JP2018168409A - Copper foil with carrier, laminate, production method of copper foil with carrier, production method of laminate, production method of printed wiring board, and production method of electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a carrier having good peel strength at the time of peeling a carrier and satisfactorily suppressing variation in peel strength. A copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order. The copper foil with a carrier is thermocompression bonded to an insulating substrate at 220 ° C. for 90 minutes, and then conforms to JIS C 6471. Then, when the carrier is peeled off, the surface roughness Sp of the carrier on the ultrathin copper layer side measured at 256 μm × 256 μm square with a laser microscope is 0.1 μm or more and 3.5 μm or less, and the carrier A copper foil with a carrier having a standard deviation of surface roughness Sp of 0.8 μm or less when the surface is measured at 16 points. [Selection diagram] Fig. 1

Description

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

  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 (Patent Document 1).

JP 2004-169181 A

  When peeling an ultrathin copper layer from a carrier, if the peel strength is too large, the ultrathin copper layer may be damaged. Moreover, when peeling strength is too small, there exists a possibility that the carrier and an ultra-thin copper layer may peel at the time of handling of copper foil with a carrier in manufacturing processes, such as a printed wiring board. Further, when the ultrathin copper layer is peeled from the carrier, if the peel strength in the peeling direction varies, there is a possibility that the productivity of a printed wiring board using the carrier-attached copper foil deteriorates. Then, this invention makes it a subject to provide the copper foil with a carrier with which the peeling strength at the time of carrier peeling was favorable, and the dispersion | variation in peeling strength was suppressed favorably.

  In order to achieve the above object, the present inventor has determined the surface roughness Sp of the carrier on the ultrathin copper layer side measured by a laser microscope when the carrier is peeled off under predetermined conditions, and the surface of the carrier at 16 points. By controlling so that the standard deviation of the measured surface roughness Sp satisfies a predetermined condition, the carrier-attached copper has good peel strength at the time of carrier peeling, and the variation in peel strength is well suppressed. It has been found that a foil can be provided.

  The present invention has been completed on the basis of the above knowledge. In one aspect, the present invention is a copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order. When the carrier is peeled off in accordance with JIS C 6471 after thermocompression bonding with the insulating substrate, the surface roughness of the surface on the ultrathin copper layer side of the carrier measured at 256 μm × 256 μm square with a laser microscope The carrier-attached copper foil has a thickness Sp of 0.1 μm or more and 3.5 μm or less, and a standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less.

  In one embodiment of the carrier-attached copper foil of the present invention, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.7 μm or less.

  In another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.6 μm or less.

In yet another embodiment the copper foil with carrier of the present invention, Ni deposition amount of the intermediate layer is 100 [mu] g / dm ² or more 40000μg / dm ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the Cr adhesion amount of the intermediate layer is 1 μg / dm ² or more and 100 μg / dm ² or less.

  In yet another embodiment of the carrier-attached copper foil of the present invention, the surface roughness Sz of the carrier on the ultrathin copper layer side is 0.3 μm or more and 4.5 μm or less, and the surface of the carrier is 16 points. The standard deviation of the surface roughness Sz when measured is 1.0 μm or less.

  In yet another embodiment, the carrier-attached copper foil of the present invention has a surface roughness Rz of 0.1 μm or more on the ultrathin copper layer side of the carrier when measured on a surface perpendicular to the MD direction of the carrier. It is 2.2 μm or less, and the standard deviation of the surface roughness Rz when the surface of the carrier is measured at 16 points is 0.3 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention has an ultrathin copper layer on one side of the carrier, and the carrier-side copper foil according to the present invention has the ultrathin copper layer side and the carrier side. On at least one surface, or both surfaces, or when the copper foil with a carrier of the present invention has an ultrathin copper layer on both sides of the carrier, on the surface of the one or both ultrathin copper layers. And one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer.

  In still another embodiment, the carrier-attached copper foil of the present invention is at least one selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. A resin layer is provided on the layer.

  In still another embodiment of the copper foil with a carrier according to the present invention, at least one of the rust preventive layer and the heat resistant layer contains one or more elements selected from nickel, cobalt, copper, and zinc.

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

  In still another embodiment of the copper foil with a carrier according to the present invention, the resin layer includes a dielectric.

  In another aspect, the present invention is a method for producing a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the carrier is etched or formed on the surface of the carrier. A step of adjusting the surface roughness of the carrier by plating up copper, and a step of providing the intermediate layer and the ultrathin copper layer in this order on the etched or plated-up surface side of the carrier. It is a manufacturing method of the copper foil with a carrier containing.

