JP6591766B2 - Copper foil with carrier, printed wiring board, laminate, electronic device and method for manufacturing printed wiring board - Google Patents

Description

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

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After a circuit pattern is formed with a resist on the exposed ultrathin copper layer, a predetermined circuit is formed (Patent Document 1, etc.).

WO2004 / 005588

  As described above, the carrier-attached copper foil is used after the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded (heat press), and then the carrier is peeled off. The carrier peel strength at this time is preferably the strength desired by the user. However, the peel strength of the carrier adjusted at the stage of manufacturing the copper foil with a carrier is lowered after the heat press with the insulating substrate, and the user who uses the copper foil with the carrier bonded to the insulating substrate is desired. There arises a problem that the peel strength of the carrier cannot be obtained. When such a desired peel strength cannot be obtained, when the carrier is peeled and removed from the carrier-attached copper foil bonded to the insulating substrate, the peel becomes difficult and the yield decreases, or the peel is impossible. The problem is that wrinkles occur in the ultrathin copper layer due to the force applied.

  Then, this invention makes it a subject to provide the copper foil with a carrier by which the change of the peeling strength of a carrier was suppressed favorably before and behind the hot press of the copper foil with a carrier.

  In order to achieve the above object, the present inventor has conducted extensive research and found that the change in the peel strength of the carrier before and after the hot pressing of the carrier-added copper foil is the tensile strength (tensile strength of the carrier before and after the hot pressing of the copper foil with the carrier. ) Was found to be controllable by adjusting the rate of decrease. And by controlling the decrease rate of the tensile strength (tensile strength) of the carrier before and after the hot pressing of the copper foil with carrier to a predetermined range, the change in the peel strength of the carrier before and after the hot pressing of the copper foil with carrier is good. It was found that it can be suppressed.

The present invention has been completed on the basis of the above knowledge, and in one aspect, a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the thickness of the carrier is 5 μm or more. 70 μm or less, the ultrathin copper layer is thinner than the carrier, and the carrier-reduced copper foil is pressed under pressure at 20 kgf / cm ² at 220 ° C. for 2 hours after the carrier is pressed. It is a copper foil with a carrier whose rate A is 0.0001% or more and 20% or less.

Another aspect of the present invention is a copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the copper foil with a carrier has a pressure of 20 kgf / cm ² and 220 ° C. With the carrier, the tensile strength reduction rate B of the carrier is 0.0001% or more and 20% or less after being heated and pressed at 2 hours under pressure and then heated under no pressure at 220 ° C. for 4 hours. Copper foil.

In one embodiment, the copper foil with a carrier of the present invention satisfies at least one of the following (3-1) and (3-2).
(3-1) The tensile strength reduction rate A of the carrier is 15% or less .
(3-2) The tensile strength reduction rate B of the carrier is 15% or less .

In another embodiment, the copper foil with a carrier of the present invention satisfies at least one of the following (4-1) and (4-2).
(4-1) The tensile strength reduction rate A of the carrier is 12% or less .
(4-2) The tensile strength reduction rate B of the carrier is 12% or less .

In yet another embodiment, the carrier-attached copper foil of the present invention satisfies at least one of the following (5-1) and (5-2).
(5-1) The tensile strength reduction rate A of the carrier is 10% or less .
(5-2) The tensile strength reduction rate B of the carrier is 10% or less .

In yet another embodiment, the carrier-attached copper foil of the present invention satisfies at least one of the following (6-1) and (6-2).
(6-1) The tensile strength reduction rate A of the carrier is 8% or less .
(6-2) The tensile strength reduction rate B of the carrier is 8% or less .

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

  In another embodiment of the copper foil with a carrier of the present invention, the roughening treatment layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is a layer made of any single substance or an alloy containing one or more kinds.

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

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

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

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

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

  In another embodiment, the copper foil with a carrier of the present invention is a copper foil with a carrier having an intermediate layer and an ultrathin copper layer in this order on one surface of the carrier, and the ultrathin copper of the carrier. The roughening treatment layer is provided on the surface opposite to the surface on the layer side.

