JP2017088943A - Copper foil with carrier, laminate, manufacturing method of laminate, manufacturing method of printed wiring board and manufacturing method of electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a carrier good in circuit formation property.SOLUTION: There is provided a copper foil with a carrier having the carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the abnormal electrodeposition number of an ultra-thin copper layer side surface is 5000/mmor less and one or both of the ultra-thin copper film layer surface and the carrier has a roughening treated layer. Preferably the abnormal electrodeposition number is 2000/mmor less, more preferably 1000/mmor less and especially preferably 600/mmor less.SELECTED DRAWING: Figure 1

Description

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

  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. In particular, when an IC chip is mounted on a printed wiring board, a fine pitch of L (line) / S (space) = 20 μm / 20 μm or less is required.

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

  Along with the fine pitch, the thickness of the copper foil used for the copper clad laminate is also 9 μm, and further, 5 μm or less. However, when the foil thickness is 9 μm or less, the handleability when forming a copper clad laminate by the above-described lamination method or casting method is extremely deteriorated. Therefore, a copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is formed on the metal foil via a release layer. As a general method of using the copper foil with a carrier, as disclosed in Patent Document 1, etc., the surface of an ultrathin copper layer is bonded to an insulating substrate, and after thermocompression bonding, the carrier is passed through a release layer. Peel off.

  In the production of a printed wiring board using a carrier-attached copper foil, a typical method for using the carrier-attached copper foil is to first laminate the carrier-attached copper foil on an insulating substrate and then peel the carrier from the ultrathin copper layer. Next, a plating resist formed of a photocurable resin is provided on the ultrathin copper layer exposed by peeling off the carrier. Next, the said area | region is hardened by exposing with respect to the predetermined area | region of a plating resist. Subsequently, after removing the uncured plating resist in the non-exposed area, an electrolytic plating layer is provided in the resist removed area. Next, by removing the cured plating resist, an insulating substrate on which a circuit is formed is obtained, and a printed wiring board is produced using the insulating substrate.

JP 2006-022406 A

  When producing a copper foil with a carrier, an intermediate layer and an ultrathin copper layer are provided on the carrier in this order by electrolytic plating or the like. At this time, abnormal electrodeposition is performed on the surface of the obtained copper foil with a carrier on the ultrathin copper layer side. May occur. When a printed wiring board is produced as described above using the carrier-added copper foil in which a large amount of abnormal electrodeposition has occurred, there is a problem that a short circuit due to the abnormal electrodeposition occurs in the formed circuit.

  Then, this invention makes it a subject to provide the copper foil with a carrier with favorable circuit formation property.

  In order to achieve the above object, the present inventor has conducted extensive research and found that the circuit formability is improved by controlling the number of abnormal electrodepositions on the surface of the ultrathin copper layer to a predetermined value or less.

The present invention has been completed on the basis of the above knowledge, and in one aspect, a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the number of abnormal electrodepositions on the surface of the ultrathin copper layer side Is a copper foil with a carrier of 5000 pieces / mm ² or less.

In one embodiment of the copper foil with a carrier of the present invention, the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 2000 pieces / mm ² or less.

In another embodiment of the copper foil with a carrier of the present invention, the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 1000 pieces / mm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 600 pieces / mm ² or less.

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

  In another embodiment of the copper 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 yet another embodiment, the carrier-attached copper foil 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 yet another embodiment, the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. It has the above layers.

  In still another embodiment, the carrier-attached copper foil of the present invention includes a resin layer on the ultrathin copper layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention includes a resin layer on the roughening treatment layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention is 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 carrier-attached copper foil of the present invention, the resin layer is an adhesive resin.

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

  In another aspect, the present invention is a laminate having the carrier-attached copper foil of the present invention.

  In yet another aspect, the present invention is a method for manufacturing a laminate, which uses the copper foil with a carrier of the present invention to produce a laminate.

  According to still another aspect of the present invention, there is provided a laminate including the carrier-attached copper foil of the present invention and a resin, wherein the end face of the carrier-attached copper foil is partially or entirely covered with the resin. It is.

  In yet another aspect of the present invention, the carrier-attached copper foil and resin of the present invention have two sets, the ultrathin copper layer side surface of one of the two sets of the carrier-attached copper foil, and the other carrier It is the laminated body provided so that the ultra-thin copper layer side surface of an attached copper foil might each be exposed.

  In yet another aspect, the present invention provides a printed wiring board manufacturing method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

  In still another aspect of the present invention, there is provided an electronic device manufacturing method for manufacturing an electronic device using the printed wiring board of the present invention.

