layer are expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Further, it is more preferable to form a chromate treatment layer instead of chrome plating on the intermediate layer. Since chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper foil is formed by electroplating, the electrical resistance increases, and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of an ultrathin copper foil by electroplating is difficult, and pinholes can be reduced. it can. Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to. In addition, when using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  The insulating substrate includes a thin layer (for example, a chromate treatment layer) containing at least one selected from the group consisting of chromium, a chromium alloy and a chromium oxide among the intermediate layers. While the ultrathin copper layer is not peeled off from the carrier before the lamination step, the ultrathin copper layer is preferably peelable from the carrier after the lamination step on the insulating substrate. Nickel layer, cobalt layer, iron layer, tungsten layer, molybdenum layer and vanadium layer or an alloy layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium (for example, nickel-zinc A layer containing at least one selected from the group consisting of chromium, a chromium alloy and a chromium oxide (for example, a chromate treatment layer) was present at the boundary between the carrier and the ultrathin copper layer without providing an alloy layer. In some cases, the peelability may hardly improve. Further, there is no layer (for example, chromate treatment layer) containing any one or more selected from the group consisting of chromium, chromium alloy and chromium oxide, nickel layer, cobalt layer, iron layer, tungsten layer, molybdenum layer, When an ultrathin copper layer is laminated with a vanadium layer or an alloy layer (for example, a nickel-zinc alloy layer) containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium, Nickel layer, cobalt layer, iron layer, tungsten layer, molybdenum layer and vanadium layer or an alloy layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium (for example, nickel-zinc Alloy layer) nickel, cobalt, iron, tungsten, molybdenum, Suitable peel strength or peel strength is too weak or too strong, depending on the indium content may not be obtained.

  In addition, a layer containing at least one selected from the group consisting of chromium, a chromium alloy, and a chromium oxide (for example, a chromate treatment layer) includes a carrier, a nickel layer, a cobalt layer, an iron layer, a tungsten layer, a molybdenum layer, Exfoliation of an ultrathin copper layer when present at the boundary of a vanadium layer or an alloy layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium (eg nickel-zinc alloy layer) Sometimes the intermediate layer is also peeled off, that is, there is a risk of peeling between the carrier and the intermediate layer. Such a situation is not only in the case where a layer containing at least one selected from the group consisting of chromium, a chromium alloy and a chromium oxide (for example, a chromate treatment layer) is provided at the interface with the carrier. Even if a layer containing any one or more selected from the group consisting of chromium, a chromium alloy and a chromium oxide (for example, a chromate treatment layer) is provided at the interface with the thin copper layer, it may occur when the amount of chromium is too large. . This is because copper and nickel are easy to dissolve, so if they are in contact with each other, the adhesive force increases due to mutual diffusion, making it difficult to peel off, while chromium and copper are hard to dissolve and difficult to cause mutual diffusion. It is considered that the adhesion between the chromium and copper interface is weak and easy to peel off. In addition, if the nickel, cobalt, iron, tungsten, molybdenum, or vanadium in the intermediate layer is insufficient, there is only a small amount of chromium between the carrier and the ultra-thin copper layer, so that they are in close contact with each other. May be difficult to peel off.

  An intermediate layer nickel layer, cobalt layer, iron layer, tungsten layer, molybdenum layer and vanadium layer or an alloy layer containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium (for example, Nickel-zinc alloy layer) and a layer containing any one or more selected from the group consisting of chromium, chromium alloy and chromium oxide, for example, wet plating such as electroplating, electroless plating and immersion plating, or It can be formed by dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost. 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.

  In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed. In addition, when providing an intermediate | middle layer only on one side, it is preferable to provide a rust prevention layer, such as a Ni plating layer, on the opposite surface of a carrier.

Further, the nickel in the intermediate layer, cobalt, iron, tungsten, molybdenum, the total amount of deposited 1000~40000μg / dm ² of vanadium, that the adhesion amount of chromium is 5~200μg / dm ² preferably. If the total adhesion amount of nickel, cobalt, iron, tungsten, molybdenum and vanadium is less than 1000 μg / dm ² , nickel, cobalt, iron, tungsten, molybdenum and vanadium are the carrier copper and copper in the ultrathin copper layer Therefore, it may be difficult to adjust the peel strength. On the other hand, if the total adhesion amount of nickel, cobalt, iron, tungsten, molybdenum, and vanadium exceeds 40000 μg / dm ² , warping may occur due to the electrodeposition stress of nickel, cobalt, iron, tungsten, molybdenum, and vanadium. is there. Nickel, cobalt, iron, tungsten, molybdenum, the total deposition amount of vanadium is more preferably 3000~20000μg / dm ^2, even more preferably 5000~10000μg / dm ^2. If the adhesion amount of chromium is less than 5 μg / dm ² , the peel strength may be higher than the target. On the other hand, when the adhesion amount of chromium exceeds 200 μg / dm ² , the peel strength may be lower than the target. Deposition of chromium is more preferably from 10~110μg / dm ^2, still more preferably in the range of 10~70μg / dm ^2, still more preferably in the range of 10~50μg / dm ^2, 10~30μg / Even more preferred is dm ² .
The intermediate layer may include an organic material. As an organic substance contained in the intermediate layer, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids. Among the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
The organic material is preferably contained in a thickness of 5 nm to 80 nm, more preferably 8 nm to 50 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.

