JP2016193524A - Metal foil with carrier, laminate, printed wiring board, electronic device, manufacturing method of metal foil with carrier and manufacturing method of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal foil with a carrier high in adhesive force between the carrier and a metal layer before a laminating process to an insulation substrate, having no extreme increase or decrease of adhesion property between the carrier and the metal layer by the laminating process to the insulation substrate, and capable of easily peeling carrier/metal layer.SOLUTION: There is provided a metal foil with a carrier having the carrier, a first intermediate layer containing oxygen and a metal layer in this order and having average of depth from a surface of a first intermediate layer side of the peeled carrier till oxygen at 10 locations becomes 10 at% or less in terms of SiOof 0.5 nm to 15 nm and standard deviation/average value of 0.6 or less when the carrier of the metal foil with the carrier is peeled according to JIS C 6471 and analysis in a depth direction by XPS is conducted for total 10 locations of 5 locations with 20 mm interval in a width direction (TD direction) of the metal foil of the carrier and 5 locations with 20 mm interval in a longer direction (MD direction).SELECTED DRAWING: Figure 5

Description

  The present invention relates to a metal foil with a carrier, a laminate, a printed wiring board, an electronic device, a method for manufacturing a metal foil with a carrier, and a method for manufacturing 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. Thus, 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 first intermediate layer. The general usage of the carrier-attached copper foil is to bond the surface of the ultrathin copper layer to an insulating substrate and thermocompression bond, and then peel the carrier through the first intermediate layer.

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

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

  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 length 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) When E (x) is measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction, the standard deviation of E (x) is σE, and the variation coefficient of chromium concentration is XE = σE × 100 / (E (x) 20-point arithmetic average value) When XE satisfies 40.0% or less, the E (x) 20-point arithmetic average value satisfies 1-30%. It is described in Patent Document 4.

  Alternatively, a composite copper foil having a copper or copper alloy support characterized by having a nickel layer covered with an oxide film on the support side between the copper or copper alloy support and the ultrathin copper foil Patent Document 5 discloses a printed circuit board using the composite copper foil.

  Or a copper foil with a carrier comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer, wherein the intermediate layer is electrically conductive oxidized Patent Document 6 discloses a copper foil with a carrier including an object.

  Or a copper foil with a carrier comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer, wherein the intermediate layer is a spinel crystal structure Patent Document 7 discloses a carrier-attached copper foil having an oxide having the following.

  Or a copper carrier with a copper carrier comprising a rolled copper foil or an electrolytic copper foil, a nickel layer, a copper layer structure, and can be peeled off at less than 0.5 kg / cm. Patent Document 8 describes a copper foil with a copper carrier characterized by having a nickel layer on the copper layer and a nickel layer on the copper layer side.

  Alternatively, a copper carrier (A) made of rolled copper foil or electrolytic copper foil, a 0.03 to 2 μm thick nickel layer (B) formed on the copper carrier (A), and formed on the nickel layer (B) From a layer (C) made of gold, a platinum group metal or an alloy thereof having a thickness of 0.3 to 15 nm, and a copper layer (D) formed on the layer (C) made of the gold, platinum group metal or an alloy thereof Patent Document 9 describes a copper foil with a copper carrier, which is characterized in that.

JP 2006-022406 A JP 2010-006071 A JP 2007-007937 A JP 2014-195871 A JP 2002-368365 A JP 2014-172183 A JP 2014-172184 A WO2012-132572 WO2012-132578

  In the metal foil with carrier, the metal foil should not be easily peeled off from the carrier before the lamination process on the insulating substrate, while the carrier should be easily peeled off from the metal foil after the lamination process on the insulating substrate. is there.

  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 preventing layer and the first intermediate layer may be either, but the examples described are all for the carrier foil, the first intermediate layer, the diffusion preventing layer, and the electrolytic copper plating. This is the order, and the first intermediate layer / diffusion prevention layer interface may peel off during peeling. 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.

  About patent document 4, after peeling an ultra-thin copper layer from copper foil with a carrier, the in-plane distribution of peeling strength is controlled by controlling the variation of the chromium concentration on the peeling surface of the carrier and the in-plane distribution of the chromium concentration. Although it was found to be extremely effective in improving the peelability at the carrier / ultra-thin copper foil interface by controlling within a certain range, the chromium itself contains nickel and copper foil contained in the intermediate layer and The fact that there is no effect to suppress the diffusion of copper in the ultrathin copper layer over that of nickel is known in consideration of the diffusion of each metal, and it is insufficient to control the variation in peel strength only by the chromium concentration. all right.

  In Patent Documents 5, 6, and 7, since the conditions for uniformly controlling the oxide film are unclear, there arises a problem that the peel strength varies depending on the distribution of the oxide film.

  In Patent Documents 8 and 9, there are cases where the oxidation method of the Ni plating surface is atmospheric exposure, and the oxide film is thin and cannot be peeled off.

  Therefore, the present invention has high adhesion between the carrier and the metal layer before the lamination process to the insulating substrate, while there is no extreme increase or decrease in adhesion between the carrier and the metal layer due to the lamination process to the insulation substrate, It is an object to provide a metal foil with a carrier that can be easily peeled off by a carrier / metal layer.

In order to achieve the above object, the present inventor has conducted extensive research and found that in a metal foil with a carrier having a first intermediate layer containing oxygen, the carrier is peeled off by a predetermined method between the first intermediate layer / metal layer. Average depth of carrier from the first intermediate layer side surface in terms of SiO ₂ until the oxygen concentration becomes 10 at% or less when analysis in the depth direction by XPS is performed from the first intermediate layer side surface of And it discovered that the metal foil with a carrier which can solve the said subject can be provided by controlling so that a standard deviation / average value may become a predetermined range.

The present invention has been completed based on the above knowledge, and in one aspect, a carrier-attached metal foil having a carrier, an oxygen-containing first intermediate layer, and a metal layer in this order, The carrier is peeled in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, the width direction (TD direction) is spaced at 20 mm intervals and the longitudinal direction (MD direction) is spaced 20 mm. When the analysis in the depth direction by XPS is performed on a total of 10 locations in 5 locations, the first intermediate of the peeled carrier in terms of SiO ₂ until the oxygen in the 10 locations is 10 at% or less. It is a metal foil with a carrier whose average value of the depth from the layer side surface is 0.5 nm or more and 15 nm or less, and whose standard deviation / average value is 0.6 or less.

  In one embodiment of the metal foil with a carrier of the present invention, the first intermediate layer includes a chromate treatment layer.

In another embodiment of the metal foil with a carrier of the present invention, the carrier is peeled from the metal foil with a carrier in accordance with JIS C 6471, and the first intermediate layer side surface of the peeled carrier is used. When the analysis in the depth direction by XPS was performed on a total of 10 locations of 5 locations at intervals of 20 mm in the width direction (TD direction) and 5 locations at intervals of 20 mm in the longitudinal direction (MD direction), the Cr at 10 locations was 5 at. The average value of the depth from the first intermediate layer side surface of the peeled carrier in terms of SiO ₂ until it becomes% or less is 0.2 nm or more and 10 nm or less.

In still another embodiment of the metal foil with a carrier according to the present invention, the carrier is peeled from the metal foil with a carrier in accordance with JIS C 6471, and the first intermediate layer side surface of the peeled carrier is used. When the analysis in the depth direction by XPS was performed on a total of 10 locations of 5 locations at 20 mm intervals in the width direction (TD direction) and 5 locations at 20 mm intervals in the longitudinal direction (MD direction), the 10 locations of Cr The standard deviation / average value of the depth from the surface of the first intermediate layer of the peeled carrier in terms of SiO ₂ up to 5 at% or less is 0.6 or less.

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

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

In still another embodiment of the metal foil with a carrier of the present invention, the Cu concentration in a range of the depth in terms of SiO ₂ from the surface of the first intermediate layer side of the carrier until the oxygen becomes 10 at% or less. The average value of the maximum values is 15 at% or less.

  In still another embodiment of the metal foil with a carrier according to the present invention, the first intermediate layer comprises Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. One or more elements selected from the group consisting of:

In still another embodiment, the metal foil with a carrier of the present invention is Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al included in the first intermediate layer. The total adhesion amount of one or more elements selected from the group consisting of is 1000 to 50000 μg / dm ² .

  In still another embodiment, the metal foil with a carrier of the present invention has a second intermediate layer between the carrier and the first intermediate layer.

  In still another embodiment, the metal foil with a carrier of the present invention has a third intermediate layer between the first intermediate layer and the metal layer.

  In still another embodiment of the metal foil with a carrier according to the present invention, the second intermediate layer comprises Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. One or more elements selected from the group consisting of:

In still another embodiment, the metal foil with a carrier of the present invention is Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al included in the second intermediate layer. The total adhesion amount of one or more elements selected from the group consisting of is 1000 to 50000 μg / dm ² .