In another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention and an insulating substrate,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

In another aspect of the present invention, a process of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

In another aspect of the present invention, the step of laminating the carrier-attached copper foil of the present invention on the resin substrate from the carrier side,
Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier with favorable circuit formation property 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 typical SEM image of copper abnormal electrodeposition. It is the SEM image of the abnormal electrodeposition of the ultrathin copper layer side surface for showing about the example of the circle surrounding abnormal electrodeposition, and the method of counting the number of abnormal electrodepositions which a bottom part overlaps and forms a group.

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

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCD film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

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

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn (or consisting of the elements) ) An alloy layer is formed, and water of one or more elements selected from the group of elements composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn is formed thereon It can be configured by forming a layer containing (or consisting of) a hydrate, an oxide, or an organic substance.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn (or consisting of the elements) ) An alloy layer or a layer containing (or consisting of) an organic substance is formed, and selected from an element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. A single metal layer composed of one kind of element selected from the group consisting of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Alloy layers containing (or consisting of) these elements It can be configured by.
When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically 0.1 to 12 μm, more typically 0.5 to 12 μm, more typically 1 to 5 μm, more typically 1.5 to 5 μm, and more typically 2-5 μm. In addition, you may provide an ultra-thin copper layer on both surfaces of a carrier.

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

<Number of abnormal electrodeposition on the surface of the ultrathin copper layer>
Copper foil with a carrier of the present invention, abnormal electrodeposition number of ultra-thin copper layer surface is controlled to be 5000 / mm ² or less. Here, “abnormal electrodeposition” refers to electrodeposition in which the minimum diameter of the surrounding circle is 5 μm or more. With such a configuration, when producing a printed wiring board using the carrier-attached copper foil of the present invention, it is possible to satisfactorily suppress the occurrence of a short circuit in a circuit formed using the ultrathin copper layer, As a result, the circuit formability is improved. The number of abnormal electrodepositions on the surface of the thin copper layer is preferably 5000 pieces / mm ² or less, more preferably 2000 pieces / mm ² or less, and even more preferably 1000 pieces / mm ² or less. More preferably, it is 600 pieces / mm ² or less.

<Means for controlling the number of abnormal electrodeposition on the surface of the ultrathin copper layer>
When forming an ultrathin copper layer by electrolytic plating, an electrolytic solution is used. In the present invention, minute metal powders or foreign substances present in the electrolytic solution (plating solution) adhere to the surface of the ultrathin copper layer. It was found that abnormal electrodeposition occurs. Then, by filtering the electrolytic solution for forming the ultrathin copper layer with a filter having an eye having a diameter of 2.5 μm or less, the fine metal powder or foreign matter is removed from the electrolytic solution, thereby Abnormal electrodeposition occurring on the copper layer side surface can be controlled to 5000 pieces / mm ² or less. The size of the filter eyes is preferably 1 μm or less, more preferably 0.5 μm or less.

In addition, an electrolytic solution is used when an intermediate layer is formed on the carrier surface by electrolytic plating. In the present invention, ultrathin copper is controlled by controlling the immersion time of the carrier in the electrolytic solution after forming the metal layer of the intermediate layer. The occurrence of abnormal electrodeposition on the layer side surface can be suppressed. Specifically, by setting the immersion time of the carrier in the electrolytic solution after forming the metal layer of the intermediate layer to 2 to 10 seconds, abnormal electrodeposition generated on the surface of the ultrathin copper layer is reduced to 5000 pieces / mm ² or less. Can be controlled.

Also, after forming an intermediate metal layer on the carrier surface by electrolytic plating, the surface of the intermediate layer side of the carrier is pickled with a cleaning solution having a pH of 1.5 to 3, thereby generating abnormal electrodeposition on the surface of the ultrathin copper layer. Can be controlled to 5000 pieces / mm ² or less. As the cleaning solution, for example, dilute sulfuric acid, Ni plating solution or the like can be used. In addition, when forming an intermediate layer by forming a layer (chromate layer or the like) that is not dissolved by an acid such as an oxide layer after forming a metal layer on the carrier surface, the pickling is performed after the formation of the metal layer. Do. This is because it is difficult to remove the abnormal electrodeposition of the intermediate layer even if pickling is performed after forming a layer (chromate layer or the like) that is not soluble by an acid such as an oxide layer.