  In another embodiment, the copper foil with a carrier of the present invention has an intermediate layer and an ultrathin copper layer in this order on both sides of the carrier.

  In another aspect of the present invention, there is provided a laminate manufactured using 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 yet another aspect of the present invention, the carrier-attached copper foil of the present invention is separated from the carrier side or the ultrathin copper layer side of the present invention, and the carrier-side copper foil of the present invention of the present invention It is the laminated body laminated | stacked on the copper layer side.

  In one embodiment of the laminate of the present invention, the carrier-side surface or ultrathin copper layer side surface of the one carrier-attached copper foil and the carrier-side surface or ultrathin copper of the another carrier-attached copper foil. The layer-side surface is configured to be directly laminated through an adhesive as necessary.

  In another embodiment of the laminate of the present invention, the carrier or the ultrathin copper layer of the one carrier-attached copper foil and the carrier or the ultrathin copper layer of the other carrier-attached copper foil are joined. Has been.

  In another aspect of the present invention, the laminate of the present invention is a laminate in which part or all of the end surface of the laminate is covered with a resin.

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

  In another aspect of the present invention, the step of providing the laminate of the present invention with two layers of a resin layer and a circuit at least once, and after forming the resin layer and the two layers of the circuit at least once, It is a manufacturing method of a printed wiring board including the process of peeling the ultra-thin copper layer or the carrier from the copper foil with a carrier of the layered product.

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

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

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

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

  In another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention, the carrier-attached copper foil so that the circuit is buried. After forming the resin layer on the ultrathin copper layer side surface or the carrier side surface, peeling the carrier or the ultrathin copper layer, and peeling the carrier or the ultrathin copper layer, A method for producing a printed wiring board, comprising: removing an ultrathin copper layer or the carrier to expose a circuit embedded in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface It is.

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier in which the change of the peeling strength of a carrier before and behind the hot press of the copper foil with a carrier was suppressed favorably can be provided.

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

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

The carrier-attached copper foil of the present invention has a carrier tensile strength (tensile strength) reduction rate of 20% or less after heat-pressing the carrier-attached copper foil under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours. is there. According to such a structure, the change of the peeling strength of the carrier before and after the hot pressing of the copper foil with a carrier can be satisfactorily suppressed. In general, the tensile strength of a carrier changes to some extent by heating. At this time, the carrier shrinks due to recrystallization of the metal of the carrier. It is considered that a stress is applied to the intermediate layer due to the contraction of the carrier, and the peel strength when the carrier is peeled and removed from the ultrathin copper layer via the intermediate layer is changed by the stress applied to the intermediate layer. In the present invention, by adjusting the decrease rate of the tensile strength (tensile strength) of the carrier before and after the hot pressing of the copper foil with carrier, the change in the peel strength of the carrier before and after the hot pressing of the copper foil with carrier is suppressed. ing. The tensile strength reduction rate of the carrier is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, and even more preferably 8% or less. The tensile strength reduction rate of the carrier is typically 0.0001% to 20%, alternatively 0.001% to 20%, alternatively 0.01% to 20%, alternatively 0.1% to 20%. Or 0.5% to 20%, or 0.8% to 20%. The above “pressure: 20 kgf / cm ² , heat-pressed at 220 ° C. for 2 hours” shows typical heat-press conditions when a carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonded. Yes.
The rate of decrease in the tensile strength (tensile strength) of the carrier of the copper foil with carrier is realized by producing the carrier by the production method described later.