  In still another embodiment, the metal foil with a carrier of the present invention has a third intermediate layer between the first intermediate layer and the metal layer.

  In still another embodiment of the metal foil with a carrier according to the present invention, the third intermediate layer comprises Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. One or more elements selected from the group consisting of:

In still another embodiment of the metal foil with a carrier of the present invention, the first intermediate layer is a chromate-treated layer, and the amount of Cr deposited is 10 to 50 μg / dm ² .

In still another embodiment of the metal foil with a carrier of the present invention, the metal foil with a carrier is thermocompression bonded from the metal layer side to an insulating substrate in the atmosphere at a pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. The carrier is peeled off from the metal foil with a carrier in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, the width direction (TD direction) at 5 mm intervals and When the analysis in the depth direction by XPS is performed on a total of 10 locations at 20 mm intervals in the longitudinal direction (MD direction), the exfoliation in terms of SiO ₂ until the oxygen at the 10 locations becomes 10 at% or less. The average value of the depth of the carriers formed from the surface on the first intermediate layer side is not less than 0.5 nm and not more than 15 nm.

In still another embodiment of the metal foil with a carrier of the present invention, the metal foil with a carrier is thermocompression bonded from the metal layer side to an insulating substrate in the atmosphere at a pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. The carrier is peeled off from the metal foil with a carrier in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, the width direction (TD direction) at 5 mm intervals and When the analysis in the depth direction by XPS is performed on a total of 10 locations at 20 mm intervals in the longitudinal direction (MD direction), the exfoliation in terms of SiO ₂ until the oxygen at the 10 locations becomes 10 at% or less. The standard deviation / average value of the depth from the surface of the first intermediate layer side of the prepared carrier is 0.6 or less.

In still another embodiment of the metal foil with a carrier of the present invention, the metal foil with a carrier exposed by peeling the carrier from the metal foil with a carrier in accordance with JIS C 6471 and peeling the carrier. From the surface of the metal layer of the first intermediate layer side, a total of 10 locations of 5 locations at intervals of 20 mm in the width direction (TD direction) and 5 locations at intervals of 20 mm in the longitudinal direction (MD direction) in the depth direction by XPS When the analysis was performed, SiO ₂ until the total concentration of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al at the 10 locations was 5 at% or less. The average depth of the metal layer from the first intermediate layer side surface in terms of conversion is 0.5 nm or more and 300 nm or less.

In still another embodiment of the metal foil with a carrier according to the present invention, the metal with a carrier exposed by peeling the carrier from the metal foil with a carrier in accordance with JIS C 6471 and peeling the carrier. From the surface on the first intermediate layer side of the metal layer of the foil, the depth direction by XPS for a total of 10 locations of 5 locations at intervals of 20 mm in the width direction (TD direction) and 5 locations at intervals of 20 mm in the longitudinal direction (MD direction) When the above-mentioned analysis was performed, the SiO up to the total concentration of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al at 10 locations was 5 at% or less. The standard deviation / average value of the depth from the surface of the metal layer in terms of ₂ is 0.6 or less.

  In still another embodiment of the metal foil with a carrier of the present invention, the carrier is a Cu-based material.

  In still another embodiment of the metal foil with a carrier of the present invention, the metal layer is a Cu-based plating layer.

  In still another embodiment of the metal foil with a carrier of the present invention, the first intermediate layer is formed of nickel, cobalt, iron, tungsten, molybdenum, vanadium, or nickel, cobalt, iron, tungsten, molybdenum from the carrier side. And any one layer of an alloy containing one or more elements selected from the group consisting of vanadium, and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. .

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

  In still another embodiment of the metal foil with a carrier of the present invention, the carrier further has a first intermediate layer and a metal layer in this order on a surface opposite to the surface having the metal layer.

  In still another embodiment of the metal 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 metal foil with a carrier of the present invention has a roughened layer on one or both of the surface of the metal layer and the surface of the carrier.

  In still another embodiment of the metal foil with a carrier of 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 a layer made of any single substance or an alloy containing one or more kinds.

  In still another embodiment, the metal foil with a carrier of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. It has the above layers.

  In still another embodiment, the metal foil with a carrier of the present invention has at least one 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 metal layer. Has a layer.

  In yet another embodiment, the metal foil with a carrier of the present invention includes a resin layer on the metal layer.

  In still another embodiment, the metal foil with a carrier of the present invention includes a resin layer on the roughening treatment layer.

  In still another embodiment, the metal foil with a carrier according to the present invention has 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. Is provided.

  In another embodiment of the metal foil with a carrier of the present invention, the resin layer is an adhesive resin.

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

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

  In yet another aspect of the present invention, the laminate includes the metal foil with a carrier of the present invention and a resin, wherein a part or all of the end face of the metal foil with a carrier is covered with the resin. It is.

  In still another aspect, the present invention is a laminate in which one metal foil with a carrier of the present invention is laminated from the carrier side to the carrier side of another metal foil with a carrier of the present invention.

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

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

  In yet another aspect of the present invention, a step of providing at least one time a resin layer and a circuit on the surface of the laminate of the present invention, and at least once forming the resin layer and the circuit two layers. It is a manufacturing method of a printed wiring board including the process of peeling the said metal layer from the metal foil with a carrier of the said laminated body later.

  In one embodiment of the method for producing a metal foil with a carrier according to the present invention, after forming a plating layer containing nickel and the like on the carrier, a plating layer containing chromium or a chromate treatment layer is formed to form the first intermediate layer. Forming a layer and forming the metal layer on the first intermediate layer by electrolytic plating.

  In another embodiment, the method for producing a metal foil with a carrier of the present invention further includes a step of forming a roughened layer on the metal layer.

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

  In another aspect of the present invention, a step of forming a circuit on the metal layer side surface or the carrier side surface of the metal foil with carrier of the present invention, the metal of the metal foil with carrier so that the circuit is buried. A step of forming a resin layer on the layer side surface or the carrier side surface, a step of forming a circuit on the resin layer, a step of peeling the carrier or the metal layer after forming a circuit on the resin layer, and After the carrier or the metal layer is peeled off, the metal layer or the carrier is removed to expose the circuit embedded in the resin layer formed on the metal layer side surface or the carrier side surface. It is the manufacturing method of the printed wiring board including the process to make.

  In yet 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, forming a circuit on the metal layer side surface or the carrier side surface of the carrier-attached copper foil. A step, a step of forming a resin layer on the metal layer side surface or the carrier side surface of the carrier-attached copper foil so that the circuit is buried, a step of forming a circuit on the resin layer, a circuit on the resin layer After forming the carrier, the step of peeling the carrier or the metal layer, and after peeling the carrier or the metal layer, removing the metal layer or the carrier, the metal layer side surface or the carrier It is a manufacturing method of a printed wiring board including the process of exposing the circuit embedded in the resin layer formed in the side surface.

  In yet another aspect of the present invention, the step of laminating the metal layer side surface of the carrier-attached metal foil of the present invention or the carrier side surface and a resin substrate, the side of the metal foil with carrier and the side laminated with the resin substrate, Is a step of providing at least once a resin layer and a circuit on the opposite metal layer side surface or the carrier side surface, and after forming the resin layer and the circuit two layers, the carrier-attached copper foil A method for producing a printed wiring board, comprising a step of peeling the carrier or the metal layer.

  In yet another aspect of the present invention, the step of laminating the carrier-side surface of the metal foil with carrier and the resin substrate of the present invention, the metal layer on the opposite side of the metal foil with carrier and the side laminated with the resin substrate. Printed wiring including a step of providing at least one layer of a resin layer and a circuit on a side surface, and a step of peeling the carrier from the metal foil with a carrier after forming the two layers of the resin layer and the circuit It is a manufacturing method of a board.

  According to the present invention, the adhesion between the carrier and the metal layer is high before the lamination process to the insulating substrate, while there is no extreme increase or decrease in the adhesion between the carrier and the metal layer due to the lamination process to the insulation substrate, A metal foil with a carrier that can be easily peeled off by a carrier / metal layer can be provided.

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 a XPS analysis result of the depth direction before the board | substrate bonding of the surface of the 1st intermediate | middle layer side of the carrier of the partial sample of Example 15. FIG. It is the schematic of the cross section of the width direction of a circuit pattern, and the schematic of the calculation method of the etching factor using this schematic diagram.