<Roughening treatment and other surface treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve 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 treatment 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 at least one 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-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

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

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

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

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

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

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

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO2006 / 028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

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

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

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as 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 the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

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

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

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

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

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

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

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

  Further, the method for producing a printed wiring board of the present invention includes a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing at least once a resin layer and a circuit on the surface of the copper layer with carrier on the opposite side of the copper layer side surface or the carrier side surface, and forming two layers of the resin layer and the circuit Then, a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultrathin copper layer from the carrier-attached copper foil may be used. As a specific example of the coreless construction method, first, the ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. Another copper foil with a carrier may be laminated from the carrier side to the resin layer formed on the carrier side surface. In this case, a copper foil with a carrier is laminated in the order of carrier / intermediate layer / ultra-thin copper layer or ultra-thin copper layer / intermediate layer / carrier in this order on both surface sides of the resin substrate with the resin substrate as the center It has become. Thus, the copper foil with a carrier of the present invention can be used for manufacturing a coreless printed wiring board. Another ultra-thin copper layer or the exposed surface of the carrier on both ends may be provided with another resin layer, a copper layer may be further provided, and then the copper layer may be processed to form a circuit. Further, another resin layer may be provided on the circuit so as to embed the circuit. Moreover, you may provide such a circuit and formation of a resin layer 1 or more times (build-up construction method). And about a laminated body formed in this way, a coreless board | substrate can be produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer.

  In addition, in the manufacturing method of the coreless substrate described above, when a printed wiring board is manufactured by a build-up method by covering a part or all of the end face of the copper foil with a carrier with a resin, the intermediate layer is impregnated with a chemical solution. It is possible to prevent the separation of the ultrathin copper layer and the carrier due to the penetration of the chemical solution, and the yield can be improved. As the “resin that covers part or all of the end face of the copper foil with carrier” used here, a resin that can be used for the resin layer can be used. When the carrier and the ultrathin copper layer are separated, it is necessary to remove the portion covered with the resin on the end face of the carrier-attached copper foil by cutting or the like. Moreover, in the manufacturing method of the above-mentioned coreless board | substrate, when planarly viewing in copper foil with a carrier, at least one part of the outer periphery of the laminated part of copper foil with a carrier may be covered with resin or a prepreg. Moreover, the laminated body formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact so that separation | separation is mutually possible. Moreover, when planarly viewed in the said copper foil with a carrier, the whole outer periphery of the lamination | stacking part of a copper foil with a carrier may be covered with resin or a prepreg. By adopting such a configuration, when the carrier-attached copper foil is viewed in plan, the laminated portion of the carrier-attached copper foil is covered with resin or prepreg, and the other members are in the lateral direction of this portion, that is, in the lamination direction. Therefore, it is possible to prevent the copper foil with a carrier from being peeled off during handling. Further, by covering the outer periphery of the laminated portion of the copper foil with carrier with a resin or prepreg so as not to be exposed, it is possible to prevent the intrusion of the chemical liquid into this interface in the chemical treatment process as described above. Corrosion and erosion can be prevented. In addition, when separating one copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), it is covered with a resin or a prepreg. It is necessary to remove the laminated portion of the carrier-attached copper foil by cutting or the like.

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

(Examples 1-37, Comparative Examples 1-4)
1. Production of Copper Foil with Carrier As a carrier, a long electrolytic copper foil with a thickness of 35 μm (JTC made by JX Nippon Mining & Metals) and a long rolled copper foil with a thickness of 35 μm (JIS H3100 made by JX Nippon Mining & Metals) (Tough pitch copper foil standardized to Alloy No. C1100) was prepared. An intermediate layer was provided as follows for the prepared carrier. For example, “Ni / electrolytic chromate” in the column of “intermediate layer” in the table means that Ni was plated on the carrier, and electrolytic chromate treatment was performed after the Ni plating. For Example 36, the above-mentioned rolled copper foil was used for the carrier, and for the other Examples and Comparative Examples, the above-mentioned electrolytic copper foil was used for the carrier.

・ Ni plating (Ni)
By subjecting the shiny surface of the copper foil (carrier) (one surface or the other surface with respect to the rolled copper foil) to electroplating in a roll-to-roll continuous plating line under the following conditions, 4000 μm / A Ni layer having an adhesion amount of dm ² was formed.

(Liquid composition) Nickel sulfate: 250-300 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Boric acid: 15-30 g / L, Brightener: Saccharin, butynediol, dodecyl Sodium sulfate: 30-100ppm
(PH) described in Table 1 (immersion time after plating) described in Table 1 (Bath temperature) 50 to 70 ° C
(Current density) 3-15 A / dm ²

Next, after washing with water, and Examples 8 to 20, 20 to 24, and 34 to 37, the samples were pickled for 5 seconds in a state of being fixed using the pH cleaning liquid described in Table 1, and then Examples 1 to 7 were used. , 13-19, 30-33, and Comparative Examples 1-4, without performing the above-mentioned pickling, continuously on a Ni-layer on a roll-to-roll type continuous plating line of 11 μg / dm ² The deposited amount of Cr layer was deposited by electrolytic chromate treatment under the following conditions.