  The method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil. The intermediate layer is formed on the copper foil carrier by dissolving the above-mentioned organic substances in a solvent and immersing the copper foil carrier in the solvent, or showering, spraying method, dropping method on the surface on which the intermediate layer is to be formed. In addition, there is no need to employ a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of a concentration of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. in all the organic substances described above. The concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, more typically 1.5 to 5 μm, and more typically 2 to 5 μm. In addition, you may provide an ultra-thin copper layer on both surfaces of a carrier.

<Copper foil with carrier>
The copper foil with a carrier of this invention has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.

The copper foil with a carrier of the present invention peels the carrier from the copper foil with a carrier in accordance with JIS C 6471, and from the intermediate layer side surface of the peeled carrier at intervals of 20 mm in the width direction (TD direction). When analysis in the depth direction by AES was performed on 10 places and 10 places in the longitudinal direction (MD direction) at 20 mm intervals, the atomic concentration of chromium was 5 at% or less in 12 or more of the 20 places. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ up to is from 0.2 nm to 10 nm. When the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ is less than 0.2 nm until the atomic concentration of chromium becomes 5 at% or less in 9 or more of the 20 locations, the peel strength is the target. Higher than. On the other hand, when the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium reaches 5 at% or less in 9 or more of the 20 locations exceeds 10 nm, the peel strength is the target. Smaller than. For the purpose of reducing the variation in peel strength, it is preferably 16 or more of the 20 locations, more preferably 18 or more of the 20 locations, and even more preferably all 20 of the 20 locations. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less is 0.2 nm or more and 10 nm or less. Further, for the purpose of reducing the variation in peel strength, the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the chromium atomic concentration becomes 5 at% or less is preferably 0.5 nm or more and 9 nm. Or less, more preferably 1 nm or more and 9 nm or less, still more preferably 1.5 nm or more and 8 nm or less, and even more preferably 2 nm or more and 5 nm or less.

  The carrier-attached copper foil of the present invention is separated from the carrier-attached copper foil in accordance with JIS C 6471, and from the intermediate layer side surface of the carrier, 10 locations at 20 mm intervals in the width direction (TD direction) and the longitudinal direction. When analysis in the depth direction by AES was performed for 20 places in total (20 directions in the MD direction) at intervals of 20 mm, nickel, cobalt, iron, tungsten, molybdenum from the intermediate layer side surface at one or more measurement places In addition, it is preferable to have a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) in a range up to a depth where the total atoms of vanadium are 70 at% or less. According to such a configuration, there is an advantage that the peel strength can be easily set to a target value. Further, preferably at five or more measurement locations, more preferably at least 10 measurement locations, more preferably at all 20 measurement locations, nickel, cobalt, iron, tungsten, molybdenum, vanadium from the intermediate layer side surface. It is preferable to have a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) within a range where the total atoms are 70 at% or less. Further, at one or more measurement locations, preferably at least 5 measurement locations, more preferably at least 10 measurement locations, more preferably at all 20 measurement locations, nickel, cobalt, At a depth where the total atoms of iron, tungsten, molybdenum and vanadium are 70 at% or less, copper atomic concentration (at%) <chromium atomic concentration (at%) It is more preferable that the atomic concentration (at%) of chromium (at%) and the atomic concentration of copper (at%) ≦ the atomic concentration of chromium (at%) × 0.8.

The copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer in the atmosphere under a pressure of 20 kgf / cm ² and a pressure of 220 ° C. for 2 hours. Depth according to 6471 from the surface on the intermediate layer side of the carrier, the depth by AES for 20 places in the width direction (TD direction) at 20 mm intervals and 10 places in the longitudinal direction (MD direction) at 20 mm intervals. When the analysis in the vertical direction is performed, the depth from the surface in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less at 12 or more of the 20 locations is 0.2 nm or more and 10 nm or less. It is preferable. If the depth from the surface in terms of SiO ₂ is less than 0.2 nm until the atomic concentration of chromium is 5 at% or less in 9 or more of the 20 locations, the peel strength may be higher than the target. There is. On the other hand, if the depth from the surface in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 9 or more of the 20 locations exceeds 10 nm, the peel strength may be lower than the target. There is. “Thermocompression bonding under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours” indicates typical thermocompression bonding and heating conditions when the carrier-attached copper foil is bonded to an insulating substrate. For the purpose of reducing the variation in peel strength, it is preferably 16 or more of the 20 locations, more preferably 18 or more of the 20 locations, and even more preferably all 20 of the 20 locations. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less is 0.2 nm or more and 10 nm or less. Further, for the purpose of reducing the variation in peel strength and making the peel strength more preferable, the carrier from the intermediate layer side surface in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less. The depth is preferably from 0.5 nm to 9 nm, more preferably from 1 nm to 9 nm, even more preferably from 1.5 nm to 8 nm, and even more preferably from 2 nm to 5 nm.

The copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer in the atmosphere under a pressure of 20 kgf / cm ² and a pressure of 220 ° C. for 2 hours. Depth according to 6471 from the surface on the intermediate layer side of the carrier, the depth by AES for 20 places in the width direction (TD direction) at 20 mm intervals and 10 places in the longitudinal direction (MD direction) at 20 mm intervals. When the analysis in the vertical direction was performed, in one or more measurement locations, in the range from the intermediate layer side surface to a depth where the total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum, vanadium is 70 at% or less, It is preferable to have a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%). According to such a configuration, there is an advantage that the peel strength can be easily set to a target value. Further, preferably at five or more measurement locations, more preferably at least 10 measurement locations, more preferably at all 20 measurement locations, nickel, cobalt, iron, tungsten, molybdenum, vanadium from the intermediate layer side surface. It is preferable to have a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) within a range where the total atomic concentration is 70 at% or less. Further, at one or more measurement locations, preferably at least 5 measurement locations, more preferably at least 10 measurement locations, more preferably at all 20 measurement locations, nickel, cobalt, In the range where the total atomic concentration of iron, tungsten, molybdenum and vanadium is up to a depth of 70 at% or less, the atomic concentration of copper in the portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) It is more preferable that the atomic concentration (at%) of chromium (at%) and the atomic concentration of copper (at%) ≦ the atomic concentration of chromium (at%) × 0.8.

<Roughening treatment and other surface treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening layer is a layer made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. It may be. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer and a silane coupling treated layer may be formed on the surface of the roughened treated layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

For example, copper as a roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, deposition amount in the nickel-cobalt -100~1500μg / dm ² of copper -100~3000μg / dm ² of 15~40mg / dm ² Such a ternary alloy layer can be formed. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

An example of a general bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 20 to 30 A / dm ²
Plating time: 1-5 seconds

<Method for producing copper foil with carrier>
The method for producing a copper foil with a carrier according to the present invention includes a step of forming the intermediate layer by forming a plating layer containing chromium or a chromate treatment layer after forming a plating layer containing nickel on the carrier, Forming the ultrathin copper layer on the intermediate layer by electrolytic plating. Moreover, you may further include the process of forming a roughening process layer on the said ultra-thin copper layer.
In the present invention, it is preferable to control the temperature of a plating solution or a treatment solution for forming a plating layer or a chromate treatment layer containing chromium to 40 to 60 ° C. If the temperature of the plating solution or the treatment solution for forming the plating layer or the chromate treatment layer containing chromium is less than 40 ° C., there is a possibility that the dispersion strength between the carrier and the ultrathin copper layer may vary greatly due to the Cr concentration distribution. is there. When the temperature of the plating solution or the treatment solution for forming the plating layer or the chromate treatment layer containing chromium exceeds 60 ° C., there is a possibility that the selectivity of the production line constituent members may be narrowed such that it is difficult to use the heat-resistant PVC pipe. There is. The current density CrDk when forming the chromium-containing plating layer or chromate treatment layer is preferably larger than 0.1 A / dm ² and not larger than 1.5 A / dm ² . When CrDk is 0.1 A / dm ² or less, there is a possibility that the dispersion strength between the carrier and the ultrathin copper layer will vary greatly due to the variation in the concentration distribution of Cr in the depth direction. When CrDk exceeds 1.5 A / dm ² , it may be difficult to control the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less in a preferable range. There is. The treatment time for forming the plating layer or chromate treatment layer containing chromium is preferably 2 seconds or more and 100 seconds or less. If the treatment time exceeds 100 seconds, there is a risk that the dispersion strength between the carrier and the ultrathin copper layer will vary due to variations in the concentration distribution of Cr in the depth direction. Further, when the treatment time is less than 2 seconds, it becomes difficult to control the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less in a preferable range. There is a fear.

<Printed wiring boards, laminates, electronic equipment>
In this manner, a carrier-attached copper foil including a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer is manufactured. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The printed wiring board can be finally manufactured by etching the ultrathin copper layer adhered to the substrate into a desired conductor pattern.

Further, the carrier-attached copper foil comprising a carrier and an ultra-thin copper layer laminated on the intermediate layer on the carrier comprises a roughening treatment layer on the ultra-thin copper layer. Alternatively, one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be provided on the roughening treatment layer.
Further, a roughening treatment layer may be provided on the ultrathin copper layer, a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer, and a chromate treatment is performed on the heat resistance layer and the rust prevention layer. A layer may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive or may be a semi-cured (B stage) insulating resin layer for bonding. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, or the like can be given as a preferable one. .

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  These resins are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin solution, which is used on the ultrathin copper layer, the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane cup. On the ring agent layer, for example, it is applied by a roll coater method or the like, and then heat-dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

  The copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off. Thus, the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.

