JP2018009237A - Copper foil with carrier, method for producing copper foil with carrier, laminate, method for producing laminate, method for manufacturing printed wiring board and method for manufacturing electronic equipment - Google Patents

Abstract

An object of the present invention is to provide a copper foil with a carrier that can satisfactorily suppress the generation of pinholes that occur when the carrier is peeled off. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer in this order, wherein a resin is laminated on the ultra-thin copper layer side of the carrier-attached copper foil, and the resin is applied at 220° C. for 2 hours at 15 kg/cm 2 . The circularity generated in the ultrathin copper layer when the carrier is peeled off from the carrier-attached copper foil by a 90 ° peeling method in accordance with JIS C 6471 8.1 after the carrier-attached copper foil and resin are heat-pressed under the conditions of A copper foil with a carrier having a number density of holes of 0.8 or less of 10 holes/m2 or less. [Selection drawing] Fig. 3

Description

  The present invention relates to a copper foil with a carrier, a method for producing a copper foil with a carrier, a laminate, 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, ultra-thin copper foil is sometimes used in response to fine pitches. However, ultra-thin copper foil has low mechanical strength and is easy to break during the production of printed wiring boards and to generate wrinkles. Therefore, a copper foil with a carrier, in which a thick metal foil is used as a carrier and an ultrathin copper layer is electrodeposited on the metal foil via a release layer, has appeared. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After forming a circuit pattern with resist on the exposed ultra-thin copper layer, the ultra-thin copper layer is etched with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.

  Moreover, as a technique which suppresses generation | occurrence | production of the pinhole of the ultra-thin copper layer of copper foil with a carrier, Unexamined-Japanese-Patent No. 2004-169181 (patent document 1) and Unexamined-Japanese-Patent No. 2005-076091 (patent document 2) are mentioned. .

JP 2004-169181 A Japanese Patent Laying-Open No. 2005-076091

  When forming a fine pitch circuit as described above using a copper foil with a carrier having an ultrathin copper layer, a part of the ultrathin copper layer is held on the carrier side when the carrier is peeled off due to its thinness. However, there is a problem that pinholes (holes) occur in the remaining ultrathin copper layer. Pinholes generated in the ultrathin copper layer may cause circuit disconnection. Then, this invention makes it a subject to provide the copper foil with a carrier which can suppress well generation | occurrence | production of the pinhole which arises at the time of carrier peeling.

In one aspect, the present invention provides a carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein a resin is laminated on the ultrathin copper layer side of the copper foil with carrier, and 220 ° C. for 2 hours. When the carrier is peeled off from the carrier-attached copper foil by a 90 ° peeling method in accordance with JIS C 6471 8.1 after the copper foil with the carrier and the resin are thermocompression bonded under the conditions of 15 kg / cm ^2. It is a copper foil with a carrier whose number density of the hole whose circularity produced in an ultra-thin copper layer is 0.8 or less is 10 pieces / m ² or less.

In one embodiment, the carrier-attached copper foil of the present invention comprises laminating a resin on the ultrathin copper layer side of the carrier-attached copper foil, and the carrier-attached copper foil and resin under conditions of 15 kg / cm ² at 220 ° C. for 2 hours. When the carrier is peeled off from the carrier-attached copper foil by a 90 ° peeling method in accordance with JIS C 6471 8.1, the circularity generated in the ultrathin copper layer is 0.8 or less. The number density of the holes is 0 / m ² .

  In another embodiment, the copper foil with a carrier of the present invention has a peel strength of 2 to 10 N / m when the carrier is peeled from the copper foil with a carrier by a 90 ° peeling method in accordance with JIS C 6471 8.1. It is.

  In still another embodiment of the copper foil with a carrier of the present invention, the ultrathin copper layer has a thickness of 1.6 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, the ultrathin copper layer has a thickness of 1.2 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, the ultrathin copper layer has a thickness of 1.0 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, the ultrathin copper layer has a thickness of 0.9 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, the ultrathin copper layer has a thickness of 0.05 μm or more.

