JP6099778B1 - A copper foil with a carrier, a laminate, a printed wiring board, a printed wiring board manufacturing method, and an electronic device manufacturing method. - Google Patents

Abstract

Provided is a copper foil with a carrier capable of satisfactorily peeling an ultrathin copper layer from a carrier in a laminate produced by laminating a copper foil with a carrier on a resin substrate. A copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994. A copper foil with a carrier having a surface ten-point average roughness Rz of 6.0 μm or less. [Selection] Figure 1

Description

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

  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, which is a precursor of the insulating substrate material, to the surface having the copper foil coating layer, 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 and the like, after bonding the surface of an ultrathin copper layer to a resin substrate and thermocompression bonding, the carrier is passed through a release layer. Peel off.

  In the production of a printed wiring board using a copper foil with a carrier, a typical method for using the copper foil with a carrier is to first laminate the copper foil with a carrier from the ultra thin copper layer side to the resin substrate and then from the ultra thin copper layer. Remove the carrier. 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, a resin substrate on which a circuit is formed is obtained, and a printed wiring board is produced using the resin substrate.

JP 2006-022406 A

  As a method for producing a printed wiring board using a copper foil with a carrier, it is common to peel the carrier from the ultrathin copper layer after laminating the copper foil with a carrier from the ultrathin copper layer side to the resin substrate as described above. However, a resin substrate is provided on the surface of the carrier, not the ultrathin copper layer side of the copper foil with carrier, and circuit plating is formed on the surface of the ultrathin copper layer so as to cover the formed circuit plating ( There is a method (embedding / build-up method) in which an embedded resin is provided on an ultrathin copper layer and a resin layer is laminated on the ultrathin copper layer, and a copper layer is further provided on the resin layer to produce a laminate. Yes (Figure 1). Also, a resin substrate is provided on the surface of the carrier side, not the ultrathin copper layer side of the copper foil with carrier, and the laminate is prepared by providing the resin layer and the circuit at least once on the surface of the ultrathin copper layer. There is a construction method (build-up construction method).

  The ultra-thin copper layer of the laminate needs to be peeled off well from the carrier, but in the laminate formed by such a method, the peel strength between the ultra-thin copper layer and the carrier becomes significantly large, There is a problem that it becomes difficult to peel the ultrathin copper layer from the carrier satisfactorily.

  Therefore, the present invention has an object to provide a copper foil with a carrier that can peel an ultrathin copper layer from a carrier satisfactorily in a laminate produced by laminating a copper foil with a carrier on a resin substrate. To do.

  In order to achieve the above object, the present inventors have conducted intensive research and found that a laminated body having a structure in which a resin substrate is provided on the carrier side is roughened in order to bond the resin substrate to the resin surface satisfactorily. We paid attention to the fact that the processing is being performed. And depending on the degree of the roughening treatment on the bonding surface side of the carrier with the resin substrate, the roughness of the surface becomes large, and the peel strength from the carrier of the ultra-thin copper layer in the laminate is significantly increased. I found. And by controlling the surface roughness on the side of the carrier that is bonded to the resin substrate, that is, on the side opposite to the surface on which the ultrathin copper layer of the carrier is formed, the ultrathin copper layer is peeled off from the carrier well. I found out that it would be possible.

  The present invention has been completed based on the above knowledge, and in one aspect, a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, on the opposite side of the ultrathin copper layer of the carrier When the surface is measured with a laser microscope in accordance with JIS B0601-1994, the 10-point average roughness Rz of the surface is a copper foil with a carrier of 6.0 μm or less.

  Another aspect of the present invention is a copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the carrier opposite to the ultrathin copper layer is JIS B0601-1994. When measured with a laser microscope in conformity, the arithmetic average roughness Ra of the surface is a copper foil with a carrier of 1.0 μm or less.

  In still another aspect of the present invention, a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, the surface of the carrier opposite to the ultrathin copper layer is JIS B0601-2001. The maximum cross-sectional height Rt of the surface roughness curve is 7.0 μm or less when measured with a laser microscope in accordance with the above.

  In yet another embodiment of the carrier-attached copper foil of the present invention, when the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994, the surface of the carrier has a sufficient thickness. The point average roughness Rz is 0.9 μm or more.

  In another embodiment of the carrier-attached copper foil of the present invention, when the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994, the arithmetic of the surface is performed. Average roughness Ra is 0.12 μm or more.

  In yet another embodiment of the copper foil with a carrier of the present invention, when the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-2001, the surface roughness is increased. The maximum cross-sectional height Rt of the curvature curve is 1.1 μm or more.

  In another embodiment of the copper foil with a carrier of the present invention, a roughening treatment layer is formed on the surface of the carrier opposite to the ultrathin copper layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention has a heat-resistant layer, a rust-proof layer, and a chromate-treated layer on the roughened layer formed on the surface opposite to the ultra-thin copper layer of the carrier. And one or more layers selected from the group consisting of silane coupling treatment layers.

  In yet another embodiment of the carrier-attached copper foil of the present invention, the roughening layer formed on the surface of the carrier opposite to the ultrathin copper layer is made of copper, nickel, cobalt, phosphorus, tungsten, arsenic. , Molybdenum, chromium, and zinc, any one simple substance selected from the group consisting of, or an alloy containing one or more of them.

  In still another embodiment of the copper foil with a carrier of the present invention, the roughening layer formed on the surface of the carrier opposite to the ultrathin copper layer is a group consisting of an alkyl sulfate salt, tungsten and arsenic. It is formed using a sulfuric acid / copper sulfate electrolytic bath containing at least one selected from

  In another embodiment of the carrier-attached copper foil of the present invention, a roughening treatment layer is not formed on the surface of the carrier opposite to the ultrathin copper layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention is a 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 carrier opposite to the ultrathin copper layer. One or more layers selected from:

  In still another embodiment of the copper foil with a carrier according to the present invention, a roughened layer is formed on the surface of the ultrathin copper layer.

  In still another embodiment of the copper foil with a carrier according to the present invention, the roughened layer formed on the surface of the ultrathin copper layer is made of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. It is a layer made of any simple substance selected from the group consisting of or an alloy containing any one or more of them.

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

  In yet another embodiment of the copper foil with a carrier according to the present invention, a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer are formed on the surface of the roughening treatment layer formed on the surface of the ultrathin copper layer. One or more layers selected from the group consisting of:

  In another embodiment, the carrier-attached copper foil of the present invention is provided with the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the silane provided on the surface of the roughened layer formed on the surface of the ultrathin copper layer. A resin layer is provided on one or more layers selected from the group consisting of coupling treatment layers.

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

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

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

  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 another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
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 yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
A step of peeling the carrier after forming the resin layer; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

In yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

In another aspect of the present invention,
Laminating the copper foil with a carrier of the present invention on the resin substrate from the carrier side,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

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 of the copper foil with carrier,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
A step of peeling the carrier after forming the resin layer; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

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.

In yet another aspect of the present invention, the step of providing at least one of two layers of a resin layer and a circuit on one or both surfaces of the laminate of the present invention, and
It is a manufacturing method of a printed wiring board including the process of exfoliating the career or the ultra-thin copper layer from the copper foil with a carrier which constitutes the layered product after forming the resin layer and two layers of circuits.