<Career>
Carriers that can be used in the present invention are generally metal foils, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, It is provided in the form of titanium foil and titanium alloy foil, resin film, insulating resin film, polyimide film, LCD film and the like.
The metal foil that can be used in the present invention is preferably a copper-based material, preferably a copper material, from the viewpoint of raw material costs. Here, the copper-based material means a material containing copper, for example, a metal foil containing copper. The copper-based material is preferably a metal foil containing 50 mass% or more of copper, more preferably a metal foil containing 60 mass% or more of copper, more preferably a metal foil containing 70 mass% or more of copper, more preferably copper. Is a metal foil containing 80% by mass or more, more preferably a metal foil containing 90% by mass or more of copper. Moreover, a copper material means the material which has copper as a main component. A material such as a copper-based material or a copper material is generally provided in the form of a rolled copper foil or an 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 8-150 μm, more typically 8-120 μm, more typically 8-70 μm, more typically 12-70 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 occurrence of folding wrinkles, for example, it is effective to smooth the transport roll of the metal foil manufacturing apparatus with a carrier and shorten the distance between the transport roll and the next transport roll. In addition, when metal 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 metal 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 roughening treatment layer on the surface opposite to the surface on which the metal layer of the carrier is provided means that when the carrier is laminated on a support such as a resin substrate from the surface side having the roughening treatment layer, This has the advantage that the resin substrate is difficult to peel off.

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

<First intermediate layer>
A first intermediate layer is provided on one or both sides of the carrier. Thus, the carrier may further include the first intermediate layer and the metal layer in this order on the surface opposite to the surface having the metal layer.
The first intermediate layer used in the present invention needs to contain oxygen. When oxygen is contained in the first intermediate layer, diffusion of the carrier component and the metal layer component is suppressed in the first intermediate layer, and a metal foil with a carrier that can be easily peeled off by the carrier / metal layer can be provided.

The first intermediate layer is composed of oxygen and one or more elements or alloys from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. Or it is preferable that an organic substance is included.
Moreover, it is preferable that a 1st intermediate | middle layer is a layer containing 1 or more types in any one of chromium, a chromium alloy, and the oxide of chromium. Moreover, it is preferable that the layer containing any one or more of chromium, chromium alloy, and chromium oxide includes a chromate treatment layer.
Moreover, the 1st intermediate | middle layer is 1 type or 2 types or more from the group which consists of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al from a carrier side. It is preferable to have a layer containing an element, an alloy or an organic substance and a layer containing any one or more of chromium, a chromium alloy and a chromium oxide in this order. Moreover, it is preferable that the layer containing any one or more of chromium, chromium alloy, and chromium oxide includes a chromate treatment layer.

In order to have a first intermediate layer containing oxygen, a method in which each metal is oxidized by atmospheric oxidation, atmospheric heating, anodization, or the like (oxidation after the formation of the first intermediate layer), a first intermediate layer having oxygen in advance is formed. May be. Moreover, the conditions suitable for each process are applied to the process conditions of each process.
More preferably, the first intermediate layer forms a chromate treatment layer. Since chromium plating forms a dense chromium oxide layer on the surface, when forming a metal foil by electroplating, there is a risk that the electrical resistance increases and pinholes are likely to occur. A chromium oxide layer that is less dense than chromium plating is formed on the surface on which the chromate treatment layer is formed. Therefore, resistance to formation of the surface treatment foil by electroplating is difficult, and pinholes can be reduced. . Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming a metal foil by electroplating becomes lower than that of a normal chromate treatment layer, and the generation of pinholes can be further suppressed. it can. In addition, when using electrolytic copper foil as a carrier, it is preferable to provide a 1st intermediate | middle layer in a shiny surface from a viewpoint of reducing a pinhole.
Moreover, it is preferable that Cu is contained in the first intermediate layer because the peel strength at the carrier / metal layer interface can be easily adjusted. However, when Cu is immersed when the carrier is Cu-based and the first intermediate layer is an acid-based solution, Cu on the surface opposite to the surface on which the first intermediate layer is provided dissolves. Therefore, management of Cu concentration is very important.
The first intermediate layer preferably further contains zinc. When zinc is contained in the first intermediate layer, it becomes easier to adjust the peel strength at the carrier / metal layer interface. When zinc is added to the first intermediate layer forming solution, the first intermediate layer can be easily controlled.

  Here, the chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic 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.

  The first intermediate layer can be formed by, for example, electrolytic chromate or immersion chromate. In addition, when providing a 1st 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.

<Metal layer>
A metal layer is provided on the first intermediate layer. Note that another layer may be provided between the first intermediate layer and the metal layer. The metal layer is preferably composed of elements in accordance with each purpose, and for example, a Cu-based plating layer may be used. Here, the Cu-based plating layer is a plating layer containing copper. The Cu-based plating layer is preferably a plating layer containing 50 mass% or more of copper, preferably a plating layer containing 60 mass% or more of copper, and preferably a plating layer containing 70 mass% or more of copper. A plating layer containing 80% by mass or more of copper is preferable, and a plating layer containing 90% by mass or more of copper is preferable.

  The metal layer may contain one or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. The metal layer may be a metal layer made of one or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al.

  The metal layer is any one 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. A seed layer may be included, and a layer including any one or more of chromium and a chromium alloy may be included. Moreover, the metal layer may have a plurality of layers, for example, a plurality of the aforementioned layers.

  When the metal layer is an ultrathin copper layer, the ultrathin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, and copper cyanide. Since it is used with a general electrolytic copper foil and can form a copper foil at a high current density, it is preferable to form an ultrathin copper layer by electroplating using a copper sulfate bath. 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. A metal layer may be provided on both sides of the carrier.

<Second intermediate layer>
The metal foil with a carrier of the present invention preferably has a second intermediate layer between the carrier and the first intermediate layer. By this second intermediate layer, diffusion of the carrier component and the metal layer component is further suppressed, and a metal foil with a carrier that can be more easily peeled between the carrier and the first intermediate layer can be provided.

  The second intermediate layer preferably contains one or more elements from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. .

<Third intermediate layer>
The metal foil with a carrier of the present invention preferably has a third intermediate layer between the first intermediate layer and the metal layer. By this third intermediate layer, diffusion of the carrier component and the metal layer component is further suppressed, and a metal foil with a carrier that can be more easily peeled between the carrier and the first intermediate layer can be provided. Further, when the metal foil with carrier is laminated on the resin from the metal layer side and then the metal layer is peeled from the metal foil with carrier, the third intermediate layer remains on the carrier side surface of the metal layer. Therefore, when an element having good laser absorbency is used in the third intermediate layer, the laser absorbability is improved when laser processing is performed from the carrier side surface of the metal layer. It is preferable because it improves.

The third intermediate layer preferably contains one or more elements from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. . The diffusion of the carrier component and the metal layer component is further suppressed, and a metal foil with a carrier that can be more easily peeled between the carrier and the first intermediate layer can be provided, and the laser processability of the metal layer is improved. It is.
The second intermediate layer and the third intermediate layer containing one or more elements of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al are, for example, It can be formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the second intermediate layer and the third intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.

<Metal foil with carrier>
The metal foil with a carrier of the present invention has a carrier, a first intermediate layer, and a metal layer in this order. A second intermediate layer may be provided between the carrier / first intermediate layer, and a third intermediate layer may be provided between the first intermediate layer / metal layer. The method of using the metal foil with carrier itself is well known to those skilled in the art. For example, the surface of the metal layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base material. Epoxy resin, glass cloth / glass nonwoven fabric composite base material Epoxy resin and glass cloth base material Epoxy resin, polyester film, polyimide film, etc. The printed wiring board can be finally manufactured by etching the conductive pattern.

<Amount of deposited elements in the first and second intermediate layers>
The total adhesion amount of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al constituting the first intermediate layer and / or the second intermediate layer is 1000 to 50000 μg / dm ² is preferred. If it is less than 1000 μg / dm ² , the effect of providing the first intermediate layer and the second intermediate layer is small, it is difficult to suppress the diffusion of the carrier component and the metal layer component, and it may be difficult to stably obtain an appropriate peel strength. There is. On the other hand, if it exceeds 50000 μg / dm ² , the stress due to these elements increases and the carrier may be warped. The total adhesion amount of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al constituting the first intermediate layer and / or the second intermediate layer is more preferably 5000 to 30000 μg / dm ² .
When the first intermediate layer is a chromate-treated layer, the total amount of Cr deposited is preferably 10 to 50 μg / dm ² . If it is less than 10 μg / dm ² , the effect of providing a chromate treatment layer may be small (the peel strength does not change greatly). On the other hand, if it is less than 50 μg / dm ² , the chromate treatment layer may be thick and the adhesion of the metal layer may be poor.

<Amount of adhered elements in the third intermediate layer>
The total adhesion amount of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al constituting the third intermediate layer is preferably 50 to 50000 μg / dm ^2. . If it is less than 50 μg / dm ² , the effect of providing the third intermediate layer may be reduced. On the other hand, if it exceeds 50000 μg / dm ² , the stress due to these elements increases and the carrier may be warped. The total adhesion amount of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al constituting the third intermediate layer is more preferably 250 to 30000 μg / dm ² , Even more preferably, it is 500 to 25000 μg / dm ² .