  If this resin-attached copper foil with a carrier is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

  In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.

  The thickness of the resin layer is preferably 0.1 to 80 μm. When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.

  On the other hand, if the thickness of the resin layer is greater than 80 μm, it is difficult to form a resin layer having a desired thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

  Furthermore, as another product form of this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer After coating with a resin layer and making it into a semi-cured state, the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  In one embodiment of a method for producing a printed wiring board according to the present invention, 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, and with the carrier After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

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

Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  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, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as acid
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and 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;
Removing the etching resist;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-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;
Removing the etching resist;
including.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 3H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  According to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, when removing the ultrathin copper layer by flash etching as shown in FIG. In addition, the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

  Moreover, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having the said board | substrate or resin layer, the copper foil with a carrier used for the first layer is supported, and since it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer and known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification, Organic compound foils can be used.

  A laminated body (a copper clad laminated body etc.) can be produced using the copper foil with a carrier of the present invention. For example, the laminate may have a structure in which “ultra-thin copper layer / intermediate layer / carrier / resin or prepreg” is laminated in this order, and “carrier / intermediate layer / ultra-thin copper layer / resin or prepreg”. It may be a configuration laminated in this order, or may be a configuration laminated in the order of "ultra thin copper layer / intermediate layer / carrier / resin or prepreg / carrier / intermediate layer / ultra thin copper layer" The configuration may be such that “carrier / intermediate layer / ultra thin copper layer / resin or prepreg / ultra thin copper layer / intermediate layer / carrier” are laminated in this order. The resin or prepreg may be a resin layer which will be described later. A resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like used for the resin layer which will be described later. May be included. The carrier-attached copper foil may be smaller than the resin or prepreg when viewed in plan.

Further, the method for producing a printed wiring board of the present invention includes a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing at least once a resin layer and a circuit on the surface of the copper layer with carrier on the opposite side of the copper layer side surface or the carrier side surface, and forming two layers of the resin layer and the circuit Then, a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultrathin copper layer from the carrier-attached copper foil may be used. As a specific example of the coreless construction method, first, the ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. Another copper foil with a carrier may be laminated from the carrier side to the resin layer formed on the carrier side surface. In this case, a copper foil with a carrier is laminated in the order of carrier / intermediate layer / ultra-thin copper layer or ultra-thin copper layer / intermediate layer / carrier in this order on both surface sides of the resin substrate with the resin substrate as the center It has become. Another ultra-thin copper layer or the exposed surface of the carrier on both ends may be provided with another resin layer, a copper layer may be further provided, and then the copper layer may be processed to form a circuit. Further, another resin layer may be provided on the circuit so as to embed the circuit. Moreover, you may provide such a circuit and formation of a resin layer 1 or more times (build-up construction method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the production of the coreless substrate described above, a laminate having a configuration of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer described later using two copper foils with a carrier, Laminate having a structure of carrier / intermediate layer / ultra thin copper layer / ultra thin copper layer / intermediate layer / carrier, or a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer It is also possible to produce a laminated body and use the laminated body as a center. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer.
In this specification, “laminate” not specifically described as “laminate A” or “laminate B” indicates a laminate including at least laminate A and laminate B.

  In the above-described coreless substrate manufacturing method, by covering part or all of the end face of the copper foil with carrier or the laminate (laminate A) with a resin, when producing a printed wiring board by the build-up method, It is possible to prevent the infiltration of the chemical solution between one copper foil with a carrier and another copper foil with a carrier constituting the intermediate layer or laminate, and separation of the ultrathin copper layer and the carrier due to the infiltration of the chemical solution Corrosion of the copper foil with carrier can be prevented, and the yield can be improved. As the “resin that covers part or all of the end face of the copper foil with carrier” or “resin that covers part or all of the end face of the laminate” used herein, a resin that can be used for the resin layer may be used. it can. Further, in the above-described coreless substrate manufacturing method, the carrier-attached copper foil or laminate when viewed in plan, the carrier-attached copper foil or laminate portion (a laminate portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery of the laminated copper foil with carrier and another copper foil with carrier may be covered with resin or prepreg. Moreover, the laminated body (laminated body A) formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact each other so that isolation | separation is possible. Further, when viewed in plan in the copper foil with carrier, the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultrathin copper layer, or one copper foil with carrier and another copper with carrier) It may be formed by being covered with a resin or a prepreg over the entire outer periphery of the laminated portion with the foil. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Cutting a covered copper foil with a carrier or a laminated part of a laminated body (a laminated part of a carrier and an ultrathin copper layer or a laminated part of one copper foil with a carrier and another copper foil with a carrier), etc. Need to be removed.

  The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention. In addition, the carrier or ultrathin copper layer of the one copper foil with carrier and the carrier or ultrathin copper layer of the other copper foil with carrier are directly laminated through an adhesive as necessary. The obtained laminated body may be sufficient. Further, the carrier or ultrathin copper layer of the one copper foil with carrier and the carrier or ultrathin copper layer of the other copper foil with carrier may be joined. Further, part or all of the end face of the laminate may be covered with resin.