  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 manufactured by the method of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier which can peel an ultra-thin copper layer favorably from a carrier in the laminated body produced by laminating | stacking copper foil with a carrier on a resin substrate can be provided.

It is a cross-sectional schematic diagram of the laminated body formed by the embedding / build-up method. 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.

<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. A copper layer is etched into the intended conductor pattern, and finally a laminate (such as a copper clad laminate) or a printed wiring board can be produced.

<Career>
The carrier that can be used in the present invention is typically a metal foil or a resin film. Examples of metal foil include copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, rolled metal foil, electrolytic metal foil, rolled copper foil and electrolytic Provided in the form of 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. As a material of the rolled copper foil, in addition to 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, Copper alloys such as a copper alloy added with Cr, Zr, Mg, or the like, or a Corson-based copper alloy added with Ni, Si, or the like can also be used. The carrier is preferably an electrolytic copper foil or a rolled copper foil because of its high electrical conductivity, and is more preferably an electrolytic copper foil because its manufacturing cost is low and the roughness of the carrier side surface is easier to control. preferable. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included. As the resin film, an insulating resin film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin film, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyamide film, a polyamideimide film, or the like can be used. .

  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, for example, 12 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 12-300 μm, more typically 12-150 μm, more typically 12-70 μm, and more typically 18-35 μm.

<Roughness of carrier surface>
Build-up method of forming a laminate by providing a circuit board and a resin layer for circuit embedding one or more times on the ultrathin copper layer side while providing and supporting a resin substrate on the carrier side surface of the copper foil with carrier Etc., the roughness of the surface of the carrier opposite to the ultrathin copper layer affects the peel strength between the ultrathin copper layer and the carrier in the laminate. This is because, for example, if the roughness of the surface opposite to the ultrathin copper layer of the carrier is greater than a predetermined value, the intermediate layer is affected in some way when the ultrathin copper layer is formed on the carrier via the intermediate layer. This is thought to increase the peel strength. The reason for this is not clear, but because the roughness of the surface opposite to the ultrathin copper layer of the carrier is larger than the predetermined value, the path through which the current on the surface opposite to the ultrathin copper layer of the carrier flows becomes longer. The current may not easily flow to the surface, which may affect the surface of the carrier on the side of the ultra-thin copper layer, that is, the intermediate layer and the ultra-thin copper layer. . In addition, even when the surface of the carrier opposite to the ultra-thin copper layer is small during the preparation of the copper foil with carrier, after forming the copper foil with carrier, When the surface of the surface opposite to the ultrathin copper layer is roughened until the roughness becomes larger than a predetermined value, the peel strength is also increased. This is considered to be caused by a current (reverse current) flowing in the opposite direction to the direction of current when the ultrathin copper layer is formed in the intermediate layer in the roughening process.

  From such a viewpoint, in the copper foil with a carrier of the present invention, when the surface opposite to the ultrathin copper layer of the carrier is measured with a laser microscope in accordance with JIS B0601-1994, the ten-point average roughness of the surface is measured. The thickness Rz is controlled to 6.0 μm or less. When the 10-point average roughness Rz of the surface opposite to the ultrathin copper layer of the carrier is 6.0 μm or less, the peel strength of the ultrathin copper layer from the carrier is suppressed, and the ultrathin copper layer is improved from the carrier. It can be peeled off. Rz is preferably 5.0 μm or less, more preferably 4.0 μm or less, and more preferably 3.5 μm or less. However, Rz is preferably 0.9 μm or more, more preferably 1.0 μm or more, and preferably 1.1 μm or more, because if Rz is too small, the adhesion to the resin substrate is reduced. More preferably, it is 1.5 μm or more, and even more preferably 2.0 μm or more.

  In another aspect of the copper foil with a carrier of the present invention, when the surface opposite to the ultrathin copper layer of the carrier is measured with a laser microscope in accordance with JIS B0601-1994, the arithmetic average roughness of the surface is measured. Ra is controlled to 1.0 μm or less. When the arithmetic average roughness Ra of the surface opposite to the ultrathin copper layer of the carrier is 1.0 μm or less, the peeling strength of the ultrathin copper layer from the carrier is suppressed, and the ultrathin copper layer is peeled off from the carrier well. It becomes possible to make it. Ra is preferably 0.8 μm or less, more preferably 0.7 μm or less, and more preferably 0.6 μm or less. However, Ra is preferably 0.12 μm or more, more preferably 0.15 μm or more, and more preferably 0.2 μm or more, since the adhesive strength with the resin substrate is reduced when the Ra is too small. Preferably, it is 0.22 μm or more, more preferably 0.3 μm or more.

Moreover, when the copper foil with a carrier of the present invention is measured on a surface opposite to the ultrathin copper layer of the carrier with a laser microscope in accordance with JIS B0601-2001, the surface roughness of the carrier is further determined. The maximum section height Rt of the curve is controlled to 7.0 μm or less. When the maximum cross-sectional height Rt on the surface opposite to the ultrathin copper layer of the carrier is 7.0 μm or less, the peel strength of the ultrathin copper layer from the carrier is suppressed, and the ultrathin copper layer is peeled off from the carrier well. It becomes possible to make it. Rt is preferably 6.0 μm or less, more preferably 5.0 μm or less, and more preferably 4.0 μm or less. However, Rt is preferably 1.1 μm or more, preferably 1.2 μm or more, and preferably 1.3 μm or more, because if the Rt is too small, the adhesion with the resin substrate is reduced. More preferably, it is 1.5 μm or more, and even more preferably 2.0 μm or more.
In the present invention, the roughness (Rz, Ra, Rt) of the surface opposite to the ultrathin copper layer of the above-mentioned carrier is the roughened layer when a roughened layer described later is formed. Indicates the roughness of the surface, and when the heat treatment layer, rust prevention layer, chromate treatment layer and / or silane coupling treatment layer described later is further formed on the surface of the roughening treatment layer, the surface of the outermost layer among them The roughness of is shown. In addition, when the heat treatment layer, the rust prevention layer, the chromate treatment layer and / or the silane coupling treatment layer are formed directly on the carrier without the roughening treatment layer being formed, the surface roughness of the outermost layer among them is also formed. It shows.

<Intermediate layer>
An intermediate layer is provided on 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 forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, From hydrates or oxides or organic substances of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can comprise by forming the layer which becomes.
Further, for example, the intermediate layer is a single metal layer made of any one element of the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr , Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, an alloy layer made of one or more elements selected from the element group, or an organic layer, and then Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, a single metal layer made of any one element, or Cr, Ni, Co, Fe, Mo, Ti, W, P , Cu, Al, and Zn, and an alloy layer made of one or more elements selected from the element group. Moreover, you may use the layer structure which can be used as an intermediate | middle layer for another layer.

Further, for example, the intermediate layer can be configured by laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer 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 less than 100 [mu] g / dm ² or more 1000μg / dm ^2, the adhesion amount of chromium is preferably 5 [mu] g / dm ² or more 500 [mu] g / dm ² or less in the intermediate layer, 5 [mu] g / dm ² or more 100 [mu] g / dm ² or less More preferably.