  In still another embodiment of the copper foil with a carrier according to the present invention, when the copper foil with a carrier has an ultrathin copper layer on one surface of the carrier, at least one of the ultrathin copper layer side and the carrier side. When the copper foil with a carrier has an ultrathin copper layer on both sides of the carrier, roughening treatment is performed on the surface of one or both of the ultrathin copper layers. It has 1 or more types of layers selected from the group which consists of a layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment 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 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, 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 of the present invention, the intermediate layer is formed on the carrier by electrolytic treatment with a current density of 0.5 A / dm ² or less, and the ultrathin film is formed on the surface of the carrier on the intermediate layer side. It is a manufacturing method of the copper foil with a carrier of this invention provided with the process of forming a copper layer.

  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.

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

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

  In yet another aspect of the present invention, the carrier-attached copper foil of the present invention is separated from the carrier side or the ultrathin copper layer side of the present invention, and the carrier-side copper foil of the present invention of the 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 laminating, a copper clad laminate is formed through a step of peeling the copper foil carrier of the carrier-attached copper foil, and then by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. A method of manufacturing a printed wiring board including a step of forming a circuit.

  In another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention, the carrier-attached copper foil so that the circuit is buried. 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 which can suppress suitably generation | occurrence | production of the pinhole which arises at the time of carrier peeling 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 of the present invention is obtained by laminating a resin on the ultrathin copper layer side of the copper foil with a carrier and thermocompression bonding the copper foil with a carrier and the resin under conditions of 15 kg / cm ² at 220 ° C. for 2 hours. When the carrier is peeled off from the copper foil with a carrier by a 90 ° peeling method in accordance with JIS C 6471 8.1, the number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer is 10 / m Controlled to ² or less. With such a configuration, it is possible to satisfactorily suppress the occurrence of pinholes in the ultrathin copper layer that may cause circuit disconnection. Also, a resin is laminated on the ultrathin copper layer side of the copper foil with carrier, and the copper foil with resin and the resin are thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. The number density of holes having a circularity of 0.8 or less when the carrier is peeled off from the copper foil with a carrier by a compliant 90 ° peeling method is preferably 8 / m ² or less. 7 / m ² or less, more preferably 4 / m ² or less, more preferably 3.5 / m ² or less, and 3 / m ² or less. Is more preferably 2 pieces / m ² or less, more preferably 1 piece / m ² or less, more preferably 0.5 pieces / m ² or less, and 0.3 pieces more preferably / m ² or less, it is 0.2 pieces / m ² or less Ri preferably, more preferably 0.1 or / m ² or less, more preferably 0.05 pieces / m ² or less, and even more preferably is 0 / m ^2.

The hole having a circularity of 0.8 or less means a so-called “breach pinhole”. A “breaking pinhole” is a pinhole that is originally formed when an ultrathin copper layer is formed (close to a circle (roundness greater than 0.8), and has a roundness of 0.8 or less, which is somewhat different from a circle) More specifically, in the present invention, “circularity” is defined by the following equation using the area S and the peripheral length L of the hole (pinhole).
Circularity = 4π × (area S) ÷ (peripheral length L) ²

  The carrier-attached copper foil of the present invention preferably has a peel strength of 2 to 10 N / m when the carrier is peeled off from the carrier-attached copper foil by a 90 ° peeling method in accordance with JIS C 6471 8.1. . If the peeling strength exceeds 10 N / m when the carrier is peeled off from the copper foil with a carrier by the 90 ° peeling method according to JIS C 6471 8.1, a part of the ultrathin copper layer becomes a carrier when the carrier is peeled off. There is a possibility that the portion may be pinholes in the ultrathin copper layer. On the other hand, if the peel strength between the carrier and the ultrathin copper layer is less than 2 N / m, the adhesion between them may be poor. In addition, the copper foil with a carrier of the present invention is controlled to have a peel strength of 3 to 10 N / m when the carrier is peeled from the copper foil with a carrier by a 90 ° peeling method in accordance with JIS C 6471 8.1. Is preferably controlled to 3 to 9 N / m, more preferably 3 to 8 N / m, and still more preferably 3 to 5 N / m.

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

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. The thickness of the carrier is typically 8-70 μm, more typically 12-70 μm, and more typically 18-35 μm. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll.

An example of manufacturing conditions when using electrolytic copper foil as a carrier is shown below.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.
In addition, as long as there is no description in particular, the remainder of the electrolyte solution, plating solution, etc. described in the present invention is water.

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

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

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the copper foil 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 an alloy layer made of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an organic layer A hydrate of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can be configured by forming a layer made of an oxide or an organic substance.