Lamination of carriers can be performed by, for example, the following method, in addition to simply overlapping.
(A) Metallurgical joining method: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, Friction stir welding), brazing;
(B) Mechanical joining method: caulking, joining with rivets (joining with self-piercing rivets, joining with rivets), stitcher;
(C) Physical joining method: adhesive, (double-sided) adhesive tape

  By joining a part or all of one carrier and a part or all of the other carrier using the joining method described above, one carrier and the other carrier are stacked, and the carriers are brought into contact with each other in a separable manner. It is possible to manufacture a laminated body configured as described above. When one carrier and the other carrier are weakly joined and one carrier and the other carrier are laminated, one carrier is not removed even if the joint between the one carrier and the other carrier is not removed. And the other carrier can be separated. In addition, when one carrier and the other carrier are strongly bonded, the portion where one carrier and the other carrier are bonded is removed by cutting, chemical polishing (etching, etc.), mechanical polishing, or the like. Thus, one carrier and the other carrier can be separated.

  Moreover, after forming the two layers of the resin layer and the circuit at least once on the surface of the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, A printed wiring board can be produced by carrying out the step of peeling the ultrathin copper layer from the copper foil with carrier. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

(Examples 1-26, Comparative Examples 1-7)
1. Manufacture of copper foil with carrier As a carrier, long electrolytic copper foil (JTC made by JX Nippon Mining & Metals Co., Ltd.) and rolled copper foil (Tough pitch copper foil JIS H3100 alloy number C1100 made by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 35 μm And an intermediate layer was formed on the surface. The intermediate layer was provided on one side of the carrier. The formation of the intermediate layer was performed according to the processing order described in the item “Method for forming intermediate layer” in Table 1. That is, for example, what is described as “Ni plating / zinc chromate” indicates that after the treatment of “Ni plating” is performed, the treatment of “zinc chromate” is performed. In the “intermediate layer” item, “Ni plating” indicates that pure nickel plating was performed, and “pure chromate” indicates that pure chromate treatment was performed. This means that “zinc chromate” means that the zinc chromate treatment was performed. Each processing condition is shown below. When increasing the amount of each element such as Ni, Zn, Cr, etc., set the current density higher and / or set the plating time longer, including wet plating and dry plating, And / or increasing the concentration of each element in the plating solution. In addition, when reducing the amount of deposition of Ni, Zn, Cr, etc., set the current density lower and / or set the plating time shorter including wet plating and dry plating, and / or The concentration of each element in the plating solution was lowered. The balance of the liquid composition such as a plating solution is water.

"Ni plating": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 4-6
(Liquid temperature) 55-65 degreeC
(Current density) 1 to 11 A / dm ²
(Energization time) 1 to 20 seconds

-"Pure chromate (electrolysis)": Electrolytic pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 2-4, 7-10
(Liquid temperature) 30-60 ° C
(Current density) 0.1-1.5 A / dm ²
(Energization time) 0.5 to 100 seconds

・ "Ni sputtering", "Co sputtering", "Fe sputtering", "W sputtering", "Mo sputtering", "V sputtering", "Cr sputtering"
Each metal layer was formed using a sputtering target having a composition of 99 mass% or more of each metal.
・ "Co-Ni Spatter"
Each metal layer was formed using a sputtering target having a composition of Co 49 mass% or more and Ni 49 mass% or more.
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

-"Zinc chromate (electrolysis)": Electrolytic zinc chromate treatment In the above electrolytic pure chromate treatment conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the solution, and the zinc concentration is in the range of 0.05 to 5 g / L. It adjusted and the zinc chromate process was performed.

  After forming the intermediate layer, an ultrathin copper layer having a thickness of 1 to 10 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier. In addition, about Example 12, as a result of producing and evaluating the copper foil with a carrier when the thickness of the ultrathin copper layer was 10 μm, the same evaluation result as the copper foil with a carrier when the thickness of the ultrathin copper layer was 5 μm It became.

-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

In Example 14, a roughening layer, a heat-resistant layer, a chromate layer, and a silane coupling layer were further provided on the ultrathin copper layer of Example 1. In Example 15, a heat-resistant treatment layer, a chromate layer, and a silane coupling treatment layer were further provided on the ultrathin copper layer of Example 1. In Example 16, a chromate layer and a silane coupling treatment layer were further provided on the ultrathin copper layer of Example 1.
・ Roughening treatment Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
Temperature: 40-50 ° C
Current density Dk: 20 to 30 A / dm ²
Time: 1 to 5 seconds Cu adhesion amount: 15 to 40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Heat-resistant treatment Zn: 0-20g / L
Ni: 0 to 5 g / L
pH: 3.5
Temperature: 40 ° C
Current density Dk: 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 30-60 ° C
Current density: 0.1 to 1.5 A / dm ²
Time: 0.5 to 100 seconds Cr adhesion amount:
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Time: 5-30 seconds

  Each evaluation was implemented with the following method about the copper foil with a carrier of the Example and comparative example which were obtained as mentioned above.