  The chromium-containing layer may be a chromium plating layer, a chromium alloy plating layer, or a chromate treatment layer. Here, the chromate-treated 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 chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

The intermediate layer of the carrier-attached copper foil of the present invention is laminated in the order of a nickel layer or an alloy layer containing nickel, and an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on the carrier. The adhesion amount of nickel in the intermediate layer may be 100 to 40,000 μg / dm ² .

Moreover, for example, as the organic substance contained in the intermediate layer, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids. Among the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
The aforementioned organic substance is preferably contained in a thickness of 8 nm to 80 nm, more preferably 30 nm to 70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
In addition, the thickness of organic substance can be measured as follows.

<Thickness of organic material in the intermediate layer>
After peeling off the ultrathin copper layer of the carrier-attached copper foil from the carrier, the surface of the exposed ultrathin copper layer on the intermediate layer side and the exposed surface of the intermediate layer side of the carrier are subjected to XPS measurement to create a depth profile. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth can be defined as B (nm), and the sum of A and B can be defined as the thickness (nm) of the organic substance in the intermediate layer.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (SiO ₂ conversion)

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

Further, for example, the intermediate layer can be configured by stacking nickel and molybdenum, cobalt, or a molybdenum-cobalt alloy in this order on a carrier. Since the adhesion force between nickel and copper is higher than the adhesion force between molybdenum or cobalt and copper, when peeling the ultrathin copper layer, the interface between the ultrathin copper layer and molybdenum or cobalt or molybdenum-cobalt alloy It will come off. 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.
In the intermediate layer, the adhesion amount of nickel is 100 to 40000 μg / dm ² , the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and the adhesion amount of cobalt is 10 to 1000 μg / dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultrathin copper layer, the intermediate layer is made of a metal species (Co, Mo) that suppresses the diffusion of Ni to the ultrathin copper layer side while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this viewpoint, the amount of nickel deposited is preferably to 100~40000μg / dm ^2, preferably to 200~20000μg / dm ^2, more preferably to 300~15000μg / dm ^2, 300~10000μg / Dm ² is more preferable. If included molybdenum in the intermediate layer, a molybdenum deposition amount is preferably set to 10~1000μg / dm ^2, the molybdenum deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably. If included cobalt in the intermediate layer, the cobalt coating weight is preferably set to 10~1000μg / dm ^2, cobalt deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably.
As described above, the intermediate layer is plated for providing a molybdenum, cobalt, or molybdenum-cobalt alloy layer when nickel and molybdenum, cobalt, or a molybdenum-cobalt alloy are stacked in this order on a carrier. When the current density in the treatment is lowered and the carrier transport speed is lowered, the density of the molybdenum, cobalt, or molybdenum-cobalt alloy layer tends to increase. When the density of the layer containing molybdenum and / or cobalt increases, nickel in the nickel layer becomes difficult to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled.
The intermediate layer can be provided on the carrier by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD, and PVD. In addition, when providing an intermediate | middle layer by wet plating using a resin film for a carrier, it is necessary to perform the pretreatment for performing wet plating with respect to carriers, such as an activation process, before intermediate | middle layer formation. As the above-mentioned pretreatment, any treatment can be used as long as wet plating can be performed on the resin film, and a known treatment can be used.

<Strike plating>
An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Other layers 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 0.05-12 μm, more typically 0.1-12 μm, 0.5-12 μm, more typically 1.5-5 μm, more typically Is 2-5 μm. Moreover, you may use the layer of the structure which can be used as an intermediate | middle layer for another layer.

<Roughening treatment of carrier surface and ultrathin copper layer surface>
A roughening treatment layer may be provided on the surface opposite to the ultrathin copper layer side of the carrier by performing a roughening treatment, for example, in order to improve adhesion to the resin substrate. According to such a configuration, when performing the process of laminating the copper foil with a carrier of the present invention on the resin substrate from the carrier side, the adhesion between the carrier and the resin substrate is improved, and in the manufacturing process of the printed wiring board, the carrier and It becomes difficult to peel off from the resin substrate.
Further, it is not necessary to form a roughening treatment layer on the surface of the carrier opposite to the ultrathin copper layer side. If the roughening layer is not formed on the surface opposite to the ultrathin copper layer side of the carrier, there is an advantage that the peel strength between the carrier and the ultrathin copper layer can be easily controlled.
Further, a roughened layer may be provided on the surface of the ultrathin copper layer by performing a roughening process, for example, in order to improve the adhesion to the insulating substrate.

  In the present invention, a surface treatment layer such as a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer or the like is formed, or a roughening treatment layer is not formed. The “surface opposite to the ultrathin copper layer” is not particularly limited as long as it is a surface located on the side opposite to the ultrathin copper layer with respect to the carrier. For example, the surface of the carrier itself may be used. When the surface treatment layer is formed on the opposite side of the carrier from the ultrathin copper layer, the surface of any one of the surface treatment layers (including the surface of the outermost layer) may be used.

The roughening treatment applied to the carrier or the ultrathin copper layer 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, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. Also good. 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. The roughening treatment layer may be formed by using a sulfuric acid / copper sulfate electrolytic bath containing one or more selected from the group consisting of alkyl sulfate salts, tungsten and arsenic. The roughening treatment can be performed with the following electrolytic bath and conditions. In addition, after the roughening treatment, covering plating may be performed in order to prevent the roughening treatment particles from falling off.
・ Roughening treatment (liquid composition)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating conditions)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, cover plating (liquid composition)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating conditions)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds 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 is further treated with chromate treatment, silane coupling treatment, etc. May be applied. 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-treated layer, and a silane coupling-treated layer may be formed on the surface of the roughened 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 of the layer. 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.). These surface treatments hardly affect the surface roughness of the carrier and the ultrathin copper layer.

  The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment layer is preferably composed of fine particles from the viewpoint of fine pitch formation. Regarding the electroplating conditions for forming the roughened particles, if the current density is increased, the copper concentration in the plating solution is decreased, or the amount of coulomb is increased, the particles tend to become finer.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer is a nickel - molybdenum alloy, nickel - zinc alloys, nickel - molybdenum -You may be comprised by either 1 type of a cobalt alloy and a nickel- tin alloy. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  The chromate-treated 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 chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

The silane coupling treatment layer may be formed using a known silane coupling agent, such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, triazine. You may form using silane coupling agents, such as silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.
Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The above-mentioned amino-based silane coupling agents are N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3- Acrylicoxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tri Methoxysilane, N- ( -Aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl- 1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2-N -Benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N-dimethyl- 3-aminopropyl) trime Toxisilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β It may be selected from the group consisting of (aminoethyl) γ-aminopropyltrimethoxysilane and N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane.

The silane coupling treatment layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

  In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer, or a chromate treatment layer, International Publication No. Surface treatment described in International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A be able to.