<Structure of metal foil with carrier>
In the metal foil with a carrier of the present invention, the carrier is peeled from the metal foil with a carrier in accordance with JIS C 6471, and from the surface on the first intermediate layer side of the peeled carrier in the width direction (TD direction). When the analysis in the depth direction by XPS was performed on a total of 10 sites at 5 sites at 20 mm intervals and 5 sites at 20 mm intervals in the longitudinal direction (MD direction), the SiO up to 10 at% or less of oxygen at the 10 sites was analyzed. The average value of the depth of the peeled carrier from the first intermediate layer side surface in terms of ₂ needs to be 0.5 nm or more and 15 nm or less, and the standard deviation / average value needs to be 0.6 or less. When the average value is less than 0.5 nm, the peel strength becomes higher than the target. When the average value exceeds 15 nm, the adhesion of the metal layer is deteriorated, and the problem that the peel strength is lower than the target is caused. The average value is preferably 5 nm or more and 10 nm or less. Further, when the standard deviation / average value exceeds 0.6, there arises a problem that the variation in peel strength increases.

Further, the carrier is peeled from the carrier-attached metal foil in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, at 5 locations at intervals of 20 mm in the width direction (TD direction) and When the analysis in the depth direction by XPS is performed on a total of 10 locations at intervals of 20 mm in the longitudinal direction (MD direction), the exfoliation in terms of SiO ₂ until the Cr at 10 locations is 5 at% or less. It is preferable that the average value of the depth of the generated carriers from the surface on the first intermediate layer side is 0.2 nm or more and 10 nm or less. If the average value is less than 0.2 nm, the effect of the presence of Cr may be small (the peel strength does not change significantly). On the other hand, when the average value exceeds 10 nm, the adhesion of the metal layer may be deteriorated, and there may be a problem that the peel strength is lower than the target. The average value is more preferably 2.5 nm or more and 5 nm or less.

Further, the carrier is peeled from the carrier-attached metal foil in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, at 5 locations at intervals of 20 mm in the width direction (TD direction) and When the analysis in the depth direction by XPS is performed on a total of 10 locations at intervals of 20 mm in the longitudinal direction (MD direction), the exfoliation in terms of SiO ₂ until the Cr at 10 locations is 5 at% or less. It is preferable that the standard deviation / average value of the depth of the formed carrier from the surface on the first intermediate layer side is 0.6 or less. If the standard deviation / average value exceeds 0.6, the peel strength may vary greatly.

It is preferable that the average value of the maximum value of Cu concentration in the range of the depth in terms of SiO ₂ from the surface of the carrier on the first intermediate layer side until the oxygen becomes 10 at% or less is 15 at% or less. If the average of the maximum Cu concentration is 15 at% or more, the peel strength may increase.

The carrier-attached metal foil is thermocompression bonded from the metal layer side to the insulating substrate in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is compliant with JIS C 6471 according to the carrier-attached metal foil. From the surface on the first intermediate layer side of the peeled carrier, a total of 10 points of 5 points at intervals of 20 mm in the width direction (TD direction) and 5 points at intervals of 20 mm in the longitudinal direction (MD direction) When the analysis in the depth direction by XPS was performed, the depth from the surface of the first intermediate layer side of the peeled carrier in terms of SiO ₂ until the oxygen at the 10 locations became 10 at% or less. The average value is preferably 0.5 nm or more and 15 nm or less. If the average value is less than 0.5 nm, the peel strength may be higher than the target. On the other hand, when the average value exceeds 15 nm, the adhesion of the metal layer may be deteriorated, and there may be a problem that the peel strength is lower than the target.

The carrier-attached metal foil is thermocompression bonded from the metal layer side to the insulating substrate in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is compliant with JIS C 6471 according to the carrier-attached metal foil. From the surface on the first intermediate layer side of the peeled carrier, a total of 10 points of 5 points at intervals of 20 mm in the width direction (TD direction) and 5 points at intervals of 20 mm in the longitudinal direction (MD direction) When the analysis in the depth direction by XPS was performed, the depth from the surface of the first intermediate layer side of the peeled carrier in terms of SiO ₂ until the oxygen at the 10 locations became 10 at% or less. The standard deviation / average value is preferably 0.6 or less. If the standard deviation / average value exceeds 0.6, there may be a problem that the variation in peel strength increases.

The carrier is peeled from the metal foil with a carrier in accordance with JIS C 6471, and from the surface of the peeled metal layer on the first intermediate layer side, at 5 locations at intervals of 20 mm in the width direction (TD direction) and the longitudinal direction. When analysis in the depth direction by XPS was performed on a total of 10 locations at intervals of 20 mm in the (MD direction), Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, It is preferable that the average value of the depth from the surface of the metal layer in terms of SiO ₂ until the total concentration of Ni, Zn and Al is 5 at% or less is 0.5 nm or more and less than 300 nm. When the average value is less than 0.5 nm, the laser processability may not be improved. On the other hand, when the thickness is 300 nm or more, the etching property of the metal layer may deteriorate. The average value is more preferably 5 nm or more and less than 100 nm.

The carrier is peeled from the metal foil with a carrier in accordance with JIS C 6471, and from the surface of the peeled metal layer on the first intermediate layer side, at 5 locations at intervals of 20 mm in the width direction (TD direction) and the longitudinal direction. When analysis in the depth direction by XPS was performed on a total of 10 locations at intervals of 20 mm in the (MD direction), Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, It is preferable that the standard deviation / average value of the depth from the surface of the metal layer in terms of SiO ₂ until the total concentration of Ni, Zn and Al is 5 at% or less is 0.6 or less. If the standard deviation / average value exceeds 0.6, there may be a problem that variations in laser processability and etching performance increase.

<Roughening treatment and other surface treatment>
On the surface of the metal layer, for example, a roughening treatment layer may be provided by performing a roughening treatment in order to improve 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 treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, and the surface of the metal layer may be formed. One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer may be formed. 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 metal foil with carrier>
The manufacturing method of the metal foil with a carrier of this invention forms a 1st intermediate | middle layer on a carrier, and forms a metal layer after that. A second intermediate layer may be formed between the carrier / first intermediate layer. A third intermediate layer may be formed between the first intermediate layer / metal layer.
The first intermediate layer forming method of the present invention uses air oxidation, atmospheric heating, anodization, chromate treatment, and the like. In order to control the oxygen concentration of the first intermediate layer, time in the case of air oxidation, temperature and time in the case of atmospheric heating, liquid temperature, current density and time in the case of anodization, and in the case of chromate treatment Controls conditions such as liquid composition, liquid temperature, current density, and time.

For more specific conditions, in the case of atmospheric heating, if the temperature is low, the processing time until the predetermined oxide layer is provided becomes long. On the other hand, if the temperature is high, the oxidation rate is fast and the concentration distribution in the in-plane oxide layer varies. Since it arises, 50-150 degreeC is preferable. Since it is difficult to form a predetermined oxide layer if the time is too short or too long, 10 to 100 s is preferable. In the case of anodic oxidation, if the current density is low, the processing time until the predetermined oxide layer is provided becomes long. On the other hand, if the current density is high, the oxidation rate is high and there is a possibility that the concentration distribution of the oxide layer in the surface varies. Therefore, 0.5 to 5 A / dm ₂ is preferable. What is necessary is just to adjust time so that a predetermined oxide layer may be formed, and in the case of this invention, around 30 s is preferable. In the case of chromate treatment, it is preferable to control the temperature of a plating solution or a treatment solution for forming a chromium-containing plating layer or a chromate treatment layer to 30 to 60 ° C. When the temperature of the plating solution or the treatment solution for forming the chromium-containing plating layer or the chromate treatment layer is less than 40 ° C., there may be a large variation in the peeling strength between the carrier and the ultrathin copper layer 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 may be a large variation in the peel strength between the carrier and the ultrathin copper layer 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 the chromate treatment layer containing chromium is preferably 2 seconds or more and 60 seconds or less. When the treatment time exceeds 60 seconds, there may be a large variation in the peel strength between the carrier and the ultrathin copper layer due to the variation 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.

The method for forming the second intermediate layer of the present invention is formed by plating or sputtering. In the case of plating, the liquid composition, pH, liquid temperature, current density and time are controlled, and in the case of sputtering, the conditions such as sputtering output, argon pressure and time are controlled to form the second intermediate layer.
The third intermediate layer forming method of the present invention is the same as the second intermediate layer forming method.

<Printed wiring boards, laminates, electronic equipment>
The method of using the metal foil with carrier itself is well known to those skilled in the art. For example, the surface of the metal layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base material. Epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, etc. The bonded metal layer can be etched into the intended conductor pattern, and finally a printed wiring board can be manufactured.