  In yet another aspect, the present invention is a method for producing a laminate using the carrier-attached copper foil of the present invention.

  In yet another aspect, the present invention is a method for producing a printed wiring board using the copper foil with a carrier 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 other is provided. It is the laminated body laminated | stacked on the copper layer side.

  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 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, the copper foil with carrier and the insulating substrate, After the lamination, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then the circuit is formed by any of the semi-additive method, the subtractive method, the partial additive method, or the modified semi-additive method. It is a manufacturing method of a printed wiring board including the process of forming.

  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. A step of providing at least once a resin layer and a circuit on the surface of the ultrathin copper layer opposite to the side or the carrier side surface, and forming the resin layer and the circuit at least once 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 later.

  In yet another aspect, the present invention is a method of manufacturing an electronic device using a printed wiring board manufactured by the method for manufacturing a printed wiring board of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier by which the peeling strength at the time of carrier peeling was favorable and the dispersion | variation in peeling strength 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 this invention has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order. Further, an intermediate layer and an ultrathin copper layer may be provided on one or both sides of the carrier, and the ultrathin copper layer on the one side and the carrier on the other side or the ultrathin copper on both sides The layer may be subjected to a surface treatment such as a roughening treatment. 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. Substrate epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer, fluororesin, etc. Then, the ultrathin copper layer bonded to the insulating substrate is etched into the intended conductor pattern, and finally a laminate (such as a copper clad laminate) or a printed wiring board can be produced.

  The copper foil with a carrier according to the present invention is obtained by thermally bonding the copper foil with a carrier at 220 ° C. for 90 minutes and then peeling the carrier according to JIS C 6471 using a laser microscope. The surface roughness Sp (maximum peak height) of the surface on the ultrathin copper layer side of the carrier measured by the corner is 0.1 μm or more and 3.5 μm or less. Since the surface roughness Sp of the surface of the carrier on the side of the ultra-thin copper layer is 0.1 μm or more, the carrier and the ultra-thin copper layer are peeled off when handling the copper foil with a carrier in the manufacturing process of a printed wiring board or the like. Can be suppressed. Further, since the surface roughness Sp of the surface of the carrier on the side of the ultrathin copper layer is 3.5 μm or less, the ultrathin copper layer can be prevented from being damaged when the carrier is peeled off. The surface roughness Sp of the surface of the carrier on the ultrathin copper layer side is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 2.5 μm or less, and more preferably 0.1 μm or more. It is more preferably 2.0 μm or less, and more preferably 0.1 μm or more and 1.5 μm or less.

  In the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less. When the standard deviation of the surface roughness Sp when measuring the surface of the carrier at 16 points is 0.8 μm or less, the carrier-attached copper foil with suppressed variation in peel strength is obtained. The standard deviation of the surface roughness Sp when measuring 16 points on the surface of the carrier is preferably 0.7 μm or less, more preferably 0.6 μm or less, and even more preferably 0.5 μm or less.

  When the copper foil with a carrier is prepared, before the intermediate layer is provided on the carrier, the surface of the carrier on which the intermediate layer is provided is etched by etching the surface of the carrier or by plating up copper (Sp, Sz, By controlling the average and standard deviation of Rz), it is possible to produce a carrier-attached copper foil in which variation in peel strength is suppressed. In the copper foil with a carrier, after peeling the carrier, a hole is made in the surface of the ultrathin copper layer with a carbon dioxide laser. However, if the laser absorption of the ultrathin copper layer is poor, the laser holeability is adversely affected. In the present invention, the surface of the ultrathin copper layer can be roughened by etching and roughening the surface on the side where the carrier intermediate layer is provided in order to improve laser drillability. On the other hand, there is a usage method that does not pierce with a carbon dioxide gas laser. In that case, in order to improve the fine etching property of the ultra-thin copper layer, a request to smooth the ultra-thin copper layer and improve the foil thickness accuracy over the conventional one There is also. Therefore, in the present invention, the carrier surface can be smoothed by plating the surface on the side where the carrier intermediate layer is provided with a smooth copper plating solution.

The average value of the surface roughness Sp (maximum peak height) when measuring the carrier surface on the ultrathin copper layer side of the carrier at 16 points is 0.1 μm or more and 3.5 μm or less, and the carrier surface is 16 points. The standard deviation of the surface roughness Sp when measured is preferably 0.8 μm or less. According to such a configuration, variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Sp when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is more preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 2.5 μm. Or less, more preferably 0.1 μm or more and 2.0 μm or less. Further, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is more preferably 0.8 μm or less, more preferably 0.7 μm or less, and 0.6 μm or less. Is more preferable.