<Printed wiring boards and laminates>
A laminated body (copper-clad laminated body etc.) can be produced by attaching a copper foil with a carrier to an insulating resin plate from the ultra-thin copper layer side, thermocompression bonding, and peeling the carrier. Thereafter, the copper circuit of the printed wiring board can be formed by etching the ultrathin copper layer portion. The insulating resin board used here is not particularly limited as long as it has characteristics applicable to a printed wiring board. For example, a paper base phenolic resin, a paper base epoxy resin, a synthetic fiber cloth base for rigid PWB are used. Material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin, glass cloth base material epoxy resin, etc. can be used, polyester film or polyimide film etc. can be used for FPC it can. The printed wiring board and the laminate produced in this way can be mounted on various electronic components that require high-density mounting of the mounted components.
In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. An electronic device can also be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring.

Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on the ultrathin copper layer, and the heat treatment layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer on the roughening treatment layer. One or more layers selected from the group may be provided.
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 layer may be provided on the heat resistance layer and the rust prevention layer. Alternatively, 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 adhesive, or an insulating resin layer in a semi-cured state (B stage state) 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. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, 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. 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.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine tree Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). The surface of the copper foil with a carrier is coated on the surface of the ultrathin copper layer by, for example, a roll coater method, 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 composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. In a state where the samples were stacked (laminate), the samples were bonded together under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm ² , and a press time of 10 minutes, and the resin outflow weight at that time was measured. Value.

  The surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the thickness of the resin layer is such that interlayer insulation can be ensured 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 500 μm, more preferably 0.1 to 300 μm, more preferably 0.1 to 200 μm, and preferably 0.1 to 120 μm. More preferred.

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 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the copper foil with a carrier having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.

When the thickness of the resin layer is 0.1 μm to 5 μm, a heat resistant layer and / or a rust preventive layer is formed on the ultrathin copper layer in order to improve the adhesion between the resin layer and the carrier-attached copper foil. After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, rust prevention layer, chromate treatment layer or silane coupling treatment layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.

  Furthermore, as another product form of the copper foil with a carrier with a resin, the ultra-thin copper layer, or the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane After coating with a resin layer on the coupling treatment layer and making it into a semi-cured state, it is also possible to peel off the carrier and manufacture in the form of a resin-coated copper foil without the carrier.

<Method for manufacturing printed wiring board>
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, the carrier After laminating the attached 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, The method includes a step of forming a circuit by any one of the modified semi-additive method, the partly 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 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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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 selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.

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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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.
First, as shown to FIG. 2-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. 2B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 2C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 3D, an embedded 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. 3-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 3F, laser drilling is performed at a predetermined position of the resin layer to expose circuit plating and form a blind via.
Next, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 4-H, circuit plating is formed on the via fill as shown in FIGS. 2-B and 2-C.
Next, as shown to FIG. 4-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 5J, the ultrathin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 5K, 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.
In the above-described printed wiring board manufacturing method, “ultra-thin copper layer” is used as a carrier, “carrier” is read as an ultra-thin copper layer, and a circuit is formed on the carrier-side surface of the copper foil with carrier. It is also possible to manufacture a printed wiring board by embedding a circuit with resin.

  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. 4-H, and these circuits may be formed using 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.

  Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate or resin layer, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

  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).

  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. 5-J and 5-K, when the ultrathin 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.

The copper foil with a carrier according to the present invention is a white plate on the surface of an ultrathin copper layer (when the light source is D65 and a 10-degree field of view, the white plate X ₁₀ Y ₁₀ Z ₁₀ color system (JIS Z8701 1999) The tristimulus values of X ₁₀ = 80.7, Y ₁₀ = 85.6, Z ₁₀ = 91.5, and the object color of the white plate in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* = − 0.90, b ^* = 0.24), and the color difference ΔE ^* ab based on JISZ8730 satisfies 45 or more. It is preferable to be controlled. The aforementioned color difference ΔE ^* ab is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more. When the color difference ΔE ^* ab based on JIS Z8730 on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, the ultrathin copper layer and the circuit As a result, the visibility is improved and the circuit alignment can be performed with high accuracy. In the present invention, the "color difference on the surface of the ultrathin copper layer" refers to the color difference on the surface of the ultrathin copper layer, or various types such as a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, or a silane coupling treatment layer. When the surface treatment layer is provided, the color difference of the surface treatment layer surface (outermost surface) is shown.

Here, the aforementioned color difference ΔE ^* ab is expressed by the following equation. Here, the color differences ΔL, Δa, Δb in the following formulas are respectively measured by a color difference meter, and L ^* a ^* b ^* based on JIS Z8730 (2009) taking black / white / red / green / yellow / blue into account ^. It is a comprehensive index shown using a color system, and is expressed as ΔL: black and white, Δa: red-green, Δb: yellow-blue. The color differences (ΔL, Δa, Δb) can be measured using, for example, a color difference meter MiniScan XE Plus manufactured by HunterLab. The color differences ΔL, Δa, and Δb are color differences based on JIS Z8730 (2009) on the surface of the ultrathin copper layer when the above-described white plate object color is used as a reference, and ΔL is JIS Z8729 (2004). ) defined in L ^* a ^* b ^* is the difference in CIE lightness L ^* of the two object colors in a color system, .DELTA.a, [Delta] b is in the L ^* a ^* b ^* color system defined in JIS Z8729 (2004) It is the difference between the color coordinates a ^* or b ^* of the two object colors.

The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughening treatment layer, the current density is made higher than conventional (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm ² ), and the processing time can be shortened (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm ² ), and the processing time can be set long (20 to 40 seconds).

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, an 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 to form a laminate (copper-clad laminate, copper-clad laminate). (Also referred to as a laminate). 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. You may laminate | stack another copper foil with a carrier from the carrier side or the ultra-thin copper layer side to the resin layer formed in the carrier side surface or the ultra-thin copper layer side surface. Also, a structure in which 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 on both surfaces of the resin substrate with the resin substrate as the center. Or a laminate having a structure in which the layers are laminated in the order of “carrier / intermediate layer / ultra thin copper layer / resin substrate / ultra thin copper layer / intermediate layer / carrier” or “carrier / intermediate layer / ultra thin copper layer / Laminated body having a structure in which the order of “resin substrate / carrier / intermediate layer / ultra thin copper layer” is laminated or “ultra thin copper layer / intermediate layer / carrier / resin substrate / carrier / intermediate layer / ultra thin copper layer”. You may use the laminated body which has the laminated structure for the manufacturing method (coreless construction method) of the above-mentioned printed wiring board. And, on the exposed surface of the ultra-thin copper layer or carrier at both ends of the laminate, another resin layer is provided, and after further providing a copper layer or a metal layer, the copper layer or the metal layer is processed. A circuit may be formed. Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed one or more times (build-up method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the production of the coreless substrate described above, a laminate having a configuration of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer described later using two copper foils with a carrier, Laminate having a structure of carrier / intermediate layer / ultra thin copper layer / ultra thin copper layer / intermediate layer / carrier, or a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer It is also possible to produce a laminated body and use the laminated body as a center. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer. The above-mentioned laminated body has other surfaces between the surface of the ultrathin copper layer, the surface of the carrier, between the carrier, between the ultrathin copper layer and the ultrathin copper layer, and between the ultrathin copper layer and the carrier. You may have a layer. The other layer may be a resin layer or a resin substrate. In this specification, “surface of ultrathin copper layer”, “surface of ultrathin copper layer side”, “surface of ultrathin copper layer”, “surface of carrier”, “surface of carrier side”, “carrier surface”, “ "Surface of laminated body" and "laminated body surface" means an ultrathin copper layer, a carrier, and a laminated body, if the ultrathin copper layer surface, carrier surface, and laminated body surface have other layers, the other layer The concept includes the surface (outermost surface). Moreover, it is preferable that a laminated body has the structure of an ultra-thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra-thin copper layer. This is because, when a coreless substrate is manufactured using the laminate, an ultrathin copper layer is disposed on the coreless substrate side, so that a circuit can be easily formed on the coreless substrate using the modified semi-additive method. In addition, since the thickness of the ultrathin copper layer is thin, it is easy to remove the ultrathin copper layer, and it becomes easier to form a circuit on the coreless substrate using the semi-additive method after the ultrathin copper layer is removed. .
In this specification, “laminate” not specifically described as “laminate A” or “laminate B” indicates a laminate including at least laminate A and laminate B.