・ Electrolytic chromate treatment (electrolytic chromate)
(Liquid composition) potassium dichromate: 1 to 10 g / L, zinc: 0 to 5 g / L
(PH) 3-4
(Liquid temperature) 50-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5-30 As / dm ²

・ Ni-Mo layer (nickel molybdenum alloy plating)
For Example 25, a Ni—Mo layer having an adhesion amount of 3000 μg / dm ² was formed on a carrier by electroplating on a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(PH) described in Table 1 (immersion time after plating) described in Table 1 (Liquid temperature) 30 ° C.
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

・ Organic material layer (Organic material layer formation treatment)
For Example 26, after forming the above-mentioned “Ni plating (Ni)”, pickling was performed for 5 seconds in a state of being fixed using the cleaning solution having the pH shown in Table 1, and Example 29 was applied to the carrier. Then, an organic substance layer was formed by spraying an aqueous solution containing carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g / L and having a liquid temperature of 40 ° C. and a pH of 5 for 20 to 120 seconds. In Example 29, after the organic layer was formed, the above-mentioned “Ni plating (Ni)” was formed, and then pickled for 5 seconds in a state of being fixed using a cleaning solution having a pH shown in Table 1.

・ Co-Mo layer (cobalt molybdenum alloy plating)
In Example 27, the above-mentioned “Ni plating (Ni)” was formed on the carrier, and in Example 28, the above-mentioned “Ni plating (Ni)” was formed and then fixed using the cleaning solution having the pH shown in Table 1. After pickling for 2 seconds, a Co—Mo layer having an adhesion amount of 4000 μg / dm ² was formed by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below. In Examples 27 and 28, after the Co—Mo layer was formed, pickling was further performed for 5 seconds in a state of being fixed using a cleaning solution having a pH described in Table 1.
(Liquid composition) Co sulfate 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(PH) described in Table 1 (immersion time after plating) described in Table 1 (Liquid temperature) 30 ° C.
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

Subsequently, an ultrathin copper layer having a thickness of 2 μm was formed on the intermediate layer on the roll-toe-roll type continuous plating line by electroplating in the electrolytic cell under the following electrolysis conditions, and the copper with carrier A foil was produced. Also, at this time, by providing a filter having a filter diameter as shown in Table 1 in the middle of the liquid supply pipe connected to the electrolytic cell, the liquid immediately after the liquid that goes up to the electrolytic cell passes through the filter. As a result, fine metal powders and foreign matters in the electrolytic solution were removed. In addition, about Example 1, 2, 14, 28, it manufactured also about the copper foil with a carrier in case the thickness of an ultra-thin copper layer was 1, 3, and 5 micrometers, respectively, and performed the same evaluation. As a result, the same results were obtained as when the thickness of the ultrathin copper layer was 2 μm.
(Electrolysis conditions)
Liquid composition: Copper concentration: 30 to 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

For Examples 13 to 24 and Comparative Examples 3 to 4, the following roughening treatment, antirust treatment as surface treatment such as roughening treatment, etc. on the surface of the ultrathin copper layer of the copper foil with carrier obtained by the above method, Chromate treatment and silane coupling treatment were performed in this order.
・ Roughening treatment Cu: 5 to 30 g / L (added as copper sulfate pentahydrate)
H ₂ SO _4: 30~120g / L
W: 10 mg / L (added as sodium tungstate dihydrate)
Liquid temperature: 30 ° C
Current density Dk: 20 to 40 A / dm ²
Time: 4 seconds, rust prevention treatment Zn: over 0 to 20 g / L
Ni: more than 0 to 5 g / L
pH: 2.5-4.5
Liquid temperature: 30-50 degreeC
Current density Dk: more than 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: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Bath temperature: 25-60 ° C
Immersion time: 5 to 30 seconds