The average value of the surface roughness Sz (maximum height) when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is 0.3 μm or more and 4.5 μm or less, and the surface of the carrier is 16 points. The standard deviation of the surface roughness Sz when measured is preferably 1.0 μm or less. According to such a configuration, variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Sz when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is more preferably 0.3 μm or more and 4.0 μm or less, more preferably 0.3 μm or more and 3.5 μm. Or less, more preferably 0.3 μm or more and 3.0 μm or less. Further, the standard deviation of the surface roughness Sz when the surface of the carrier is measured at 16 points is more preferably 0.8 μm or less, more preferably 0.7 μm or less, and 0.6 μm or less. Is more preferable.

Surface roughness when measuring the surface of the carrier at 16 points when measuring the surface in the direction perpendicular to the MD direction (TD direction) in the MD direction of the carrier (direction in which the carrier is conveyed in the apparatus for forming an ultrathin copper layer) The average value of the roughness Rz (10-point average roughness) is 0.1 μm or more and 2.2 μm or less, and the standard deviation of the surface roughness Rz when the surface of the carrier is measured at 16 points is 0.3 μm or less. Is preferred. According to such a configuration, variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Rz when measuring the surface of the carrier when measuring the surface in the direction perpendicular to the MD direction of the carrier (TD direction) is 0.1 μm or more and 1.8 μm or less. More preferably, it is 0.1 μm or more and 2.0 μm or less, and more preferably 0.1 μm or more and 1.6 μm or less. Further, the standard deviation of the surface roughness Rz when the surface of the carrier is measured at 16 points is more preferably 0.25 μm or less, more preferably 0.20 μm or less, and 0.15 μm or less. Is more preferable.

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

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Therefore, the thickness of the carrier is typically 8 μm or more and 70 μm or less, more typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less. 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.

Below, an example of manufacturing conditions in the case of using electrolytic copper foil as a carrier is shown.
<Electrolytic solution composition>
Copper: 90 g / L or more and 110 g / L or less Sulfuric acid: 90 g / L or more and 110 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 ppm or more and 30 ppm or less Leveling agent 2 (Amine compound): 10 ppm or more and 30 ppm or less An amine compound having the following chemical formula can be used as the above amine compound.

  The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

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

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, 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, or an organic substance Or a single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al It can be constructed by forming an alloy layer made of a selected one or more elements from the configured group of elements in Zn.

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 adhesion amount of chromium in the intermediate layer is preferably 1 μg / dm ² or more and 100 μg / dm ² or less, preferably 5 μg / dm ² or more and 100 μg / dm ² or less. More preferably.

<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. 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 μm or more and 12 μm or less, more typically 1 μm or more and 5 μm or less, more typically 1.5 μm or more and 4 μm or less, and more typically 2 μm or more and 3.5 μm or less. In addition, you may provide an ultra-thin copper layer on both surfaces of a carrier.

<Roughening treatment and other surface treatment>
Either or both of the surface of the ultra-thin copper layer and the surface of the carrier may be provided with a roughening treatment layer by applying a roughening treatment to improve adhesion to the insulating substrate, for example. Good. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. Also good. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer and / or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be subjected to a treatment such as chromate treatment or silane coupling treatment. . Alternatively, a heat-resistant layer and / or rust-preventing layer is formed with nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface is further treated with chromate treatment, silane coupling treatment, etc. May be. 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.).
Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