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

  The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention. Moreover, the said carrier side surface or said ultra-thin copper layer side surface of said one copper foil with a carrier and the said carrier side surface or said ultra-thin copper layer side surface of said another copper foil with a carrier are as needed. Alternatively, a laminate obtained by directly laminating through an adhesive may be used. Further, the carrier or ultrathin copper layer of the one copper foil with carrier and the carrier or ultrathin copper layer of the other copper foil with carrier may be joined. Here, in the case where the carrier or the ultrathin copper layer has a surface treatment layer, the “joining” includes a mode in which the carriers or the ultrathin copper layer are joined to each other via the surface treatment layer. Further, part or all of the end face of the laminate may be covered with resin.

Lamination of carriers, ultrathin copper layers, carriers and ultrathin copper layers, and copper foils with a carrier can be performed by the following method, for example, in addition to superimposing.
(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 part or all of one carrier and part or all of the other carrier or part or all of the ultrathin copper layer using the joining method, one carrier and the other carrier or pole A laminated body constituted by laminating thin copper layers and contacting the carriers or the carrier and the ultrathin copper layer in a separable manner can be produced. When one carrier and the other carrier or ultrathin copper layer are weakly bonded and one carrier and the other carrier or ultrathin copper layer are laminated, one carrier and the other carrier or ultrathin copper layer Even without removing the junction with the thin copper layer, one carrier and the other carrier or ultrathin copper layer can be separated. In addition, when one carrier and the other carrier or ultrathin copper layer are strongly bonded, the portion where one carrier and the other carrier or ultrathin copper layer are bonded is cut or chemically polished ( One carrier and the other carrier or the ultrathin copper layer can be separated by removing them by etching or the like.

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

  The resin substrate, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. An accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like may be included. The copper foil with carrier may be smaller than the resin substrate, resin layer, resin or prepreg when viewed in plan.

  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 Copper Foil with Carrier As Examples 1 to 23 and Comparative Example 1, an electrolytic copper foil or a rolled copper foil (tough pitch copper foil JIS H3100 alloy number: C1100) having a thickness of 12 to 70 μm is used as a carrier by the following method. An intermediate layer and an ultrathin copper layer were formed on the carrier in this order to obtain a copper foil with a carrier having a thickness of 1 to 5 μm.
In addition, the surface roughness of rolled copper foil can be controlled by controlling the surface roughness of the rolling roll used at the time of rolling. By increasing the surface roughness of the rolling roll used at the time of rolling, the surface roughness of the rolled copper foil can be increased. Moreover, the surface roughness of rolled copper foil can be made small by reducing the surface roughness of the rolling roll used at the time of rolling. The surface roughness of the rolling roll is preferably Ra = 0.1 μm or more and 2.0 μm or less, for example.
Moreover, the surface roughness of the shiny surface (glossy surface) of the electrolytic copper foil can be controlled by controlling the surface roughness of the electrolytic drum used during the production of the electrolytic copper foil. By increasing the surface roughness of the electrolytic drum, the surface roughness of the shiny surface (glossy surface) of the electrolytic copper foil can be increased. Moreover, the surface roughness of the shiny surface (glossy surface) of the electrolytic copper foil can be reduced by reducing the surface roughness of the electrolytic drum. The roughness of the electrolytic drum may be, for example, Rz = 1.0 μm or more and 6.0 μm or less.
Moreover, the surface roughness of the mat | matte surface (deposition surface) of electrolytic copper foil can be controlled by controlling the copper concentration of the electrolytic solution at the time of electrolytic copper foil manufacture, current density, and electrolytic solution temperature. The surface roughness of the matte surface (deposition surface) of the electrolytic copper foil can be increased by lowering the copper concentration of the electrolytic solution during the production of the electrolytic copper foil, increasing the current density, and lowering the temperature of the electrolytic solution. . Moreover, the surface roughness of the matte surface (deposition surface) of the electrolytic copper foil is reduced by increasing the copper concentration of the electrolytic solution during the production of the electrolytic copper foil, decreasing the current density, and increasing the temperature of the electrolytic solution. Can do. For example, the copper concentration of the electrolytic solution during production of the electrolytic copper foil may be 50 to 130 g / L, the current density may be 50 to 120 A / dm ² , and the electrolytic solution temperature may be 40 to 90 ° C. In addition, the aqueous solution of a sulfuric acid and copper sulfate was used as electrolyte solution at the time of electrolytic copper foil manufacture. Further, when it is desired to reduce the surface roughness of the matte surface (deposition surface) of the electrolytic copper foil (for example, Rz is 1.5 μm or less or Rz = 1.0 to 1.5 μm), a brightener is added to the electrolytic solution. Good. A known brightener can be used as the brightener. In addition, about Example 6, as a brightener, Cl < ^- >: 20-50 mass ppm, polyethyleneglycol: 10-100 mass ppm, bis (3 sulfopropyl) disulfide: 10-30 mass ppm, thiourea: 10-50 mass ppm Was added. Moreover, about Example 23, Cl < ^- >: 30-80 mass ppm, bis (3 sulfopropyl) disulfide: 10-50 mass ppm, and thiourea: 10-50 mass ppm were added as a brightener. An amine compound represented by the following structural formula: 10 to 50 ppm was added. (R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aromatic group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

Intermediate layer formation As described in the “intermediate layer” column of the table, an intermediate layer was formed on the carrier. The processing conditions are shown below. For example, “Ni / organic matter” means that the organic matter treatment was performed after the nickel plating treatment.
On the glossy surface (shiny surface) or rolled copper foil of the electrolytic copper foil, an intermediate layer was provided in a roll-to-roll-type continuous plating line under the following conditions.
(1) “Ni”: Ni treatment (Ni plating)
Liquid composition: nickel sulfate concentration 200-300 g / L, trisodium citrate concentration 2-10 g / L
pH: 2-4
Liquid temperature: 40-70 degreeC
Current density: 1-15 A / dm ²
Ni adhesion amount: 8000 μg / dm ²
The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.