Moreover, the metal foil with a carrier provided with the carrier and the first intermediate layer laminated on the carrier and the metal layer laminated on the first intermediate layer includes a roughening treatment layer on the metal 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 metal layer, a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer, and a chromate treatment layer is provided on the heat resistance layer and the rust prevention layer. It may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
The metal foil with a carrier may include a resin layer on the metal layer, the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, or the silane coupling treatment layer. good. 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. 2002-179722, 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 liquid, which is used on the metal layer, the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane coupling agent. On the layer, for example, it is applied by a roll coater method or the like, and then heated and 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 metal foil with a carrier provided with the resin layer (metal foil with a carrier with resin) is laminated with the resin layer on a base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off. The metal layer is exposed (which is naturally exposed on the surface of the metal layer on the first intermediate layer side), and a predetermined wiring pattern is formed thereon.

  When this metal foil with a carrier with resin is used, the number of prepreg materials used at the time of 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 becomes less than 0.1 μm, the adhesive strength is reduced, and when this metal foil with a carrier with a 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 the metal foil with a carrier with a resin, a resin layer on the metal layer, the heat-resistant layer, the rust preventive layer, the chromate-treated layer, or the silane coupling-treated layer. It is also possible to manufacture in the form of a resin-coated copper foil in which no carrier is present after the carrier is coated with a semi-cured state and then peeled off.

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 metal foil with a carrier which concerns on this invention are shown.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing a metal foil with a carrier and an insulating substrate according to the present invention, a step of laminating the metal foil with a carrier and an insulating substrate, and with the carrier After laminating the metal foil and the insulating substrate so that the metal layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the metal foil with carrier, and then a semi-additive method and a modified semi-additive method And a step of forming a circuit by any one of the partial additive method and the 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 the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the metal foil with carrier and the insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Removing all of the metal 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 metal 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 metal foil with a carrier and an insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the metal 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 metal 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 a region including the resin and the through holes or / and blind vias exposed by removing the metal 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 metal foil with a carrier and an insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the metal layer exposed by peeling the carrier and the insulating resin substrate;
Removing all of the metal 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 a region including the resin and the through holes or / and blind vias exposed by removing the metal 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 metal foil with a carrier and an insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Removing all of the metal 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 metal 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 metal 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 metal foil with carrier and the insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the insulating layer and the metal 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 exposed metal layer surface by peeling off the carrier;
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the metal 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 metal foil with carrier and the insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a plating resist on the exposed metal 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 metal 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 the partly additive method, a step of preparing the metal foil with carrier and the insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the insulating layer and the metal 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 metal layer exposed by peeling the carrier;
Exposing the etching resist to form a circuit pattern;
Removing the metal 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 metal layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an 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 a method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the metal foil with a carrier and an insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the insulating layer and the metal 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 metal layer;
Exposing the etching resist to form a circuit pattern;
Removing the metal 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 a metal foil with a carrier and an insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, the step of peeling the carrier of the metal foil with carrier,
Providing a through hole or / and a blind via in the insulating layer and the metal 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 metal layer;
Exposing the etching resist to form a circuit pattern;
Removing the metal 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 metal foil with a carrier of this invention is demonstrated in detail using drawing. In addition, although an ultra-thin copper layer is mentioned as a metal layer here and it demonstrates to an example about the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer was further formed, not only this but a roughening process layer is Even when a metal foil with a carrier having a metal layer that is not formed is used, the following method for producing a printed wiring board can be similarly performed.
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 laminate (such as a copper clad laminate) can be produced using the metal foil with a carrier of the present invention. Here, the first intermediate layer of the present invention is a single one, laminated with the third intermediate layer, laminated with the second intermediate layer, laminated with the second intermediate layer and the third intermediate layer. When the intermediate layer is collectively referred to as an “intermediate layer”, for example, the laminate may have a structure in which “metal layer / intermediate layer / carrier / resin or prepreg” are laminated in this order. Layer / metal layer / resin or prepreg ”may be laminated in this order, or“ metal layer / intermediate layer / carrier / resin or prepreg / carrier / intermediate layer / metal layer ”. Alternatively, a structure in which “carrier / intermediate layer / metal layer / resin or prepreg / metal layer / intermediate layer / carrier” are laminated in this order may be employed. The resin or prepreg may be the resin layer described above, and the resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc. used in the resin layer described above may be used. May be included. The metal foil with carrier may be smaller than the resin or prepreg when viewed in plan.

Moreover, the manufacturing method of the printed wiring board of this invention is the process of laminating | stacking the said metal layer side surface or the said carrier side surface and resin substrate of the metal foil with a carrier of this invention, The metal layer side surface laminated | stacked with the said resin substrate. Or, after forming the two layers of the resin layer and the circuit at least once on the surface of the metal foil with carrier on the opposite side of the surface on the carrier side, and after forming the two layers of the resin layer and the circuit, It may be a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the metal layer from the metal foil with a carrier. As a specific example of the coreless construction method, first, the metal layer side surface or carrier side surface of the metal foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the metal foil with carrier opposite to the surface on the metal layer side or the carrier side surface laminated with the resin substrate. In the resin layer formed on the carrier side surface, another metal foil with a carrier may be laminated from the carrier side. In this case, a metal foil with a carrier is laminated in the order of carrier / first intermediate layer / metal layer or metal layer / first intermediate layer / carrier on both surfaces of the resin substrate with the resin substrate as the center. It has become. Another resin layer may be provided on the exposed metal layer or the exposed surface of the carrier, and 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 core layer board | substrate can be produced by peeling the metal layer or carrier of each metal foil with a carrier from a carrier or a metal layer. In addition, for the production of the coreless substrate described above, using two metal foils with a carrier, a laminate having a configuration of a metal layer / first intermediate layer / carrier / carrier / first intermediate layer / metal layer described later, Laminate having the structure of carrier / first intermediate layer / metal layer / metal layer / first intermediate layer / carrier, or the structure of carrier / first intermediate layer / metal layer / carrier / first intermediate layer / metal layer It is also possible to produce a laminated body and use the laminated body as a center. After providing two or more layers of the resin layer and the circuit on the surface of the metal layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and providing the resin layer and the two layers of the circuit once or more, The coreless substrate can be manufactured by peeling the metal layer or carrier of each metal foil with carrier from the carrier or metal 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 addition, in the manufacturing method of the coreless substrate described above, by covering a part or all of the end face of the metal foil with a carrier or the laminate (laminate A) with a resin, when producing a printed wiring board by a build-up method, The infiltration of the chemical solution between one metal foil with a carrier and another metal foil with a carrier constituting the first intermediate layer or laminate can be prevented, and the metal layer and the carrier can be separated by the infiltration of the chemical solution. Corrosion of the metal foil with the carrier can be prevented, and the yield can be improved. As the “resin that covers part or all of the end face of the metal 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 method of manufacturing a coreless substrate, the metal foil with a carrier or the laminated portion of the metal foil with a carrier or the laminated body (a laminated portion of the carrier and the metal layer, or one carrier with the carrier foil) At least a part of the outer periphery of the laminated portion of the metal foil and another metal foil with a 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 metal foil with a carrier contact each other so that isolation | separation is possible. In addition, when viewed in plan in the metal foil with carrier, a metal foil with carrier or a laminated part of a laminate (a laminated part of a carrier and a metal layer, or one metal foil with a carrier and another metal foil with a carrier) The laminate may be covered with a resin or a prepreg over the entire outer periphery. With such a configuration, when the metal foil or laminate with a carrier is viewed in plan, the laminated portion of the metal foil with carrier or the laminate is covered with 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 between the carrier and the metal layer or the metal foil with the carrier during handling can be reduced. Further, by covering the outer periphery of the metal 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 metal foil with the carrier can be prevented. When separating a metal foil with a carrier from a pair of metal foils with a carrier of the laminate, or when separating a carrier of a metal foil with a carrier and a copper foil (metal layer), it is covered with a resin or a prepreg. It is necessary to remove the laminated metal foil with carrier or laminated part (laminated part of carrier and metal layer or laminated part of one metal foil with carrier and another metal foil with carrier) by cutting or the like There is.

  The metal foil with a carrier of the present invention may be laminated from the carrier side or the metal layer side to the carrier side or the metal layer side of another metal foil with a carrier of the present invention. Further, a laminate obtained by directly laminating the carrier or metal layer of the one metal foil with carrier and the carrier or metal layer of the other metal foil with carrier, if necessary, via an adhesive. It may be a body. The carrier or metal layer of the one metal foil with carrier and the carrier or metal layer of the other metal foil with carrier may be bonded. 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 performing a step of peeling the metal layer from the metal foil with a 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.