Another aspect of the copper foil with a carrier according to the present invention is that the copper foil with a carrier is hot-pressed under a pressure of 20 kgf / cm ² and a temperature of 220 ° C. for 2 hours, followed by no pressure and a pressure of 4 at 220 ° C. The rate of decrease in the tensile strength (tensile strength) of the carrier after heating under conditions of time is 20% or less. After heat-pressing to attach the carrier-attached copper foil to the insulating substrate, when the insulating substrate is a resin substrate, etc., when the printed wiring board using the substrate is manufactured, it is laminated on another substrate and heat-treated If this is done, the resin shrinks and the dimensions of the resin substrate change, causing problems in the production of a printed wiring board with high accuracy. In order to prevent shrinkage of the resin during the production of such a printed wiring board, heat treatment may be performed in advance to sufficiently cure the resin. Here, there is a problem that the peel strength of the carrier changes before and after the heat treatment performed in order to sufficiently cure the resin in advance, but in the present invention, as described above, the tensile strength of the carrier before and after the heat treatment ( Since the decrease rate of (tensile strength) is controlled, a change in the peel strength of the carrier can also be satisfactorily suppressed. The tensile strength reduction rate of the carrier is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, and even more preferably 8% or less. The tensile strength reduction rate of the carrier is typically 0.0001% to 20%, alternatively 0.001% to 20%, alternatively 0.01% to 20%, alternatively 0.1% to 20%. Or 0.5% to 20%, or 0.8% to 20%. The “heating under no pressure at 220 ° C. for 4 hours” is performed after the carrier-attached copper foil is bonded to the insulating substrate and thermocompression bonded, in order to shrink the insulating substrate in advance. Typical heat treatment conditions are shown.
The rate of decrease in the tensile strength (tensile strength) of the carrier of the copper foil with carrier is realized by producing the carrier by the production method described later.

<Career>
The carrier that can be used in the present invention is a metal foil, and is provided in the form of, for example, copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil. The
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

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

The carrier of the present invention can be produced under the following conditions for producing an electrolytic copper foil. The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.
<Electrolyte composition>
Copper: 80-110 g / L
Sulfuric acid: 70-110 g / L
Chlorine: 10-100 ppm by mass
Nika: 1 to 15 ppm by mass, preferably 1 to 10 ppm by mass (in the case where the concentration of glue is 5 ppm by mass or more, chlorine is unnecessary).

<Production conditions>
Current density: 50 to 200 A / dm ²
Electrolyte temperature: 40-70 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer. 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, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

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

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

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

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

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

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

Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on an ultrathin copper layer, and the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the roughening treatment layer. One or more layers selected from the above may be provided.
In addition, a roughened layer may be provided on the ultrathin copper layer, a heat-resistant layer and a rust-proof layer may be provided on the roughened layer, and a chromate-treated layer may be provided on the heat-resistant layer and the rust-proof layer. Alternatively, a silane coupling treatment layer may be provided on the chromate treatment layer.
The carrier-attached copper foil may be provided with a resin layer on an ultrathin copper layer, a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, or a silane coupling-treated layer. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive, an adhesive resin, or an insulating resin layer in a semi-cured state (B stage state) for adhesion. 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 type is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polyvinyl acetal resin, urethane resin, polyethersulfone, polyethersulfone resin, aromatic Polyamide resin, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, polyhydric carboxylic acid anhydride A resin or prepreg containing a liquid crystal polymer, a fluororesin, or the like can be mentioned as a preferable one.

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

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

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

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

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of this resin layer is preferably 0.1 to 80 μm.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The method for producing a printed wiring board of the present invention includes a step of forming a circuit on the surface of the ultrathin copper layer or the surface of the carrier of the copper foil with a carrier of the present invention, and the copper foil with a carrier so that the circuit is buried. A step of forming a resin layer on the surface of the ultrathin copper layer or the surface of the carrier, a step of forming a circuit on the resin layer, a circuit on the resin layer, the carrier or the ultrathin copper Forming the layer on the surface of the ultrathin copper layer or the carrier side by removing the ultrathin copper layer or the carrier after peeling the carrier or the ultrathin copper layer. The step of exposing the circuit buried in the resin layer may be included. Moreover, the manufacturing method of a printed wiring board is the process of forming a circuit in the said ultra-thin copper layer side surface or the said carrier side surface of the copper foil with a carrier of this invention, The said copper foil with a carrier so that the said circuit may be embedded. After forming the resin layer on the ultrathin copper layer side surface or the carrier side surface, peeling the carrier or the ultrathin copper layer, and peeling the carrier or the ultrathin copper layer, You may include the process of exposing the circuit embedded in the said resin layer formed in the said ultra-thin copper layer side surface or the said carrier side surface by removing an ultra-thin copper layer or the said carrier.