(2) “Chromate”: Electrolytic Chromate Treatment A Cr layer having an adhesion amount of 10 μg / dm ² was attached by subjecting it to electrolytic chromate treatment under the following conditions.
Liquid composition: potassium dichromate concentration 1-10 g / L, zinc concentration 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-3.0 A / dm ²

-"Organic substance": Organic substance layer formation process It carried out by showering for 20 to 120 seconds and spraying the aqueous solution of liquid temperature 40 degreeC and pH5 containing the carboxybenzotriazole (CBTA) with a density | concentration of 1-30 g / L.
As a result of measuring the thickness of the organic layer by the method described above, the thickness of the organic layer was 13 nm.

"Ni-Mo": nickel molybdenum alloy plating (Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds Ni adhesion amount: 3250 μg / dm ²
Mo adhesion amount: 420 μg / dm ²

- "Cr": chromium plating (liquid _{composition) CrO 3: 200~400g / L,} H 2 SO 4: 1.5~4g / L
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²
(Energization time) 1 to 20 seconds Cr adhesion amount: 350 μg / dm ²

"Co-Mo": Cobalt molybdenum alloy plating (Liquid composition) Co sulfate 50 g / dm ³ , Sodium molybdate dihydrate: 60 g / dm ³ , Sodium citrate 90 g / dm ³
(Liquid temperature) 30-80 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds Co adhesion amount: 420 μg / dm ²
Mo adhesion amount: 560 μg / dm ²

"Ni-P": Nickel phosphorus alloy plating (Liquid composition) Ni: 30 to 70 g / L, P: 0.2 to 1.2 g / L
(PH) 1.5-2.5
(Liquid temperature) 30-40 ° C
(Current density) 1.0-10.0 A / dm < ² >
(Energization time) 0.5 to 30 seconds Ni adhesion amount: 5320 μg / dm ²
P adhesion amount: 390 μg / dm ²

-Ultra-thin copper layer formation Subsequently, an ultra-thin copper layer having a thickness of 1-5 μm is formed on the intermediate layer by electroplating under the conditions shown below on a roll-to-roll-type continuous plating line. A copper foil with a carrier was produced.
Solution composition: copper concentration 30 to 120 g / L, sulfuric acid concentration 20~120g ^/ L, Cl -: 20~50 mass ppm, polyethylene glycol: 10 to 100 ppm by weight, bis (3-sulfopropyl) disulfide: 10 to 30 mass ppm , Thiourea: 10-50 ppm by mass
Liquid temperature: 20-80 degreeC
Current density: 10 to 100 A / dm ²

  Next, the surface of the carrier side of the copper foil with carrier and / or the surface of the ultrathin copper layer is subjected to any of roughening treatments (1) to (3), heat treatment, rust prevention treatment, and silane coupling agent application. Each surface treatment was applied. In Examples 1, 8 to 14, and 23, neither the carrier-side roughening treatment nor the ultrathin copper layer-side roughening treatment was performed. Each processing condition is shown below.

[Roughening treatment]
・ Roughening treatment (1) (coarse roughening):
Electrolytic solution composition: Cu 10-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid 80-120 g / L
Liquid temperature: 20-40 degreeC
Current density: 120 to 140 A / dm ²
In the copper electrolytic bath made of sulfuric acid / copper sulfate on the carrier side surface or ultrathin copper layer side surface of the copper foil with carrier subjected to the above roughening treatment (1) in order to prevent the roughened particles from dropping and to improve the peel strength. Cover plating was performed. The covering plating conditions are described below.
Liquid composition: copper concentration 20-40 g / L, sulfuric acid concentration 80-120 g / L
Liquid temperature: 40-50 degreeC
Current density: 10 to 50 A / dm ²

・ Roughening treatment (2) (medium roughening):
Liquid composition: copper concentration 10-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid concentration 80-120 g / L
Liquid temperature: 20-40 degreeC
Current density: 80-100 A / dm ²

A copper electrolytic bath made of sulfuric acid / copper sulfate is used on the carrier-side surface or ultrathin copper layer-side surface of the copper foil with carrier that has been subjected to the above-mentioned roughening treatment (2) in order to prevent falling off of the roughened particles and to improve the peel strength. Cover plating was performed. The covering plating conditions are described below.
Liquid composition: copper concentration 20-40 g / L, sulfuric acid concentration 80-120 g / L
Liquid temperature: 40-50 degreeC
Current density: 10 to 50 A / dm ²

-Roughening treatment (2) -2 (medium roughening):
Liquid composition: copper concentration 10-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid concentration 80-120 g / L
Liquid temperature: 20-40 degreeC
Current density: 105 to 115 A / dm ²

A copper electrolytic bath made of sulfuric acid / copper sulfate is used on the carrier-side surface or ultrathin copper layer-side surface of the copper foil with carrier that has been subjected to the above-mentioned roughening treatment (2) in order to prevent falling off of the roughened particles and to improve the peel strength. Cover plating was performed. The covering plating conditions are described below.
Liquid composition: copper concentration 20-40 g / L, sulfuric acid concentration 80-120 g / L
Liquid temperature: 40-50 degreeC
Current density: 10 to 50 A / dm ²

・ Roughening treatment (3) (fine roughening):
Liquid composition: copper concentration 10-20 g / L, cobalt concentration 1-10 g / L, nickel concentration 1-10 g / L
pH: 1-4
Liquid temperature: 30-50 degreeC
Current density: 20-30 A / dm ²

On the ultrathin copper layer side surface of the copper foil with carrier subjected to the roughening treatment (3) under the above conditions, Co—Ni was plated to form a heat-resistant layer. The plating conditions are described below.
Liquid composition: cobalt concentration 1-30 g / L, nickel concentration 1-30 g / L
pH: 1.0-3.5
Liquid temperature: 30-80 degreeC
Current density 1-10 A / dm ²

[Heat-resistant treatment]
・ Heat-resistant layer (zinc / nickel plating) formation treatment:
Liquid composition: nickel concentration 10-30 g / L, zinc concentration 1-15 g / L
Liquid temperature: 30-50 degreeC
Current density 1-10 A / dm ²

[Rust prevention treatment]
・ Chromate treatment:
Liquid composition: potassium dichromate concentration 3-5 g / L, zinc concentration 0.1-1 g / L
Liquid temperature: 30-50 degreeC
Current density 0.1-3.0 A / dm ²

[Silane coupling treatment]
By spraying a solution having a pH of 7 to 8 containing 0.2 to 2% by weight of alkoxysilane, a silane coupling agent was applied to carry out the treatment.

(Example 1, 8-14, 23)
Prepare a copper foil with a carrier with the thickness shown in the table by the above method and heat-treat the carrier side surface and the ultrathin copper layer side surface without subjecting the carrier side surface and the ultrathin copper layer side surface to roughening treatment. The copper foil which gave only the rust prevention process and the silane coupling process was produced.

(Examples 2, 15, and 22)
The copper foil with a carrier having the thickness shown in the table is prepared by the above-mentioned method, and the surface of the ultrathin copper layer is subjected to roughening treatment (2) (medium roughening), and further heat-resistant treatment, antirust treatment, The copper foil which performed the silane coupling process was produced.