  Further, for example, the intermediate layer is a single metal layer made of any one element of the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr , Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, an alloy layer made of one or more elements selected from the element group, or a layer made of organic matter, and then Cr, Ni, Co, A single metal layer made of any one of elements of Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu It can be composed of an alloy layer made of one or more elements selected from the group of elements Al, Zn. Moreover, you may use the layer structure which can be used as an intermediate | middle layer for another layer.

  When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a roughened layer or 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 formed by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and a chromium-containing layer in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. The chromium-containing layer is preferably a chromate-treated layer, a chromium layer, or a chromium alloy layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, and other elements (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.
The intermediate layer may contain Ni and Cr as main components. The coating weight of the nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 200 [mu] g / dm ² or more 30000μg / dm ² or less, more preferably 300 [mu] g / dm ² or more 20000μg / dm ² or less , more preferably less than 400 [mu] g / dm ² or more 15000μg / dm ^2, the adhesion amount of chromium is preferably 5 [mu] g / dm ² or more 150 [mu] g / dm ² or less in the intermediate layer, 5 [mu] g / dm ² or more 100 [mu] g / dm ² The following is preferable.
The organic substance contained in the intermediate layer is preferably one or more organic substances selected from the group consisting of nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
The organic material is preferably contained in a thickness of 5 nm to 80 nm, more preferably 10 nm to 70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
The thickness of the organic substance can be measured as follows.

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

<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. Ultrathin copper layers may be provided on both sides of the carrier. The ultra-thin copper layer may be an electrolytic copper layer. Here, the said electrolytic copper layer means the copper layer formed by electroplating (electrolytic plating). The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, and copper cyanide, and is used in general electrolytic copper layers with a high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. In addition, you may add a brightener to the plating solution used in order to form an ultra-thin copper layer. Although the thickness of an ultra-thin copper layer is not specifically limited, It can be 0.01-12 micrometers. The thickness of the ultrathin copper layer may be controlled to 1.6 μm or less. With such a configuration, an extremely fine circuit can be formed using the ultrathin copper layer. The thinner the ultrathin copper layer, the easier it is to improve the circuit formability. Therefore, the thickness is preferably 1.2 μm or less, preferably 1.0 μm or less, preferably 0.9 μm or less, 0 .85 μm or less is preferred, 0.80 μm or less is more preferred, 0.75 μm or less is even more preferred, 0.70 μm or less is even more preferred, and 0.65 μm or less is preferred. Is more preferably 0.60 μm or less, still more preferably 0.50 μm or less, still more preferably 0.45 μm or less, and 0.40 μm or less. Even more preferably, it is still more preferably 0.35 μm or less, still more preferably 0.32 μm or less, still more preferably 0.30 μm or less, 0.2 Still more preferably of at μm or less. If the thickness of the ultra-thin copper layer is too small, it may cause a problem that handling becomes difficult. Therefore, the thickness is preferably 0.01 μm or more, preferably 0.05 μm or more, and 0.10 μm or more. The thickness is preferably 0.15 μm or more. The thickness of the ultra-thin copper layer is typically 0.01-0.9 μm, typically 0.05-0.9 μm, more typically 0.1-0.9 μm Even more typically, it is 0.15 to 0.9 μm.

<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 may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat resistant layer and / or 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 heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt Or any one of nickel-tin alloys. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Moreover, it is preferable that the above-mentioned heat-resistant layer and / or rust preventive layer are [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. It is more preferable. When the heat-resistant layer and / or the rust-preventing layer is used, the carrier peel-off 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 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the substrate and the surface-treated copper foil can be further improved.

In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. 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 roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer may each be composed of a single layer or a plurality of layers.

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 insulating resin layer.
The resin layer may be composed of a single layer or a plurality of layers.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polyvinyl acetal resin, urethane resin, polyethersulfone, polyethersulfone resin, aromatic Polyamide resin, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, polyhydric carboxylic acid anhydride , Linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenol compounds, 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 Preferred examples include resins containing at least one selected from the group consisting of group polyamides, fluororesins, bisphenols, block copolymerized polyimide resins, and cyanoester resins.