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

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

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

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

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

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board of the present invention. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate.

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 ultra-thin copper layer from the copper foil with carrier may be used. As a specific example of the coreless construction method, first, the ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. 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. In this case, a copper foil with a carrier is laminated in the order of carrier / intermediate layer / ultra-thin copper layer or ultra-thin copper layer / intermediate layer / carrier in this order on both surface sides of the resin substrate with the resin substrate as the center It has become. Even if an ultrathin copper layer on both ends or the exposed surface of the carrier is provided with another resin layer, and further provided with a copper layer or metal layer, a circuit may be formed by processing the copper layer or metal layer. Good. 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, which will be 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. 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, 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 can be prevented, and the ultra-thin copper layer and the carrier are separated or impregnated with the chemical solution. Corrosion of the copper foil can be prevented and the yield can be improved. As the “resin that covers part or all of the end face of the copper foil with carrier” or “resin that covers part or all of the end face of the laminate” used herein, a resin that can be used for the resin layer may be used. it can. Further, in the above-described coreless substrate manufacturing method, the carrier-attached copper foil or laminate when viewed in plan, the carrier-attached copper foil or laminate portion (a laminate portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery of the laminated copper foil with carrier and another copper foil with carrier may be covered with resin or prepreg. Moreover, the laminated body (laminated body A) formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact each other so that isolation | separation is possible. Further, when viewed in plan in the copper foil with carrier, the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultrathin copper layer, or one copper foil with carrier and another copper with carrier) It may be formed by being covered with a resin or a prepreg over the entire outer periphery of the laminated portion with the foil. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Cutting a covered copper foil with a carrier or a laminated part of a laminated body (a laminated part of a carrier and an ultrathin copper layer or a laminated part of one copper foil with a carrier and another copper foil with a carrier), etc. Need to be removed.

  The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention. 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 can be performed by, for example, the following method, in addition to simply overlapping.
(A) Metallurgical joining method: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, Friction stir welding), brazing;
(B) Mechanical joining method: caulking, joining with rivets (joining with self-piercing rivets, joining with rivets), stitcher;
(C) Physical joining method: adhesive, (double-sided) adhesive tape

  By joining a part or all of one carrier and a part or all of the other carrier using the joining method described above, one carrier and the other carrier are stacked, and the carriers are brought into contact with each other in a separable manner. It is possible to manufacture a laminated body configured as described above. When one carrier and the other carrier are weakly bonded and one carrier and the other carrier are laminated, one of the carriers and the other carrier can be removed without removing the bonding portion. One carrier and the other carrier can be separated. In addition, when one carrier and the other carrier are strongly bonded, the portion where one carrier and the other carrier are bonded is removed by cutting, chemical polishing (etching, etc.), mechanical polishing, or the like. Thus, one carrier and the other carrier can be separated.

  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 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. Preparation of copper foil with carrier [Carrier]
An electrolytic copper foil was produced under the following conditions and used as a carrier. Table 1 shows the glue concentration in each electrolyte composition.
(Example carrier)
<Electrolyte composition>
Copper: 80-110 g / L
Sulfuric acid: 70-110 g / L
Chlorine: 10-100 ppm by mass
Nika: 1 to 10 ppm by mass (Note that chlorine was not added in Examples 6, 7, 10, and 11 where the Nika concentration was 5 ppm by mass or more.)
<Production conditions>
Current density: 50 to 200 A / dm ²
Electrolyte temperature: 40-70 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

(Comparative carrier)
<Electrolyte composition>
Copper: 80-110 g / L
Sulfuric acid: 70-110 g / L
Chlorine: 10-100 ppm by mass
Nika: 0.01-0.1 mass ppm
<Production conditions>
Current density: 50 to 200 A / dm ²
Electrolyte temperature: 40-70 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