  Note that providing a roughening treatment layer on the surface opposite to the surface on which the ultrathin copper layer of the carrier is provided means that the carrier is laminated on a support such as a resin substrate from the surface side having the roughening treatment layer. At this time, there is an advantage that the carrier and the resin substrate are hardly separated. As described above, by forming a surface treatment layer such as a heat-resistant layer on the ultrathin copper layer or the roughening treatment layer on the surface of the carrier, the ultrathin copper layer or the copper from the carrier is formed on the resin base material to be laminated. It is possible to satisfactorily suppress the diffusion of the elements, and the adhesion by thermocompression bonding at the time of lamination with the resin base material is improved.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer is 5 mg / m ² or more and 1000 mg / m ² or less, preferably 10 mg / m ² or more and 500 mg / m ² or less, preferably 20 mg / m ² or more and 100 mg / m ^2. It may be the following. Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 or more and 10 or less. Preferably there is. Moreover, it is preferable that the adhesion amount of nickel of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is 0.5 mg / m ² or more and 500 mg / m ² or less, preferably 1 mg / m ² or more and 50 mg / m ^2. The following is more preferable. When the heat resistant layer and / or the rust preventive layer is a layer containing a nickel-zinc alloy, the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer having an adhesion amount of 1 mg / m ² or more and 100 mg / m ² or less, preferably 5 mg / m ² or more and 50 mg / m ² or less, and an adhesion amount of 1 mg / m ² or less. m ² or more and 80 mg / m ² or less, preferably 5 mg / m ² or more and 40 mg / m ² or less of a tin layer may be sequentially laminated, and the nickel alloy layer may be nickel-molybdenum, nickel-zinc, nickel -It may be composed of any one of molybdenum-cobalt and nickel-tin alloys. Further, the heat-resistant layer and / or the rust preventive layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m ² or more and 150 mg / m ² or less, and 10 mg / m ² or more and 70 mg / m ² or less. It is more preferable that Further, the heat-resistant layer and / or the antirust layer described above is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 or more and 10 or less, and 0.33 or more and 3 or less. It is more preferable that When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used in order to provide a silane coupling process layer, for example, an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling An agent may be used. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a known silane coupling agent, such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, triazine. You may form using silane coupling agents, such as silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

The silane coupling treatment layer is, in terms of silicon atom, 0.05 mg / m ² or more and 200 mg / m ² or less, preferably 0.15 mg / m ² or more and 20 mg / m ² or less, preferably 0.3 mg / m ² or more 2 It is desirable to be provided in a range of 0.0 mg / m ² or less. In the case of the above-mentioned range, the adhesiveness of a base material and a copper foil with a carrier can be improved more.

  In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-1111169, Patent No. 5024930 , International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A. be able to.

  The copper foil with a carrier of the present invention is a resin layer on the ultrathin copper layer, on the roughened layer, on the heat-resistant layer, rust-proof layer, chromate-treated layer, or silane coupling-treated layer. May be provided.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin , Polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin , Polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting poly Nylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having a crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) Propane, phosphorus-containing phenolic compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin , Isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin. It can be mentioned resins as preferred.

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

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

  These resins described above are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to form a resin liquid, which is formed on the ultrathin copper layer, the heat resistant layer, the rust preventive layer, the chromate film layer, or the above On the surface treatment layer including the silane coupling agent layer and the like, it is applied by, for example, a roll coater method or the like, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 ° C. or higher and 250 ° C. or lower, preferably 130 ° C. or higher and 200 ° C. or lower.

  The copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is obtained by superposing the resin layer on a substrate and then thermocompressing the entire resin layer to thermally cure the resin layer. In this case, the carrier is peeled off to expose the ultrathin copper layer (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed on the ultrathin copper layer. Is used in the form of forming.

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

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

  Furthermore, as another product form of the copper foil with a carrier with resin, the surface treatment layer of the ultra-thin copper layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling treatment It is also possible to manufacture in the form of a resin-coated copper foil in which no carrier is present after coating the layer with a resin layer to make it a semi-cured state and then peeling the carrier.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, although demonstrated using the copper foil with a carrier by which the roughening process layer was formed on the surface of an ultra-thin copper layer here, even if it uses the copper foil with a carrier which does not provide surface treatment layers, such as a roughening process layer, good.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.
In the above-described printed wiring board manufacturing method, “ultra-thin copper layer” is used as a carrier, “carrier” is read as an ultra-thin copper layer, and a circuit is formed on the carrier-side surface of the copper foil with carrier. It is also possible to manufacture a printed wiring board by embedding a circuit with resin.