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. The epoxy resin is 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 isocyania Glycidyl amine compounds such as nurate, N, N-diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, One type or two or more types selected from the group consisting of a phenyl type epoxy resin, a biphenyl novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetraphenylethane type epoxy resin can be used, or the epoxy resin These hydrogenated products and halogenated products 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 skeletal material, the aforementioned resin, the aforementioned compound, 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.

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

  The resin and / or resin composition and / or compound contained in the resin layer is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin liquid, which is used on the ultrathin copper layer or the heat-resistant layer. Then, it is coated on the rust preventive layer, the chromate film layer, or the silane coupling agent layer by, for example, a roll coater method, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

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

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

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

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

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

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

  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 a copper foil and an insulating substrate, a copper clad laminate is formed through a process of peeling the copper foil carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-additive method, a partially additive method, and a subtractive method. Forming a circuit by any of the methods. 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;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

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

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

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

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

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

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

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

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

  The method for producing a printed wiring board of the present invention includes a step of forming a circuit on the surface of the ultrathin copper layer or the surface of the carrier of the copper foil with a carrier of the present invention, and the copper foil with a carrier so that the circuit is buried. After forming the resin layer on the ultrathin copper layer side surface or the carrier side surface of the step, peeling the carrier or the ultrathin copper layer, and peeling the carrier or the ultrathin copper layer, A step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer or the surface of the carrier by removing the ultrathin copper layer or the carrier may be included. Moreover, the manufacturing method of the printed wiring board of this invention is the process of forming a circuit in the said ultra-thin copper layer side or the said carrier side surface of the copper foil with a carrier of this invention, The said copper with a carrier so that the said circuit may be buried. Forming a resin layer on the surface of the ultrathin copper layer or the carrier side of the foil, forming a circuit on the resin layer, forming a circuit on the resin layer, and then forming the carrier or the ultrathin copper Forming the layer on the surface of the ultrathin copper layer or the carrier side by removing the ultrathin copper layer or the carrier after peeling the carrier or the ultrathin copper layer. The step of exposing the circuit buried in the resin layer may be included. In addition, the step of forming a circuit on the resin layer includes bonding a carrier-attached copper foil on the resin layer from the ultrathin copper layer side or the carrier side, and attaching the carrier-attached copper foil to the resin layer. It may be a step of forming the circuit by using. Moreover, the copper foil with a carrier of the present invention may be another copper foil with a carrier to be bonded onto the resin layer.

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 the copper foil with a carrier by which the roughening process layer was formed on the ultra-thin copper layer surface is demonstrated as an example here, the roughening process layer does not need to be formed.
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.

  When the above-described embedding method is performed using the copper foil with a carrier of the present invention, since the ultrathin copper layer is thin, the etching for exposing the embedded circuit is completed in a short time, and the productivity is dramatically improved. To do.

  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.

  When the semi-additive method or the modified semi-additive method is performed using the copper foil with a carrier of the present invention, since the ultrathin copper layer is thin, the flash etching is completed in a short time, and the productivity is dramatically improved.

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

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

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. The embedding resin may include a thermosetting resin or a thermoplastic resin. The embedding resin may include a thermoplastic resin. The type of the embedded resin is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polyvinyl acetal resin, urethane resin, block copolymer polyimide resin, block copolymer Polyimide resin, polyethersulfone, polyethersulfone resin, aromatic polyamide resin, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene Resin containing oxide resin, cyanate ester resin, polycarboxylic acid anhydride, paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite Preferred examples include composite base epoxy resins, glass cloth / glass nonwoven fabric composite base epoxy resins and glass cloth base epoxy resins, polyester films, polyimide films, liquid crystal polymer films, fluororesin films, and the like. Moreover, the resin layer and / or resin and / or prepreg and / or film which are described in this specification can be used for the said embedding resin (resin).

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

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

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

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

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

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

Also, a step of providing at least one layer of the resin layer and the circuit on the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, the carrier of the laminate is provided with a carrier. A printed wiring board can be produced by carrying out a process of peeling the ultrathin copper layer or carrier from the copper foil. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.
The resin substrate, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. An accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like may be included. The carrier-attached copper foil may be smaller than the resin or prepreg when viewed in plan.