[Middle layer]
As shown in Table 1 for each example and comparative example, the following intermediate layer was provided.
For example, “Ni / chromate” in Table 1 means that the following chromate treatment layer is provided after the following Ni layer is provided on the surface of the carrier.
“Ni”: Ni layer A Ni layer having an adhesion amount of 8000 μg / dm ² was formed on the shiny surface of this copper foil by electroplating on a roll-to-roll-type continuous plating line under the following conditions. .
<Electrolyte composition>
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-25 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 mass ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 7 to 11 A / dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm ² was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
・ "Chromate": Chromate treatment layer / Electrolytic chromate treatment Liquid composition: Potassium dichromate 1-10g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²
・ "Ni-Mo": Ni-Mo layer (nickel molybdenum alloy plating)
A Ni—Mo layer having an adhesion amount of 3000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Ni sulfate 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 ・ "Organic substance": Organic substance layer (Organic substance layer forming treatment)
An organic layer was formed by showering and spraying an aqueous solution having a liquid temperature of 40 ° C. and pH 5 containing carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L on the above Ni layer for 20 to 120 seconds. .
"Co-Mo": Co-Mo layer (cobalt molybdenum alloy plating)
A Co—Mo layer having an adhesion amount of 4000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Co sulfate 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
(Energizing time) 3 to 25 sec. “Cr”: chromium layer A carrier layer of 500 μg / dm ² is deposited by electroplating a carrier on a roll-to-roll-type continuous plating line under the following conditions. Formed. Specific plating conditions are described below.
(Liquid composition) CrO ₃ : 200 to 400 g / L, H ₂ SO ₄ : 1.5 to ₄ g / L
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²

(Ultra-thin copper layer)
Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 2 to 10 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.
Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

[Surface treatment layer]
For Example 2 and Comparative Example 2, the surface of the ultrathin copper layer was subjected to the following roughening treatment, rust prevention treatment, chromate treatment, and silane coupling treatment in this order.
・ Roughening Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1 to 10 g / L
pH: 1-4
Liquid temperature: 40-50 degreeC
Current density Dk: 20 to 30 A / dm ²
Time: 1-5 seconds Cu adhesion amount: 15-40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Rust prevention treatment Zn: over 0 to 20 g / L
Ni: more than 0 to 5 g / L
pH: 2.5-4.5
Liquid temperature: 30-50 degreeC
Current density Dk: over 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Bath temperature: 25-60 ° C
Immersion time: 5 to 30 seconds

For Examples 3, 6, and 11 and Comparative Example 3, the following roughening treatment 1, roughening treatment 2, antirust treatment, chromate treatment, and silane coupling treatment were applied to the surface of the ultrathin copper layer. I went in order.
・ Roughening 1
(Liquid composition 1)
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 condition 1)
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, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
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, rust prevention treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

For Example 4 and Comparative Example 4, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order on the surface of the ultrathin copper layer.
・ Roughening 1
Liquid composition: Copper 10-20 g / L, sulfuric acid 50-100 g / L
Liquid temperature: 25-50 degreeC
Current density: 1 to 58 A / dm ²
Coulomb amount: 4 to 81 As / dm ²
・ Roughening 2
Liquid composition: Copper 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L
pH: 2-3
Liquid temperature: 30-50 degreeC
Current density: 24 to 50 A / dm ²
Coulomb amount: 34 to 48 As / dm ²
・ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
-Chromate treatment Liquid composition: Potassium dichromate 1-10 g / L, Zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0 to ^{2 A} / dm ² (Can also be electroless because of immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (can also be electroless because of immersion chromate treatment)
Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)

2. Evaluation of copper foil with carrier <Evaluation of thickness of ultrathin copper layer>
The thickness of the ultra-thin copper layer of the produced copper foil with a carrier was observed using FIB-SIM (magnification: 10,000 to 30,000 times). By observing the cross section of the ultrathin copper layer, five points were measured at intervals of 30 μm, and the average value was obtained.