<Thickness of ultrathin copper layer>
The thickness of the ultrathin copper layer of the produced copper foil with a carrier was measured by a weight method.
First, after measuring the weight of the copper foil with a carrier, the ultrathin copper layer was peeled off, the weight of the obtained carrier was measured, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. The ultra-thin copper layer piece to be measured was a 10 cm square sheet punched out with a press. And the thickness of the ultra-thin copper layer was computed with the following formula | equation.
Ultrathin copper layer thickness (μm) = Ultrathin copper layer weight (g) / {Copper density (8.94 g / cm ³ ) × Ultrathin copper layer area (100 cm ² )} × 10 ⁴ (μm / cm)
Moreover, HF-400 by A & D Co., Ltd. was used for the weight scale, and HAP-12 by Noguchi Press Co., Ltd. was used for the press machine.

<Metal adhesion amount of intermediate layer>
The adhesion amount of nickel, cobalt, iron, tungsten, molybdenum, vanadium and chromium was measured by ICP emission analysis after dissolving the sample with hydrochloric acid having a concentration of 20% by mass. In the analysis of the sample, the intermediate layer is formed in order to eliminate the adhesion amount of nickel and chromium slightly adhering to the surface (carrier M surface) opposite to the surface forming the intermediate layer (carrier S surface). An insulating substrate was laminated on the surface opposite to the surface, and thermocompression bonded in the atmosphere under the conditions of a pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Then, after peeling the ultrathin copper layer side from the copper foil with carrier, the exposed carrier surface is hydrochloric acid having a concentration of 20% by mass so that the intermediate layer is completely dissolved (for example, 1 μm to 3 μm in thickness). And dissolved in
In addition, when the above-mentioned nickel, cobalt, iron, tungsten, molybdenum, vanadium and chromium are not sufficiently dissolved with hydrochloric acid having a concentration of 20% by mass, a solution in which nickel, cobalt, iron, tungsten, molybdenum, vanadium and chromium are dissolved. It may be measured by ICP emission analysis after being dissolved using aqua regia, a mixed aqueous solution of hydrochloric acid and nitric acid, or the like.

<AES analysis>
The carrier is peeled off from the copper foil with a carrier in accordance with the 90 ° peeling method (JIS C 6471), and 10 points are provided at intervals of 20 mm in the width direction (TD direction) from the intermediate layer side surface of the carrier exposed by peeling. In addition, AES analysis was performed in the depth direction (direction parallel to the thickness direction of the carrier) using the following AES measuring apparatus at a total of 20 locations at 20 mm intervals in the longitudinal direction (MD direction).
Apparatus: AES measuring apparatus (manufactured by JEOL Ltd., model JAMP-7800F)
・ Degree of vacuum: 2.0 × 10 ⁻⁸ Pa
Sample tilt angle: 30 degrees Filament current: 2.22A
・ Probe voltage: 10kV
Probe current: 2.8 × 10 ⁻⁸ A
・ Probe diameter: about 500nm
・ Sputtering rate 1.9 nm / min (SiO ₂ conversion)
The analyzed elements were intermediate layer constituent metals (Ni, Co, Fe, W, Mo, V, Cr) and Cu, Zn, C and O. These elements were designated elements. Further, the concentration (at%) of each element was analyzed with the total of the designated elements as 100 at%. Depth (nm) is a sputtering rate at which the SiO ₂ and the object of the sputtering 1.9 nm / min (SiO ₂ equivalent) was calculated from the following equation based on the time of performing sputtering (min) .
Depth of measurement location (nm) = Sputtering rate 1.9 nm / min (SiO ₂ conversion) × Sputtering time (min)
Therefore, the depth (nm) means the depth (nm) (SiO ₂ equivalent depth (nm)) when SiO ₂ is sputtered. With respect to the obtained data, the concentration (at%) of each element was obtained using data processing software “Spectra investigator (Version 1.08)”.
In addition, an insulating substrate BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is applied to the ultrathin copper layer side of the copper foil with carrier under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours. It measured similarly about the copper foil with a carrier after making it thermocompression-bonded by.
And in each measurement location, the depth (distance) (nm) from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less is measured, and the intermediate layer side of the carrier In the range from the surface to a depth where the total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum and vanadium is 70 at% or less, the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) The presence or absence was confirmed.
In the “ASE analysis” column of Tables 2 and 3, for example, “2 to 5” in the “depth from the outermost surface until reaching Cr 5 at% [nm]” column is the atomic concentration of chromium in the above-described measurement at 20 locations. The minimum value and the maximum value of the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the value becomes 5 at% or less. That is, at the measurement location where the depth from the surface of the intermediate layer side of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less, the depth is 2 nm, and the measurement is the largest. In a place, it means that the depth was 5 nm.
Also, “Cu <Cr” in the “Relationship between Crat% and Cuat%” column in the “ASE analysis” column of Tables 2 and 3 indicates the intermediate layer of the carrier at 12 or more of the total of 20 measurement points described above. A portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) in a range from the side surface to a depth where the total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum and vanadium is 70 at% or less It means that there was. In addition, “Cu> Cr” has a total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum and vanadium from the surface on the intermediate layer side of the carrier in one or more of the above-mentioned 20 measurement locations. It means that there was no portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%) in the range up to a depth of 70 at% or less.