1. Production of metal foil with carrier As a carrier, a long electrolytic copper foil having a thickness of 35 μm (JTC manufactured by JX Nippon Mining & Metals) and rolled copper foil (tough pitch copper foil manufactured by JX Nippon Mining & Metals JIS H3100 alloy number C1100) Then, a long rolled copper material having a thickness of 100 μm (Tough pitch copper foil JIS H3100 alloy number C1100 manufactured by JX Nippon Mining & Metals) was prepared, and a first intermediate layer and a metal layer were formed on the surface. In addition, when using electrolytic copper foil as a carrier, the 1st intermediate | middle layer was provided in the S surface (glossy surface) side. For some samples, a second intermediate layer and a third intermediate layer were also provided. Some samples were provided in the order of the second intermediate layer, the first intermediate layer, and the third intermediate layer. Some samples were provided in the order of the second intermediate layer and the first intermediate layer. The first intermediate layer, the metal layer, the second intermediate layer, and the third intermediate layer were provided on one side of the carrier. The formation of the first intermediate layer, the metal layer, the second intermediate layer, and the third intermediate layer was performed under the conditions described in Table 1, Table 5, and Table 9. The 10-point average roughness Rz (JIS B0601 1994) of the surface of the carrier on the side where the first intermediate layer or the second intermediate layer is provided is described in the “carrier roughness Rz [μm]” column of Tables 1, 5, and 9. . About the roughness of the S surface (gloss surface) of electrolytic copper foil, it controlled by adjusting the roughness of the surface of the cathode drum which deposits copper of an electrolytic copper foil manufacturing apparatus. By increasing the roughness of the surface of the cathode drum, the roughness of the S surface (glossy surface) of the electrolytic copper foil can be increased. Moreover, the roughness of the S surface (glossy surface) of the electrolytic copper foil can be increased by reducing the surface roughness of the cathode drum. Moreover, about the surface roughness of rolled copper foil, it controlled by adjusting the roughness of the rolling roll used at the time of rolled copper foil manufacture. By increasing the surface roughness of the rolling roll, the surface roughness of the rolled copper foil can be increased. Moreover, the roughness of the surface of a rolled copper foil can be made small by making the surface roughness of a rolling roll small. In the notation, “Ni” means that pure nickel plating was performed, and “Pure chromate” means that pure chromate treatment was performed, and “zinc chromate”. It means that the zinc chromate treatment was performed. Each processing condition is shown below. 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, Boric acid: 30-40 g / L, Brightener : Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55 to 75 ppm
(PH) 2-6
(Liquid temperature) 40-60 ° C
(Current density) 1 to 11 A / dm ²

"Each element sputtering": Sputtering of each element Each metal layer was formed under the following conditions using a sputtering target having a composition of 99 mass% or more of each metal.
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Pure chromate": Pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 2-5
(Liquid temperature) 30-60 ° C

-"Zinc chromate": Zinc chromate treatment In the above pure chromate treatment conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the solution, and the zinc concentration is adjusted in the range of 0.05 to 5 g / L. Processed.
Note that if the chromate treatment of the electrolyte was processed at a current density 0.1~1.5A / dm ^2.

“Air oxidation”: Oxidized at room temperature of 25 ° C. In addition, about the Example and comparative example which provided the 2nd intermediate | middle layer, after providing the 2nd intermediate | middle layer, a 2nd intermediate | middle layer is oxidized at room temperature 25 degreeC, and a 1st intermediate | middle layer is formed on a 2nd intermediate | middle layer. Formed.

“Atmospheric heating”: A condition on the hot plate where the carrier is at a predetermined temperature (the temperature described in the first intermediate layer forming condition column described in Table 1, Table 5 and Table 9) is found, and a predetermined time ( The heat treatment was performed for the time described in the first intermediate layer forming condition column described in Table 1, Table 5, and Table 9. In addition, about the Example and comparative example which provided the 2nd intermediate | middle layer, after providing the 2nd intermediate | middle layer in a carrier, the above-mentioned heat processing is performed with respect to a carrier, A 1st intermediate | middle is carried out on a 2nd intermediate | middle layer. A layer was formed.

“Anodizing”: Anodized for a predetermined time under the following conditions.
NaOH concentration 0.5-20g / L
Liquid temperature: 20-50 degreeC
Current density: 1-10 A / dm ²
In addition, about the Example and comparative example which provided the 2nd intermediate | middle layer, after providing the 2nd intermediate | middle layer in a carrier, by performing the above-mentioned anodic oxidation with respect to the surface of a 2nd intermediate | middle layer, the 2nd intermediate | middle layer A first intermediate layer was formed thereon.

・ "Cu plating": Copper plating 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

"Co plating": Cobalt plating (Liquid composition) Cobalt sulfate: 270-280 g / L, Boric acid: 30-40 g / L, Brightener: Saccharin, Butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 2-6
(Liquid temperature) 40-60 ° C
(Current density) 1 to 11 A / dm ²

In Example 40, a roughened layer, a heat-resistant layer, a chromate layer, and a silane coupling layer were further provided on the ultrathin copper layer of Example 15. In Example 41, a heat-resistant treatment layer, a chromate treatment layer, and a silane coupling treatment layer were further provided on the ultrathin copper layer of Example 15. In Example 42, a chromate treatment layer and a silane coupling treatment layer were further provided on the ultrathin copper layer of Example 15.
・ 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 metal foil with a carrier of the Example and comparative example which were obtained as mentioned above.

<Thickness of surface treatment layer>
The thickness of the Cu plating (surface treatment layer) of the produced metal foil with carrier was measured by a weight method.
First, Cu plating (surface treatment layer) was peeled off from the metal foil with carrier, and the peeled Cu plating was dissolved in hydrochloric acid having a concentration of 20% by mass, and ICP emission analysis was performed. The sample size (area) and the result of ICP analysis or the thickness of the Cu plating (metal layer) were calculated.

<Metal adhesion amount on the carrier side when the metal layer is peeled off from the metal foil with carrier>
Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al were measured by ICP emission analysis after dissolving a sample with hydrochloric acid having a concentration of 20% by mass. The sample analysis excludes the amount of metal component adhering slightly to the surface (carrier M surface) opposite to the surface forming the first intermediate layer of the carrier (carrier S surface). Therefore, an insulating substrate was laminated on the surface opposite to the surface on which the first intermediate layer was formed, and thermocompression bonded in the atmosphere under a pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Then, after peeling off the metal layer side from the metal foil with carrier, the exposed carrier surface is so dissolved that the first intermediate layer and the second intermediate layer are completely dissolved (for example, 1 μm to 3 μm in thickness). Measurement was performed by dissolving in hydrochloric acid having a concentration of 20% by mass.
Note that Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al are not sufficiently dissolved in hydrochloric acid having a concentration of 20% by mass. , Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al are dissolved using a solution (such as aqua regia, a mixed aqueous solution of hydrochloric acid and nitric acid) and then analyzed by ICP emission spectrometry. You may measure.

<Metal adhesion amount on the metal layer side when the metal layer is peeled off from the metal foil with carrier>
Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al were measured by ICP emission analysis after dissolving a sample with hydrochloric acid having a concentration of 20% by mass. In the analysis of the sample, the metal foil with a carrier was attached to the metal layer in order to eliminate the adhesion amount of the metal component slightly adhering to the surface of the metal layer opposite to the surface on which the third intermediate layer is adhered. An insulating substrate was laminated from the side opposite to the carrier side, and thermocompression bonded under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours in the atmosphere. Thereafter, the surface of the exposed carrier is dissolved with hydrochloric acid having a concentration of 20% by mass so that the third intermediate layer is completely dissolved after the carrier is peeled off (for example, 0.5 μm to 3 μm in thickness). went. Note that Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al are not sufficiently dissolved in hydrochloric acid having a concentration of 20% by mass. , Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al are dissolved using a solution (such as aqua regia, a mixed aqueous solution of hydrochloric acid and nitric acid) and then analyzed by ICP emission spectrometry. You may measure.

<XPS analysis>
The carrier is peeled from the metal foil with a carrier in accordance with a 90 ° peeling method (JIS C 6471), and the width direction is determined from the surface of the exposed first intermediate layer side of the carrier and the exposed first intermediate layer side surface of the metal layer. XPS analysis was performed using the following XPS measuring apparatus for a total of 10 locations (5 locations at 20 mm intervals in the (TD direction) and 5 locations at 20 mm intervals in the longitudinal direction (MD direction).
Apparatus: XPS measuring apparatus (ULVAC-PHI, model PHI5000 Versa Probe II)
・ Achieved vacuum: 4.8 × 10 ⁻⁸ Pa
X-ray: monochromatic AlKα, output 25 W, detection area 100 μmφ, incident angle 90 degrees, extraction angle 45 degrees ion beam: ion species Ar ⁺ , acceleration voltage ² kV, sweep area 3 mm × 3 mm, sputtering rate 2.9 nm / min ( SiO ₂ conversion)

In addition, copper with a carrier in which an insulating substrate BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is thermocompression bonded to the metal layer under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours. It measured similarly about foil.

The analyzed elements were carrier, second intermediate layer, first intermediate layer, third intermediate layer, metal layer constituent elements 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 2.9 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 2.9 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.