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

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

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

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

Further, the method for producing a printed wiring board of the present invention includes a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing at least once a resin layer and a circuit on the surface of the copper layer with carrier on the opposite side of the copper layer side surface or the carrier side surface, and forming two layers of the resin layer and the circuit Then, a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultra-thin copper layer from the copper foil with carrier may be used. As a specific example of the coreless construction method, first, an ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated to form a laminate (copper-clad laminate, copper-clad laminate). (Also referred to as a laminate). Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. You may laminate | stack another copper foil with a carrier from the carrier side or the ultra-thin copper layer side to the resin layer formed in the carrier side surface or the ultra-thin copper layer side surface. Also, centering on the resin substrate or resin or prepreg, on the surface side of both the resin substrate or resin or prepreg, in the order of carrier / intermediate layer / ultra thin copper layer or ultra thin copper layer / intermediate layer / carrier. A laminated body having a structure in which a copper foil with a carrier is laminated or a structure laminated in the order of “carrier / intermediate layer / ultra thin copper layer / resin substrate or resin or prepreg / carrier / intermediate layer / ultra thin copper layer”. Laminate or “laminate / intermediate layer / ultra-thin copper layer / resin substrate / carrier / intermediate layer / ultra-thin copper layer” in the order of laminate or “ultra-thin copper layer / intermediate layer / carrier / resin” You may use the laminated body which has the structure laminated | stacked in order of "board | substrate / carrier / intermediate layer / ultra-thin copper layer" in the above-mentioned printed wiring board manufacturing method (coreless construction method). And, on the exposed surface of the ultra-thin copper layer or carrier at both ends of the laminate, another resin layer is provided, and after further providing a copper layer or a metal layer, the copper layer or the metal layer is processed. A circuit may be formed. Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed one or more times (build-up method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the production of the coreless substrate described above, a laminate having a configuration of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer described later using two copper foils with a carrier, Laminate having a structure of carrier / intermediate layer / ultra thin copper layer / ultra thin copper layer / intermediate layer / carrier, or a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer It is also possible to produce a laminated body and use the laminated body as a center. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer. The above-mentioned laminated body has other surfaces between the surface of the ultrathin copper layer, the surface of the carrier, between the carrier, between the ultrathin copper layer and the ultrathin copper layer, and between the ultrathin copper layer and the carrier. You may have a layer. The other layer may be a resin substrate or a resin 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 coreless substrate manufacturing method, a printed wiring board is manufactured by a build-up method by covering part or all of the end face of the copper foil with carrier or the above-mentioned laminated body (including laminated body A) with a resin. In doing so, it is possible to prevent infiltration of the chemical solution between one copper foil with a carrier and another copper foil with a carrier constituting the intermediate layer or laminate, and an ultrathin copper layer due to the infiltration of the chemical solution, The separation of the carrier and the corrosion of the copper foil with the carrier can be prevented, and the yield can be improved. As used herein, “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” may be a resin that can be used for the resin layer or a known resin. Can be used. 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 or the entire surface of the laminated portion. In addition, when viewed in plan, the resin or prepreg is preferably larger than the copper foil with carrier or the laminate or the laminated portion of the laminate, and the resin or prepreg is laminated on both sides of the carrier-attached copper foil or laminate, It is preferable to use a laminated body having a configuration in which the attached copper foil or the laminated body is bound (wrapped) with a resin or a prepreg. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Covered copper foil with carrier or laminated part of laminated body (laminated part of carrier and ultrathin copper layer, or laminated part of one copper foil with carrier and another copper foil with carrier) is resin or When the prepreg or the like is firmly attached, it may be necessary to remove the laminated portion by cutting or the like.

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

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

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

Also, a step of providing at least one layer of the resin layer and the circuit on the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, the carrier of the laminate is provided with a carrier. The printed wiring board which does not have a core is producible by implementing the process of peeling the said ultra-thin copper layer or carrier from copper foil. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.
The resin substrate, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. An accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like may be included. In addition, the above-mentioned copper foil with a carrier or laminated body may be smaller than resin, a prepreg, a resin substrate, or a resin layer when planarly viewed.

  The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board and the like. For example, for a rigid PWB, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base Epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film for FPC Fluorine resin can be used. In addition, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the copper foil with a carrier tends to be smaller than when a polyimide film is used. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the copper circuit is covered with a coverlay after the copper circuit is formed, so that the film and the copper circuit are not easily peeled off, and the peel strength is reduced. The film can be prevented from peeling off from the copper circuit.

  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.

-Carrier production method (Examples 1, 2, 4, Comparative Examples 1-3)
A rotating drum (electrolytic drum) made of titanium was prepared. Next, the electrode was placed in the electrolytic cell with a predetermined distance between the electrolytic drum and the drum. Next, electrolysis was performed in the electrolytic bath under the following conditions, and copper was deposited on the surface of the electrolytic drum while rotating the electrolytic drum.
<Electrolytic solution composition>
Copper: 80 g / L or more and 110 g / L or less Sulfuric acid: 70 g / L or more and 110 g / L or less Chlorine: 10 mass ppm or more and 100 mass ppm or less <Production conditions>
Current density: 50 A / dm ² or more and 200 A / dm ² or less Electrolyte temperature: 40 ° C. or more and 70 ° C. or less Electrolyte linear velocity: 3 m / sec or more and 5 m / sec or less Electrolysis time: 0.5 minutes or more and 10 minutes or less Next The copper deposited on the surface of the rotating electrolytic drum was peeled off to obtain a carrier.
In addition, formation of the intermediate | middle layer to the below-mentioned electrolytic copper foil was implemented in the glossy surface side of the electrolytic copper foil.