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

<Number of abnormal electrodeposition on the surface of the ultrathin copper layer>
The copper foil with a carrier was placed on a stage inclined 45 ° from a horizontal position, and an SEM photograph was taken with respect to the ultrathin copper layer side surface at a magnification of 500 times. FIG. 5 shows an example of a typical SEM image of abnormal electrodeposition on the ultrathin copper layer side surface. The convex portion observed in the portion surrounded by the frame line is abnormal electrodeposition. In addition, FIG. 6 shows an example of a circle surrounding abnormal electrodeposition, and abnormal electrodeposition on the surface of the ultrathin copper layer for showing how to count the number of abnormal electrodepositions in which the tailings overlap to form a group. An example of an SEM image is shown. As shown in FIG. 6, the diameter of abnormal electrodeposition was set to a circle that encloses the skirt, taking the diameter of the circle. In addition, the number of abnormal electrodepositions in which a group of overlapping skirts overlaps is the number of vertices in the group. The number of abnormal electrodepositions was measured by observing 10 fields of view with a sample size of 1 field of view of 250 μm × 270 μm.
In the SEM photograph, the number of abnormal electrodepositions in which the minimum diameter of the circle surrounding the abnormal electrodeposition was 5 μm or more and had a shadow was counted, and the abnormal electrodeposition density pass / fail judgment was performed according to the following evaluation criteria. This is because the abnormal electrodeposition having a shadow is higher in height than the abnormal electrodeposition not having a shadow and has a high possibility of adversely affecting circuit formation.
◎: 600 pieces / mm ² or less ○: 600 pieces / mm ² more than 1000 pieces / mm ² or less △: 1000 pieces / mm ² more than 5000 pieces / mm ² or less ×: 5000 pieces / mm ² or less

<Circuit formability>
L (line) / S (space) = 30 μm / 30 μm, 25 μm / 25 μm, 20 μm / 20 μm, 15 μm / 20 μm and 15 μm / 15 μm by MSAP (Modified Semi-additive) method for the ultra-thin copper layer of the copper foil with carrier Of the circuit (100 circuits of each L / S). Of the 100 circuits produced, the percentage of circuit shorts that occurred was less than 30% (less than 30 shorted circuits) was judged as ○, and 30% or more (30 or more shorted circuits). The thing was determined as x.
Test conditions and test results are shown in Tables 1 and 2.

(Evaluation results)
In each of Examples 1 to 37, the number of abnormal electrodepositions on the surface of the ultrathin copper layer was 5000 / mm ² or less, and the circuit formability was good.
In each of Comparative Examples 1 to 4, the filter used for filtering the electrolytic solution for forming the ultrathin copper layer has eyes having a size larger than 2.5 μm in diameter. The number of abnormal electrodepositions exceeded 5000 / mm ² , and the circuit formability was poor.

Claims (24)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
A copper foil with a carrier, wherein the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 5000 / mm ² or less. The copper foil with a carrier according to claim 1, wherein the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 2000 pieces / mm ² or less. The copper foil with a carrier according to claim 2, wherein the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 1000 pieces / mm ² or less. The copper foil with a carrier according to claim 3, wherein the number of abnormal electrodepositions on the surface of the ultrathin copper layer is 600 pieces / mm ² or less.   The copper foil with a carrier as described in any one of Claims 1-4 which has a roughening process layer in any one or both of the said ultra-thin copper layer surface and the surface of the said carrier.   The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. The copper foil with a carrier according to claim 5 which is a layer.   The copper with a carrier according to claim 5 or 6 which has one or more sorts of layers chosen from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of said roughening treatment layer. Foil.   The surface of the ultra-thin copper layer has at least one layer selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier of description.   The copper foil with a carrier as described in any one of Claims 1-7 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 5 or 6, comprising a resin layer on the roughening treatment layer.   The copper foil with a carrier according to claim 7 or 8, comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.   The said resin layer is resin for adhesion | attachment, Copper foil with a carrier as described in any one of Claims 9-11.   The copper foil with a carrier according to any one of claims 9 to 12, wherein the resin layer is a semi-cured resin.   The laminated body which has a copper foil with a carrier as described in any one of Claims 1-13.   The manufacturing method of the laminated body which manufactures a laminated body using the copper foil with a carrier as described in any one of Claims 1-13.   It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-13, Comprising: The laminated body with which one part or all part of the end surface of the said copper foil with a carrier is covered with the said resin. .   It has two sets of copper foil with a carrier and resin as described in any one of Claims 1-13, the ultra-thin copper layer side surface of one copper foil with a carrier of the said two sets, and the other carrier The laminated body provided so that the ultra-thin copper layer side surface of an attached copper foil might each be exposed.   The manufacturing method of a printed wiring board which manufactures a printed wiring board using the copper foil with a carrier as described in any one of Claims 1-13.   The manufacturing method of the electronic device which manufactures an electronic device using the printed wiring board of Claim 18. Preparing the carrier-attached copper foil according to any one of claims 1 to 13 and an insulating substrate;
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 13,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. A step of laminating the carrier-attached copper foil according to any one of claims 1 to 13 on the resin substrate from the carrier side,
Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 13 and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. A step of laminating the carrier-side surface of the copper foil with a carrier according to any one of claims 1 to 13 and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method for producing a printed wiring board, comprising the step of peeling the carrier from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.