Then, at each measurement point, when the analysis in the depth direction by XPS is performed from the surface of the first intermediate layer side of the carrier that has been peeled and exposed as described above, in terms of SiO ₂ until oxygen becomes 10 at% or less. The depth of the peeled carrier from the surface on the first intermediate layer side was measured. And the average of the depth measured from the first intermediate layer side surface of the peeled carrier in terms of SiO ₂ until the oxygen was 10 at% or less was measured for the above-mentioned 10 locations. Value. Moreover, based on the value of the depth measured about the above-mentioned 10 places, the standard deviation of the depth from the first intermediate layer side surface of the peeled carrier in terms of SiO ₂ until oxygen becomes 10 at% or less, and The standard deviation / average value was calculated. Moreover, to calculate the average value of the maximum value of the Cu concentration in the depth range in terms of SiO ₂ to the oxygen of the aforementioned is less 10at%.

Further, at each measurement point of the metal layer, SiO ₂ until the total concentration of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al becomes 5 at% or less. The depth from the surface of the first intermediate layer side of the metal layer in terms of conversion is measured, and the arithmetic average value of the depths of 10 locations is calculated as Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe The average value of the depth from the surface of the first intermediate layer side of the metal layer in terms of SiO ₂ until the total concentration of Co, Ni, Zn and Al is 5 at% or less. Further, the metal layer in terms of SiO ₂ until the total concentration of 10 locations of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al is 5 at% or less. The standard deviation of the depth from the first intermediate layer side surface and the standard deviation / average value were calculated.

<Peel strength>
The surface-treated foil side of the metal foil with carrier is thermocompression bonded to BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours. I pasted it. 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.

<Metal layer adhesion>
A metal foil with a carrier was laminated on a prepreg from the carrier side to produce a metal-clad laminate. And the circuit was formed on the ultra-thin metal layer of the metal foil with a carrier of a metal-clad laminated board, and the resin layer was laminated | stacked so that a circuit might be embedded. Then, after providing the circuit and the resin layer twice on the resin layer, the ultrathin metal layer was peeled off from the carrier, and then the ultrathin metal layer was etched to form a four-layer circuit board. When the four-layer circuit board was prepared 10 times and the metal layer was peeled from the carrier 8 times or more during the production of the 4-layer circuit board, the adhesion of the metal layer was “x”. Moreover, when it peeled 4-7 times, metal layer adhesiveness was set to "(triangle | delta)", and when it did not peel or peeled 1-3 times, metal adhesiveness was set to "(circle)".

<Laser workability>
A copper foil carrier and a base material (Mitsubishi Gas Chemical Co., Ltd. product: GHPL-832NX-A) were laminated and heated at 220 ° C. for 2 hours, and then the copper foil carrier was replaced with JIS C 6471 (1995, The method of peeling the copper foil is as follows: 8.1 Stripping strength of the copper foil 8.1.1 Type of test method (1) Method A (copper foil is pulled in the 90 ° direction with respect to the copper foil removal surface) It was peeled off in accordance with the method described above) to expose the intermediate layer side surface of the ultrathin copper layer. Then, the exposed surface of the ultrathin copper layer of the copper foil with carrier on the intermediate layer side was irradiated with a laser for one or two shots under the following conditions, and the hole shape after irradiation was observed with a microscope to perform measurement. . In the table, as the “real number” of drilling, it was attempted to drill at 100 points and observed how many holes were not actually drilled (number of unopened holes). The diameter of the hole was the diameter of the smallest circle surrounding the hole.
・ Gas type: CO ₂
・ Copper foil opening diameter (target): 50 μm diameter ・ Beam shape: Top hat ・ Output: 2.40 W / 10 μs
・ Pulse width: 33μs
·number of shots:
1 shot (when the thickness of the ultra-thin copper layer is 0.8-2 μm)
2 shots (when the thickness of the ultra-thin copper layer is 3-5 μm)

<Etching property>
The carrier-attached copper foil was affixed to the polyimide substrate and heat-pressed at 220 ° C. for 2 hours, and then the ultrathin copper layer was peeled off from the copper foil carrier. Subsequently, after applying a photosensitive resist to the surface of the ultra-thin copper layer on the polyimide substrate, 50 L / S = 5 μm / 5 μm wide circuits are printed by an exposure process to remove unnecessary portions of the copper layer. The etching process was performed under the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, the time until the circuit top width reached 4 μm was measured, and the circuit bottom width (the length of the base X) and the etching factor at that time were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 6 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. By using this etching factor, it is possible to easily determine whether the etching property is good or bad. In the present invention, an etching factor of 5 or higher was evaluated as an etching property: ◯, an etching factor of 2.5 or more and less than 5 was evaluated as an etching property: Δ, less than 2.5, or an uncalculated value was evaluated as an etching property: ×. In the table, “connection” in “the length of the base X” indicates that the circuit cannot be formed because it is connected to an adjacent circuit at least at the base.

<Warpage amount>
The amount of warpage is determined by cutting the metal foil with a carrier into a 10 cm square sheet and leaving it on the horizontal plane for 24 hours or more with the ultrathin metal layer side up, and then lifting the height of the sheet 4 corner from the horizontal plane. The maximum value was measured. When the sheet corner was not lifted and warped downward, the maximum height of the sheet lift at the corner of the sheet was measured with the ultrathin metal layer side down.
The amount of warpage was 20 mm or less as good as “◯”, and when it exceeded 20 mm, it was judged as defective as “x”.
The above test conditions and results are shown in Tables 1-12.

(Evaluation results)
In Examples 1 to 60, in the XPS analysis of the first intermediate layer side surface of the carrier, the first intermediate layer side surface of the peeled carrier in terms of SiO ₂ until 10 oxygen atoms are 10 at% or less Since the average value of the depth from 0.5 to 15 nm and the standard deviation / average value was 0.6 or less, the metal layer adhesion and peelability were good.
As for Comparative Examples 1-9, in the XPS analysis of the first intermediate layer side surface of the carrier, the first intermediate layer side surface of the carrier separated in terms of SiO ₂ until 10 oxygen atoms are 10 at% or less The average value of the depth from the outside was outside the range of 0.5 nm or more and 15 nm or less, or the standard deviation / average value was outside the range of 0.6 or less, so the metal layer adhesion and / or peelability was good. It was.
In FIG. 5, the XPS analysis result of the depth direction before the board | substrate bonding of the 1st intermediate | middle layer side surface of the carrier of the partial sample of Example 15 is shown.

Claims (49)