<Method for producing copper foil with carrier>
Next, the manufacturing method of the copper foil with a carrier which concerns on this invention is demonstrated. In order to produce a copper foil with a carrier according to the present invention, an intermediate layer (also referred to as a release layer) and an ultrathin copper layer are electroplated while being supported by a drum and being conveyed by a roll-to-roll method. In the manufacturing apparatus for forming an ultrathin copper layer, the distance between the transport roll and the transport roll is shortened, and the transport tension is set to about 3 to 5 times the normal thickness to form an ultrathin copper layer. To do.
After laminating a resin on the ultrathin copper layer side of the copper foil with carrier of the present invention and thermocompression bonding the copper foil with carrier and the resin under conditions of 15 kg / cm ² at 220 ° C. for 2 hours, JIS C 6471 8.1. In order to control the number density of holes having a circular shape of 0.8 or less when the carrier is peeled from the copper foil with a carrier by a 90 ° peeling method in accordance with the above, to 10 pieces / m ² or less. The current density during plating is controlled to 0.5 A / dm ² or less. The current density is preferably 0.4 A / dm ² or less, and more preferably 0.35 A / dm ² or less.

The manufacturing method of the copper foil with a carrier which concerns on embodiment of this invention is processing a carrier on a carrier by carrying out the surface of the elongate carrier conveyed in a length direction by a roll-to-roll conveyance system. A copper foil with a carrier comprising a laminated intermediate layer and an ultrathin copper layer laminated on the intermediate layer can be produced. The method for producing a copper foil with a carrier according to an embodiment of the present invention includes plating (for example, wet plating such as electrolytic plating and electroless plating or sputtering, CVD, PVD, etc.) while supporting the carrier conveyed by a conveyance roll with a drum. A step of forming an intermediate layer on the surface of the carrier by dry plating), and plating (for example, wet plating such as electrolytic plating or electroless plating or sputtering, CVD, PVD, etc. while supporting the carrier on which the intermediate layer is formed with a drum. The process of forming an ultra-thin copper layer on the surface of the intermediate layer by dry plating), and plating (for example, wet plating such as electrolytic plating and electroless plating or sputtering, CVD, PVD, etc. while supporting the carrier with a drum) ) To form a roughened layer on the surface of the ultrathin copper layer. For example, in each process, the treatment surface of the carrier supported by the drum also serves as the cathode, and each electroplating is performed in a plating solution between this drum and an anode provided to face the drum. . In this way, while supporting the carrier with the drum, while transporting in a roll-to-roll transport system, the intermediate layer and the ultrathin copper layer are plated (for example, electroplating, electroless plating or other wet plating or sputtering, CVD, By forming by dry plating using PVD or the like, the distance between the anode and the cathode in plating is stabilized. For this reason, the variation in the thickness of the layer to be formed is suppressed satisfactorily, and an ultra-thin copper layer as in the present invention can be produced with high accuracy. In addition, when the distance between the anode and the cathode in the plating is stabilized and the variation in the thickness of the intermediate layer formed on the carrier surface is suppressed well, the diffusion of Cu from the carrier to the ultrathin copper layer is also reduced. To be suppressed. For this reason, generation | occurrence | production of the pinhole in an ultra-thin copper layer is suppressed favorably.
In addition, as a method other than supporting with a drum, in the manufacturing apparatus for forming an ultrathin copper layer, the distance between the transport roll and the transport roll is shortened, and the transport tension is set to about 3 to 5 times the usual. There is also a strategy to form an ultra-thin copper layer. By introducing a support roll or the like, the distance between the transport roll and the transport roll is shortened (for example, about 800 to 1000 mm), and further, the position of the carrier is stabilized by increasing the transport tension to about 3 to 5 times the normal. This is because the distance between the anode and the cathode is stabilized. By stabilizing the distance between the electrodes, the distance between the anode and the cathode can be made smaller than usual.
In addition, if it is formed by sputtering or electroless plating instead of the drum method, there is a problem that the manufacturing cost may be high because the running cost for maintaining the apparatus and the cost of the sputtering target, the chemical solution of the plating solution, etc. are high. is there.

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

1. Production of Copper Foil with Carrier A copper foil having the thickness shown in Table 1 was prepared as a carrier. “Electrolytic copper foil” in the table used electrolytic copper foil made by JX Metals, and “rolled copper foil” used tough pitch copper foil (JIS-H3100-C1100) made by JX Metals.

  With respect to the shiny surface of this copper foil, the intermediate layer, the ultrathin copper layer and the roughened layer shown in Table 1 are formed under the following conditions in a roll-to-roll type continuous line under the following conditions. went.