<Evaluation of tensile strength (tensile strength (tensile strength))>
(1) Tensile strength before heating press (tensile strength): For the produced copper foil with carrier, the carrier was peeled off with a load cell, and the tensile strength (tensile strength) was determined for the carrier according to JIS Z 2241 by a tensile test. .
(2) Tensile strength (tensile strength) after hot pressing: The ultrathin copper layer side of the produced copper foil with carrier is bonded onto an insulating substrate, and the atmosphere is 20 kgf / cm ² at 220 ° C. for 2 hours. Then, the carrier was peeled off with a load cell, and the tensile strength (tensile strength) of the carrier was determined by a tensile test according to JIS Z 2241.
(3) Tensile strength (tensile strength) after pressureless heating after heating press: The ultrathin copper layer side of the prepared copper foil with carrier is bonded onto an insulating substrate, and is 20 kgf / cm ² at 220 ° C. in the air. And then heated and pressed at 2 hours under no pressure (no pressing), heated at 220 ° C. for 4 hours, and then peeled off with a load cell, and the carrier is in accordance with JIS Z 2241 The tensile strength (tensile strength) was determined by a tensile test.
Decrease rate A of tensile strength (tensile strength) using each tensile strength (tensile strength) obtained in (1) to (3) above: [(Tension before heating press-Tensile strength after heating press) / Before heating press Tensile strength] × 100%), and decrease rate B of tensile strength (tensile strength): [(Tension before heating press-Tensile strength after no pressure heating after heating press) / Tension before heating press] × 100% ) Was calculated.

<Evaluation of peel strength>
(1) Peeling strength before hot pressing: About the produced copper foil with a carrier, the carrier side was pulled with the load cell, and it measured based on the 90 degree peeling method (JIS C6471 8.1).
(2) Peel strength after hot pressing: The ultrathin copper layer side of the produced copper foil with carrier is bonded to an insulating substrate, and heated and pressed in air at 20 kgf / cm ² and 220 ° C. for 2 hours. Then, the carrier side was pulled with a load cell, and measurement was performed in accordance with a 90 ° peeling method (JIS C 6471 8.1).
(3) Peel strength after pressureless heating after heating press: The ultrathin copper layer side of the produced copper foil with carrier is bonded onto an insulating substrate, and the atmosphere is 20 kgf / cm ² at 220 ° C. for 2 hours. Then, after heating and pressing under the conditions of no pressure (no pressing) and heating at 220 ° C. for 4 hours, the carrier side was pulled with a load cell and the 90 ° peeling method (JIS C 6471 8.1). ) And measured.
Using each of the peel strengths obtained in the above (1) to (3), the peel strength change rate A: (| Peel strength before heating press-Peel strength after heat press | / Peel strength before heat press) X100% and peel strength change rate B: (| peeling strength before heating press-peeling strength after pressureless heating after pressure-pressing | / peeling strength before heating press) / 100% was calculated.
Table 1 shows the test conditions and test results.

(Evaluation results)
In each of Examples 1 to 11, the carrier tensile strength reduction rate after heat-pressing the carrier-attached copper foil under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 20% or less. The carrier-attached copper foil was heated and pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours, and subsequently the tensile strength of the carrier was reduced after heating under no pressure at 220 ° C. for 4 hours. The rate was 20% or less. For this reason, in all of Examples 1 to 11, the rate of change in peel strength was well suppressed.
In each of Comparative Examples 1 to 9, the carrier tensile strength reduction rate after heat-pressing the copper foil with carrier under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours exceeds 20%, Moreover, the carrier tensile strength after the copper foil with a carrier was heated and pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours and then heated under the condition of no pressure and 220 ° C. for 4 hours. The decrease rate exceeded 20%. For this reason, all of Comparative Examples 1 to 9 had a poor rate of change in peel strength.