Carrier production method (Example 3)
After producing a copper ingot having a composition in which Sn is added to oxygen-free copper specified in JIS H3100 at 1200 wtppm and hot rolling at 800 ° C. or higher and 900 ° C. or lower, annealing is performed on a continuous annealing line at 300 ° C. or higher and 700 ° C. or lower. Cold rolling was repeated once to obtain a rolled plate having a thickness of 1 mm or more and 2 mm or less. This rolled sheet is annealed in a continuous annealing line of 600 ° C. or higher and 800 ° C. or lower and recrystallized, and finally cold-rolled to a thickness of 7 μm or more and 50 μm or less with a reduction ratio of 95% or more and 99.7% or less, and rolled copper A foil was prepared and used as a carrier.

-Control of intermediate layer side surface of carrier In Example 2 and Comparative Example 1, before providing the intermediate layer on the carrier, a part of the carrier surface is used for the carrier by etching the surface of the carrier under the following conditions: Rougher than the surface of the original foil.
(Etching conditions)
Liquid composition: sodium persulfate 50 g / L to 150 g / L, sodium hydrogen sulfate 5 g / L to 20 g / L, sulfuric acid 60 g / L to 180 g / L liquid temperature: 25 ° C. to 40 ° C. Immersion time: 10 s or more 120 s or less For Example 4 and Comparative Example 1, before providing the intermediate layer on the carrier, the surface of the carrier is plated up to a thickness of 1 μm or more and 3 μm or less according to the following conditions, thereby making the carrier surface rough. It was controlled more smoothly than the surface of the raw foil used.
(Plating up condition)
Copper concentration: 30 g / L or more and 120 g / L or less H ₂ SO ₄ concentration: 20 g / L or more and 120 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 ppm or more and 30 ppm or less Leveling agent 2 (amine compound): 10 ppm to 30 ppm An amine compound having the following chemical formula was used as the amine compound.

(In the above chemical formula, R 1 and R 2 are selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups.)
Electrolyte temperature: 20 ° C. or more and 80 ° C. or less Current density: 10 A / dm ² or more and 100 A / dm ² or less

-Formation of intermediate layer Subsequently, for Example 2 and Comparative Example 1, a nickel sputtered film having a thickness of 50 nm was formed, and then electroplated on a roll-to-roll-type continuous plating line to thereby obtain a nickel sputtered film. A Cr layer having an adhesion amount of 11 μg / dm ² was deposited thereon by electrolytic chromate treatment under the following conditions.
Electrolytic chromate treatment Liquid composition: potassium dichromate 1 g / L to 10 g / L, zinc 0 g / L to 5 g / L pH: 3 to 4 Liquid temperature: 50 ° C. to 60 ° C. Current density: 0.1 A / dm ² or more 2.6A / dm ² or less coulombs: 0.5As / dm ² or more 30AS / dm ² or less

For Examples 1, 3, and 4 and Comparative Examples 2 and 3, as an intermediate layer, an Ni layer having an adhesion amount of 4000 μg / dm ² by electroplating on a roll-to-roll continuous plating line under the following conditions Formed.

Ni layer Nickel sulfate: 250 g / L or more and 300 g / L or less Nickel chloride: 35 g / L or more and 45 g / L or less Nickel acetate: 10 g / L or more and 20 g / L or less Trisodium citrate: 15 g / L or more and 30 g / L or less Glossy agents: saccharin, butynediol like sodium dodecyl sulfate: 30 ppm or more 100ppm or less pH: 4 to 6 liquid temperature: 50 ° C. or higher 70 ° C. or less current density: 3A / dm ² or more 15A / dm ² or less

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. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1 g / L to 10 g / L, zinc 0 g / L to 5 g / L pH: 3 to 4 Liquid temperature: 50 ° C. to 60 ° C. Current density: 0.1 A / dm ² or more 2.6A / dm ² or less coulombs: 0.5As / dm ² or more 30AS / dm ² or less

-Formation of an ultrathin copper layer After forming an intermediate layer, an ultrathin copper layer having a thickness of 0.8 µm or more and 5 µm or less was formed on the intermediate layer by electroplating under the following conditions to obtain a copper foil with a carrier.
・ Ultra-thin copper layer Copper concentration: 30 g / L or more and 120 g / L or less H ₂ SO ₄ concentration: 20 g / L or more and 120 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3sulfopropyl) disulfide) : 10 ppm or more and 30 ppm or less Leveling agent 2 (amine compound): 10 ppm or more and 30 ppm or less As the amine compound, an amine compound having the following chemical formula was used.