A metal foil with a carrier having a carrier, a first intermediate layer containing oxygen, and a metal layer in this order,
The carrier is peeled from the carrier-attached metal foil in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, at five locations in the width direction (TD direction) and in the longitudinal direction. When the analysis in the depth direction by XPS was performed on a total of 10 locations at intervals of 20 mm in the (MD direction), the exfoliation in terms of SiO ₂ until the oxygen at the 10 locations was 10 at% or less. The metal foil with a carrier whose average value of the depth from the said 1st intermediate | middle layer side surface of a carrier is 0.5 nm or more and 15 nm or less, and a standard deviation / average value is 0.6 or less.   The metal foil with a carrier according to claim 1, wherein the first intermediate layer includes a chromate treatment layer. The carrier is peeled from the carrier-attached metal foil in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, at five locations in the width direction (TD direction) and in the longitudinal direction. When the analysis in the depth direction by XPS was performed on a total of 10 locations at 20 mm intervals in the (MD direction), the exfoliation in terms of SiO ₂ until the Cr at the 10 locations was 5 at% or less. The metal foil with a carrier according to claim 1 or 2, wherein the average depth of the carrier from the first intermediate layer side surface is 0.2 nm or more and 10 nm or less. The carrier is peeled from the carrier-attached metal foil in accordance with JIS C 6471, and from the surface of the peeled carrier on the first intermediate layer side, at five locations in the width direction (TD direction) and in the longitudinal direction. When the analysis in the depth direction by XPS was performed on a total of 10 locations at 20 mm intervals in the (MD direction), the exfoliation in terms of SiO ₂ until the Cr at the 10 locations was 5 at% or less. The metal foil with a carrier according to any one of claims 1 to 3, wherein the standard deviation / average value of the depth from the first intermediate layer side surface of the carrier is 0.6 or less.   The metal foil with a carrier according to any one of claims 1 to 4, wherein the first intermediate layer further contains copper.   The metal foil with a carrier according to any one of claims 1 to 5, wherein the first intermediate layer further contains zinc. The average value of the maximum value of Cu concentration in the range of the depth in terms of SiO ₂ from the surface of the carrier on the first intermediate layer side until the oxygen becomes 10 at% or less is 15 at% or less. The metal foil with a carrier according to any one of 6.   The first intermediate layer includes one or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. The metal foil with a carrier as described in any one of Claims 1-7 containing. One or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al contained in the first intermediate layer The metal foil with a carrier according to claim 8, wherein the total adhesion amount is 1000 to 50000 μg / dm ² .   The metal foil with a carrier according to any one of claims 1 to 9, further comprising a second intermediate layer between the carrier and the first intermediate layer.   The second intermediate layer contains one or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. The metal foil with a carrier of Claim 10 containing. One or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al contained in the second intermediate layer The metal foil with a carrier according to claim 10 or 11, wherein the total adhesion amount is 1000 to 50000 µg / dm ² .   The metal foil with a carrier according to any one of claims 1 to 12, further comprising a third intermediate layer between the first intermediate layer and the metal layer.   The third intermediate layer contains one or more elements selected from the group consisting of Cr, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, and Al. The metal foil with a carrier of Claim 13 containing. The metal foil with a carrier according to any one of claims 1 to 14, wherein the first intermediate layer is a chromate-treated layer, and an adhesion amount of Cr is 10 to 50 µg / dm ² . The carrier-attached metal foil is thermocompression bonded from the metal layer side to the insulating substrate in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is compliant with JIS C 6471 according to the carrier-attached metal foil. From the surface on the first intermediate layer side of the peeled carrier, a total of 10 points of 5 points at intervals of 20 mm in the width direction (TD direction) and 5 points at intervals of 20 mm in the longitudinal direction (MD direction) When the analysis in the depth direction by XPS was performed, the depth from the surface of the first intermediate layer side of the peeled carrier in terms of SiO ₂ until the oxygen at the 10 locations became 10 at% or less. An average value is 0.5 nm or more and 15 nm or less, Metal foil with a carrier as described in any one of Claims 1-15. The carrier-attached metal foil is thermocompression bonded from the metal layer side to the insulating substrate in the atmosphere under the conditions of pressure 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is compliant with JIS C 6471 according to the carrier-attached metal foil. From the surface on the first intermediate layer side of the peeled carrier, a total of 10 points of 5 points at intervals of 20 mm in the width direction (TD direction) and 5 points at intervals of 20 mm in the longitudinal direction (MD direction) When the analysis in the depth direction by XPS was performed, the depth from the surface of the first intermediate layer side of the peeled carrier in terms of SiO ₂ until the oxygen at the 10 locations became 10 at% or less. A standard deviation / average value is 0.6 or less, The metal foil with a carrier as described in any one of Claims 1-16. From the surface of the first intermediate layer side of the metal layer of the metal foil with carrier exposed by peeling the carrier from the metal foil with carrier according to JIS C 6471 and peeling the carrier, in the width direction ( When the analysis in the depth direction by XPS was performed for a total of 10 locations at 20 mm intervals in the TD direction and 5 locations in the longitudinal direction (MD direction) at 20 mm intervals, the 10 locations of Cr, Ti, Zr, Depth from the surface of the first intermediate layer side of the metal layer in terms of SiO ₂ until the total concentration of V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and Al is 5 at% or less. The average value of thickness is 0.5 nm or more and 300 nm or less, The metal foil with a carrier as described in any one of Claims 1-17. From the surface of the first intermediate layer side of the metal layer of the metal foil with carrier exposed by peeling the carrier from the metal foil with carrier in accordance with JIS C 6471 and peeling the carrier. When the analysis in the depth direction by XPS was performed on a total of 10 locations (5 directions at 20 mm intervals in the (TD direction) and 5 locations at 20 mm intervals in the longitudinal direction (MD direction), the Cr, Ti, Zr at the 10 locations were analyzed. , V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn and standard deviation of the depth from the surface of the metal layer in terms of SiO ₂ until the total concentration becomes 5 at% or less / The metal foil with a carrier according to any one of claims 1 to 18, wherein the average value is 0.6 or less.   The metal foil with a carrier according to any one of claims 1 to 19, wherein the carrier is a Cu-based material.   The metal foil with a carrier according to any one of claims 1 to 20, wherein the metal layer is a Cu-based plating layer.   The first intermediate layer includes one or more elements selected from the group consisting of nickel, cobalt, iron, tungsten, molybdenum, vanadium, or nickel, cobalt, iron, tungsten, molybdenum and vanadium from the carrier side. The metal with a carrier according to any one of claims 1 to 21, comprising any one layer of an alloy and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. Foil.   The metal foil with a carrier according to claim 22, wherein the layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium includes a chromate treatment layer.   The metal foil with a carrier according to any one of claims 1 to 23, wherein the carrier further includes a first intermediate layer and a metal layer in this order on a surface opposite to the surface having the metal layer.   The metal foil with a carrier according to any one of claims 1 to 24, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil.   The metal foil with a carrier according to any one of claims 1 to 25, further comprising a roughening treatment layer on one or both of the surface of the metal layer and the surface of the 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. 27. The metal foil with a carrier according to claim 26, which is a layer.   The metal with a carrier according to claim 26 or 27, wherein the surface of the roughening treatment layer has 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. Foil.   The surface of the said metal layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer as described in any one of Claims 1-28. Metal foil with carrier.   The metal foil with a carrier according to any one of claims 1 to 28, wherein a resin layer is provided on the metal layer.   The metal foil with a carrier according to claim 26 or 27, comprising a resin layer on the roughening treatment layer.   The metal foil with a carrier according to claim 28 or 29, wherein a resin layer is provided 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 metal foil with a carrier according to any one of claims 30 to 32, wherein the resin layer is an adhesive resin.   The metal foil with a carrier according to any one of claims 30 to 33, wherein the resin layer is a semi-cured resin.   The printed wiring board manufactured using the metal foil with a carrier as described in any one of Claims 1-34.   An electronic device manufactured using the printed wiring board according to claim 35.   The laminated body manufactured using the metal foil with a carrier as described in any one of Claims 1-34.   It is a laminated body containing metal foil with a carrier and resin as described in any one of Claims 1-34, Comprising: The laminated body by which one part or all part of the end surface of the said metal foil with carrier is covered with the said resin. .   The metal foil with a carrier according to any one of claims 1 to 34 is laminated from the carrier side to the carrier side of the metal foil with a carrier according to any one of claims 1 to 34. Laminated body.   40. The laminate according to claim 39, wherein the carrier of the one metal foil with a carrier and the carrier of the other metal foil with a carrier are directly laminated with an adhesive as required.   41. The laminate according to claim 39 or 40, wherein the carrier of the metal foil with one carrier and the carrier of the metal foil with another carrier are joined. A step of providing at least once two layers of a resin layer and a circuit on the surface of the laminate according to any one of claims 37 to 41; and
A method for producing a printed wiring board comprising a step of peeling the metal layer from the metal foil with carrier of the laminate after forming the resin layer and the two layers of the circuit at least once.   Forming a plating layer containing nickel and a plating layer on the carrier and then forming a plating layer containing chromium or a chromate treatment layer to form the first intermediate layer; and electrolytic plating on the first intermediate layer The manufacturing method of metal foil with a carrier as described in any one of Claims 1-34 including the process of forming the said metal layer by.   The manufacturing method of the copper foil with a carrier of Claim 43 which further includes the process of forming a roughening process layer on the said metal layer. A step of preparing the metal foil with a carrier according to any one of claims 1 to 34 and an insulating substrate,
Laminating the metal foil with carrier and an insulating substrate; and
After laminating the metal foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the metal foil with carrier,
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 metal layer side surface or the carrier side surface of the metal foil with a carrier according to any one of claims 1 to 34,
Forming a resin layer on the metal layer side surface or the carrier side surface of the carrier-attached metal foil so that the circuit is buried;
Forming a circuit on the resin layer;
A step of peeling the carrier or the metal layer after forming a circuit on the resin layer; and
After the carrier or the metal layer is peeled off, the metal layer or the carrier is removed to expose the circuit embedded in the resin layer formed on the metal layer side surface or the carrier side surface. A manufacturing method of a printed wiring board including a process. A step of laminating the carrier-attached copper foil according to any one of claims 1 to 34 on the resin substrate from the carrier side,
Forming a circuit on the metal layer side surface or the carrier side surface of the copper foil with carrier,
Forming a resin layer on the metal layer side surface or the carrier side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
A step of peeling the carrier or the metal layer after forming a circuit on the resin layer; and
After the carrier or the metal layer is peeled off, the metal layer or the carrier is removed to expose the circuit embedded in the resin layer formed on the metal layer side surface or the carrier side surface. A manufacturing method of a printed wiring board including a process. The step of laminating the metal layer side surface or the carrier side surface of the metal foil with a carrier according to any one of claims 1 to 34 and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the metal layer side surface opposite to the side laminated with the resin substrate of the metal foil with carrier or on the carrier side surface; and
A method for producing a printed wiring board, comprising the step of peeling the carrier or the metal layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. The step of laminating the carrier side surface of the metal foil with a carrier according to any one of claims 1 to 34 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 metal layer opposite to the side laminated with the resin substrate of the metal foil with carrier, and
A method for producing a printed wiring board, comprising the step of peeling the carrier from the metal foil with a carrier after forming the resin layer and the two layers of the circuit.