Claims (30)

A copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The thickness of the carrier is 5 μm or more and 70 μm or less, and the ultrathin copper layer is thinner than the carrier,
The carrier-attached copper foil having a tensile strength reduction rate A of 0.0001% or more and 20% or less after heat-pressing the copper foil with carrier at a pressure of 20 kgf / cm ² and 220 ° C. for 2 hours. . Tensile strength of the carrier after heating and pressing the copper foil with carrier under pressure: 20 kgf / cm ² at 220 ° C. for 2 hours and then heating under pressure at 220 ° C. for 4 hours The copper foil with a carrier according to claim 1, wherein the decrease rate B is 0.0001% or more and 20% or less. The copper foil with a carrier according to claim 1 or 2, satisfying at least one of the following (3-1) and (3-2).
(3-1) The tensile strength reduction rate A of the carrier is 15% or less.
(3-2) The tensile strength reduction rate B of the carrier is 15% or less. The copper foil with a carrier according to claim 3, which satisfies at least one of the following (4-1) and (4-2).
(4-1) The tensile strength reduction rate A of the carrier is 12% or less.
(4-2) The tensile strength reduction rate B of the carrier is 12% or less. The copper foil with a carrier according to claim 4 satisfying any one or more of the following (5-1) and (5-2).
(5-1) The tensile strength reduction rate A of the carrier is 10% or less.
(5-2) The tensile strength reduction rate B of the carrier is 10% or less. The copper foil with a carrier according to claim 5, which satisfies at least one of the following (6-1) and (6-2).
(6-1) The tensile strength reduction rate A of the carrier is 8% or less.
(6-2) The tensile strength reduction rate B of the carrier is 8% or less. The copper foil with a carrier as described in any one of Claims 1-6 which has a roughening process layer in any one or both of the said ultra-thin copper layer surface and the surface of the said carrier. The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. The copper foil with a carrier according to claim 7 which is a layer. The copper with a carrier according to claim 7 or 8 , comprising at least one layer selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. Foil. The surface of the said ultra-thin copper layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer as described in any one of Claims 1-6. The copper foil with a carrier of description. The copper foil with a carrier as described in any one of Claims 1-6 provided with a resin layer on the said ultra-thin copper layer. The copper foil with a carrier according to claim 7 or 8 , comprising a resin layer on the roughening treatment layer. The copper foil with a carrier according to claim 9 or 10 , comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. On one surface of the carrier is a copper foil with a carrier having an intermediate layer and an ultrathin copper layer in this order,
Of the carrier, the pole on the side opposite to the thin copper layer-side surface, the copper foil with carrier according to any one of the roughened layer claim wherein are provided 1-13. Copper foil with carrier according to any one of claims 1 to 13 having the intermediate layer and the ultra-thin copper layer on the surface of both the carrier in this order. The laminated body manufactured using 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 is covered with the said resin. . From one of claim 1 to 15 copper foil with carrier said 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 carrier side surface or the ultrathin copper layer side surface of the one copper foil with carrier and the carrier side surface or the ultrathin copper layer side surface of the other copper foil with carrier are bonded as necessary. The laminate according to claim 18 , wherein the laminate is directly laminated via an agent. The laminate according to claim 18 or 19 , wherein the carrier or the ultrathin copper layer of the one copper foil with carrier and the carrier or the ultrathin copper layer of the other copper foil with carrier are joined. . A laminate according to any one of claims 16-20, laminate part or all of an end face of the laminate is covered with a resin. Method for manufacturing a printed wiring board using the laminate according to any one of claims 16-21. A step of providing at least once two layers of a resin layer and a circuit on the laminate according to any one of claims 16 to 21 , and
A method for producing a printed wiring board, comprising: forming the resin layer and the circuit layer at least once, and then peeling the ultrathin copper layer or the carrier from the copper foil with a carrier of the laminate. The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-15 . The electronic device manufactured using the printed wiring board of Claim 24 . A step of preparing the carrier-attached copper foil according to any one of claims 1 to 15 and an insulating substrate,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 15 .
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 15 .
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Peeling the carrier or the ultra-thin copper layer, and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The 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 of manufacturing a printed wiring board, comprising: forming the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.