(Examples 3, 4, 6, 7, 16-19)
A copper foil with a carrier having the thickness shown in the table is prepared by the above-described method, and the carrier side surface is subjected to a roughening treatment (2) (medium roughening), followed by heat treatment, rust prevention treatment, and silane coupling. A treated copper foil was produced.

(Example 5)
The copper foil with a carrier having the thickness shown in the table is prepared by the above-described method, and the carrier side surface is subjected to a roughening treatment (3) (fine roughening), and further subjected to heat treatment, rust prevention treatment, and silane coupling treatment. The applied copper foil was produced.

(Example 20)
A copper foil with a carrier having the thickness shown in the table is prepared by the above-mentioned method, and the surface on the carrier side is subjected to a roughening treatment (2) -2 (medium roughening), followed by a heat treatment, an antirust treatment, and a silane. The copper foil which performed the coupling process was produced.

(Example 21)
The copper foil with a carrier having the thickness described in the table is prepared by the above-described method, and the carrier side surface and the ultrathin copper layer side surface are subjected to a roughening treatment (2) -2 (medium roughening), and further heat resistant. The copper foil which performed the process, the antirust process, and the silane coupling process was produced.

(Comparative Example 1)
The copper foil with a carrier having the thickness shown in the table is prepared by the above-mentioned method, and the carrier side surface is subjected to roughening treatment (1) (coarse roughening), and further subjected to heat treatment, rust prevention treatment, and silane coupling treatment. The applied copper foil was produced.

2. Evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following methods.
<Surface roughness>
The ten-point average surface roughness Rz of the surface of the copper foil with carrier opposite to the ultrathin copper layer side was measured with a laser microscope LEXT OLS4000 manufactured by Olympus in accordance with JIS B0601-1994. Rz was arbitrarily measured at 10 locations, and the average value at 10 locations of Rz was defined as the value of Rz. Further, the ten-point average surface roughness Rz of the surface of the carrier on the ultrathin copper layer side was also measured in the same manner. Further, the ten-point average surface roughness Rz of the surface of the ultrathin copper layer opposite to the intermediate layer was also measured in the same manner.

  In addition, the maximum cross-sectional height Rt of the roughness curve of the surface of the copper foil with carrier opposite to the ultrathin copper layer side is measured with an Olympus laser microscope LEXT OLS4000 according to JIS B0601-2001. It was measured. Rt was arbitrarily measured at 10 locations, and the average value at 10 locations of the Rt was defined as the Rt value.

In addition, the arithmetic average roughness Ra of the surface opposite to the ultrathin copper layer of the carrier of the copper foil with carrier was measured with a laser microscope LEXT OLS4000 manufactured by Olympus in accordance with JIS B0601-1994. Ra was measured arbitrarily at 10 locations, and the average value of 10 locations of Ra was taken as the value of Ra.
For the above Rz, Ra, and Rt, an electrolytic copper foil used as a carrier under the conditions of an evaluation length of 258 μm and a cutoff value of zero using an objective lens with a magnification of 50 times the ultrathin copper layer and the carrier surface. Values were determined by measuring the direction perpendicular to the traveling direction of the electrolytic copper foil in the production apparatus or the direction perpendicular to the traveling direction of the rolled copper foil (TD) in the rolled copper foil production apparatus. The measurement environment temperature of Rz, Ra, and Rt on the surface with a laser microscope was 23 to 25 ° C.

<Normal peel strength>
About the produced copper foil with a carrier, the carrier side was pulled with the load cell and the peeling strength between a carrier and an ultra-thin copper layer was measured based on the 90 degree peeling method (JIS C6471 8.1).

<Normal peel strength after pressing>
The ultra-thin copper layer side of the prepared copper foil with carrier is bonded to a resin substrate and heated and pressed in air at 15 kgf / cm ² at 220 ° C. for 90 minutes, and then the carrier side is pulled with a load cell. The peel strength between the carrier and the ultrathin copper layer was measured according to the 90 ° peel method (JIS C 6471 8.1).

<Peel strength after reverse press>
About the produced copper foil with a carrier, the copper plating layer was formed by further plating up the ultra-thin copper layer side surface by copper plating. At this time, the copper plating layer was formed so that the total thickness of the ultrathin copper layer and the copper plating layer was 18 μm. Next, the carrier side of the copper foil with a carrier is bonded on a resin substrate and heated and pressed in the atmosphere at 15 kgf / cm ² and 220 ° C. for 90 minutes, and then the ultrathin copper layer side is attached with a load cell. The peel strength between the carrier and the ultrathin copper layer was measured according to the 90 ° peel method (JIS C 6471 8.1). In Comparative Example 1, the ultrathin copper layer could not be peeled from the carrier. In Comparative Example 2, the carrier and the resin substrate could not be laminated, and measurement could not be performed.

<Peelability and productivity>
-Manufacture of Coreless Substrate The copper foils with carriers according to Examples and Comparative Examples are each 90 ° C. at 15 kgf / cm ² and 220 ° C. in the atmosphere on both sides of the FR-4 prepreg larger than the copper foil with carriers from the carrier side. Lamination was performed by heating and pressing under the condition of minutes to obtain a laminate. In addition, since the laminated body was manufactured using the larger prepreg than copper foil with a carrier, the end surface of copper foil with a carrier is covered with resin (prepreg) in the obtained laminated body.

  A hole having a diameter of 1 mm was formed in four portions of the laminate thus manufactured where the plate-like carrier was exposed, and used as a guide hole for positioning in the subsequent build-up process. FR-4 prepreg and copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., JTC 12 μm (product name)) are sequentially stacked on both sides of the laminate, and hot pressing is performed at 170 ° C. for 100 minutes at a pressure of 3 MPa. A copper clad laminate was prepared.

  Next, a 100 μm diameter hole penetrating the copper foil on the surface of the four-layered copper clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine. Subsequently, copper plating is performed by electroless copper plating and electrolytic copper plating on the copper foil surface on the laminate exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate. An electrical connection was formed between the copper foil on the laminate and the copper foil on the surface of the four-layer copper clad laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. In this way, a four-layer build-up substrate was produced.

  Subsequently, the four-layer build-up substrate is cut inside the portion where the end surface of the carrier-attached copper foil is bonded by the prepreg when the laminate is viewed in plan, and then the laminate-provided copper foil with the carrier Two sets of two-layer buildup wiring boards were obtained by mechanically peeling and separating the carrier and the ultrathin copper layer.

  Subsequently, the copper foil that was in close contact with the plate-like carrier on the two sets of two-layer build-up wiring boards was etched to form a wiring to obtain two sets of two-layer build-up wiring boards. .