<XPS analysis>
The carrier is peeled off from the copper foil with a carrier in accordance with the 90 ° peeling method (JIS C 6471), and 10 points in the width direction (TD direction) and the longitudinal direction (MD direction) from the intermediate layer side surface of the carrier. The XPS analysis in the depth direction was performed using the following XPS measuring apparatus at a total of 20 locations at intervals of 20 mm.
Then, the atomic concentration (%) of chromium at the depth x (unit: nm) obtained from the depth direction analysis from the surface of the intermediate layer side of the carrier by XPS is e (x), and the atomic concentration (%) of zinc is f (x), nickel atomic concentration (%) as g (x), copper atomic concentration (%) as h (x), oxygen total atomic concentration (%) as i (x), carbon The atomic concentration (%) of the carrier is j (x), the other atomic concentration (%) is k (x), and the interval of the depth direction analysis depth x (nm) from the intermediate layer side surface of the carrier [ 0, 1.0], E (x) = ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫ i (x) dx + 各 j (x) dx + ∫k (x) dx), and E (x) was calculated at each measurement location.
Thereafter, the arithmetic average value of E (x) at 20 points in the width direction (TD direction) and 10 points in the longitudinal direction (MD direction) at 10 points in the longitudinal direction (MD direction) is set to the Cr (%) average value. The standard deviation of (x) was defined as Cr (%) standard deviation. The depth x (nm) is a depth in terms of SiO ₂ as in the above-described AES analysis.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )
A carrier in which an insulating substrate BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is thermocompression bonded to the ultrathin copper layer under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. It measured similarly about the copper foil with attachment.
In the XPS analysis of Tables 2 and 3, the "Cr (%) average value" column and the "Cr (%) standard deviation" column each have 10 points at 20 mm intervals in the width direction and 10 points at 20 mm intervals in the longitudinal direction, for a total of 20 The Cr (%) average value and Cr (%) standard deviation obtained by measuring the points are shown.

<Peel strength>
Heat the copper foil with a carrier to the BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Crimped and pasted. Subsequently, the carrier side was pulled with a load cell, and 10 points were measured at intervals of 30 mm in the longitudinal direction and 10 points at intervals of 30 mm in the width direction in accordance with the 90 ° peeling method (JIS C 6471). The target peel strength is 2 to 30 N / m.
Test conditions and results are shown in Tables 1-3.

(Evaluation results)
In each of Examples 1 to 26, when the analysis in the depth direction by AES was performed, the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium became 5 at% or less. Since it was 0.2 nm or more and 10 nm or less, favorable peel strength was shown.
In all of Comparative Examples 1 to 7, the depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium was 5 at% or less was outside the range of 0.2 nm to 10 nm. The peel strength varied.
In FIG. 5, the AES analysis result of the depth direction before the board | substrate bonding of the intermediate layer side surface of the partial sample of Example 2 is shown.