(In the above chemical formula, R 1 and R 2 are selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups.)
Electrolyte temperature: 20 ° C. or more and 80 ° C. or less Current density: 10 A / dm ² or more and 100 A / dm ² or less

Electrolyte temperature: 20 ° C. or more and 80 ° C. or less Current density: 10 A / dm ² or more and 100 A / dm ² or less

-Formation of a surface treatment layer Next, about Example 1, 2, and Comparative Examples 1-3, as shown in Tables 1-3 further on a very thin copper layer, it roughens on either of the following conditions. A treatment layer was provided.
-Roughening conditions Liquid composition Cu: 10 g / L or more and 20 g / L or less Co: 1 g / L or more and 10 g / L or less Ni: 1 g / L or more and 10 g / L or less pH: 1 or more and 4 or less Liquid temperature: 50 ° C. or more and 60 ° C. The following current density Dk: 30A / dm ² or more 40A / dm ² or less time: 1 second or less than 0.2 seconds

In Examples 3 and 4, a heat-resistant treatment layer, a chromate layer, and a silane coupling treatment layer were provided on the roughening treatment layer under the following conditions.
Heat treatment Zn: 0 g / L or more and 20 g / L or less Ni: 0 g / L or more and 5 g / L or less pH: 3.5
Temperature: 40 ° C
Current density Dk: 0 A / dm ² or more and 1.7 A / dm ² or less Time: 1 second Zn adhesion amount: 5 μg / dm ² or more and 250 μg / dm ² or less Ni adhesion amount: 5 μg / dm ² or more and 300 μg / dm ² or less / chromate Treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 g / L or more and 10 g / L or less NaOH or KOH: 10 g / L or more and 50 g / L or less ZnO or ZnSO ₄ 7H ₂ O: 0.05 g / L or more and 10 g / L or less pH: 7 to 13 Liquid temperature: 20 ° C. to 80 ° C. Current density 0.05 A / dm ^{2 to} 5 A / dm ² Time: 5 seconds to 30 seconds Cr adhesion amount: 10 μg / dm ^{2 to} 150 μg / dm ²・ Silane coupling treatment Vinyl triethoxysilane aqueous solution (vinyl triethoxysilane concentration: 0.1 wt% or more and 1.4 wt% or less)
pH: 4 to 5 Time: 5 seconds to 30 seconds

About each sample of the copper foil with a carrier obtained as mentioned above, each evaluation was implemented with the following method.
・ Surface roughness Sp, Sz, Rz
After the sample was thermocompression bonded to the insulating substrate at 220 ° C. for 90 minutes, the carrier was peeled off in accordance with JIS C 6471, and the surface of the carrier on the ultrathin copper layer side on the surface of 256 μm × 256 μm square was measured with a laser microscope. Roughness Sp, Sz, and Rz were measured, respectively.
The surface roughness (Sp, Sz, Rz) of the carrier is 8 points at 15 mm intervals in the TD direction (described as N1 to N8 in Tables 1 to 3) and 8 points at 15 mm intervals in the MD direction (Table 1). -3 and N1-N8), a total of 16 points were measured. In Examples 1 and 3 and Comparative Example 3, the carrier was measured as it was. Example 2 and Comparative Example 1 were measured after etching the carrier. Example 4 and Comparative Example 2 were measured after plating the carrier with a smooth copper plating solution.

・ Peeling strength The ultrathin copper layer side is thermocompression bonded to an insulating substrate at 220 ° C. for 90 minutes under the condition of 1.5 MPa, and the sample is cut about 250 mm in the length direction and 50 mm in the width direction, and in the longitudinal direction (MD direction). The peel strength was measured by pulling under the following conditions. The measurement interval of peel strength was 150 mm in the width direction, and each sample was measured 5 times (described as N1 to N5 in Tables 1 to 3).
・ Measurement method: Method shown in JIS C 6471 ・ Tensile angle: 90 degrees ・ Speed: 50 mm / min
-Tensile test device: Autograph manufactured by Shimadzu Corporation The production conditions and evaluation results are shown in Tables 1 to 3.