The presence or absence (peelability) of peeling between the resin substrate (FR-4 prepreg) and the carrier when the two sets of two-layer build-up wiring boards were produced was evaluated. The evaluation criteria for the peelability are shown below.
◎: “No peeling during 10 times”, ○ ○: “Peeling once during 10 times”, ○: “Peeling 2-3 times during 10 times”, Δ: “Peeling four times during 10 times” ”×”: “Peeled 5 times or more out of 10 times”

The peel strength between the ultrathin copper layer and the carrier when the two sets of two-layer build-up wiring boards are produced affects the productivity of the printed wiring board. Specifically, when the peel strength between the ultrathin copper layer and the carrier is 50 N / m or more, it takes a considerable time for peeling, and the productivity is poor (10 minutes / sheet or more for peeling). Moreover, in the case of 20 N / m or more, it takes time for peeling and productivity is poor (it takes 2 minutes / sheet or more for peeling). From such a viewpoint, the evaluation criteria for productivity were as follows.
A: “All 10 times, peel strength 20 N / m or less”, “O: 10 times, 1 to less than 5 times peel strength 20 N / m or more”, ○: “10 times, 5 times or more Peel strength 20 N / m or more ”, Δ:“ 1 time or more during 10 times, peel strength 50 N / m or more ”, ×:“ 1 time or more during 10 times, peeling is not possible ”
Test conditions and results are shown in Table 1.

(Evaluation results)
In Examples 1 to 23, in a laminate produced by laminating a copper foil with a carrier on a resin substrate, the ultrathin copper layer can be favorably peeled off from the carrier, and build using the copper foil with a carrier. The peelability and productivity when an up-wiring board was produced were good.
On the other hand, in Comparative Example 1, in the laminate produced by laminating the carrier-attached copper foil on the resin substrate, the ultrathin copper layer could not be satisfactorily peeled from the carrier. Moreover, productivity was poor when a build-up wiring board was produced using a copper foil with a carrier.

Claims (29)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The copper foil with a carrier whose arithmetic mean roughness Ra of the said surface is 1.0 micrometer or less when the surface on the opposite side to the said ultra-thin copper layer of the said carrier is measured with a laser microscope based on JISB0601-1994. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
When the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994, the ten-point average roughness Rz of the surface is 6.0 μm or less,
The pole surface opposite the thin copper layer of the carrier, when measured with a laser microscope in compliance with JIS B0601-1994, the arithmetic average roughness Ra of 1.0μm or less der Ruki Yaria coated copper of the surface Foil. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
Carrier whose maximum cross-sectional height Rt of the surface roughness curve is 7.0 μm or less when the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-2001. Copper foil. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The pole surface opposite the thin copper layer of the carrier, when measured with a laser microscope in compliance with JIS B0601-2001, the maximum section height Rt of the roughness curve of the surface Ri der less 7.0μm ,
The copper foil with a carrier satisfy | filling any one or two of the following (a) or (b).
(A) When the surface opposite to the ultrathin copper layer of the carrier is measured with a laser microscope in accordance with JIS B0601-1994, the ten-point average roughness Rz of the surface is 6.0 μm or less.
(B) When the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994, the arithmetic average roughness Ra of the surface is 1.0 μm or less. The ten-point average roughness Rz of the surface is 0.9 µm or more when the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-1994. The copper foil with a carrier as described in any one of 4 . The pole surface opposite the thin copper layer of the carrier, when measured with a laser microscope in compliance with JIS B0601-1994, claim 1-5 arithmetic average roughness Ra of the surface is not less than 0.12μm The copper foil with a carrier as described in any one of these. When the surface of the carrier opposite to the ultrathin copper layer is measured with a laser microscope in accordance with JIS B0601-2001, the maximum cross-sectional height Rt of the surface roughness curve is 1.1 μm or more. Item 7. A copper foil with a carrier according to any one of items 1 to 6 . The surface of the carrier opposite to the ultrathin copper layer has at least one layer selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. copper foil with carrier according to any one of claims 1-7. The roughening treatment layer has a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. And / or
Having a layer formed using a sulfuric acid-copper sulfate electrolytic bath containing one or more selected from the group consisting of alkyl sulfate salts, tungsten and arsenic,
The copper foil with a carrier according to claim 8 . There is no roughening treatment layer on the surface opposite to the ultra-thin copper layer of the carrier, or
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 without having a roughening-treated layer on the surface opposite to the ultra-thin copper layer of the carrier Having more layers,
The copper foil with a carrier as described in any one of Claims 1-8 . Roughened layer on the ultra-thin copper layer surface, anti-heat layer, the anticorrosive layer, more of claims 1-10 comprising one or more layers selected from the group consisting of chromate treatment layer and a silane coupling treatment layer A copper foil with a carrier according to claim 1. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing at least one kind. Item 11. A copper foil with a carrier according to Item 11 . There is no roughening treatment layer on the surface of the ultra-thin copper layer, or
The surface of the ultra-thin copper layer does not have a roughening treatment layer, and 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.
Copper foil with carrier according to any one of claims 1 to 11. One type selected from the group consisting of the ultrathin copper layer surface, or a roughened layer formed on the ultrathin copper layer surface, the heat-resistant layer, the rust preventive layer, the chromate layer, and the silane coupling layer copper foil with carrier according to any one of claims 1 to 13, comprising a resin layer on the above layers. The copper foil with a carrier according to claim 14 , wherein the resin layer is an adhesive resin and / or a semi-cured resin. The laminated body provided with the copper foil with a carrier as described in any one of Claims 1-15 . It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-15 , Comprising: The laminated body by which one part or all part of the end surface of the said copper foil with a carrier was covered with the said resin. From one of claims 1 to 15 copper foil with carrier is the carrier side or the ultra-thin copper layer side according to any one of, with a carrier according to any one of another claim from 1 to 15 The laminated body laminated | stacked on the said carrier side or the said ultra-thin copper layer side of copper foil. The printed wiring board which has a copper foil with a carrier as described in any one of Claims 1-15 . The manufacturing method of the printed wiring board which manufactures a printed wiring board using the copper foil with a carrier as described in any one of Claims 1-15 . The process of preparing the copper foil with a carrier as described in any one of Claims 1-15 , and an insulated substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper 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. The process is also ultra-thin copper layer-side surface forming the circuits of the copper foil with carrier according to any one of claims 1 to 15
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
A step of peeling the carrier after forming the resin layer; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. A step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to any one of claims 1 to 15 ,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. The process of laminating | stacking the copper foil with a carrier as described in any one of Claims 1-15 on the resin substrate from the said carrier side,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. The process of laminating | stacking the copper foil with a carrier as described in any one of Claims 1-15 on the resin substrate from the said carrier side,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
A step of peeling the carrier after forming the resin layer; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. The process of laminating | stacking the said ultra-thin copper layer side surface or the said carrier side surface of the copper foil with a carrier as described in any one of Claims 1-15 , 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. The process of laminating | stacking the said carrier side surface of the copper foil with a carrier as described in any one of Claims 1-15 , 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. A step of providing two layers of a resin layer and a circuit at least once on one or both sides of the laminate according to any one of claims 16 to 18 , and
A method for producing a printed wiring board, comprising the step of peeling the carrier or the ultrathin copper layer from a copper foil with a carrier constituting the laminate after forming the resin layer and the two layers of the circuit. The manufacturing method of the electronic device which manufactures an electronic device using the printed wiring board of Claim 19 , or the printed wiring board manufactured by the method as described in any one of Claims 20-27 .