Claims (43)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The intermediate layer includes one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum and vanadium and chromium,
The carrier is peeled from the carrier-attached copper foil in accordance with JIS C 6471, and from the intermediate layer side surface of the peeled carrier, 10 places and a longitudinal direction (MD direction) at intervals of 20 mm in the width direction (TD direction). ) In the depth direction by AES for a total of 20 locations at 20 mm intervals, in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less in 12 or more of the 20 locations. The copper foil with a carrier whose depth from the surface of the intermediate layer side of the carrier is 0.2 nm or more and 10 nm or less. _2. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 16 or more of the 20 locations is 0.2 nm or more and 10 nm or less. The copper foil with a carrier as described in 2. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 18 or more of the 20 locations is 0.2 nm or more and 10 nm or less. The copper foil with a carrier as described in 2. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at all 20 of the 20 locations is 0.2 nm or more and 10 nm or less. The copper foil with a carrier as described in 2. _2. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 12 or more of the 20 locations is 0.5 nm or more and 9 nm or less. The copper foil with a carrier as described in any one of -4. 6. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium is 5 at% or less at 12 or more of the 20 locations is 1 nm or more and 9 nm or less. Copper foil with carrier. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 12 or more of the 20 locations is 1.5 nm or more and 8 nm or less. The copper foil with a carrier as described in 2. 8. The depth from the intermediate layer side surface of the carrier in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 12 or more of the 20 locations is 2 nm or more and 5 nm or less. Copper foil with carrier.   The copper foil with a carrier according to any one of claims 1 to 8, wherein the intermediate layer further contains copper.   The copper foil with a carrier according to any one of claims 1 to 9, wherein the intermediate layer further contains zinc.   When the carrier was peeled off from the copper foil with carrier in accordance with JIS C 6471 and analyzed in the depth direction by AES from the intermediate layer side surface of the carrier, nickel, cobalt, 11. A portion having an atomic concentration of copper (at%) <atomic concentration of chromium (at%) in a range up to a depth at which the total atomic concentration of iron, tungsten, molybdenum and vanadium is 70 at% or less. The copper foil with a carrier as described in any one of these. An insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off from the copper foil with carrier in accordance with JIS C 6471. When analysis in the depth direction by AES was carried out from the intermediate layer side surface of the carrier at a total of 20 locations in the width direction (TD direction) at 20 mm intervals and 10 locations in the longitudinal direction (MD direction) at 20 mm intervals. The depth from the surface in terms of SiO ₂ until the atomic concentration of chromium becomes 5 at% or less at 12 or more of the 20 locations is 0.2 nm or more and 10 nm or less. The copper foil with a carrier according to one item. An insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off from the copper foil with carrier in accordance with JIS C 6471. From the intermediate layer side surface of the carrier to the depth at which the total atomic concentration of nickel, cobalt, iron, tungsten, molybdenum and vanadium is 70 at% or less from the intermediate layer side surface when analysis in the depth direction is performed by AES The copper foil with a carrier according to claim 1, wherein the copper foil has a portion where the atomic concentration of copper (at%) <the atomic concentration of chromium (at%). In the intermediate layer, a nickel, cobalt, iron, tungsten, either the total deposition amount of molybdenum and vanadium of claims 1 to 13 1000~40000μg / dm ^2, the amount of deposition of chromium satisfy 5~200μg / dm ² one The copper foil with a carrier according to the item.   The intermediate layer is made of nickel, cobalt, iron, tungsten, molybdenum, vanadium, or an alloy containing one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum, and vanadium on a carrier. The copper foil with a carrier as described in any one of Claims 1-14 which has any one layer and the layer containing any one or more of chromium, a chromium alloy, and the oxide of chromium in this order.   The copper foil with a carrier according to claim 15, wherein the layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium includes a chromate treatment layer.   The carrier-added copper foil according to any one of claims 1 to 16, wherein the carrier further has an intermediate layer and an ultrathin copper layer in this order on a surface opposite to the surface having the ultrathin copper layer. .   The copper foil with a carrier according to any one of claims 1 to 17, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil.   The copper foil with a carrier as described in any one of Claims 1-18 which has a roughening process layer in any one or both of the said ultra-thin copper layer surface and the surface of the said carrier.   The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. The copper foil with a carrier according to claim 19 which is a layer.   21. Copper with a carrier according to claim 19 or 20, wherein the surface of the roughened layer has at least one layer selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. Foil.   The surface of the said ultra-thin copper layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier of description.   The copper foil with a carrier as described in any one of Claims 1-21 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 20, further comprising a resin layer on the roughening treatment layer.   The copper foil with a carrier according to claim 21 or 22, comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.   The copper foil with a carrier according to any one of claims 23 to 25, wherein the resin layer is an adhesive resin.   The copper foil with a carrier according to any one of claims 23 to 26, wherein the resin layer is a semi-cured resin.   The laminated body manufactured using the copper foil with a carrier as described in any one of Claims 1-27.   It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-27, Comprising: The laminated body by which one part or all part of the end surface of the said copper foil with a carrier is covered with the said resin. .   The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-27.   The electronic device manufactured using the printed wiring board of Claim 30.   The copper foil with a carrier according to any one of claims 1 to 27 is laminated on the carrier side of the copper foil with a carrier according to any one of claims 1 to 27 from the carrier side. Laminated body.   The laminate according to claim 32, wherein the carrier of the one copper foil with a carrier and the carrier of the other copper foil with a carrier are directly laminated via an adhesive as necessary.   The laminate according to claim 32 or 33, wherein the carrier of the one copper foil with a carrier and the carrier of the other copper foil with a carrier are joined. A step of providing two layers of a resin layer and a circuit at least once on the surface of the laminate according to any one of claims 28, 29 and 32-34; and
A method for producing a printed wiring board, comprising: forming the ultrathin copper layer from the carrier-attached copper foil of the laminate after forming the resin layer and the circuit layer at least once.   The manufacturing method of the printed wiring board using the laminated body as described in any one of Claim 28, 29, 32-34.   After forming a plating layer containing nickel on the carrier, forming the intermediate layer by forming a plating layer containing chromium or a chromate treatment layer, and the ultrathin copper by electrolytic plating on the intermediate layer The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-27 including the process of forming a layer.   The manufacturing method of the copper foil with a carrier of Claim 37 which further includes the process of forming a roughening process layer on the said ultra-thin copper layer. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 27 and an insulating substrate;
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 27,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. A step of laminating the carrier-attached copper foil according to any one of claims 1 to 27 on a resin substrate from the carrier side,
Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 27 and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. A step of laminating the carrier-side surface of the copper foil with a carrier according to any one of claims 1 to 27 and a resin substrate;
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method for producing a printed wiring board, comprising the step of peeling the carrier from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.