(Evaluation results)
In Examples 1 to 4, the carrier-attached copper foil was thermocompression bonded to the insulating substrate at 220 ° C. for 90 minutes, and then peeled off according to JIS C 6471. When the carrier was peeled off at 256 μm × 256 μm square using a laser microscope. The surface roughness Sp on the ultrathin copper layer side of the carrier to be measured is 0.1 μm or more and 3.5 μm or less, and the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm. Since it was the following, the carrier-attached copper foil in which the variation in the peel strength of the carrier was satisfactorily suppressed was obtained.
In Comparative Examples 1, 2, and 3, since the standard deviation of the surface roughness Sp when the surface of the carrier was measured at 16 points exceeded 0.8 μm, the variation in the carrier peeling strength was poor.

Claims (23)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
After the carrier-attached copper foil was thermocompression bonded to the insulating substrate at 220 ° C. for 90 minutes, the carrier measured according to JIS C 6471 was measured with a laser microscope at 256 μm × 256 μm square according to JIS C 6471. The surface roughness Sp on the ultrathin copper layer side is 0.1 μm or more and 3.5 μm or less, and the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less. Copper foil with carrier.   The copper foil with a carrier according to claim 1, wherein a standard deviation of the surface roughness Sp when measuring 16 points on the surface of the carrier is 0.7 μm or less.   The copper foil with a carrier according to claim 2, wherein the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.6 μm or less. The intermediate layer copper foil with a carrier according to any one of claims 1 to 3 Ni deposition amount is 100 [mu] g / dm ² or more 40000μg / dm ² following. The copper foil with a carrier according to any one of claims 1 to 4, wherein a Cr adhesion amount of the intermediate layer is 1 µg / dm ² or more and 100 µg / dm ² or less.   The surface roughness Sz on the ultrathin copper layer side of the carrier is 0.3 μm or more and 4.5 μm or less, and the standard deviation of the surface roughness Sz when the surface of the carrier is measured at 16 points is 1.0 μm or less. The copper foil with a carrier according to any one of claims 1 to 5.   The surface roughness Rz on the ultrathin copper layer side of the carrier when measured on the surface perpendicular to the MD direction of the carrier is 0.1 μm or more and 2.2 μm or less, and the surface of the carrier is 16 points. The copper foil with a carrier according to any one of claims 1 to 6, wherein a standard deviation of the surface roughness Rz when measured is 0.3 µm or less. When the copper foil with a carrier according to any one of claims 1 to 7 has an ultrathin copper layer on one surface of the carrier, at least one surface of the ultrathin copper layer side and the carrier side, or On both surfaces, or
In the case where the copper foil with a carrier according to any one of claims 1 to 7 has an ultrathin copper layer on both sides of the carrier, on one or both ultrathin copper layer side surfaces,
8. With a carrier according to any one of claims 1 to 7, which has one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer. Copper foil.   9. With a carrier according to claim 8, comprising a resin layer on one or more layers selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. Copper foil.   The copper foil with a carrier according to claim 8 or 9, wherein at least one of the rust prevention layer and the heat-resistant layer contains one or more elements selected from nickel, cobalt, copper, and zinc.   The copper foil with a carrier as described in any one of Claims 1-7 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 9 or 11, wherein the resin layer includes a dielectric. It is a method for producing a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order,
Etching the surface of the carrier, or adjusting the surface roughness of the carrier by plating up copper on the surface of the carrier;
Providing the intermediate layer and the ultra-thin copper layer in this order on the etched or plated-up surface side of the carrier;
The manufacturing method of the copper foil with a carrier containing this.   The method to manufacture a laminated body using the copper foil with a carrier as described in any one of Claims 1-12.   The method to manufacture a printed wiring board using the copper foil with a carrier as described in any one of Claims 1-12.   It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-12, Comprising: The laminated body by which one part or all part of the end surface of the said copper foil with a carrier is covered with the said resin. .   The carrier-attached copper foil according to any one of claims 1 to 12, wherein the carrier-attached copper foil according to any one of claims 1 to 12 is provided from the carrier side or the ultrathin copper layer side. The laminated body laminated | stacked on the said carrier side or the said ultra-thin copper layer side of copper foil.   The manufacturing method of the printed wiring board using the laminated body of Claim 16 or 17. A step of providing two layers of a resin layer and a circuit at least once on the laminate according to claim 16 or 17, 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. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 12 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
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. 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 12,
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 ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 12 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 carrier after forming the resin layer and the two layers of the circuit at least once.   The method to manufacture an electronic device using the printed wiring board manufactured by the manufacturing method of the printed wiring board as described in any one of Claim 15, 18-22.