(Intermediate layer formation)
The intermediate layer formation conditions were as shown in Table 1.
−Plating current density during intermediate layer formation−
The conditions for the current density during formation of the intermediate layer in Table 1 are shown below.
◎: 0.35A / dm ² or less 〇: 0.35A / dm ² ultra-0.4A / dm ² or less △: 0.4A / dm ² ultra-0.5A / dm ² or less ×: 0.5A / dm ² more than

-Intermediate layer formation method-
The conditions of the intermediate layer forming method in Table 1 are shown below.
(A) Foil handling system using drums ・ Anode: Insoluble electrode ・ Cathode: Carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes: 10 mm
・ Carrier transport tension: 0.05kg / mm
(B) Improved foil handling method with 99 folds ・ Anode: Insoluble electrode ・ Cathode: Carrier treatment surface ・ Distance between electrodes: 10 mm
・ Carrier transport tension: 0.20 kg / mm
-A support roll was provided between the conveyance rolls, and the distance between the rolls when forming the ultrathin copper layer was set to 1/2 (about 800 to 1000 mm).

  In addition, the description in the column of “intermediate layer” in the table means that the following processing was performed. For example, “Ni / chromate” means that the chromate treatment was performed after the nickel plating treatment.

"Ni": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, luster Agents: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 4-6
(Energization time) 1 to 20 seconds

・ "Chromate": Electrolytic pure chromate treatment (Liquid composition) Potassium dichromate: 1-10g / L
(PH) 7-10
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

-"Organic substance": Organic substance layer formation process It carried out by showering for 20 to 120 seconds and spraying the aqueous solution of liquid temperature 40 degreeC and pH5 containing the carboxybenzotriazole (CBTA) with a density | concentration of 1-30 g / L.

"Ni-Mo": nickel molybdenum alloy plating (Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Energization time) 3 to 25 seconds

- "Cr": chromium plating (liquid _{composition) CrO 3: 200~400g / L,} H 2 SO 4: 1.5~4g / L
(PH) 1-4
(Energization time) 1 to 20 seconds

"Co-Mo": Cobalt molybdenum alloy plating (Liquid composition) Co sulfate 50 g / dm ³ , Sodium molybdate dihydrate: 60 g / dm ³ , Sodium citrate 90 g / dm ³
(Energization time) 3 to 25 seconds

"Ni-P": Nickel phosphorus alloy plating (Liquid composition) Ni: 30 to 70 g / L, P: 0.2 to 1.2 g / L
(PH) 1.5-2.5
(Energization time) 0.5-30 seconds

(Ultra-thin copper layer formation)
The ultra-thin copper layer was formed by the following foil transport method.
・ Anode: Insoluble electrode ・ Cathode: Carrier surface supported on a drum with a diameter of 100 cm ・ Distance between electrodes: 10 mm
Electrolyte composition: copper concentration 80-120 g / L, sulfuric acid concentration 80-120 g / L
-Electroplating bath temperature: 50-80 ° C
-Current density of electroplating: 90 A / dm ²
・ Carrier transport tension: 0.05kg / mm

(Roughening treatment layer formation)
About the Example and comparative example whose column of the presence or absence of the roughening process of Table 1 is "Yes", the roughening process layer was further formed on the ultrathin copper layer after the above-mentioned ultrathin copper layer formation.
The roughening treatment layer was formed by the following foil transport method using a drum.
・ Anode: Insoluble electrode ・ Cathode: Carrier surface supported on a drum with a diameter of 100 cm ・ Distance between electrodes: 10 mm
・ Carrier transport tension: 0.05kg / mm

Moreover, roughening process conditions are shown below.
(Liquid composition)
Cu: 10 to 20 g / L
Ni: 5-15 g / L
Co: 5 to 15 g / L
(Electroplating conditions)
Temperature: 25-60 ° C
Current density: 35 to 55 A / dm ²
Roughening coulomb amount: 5-50 As / dm ²
Plating time: 0.1 to 1.4 seconds

Moreover, after forming a roughening process layer on the conditions shown below, the heat-resistant layer, the antirust layer, and the silane coupling process layer were further formed.
(Heat-resistant layer formation)
"Cu-Zn": Copper-zinc alloy plating (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds

(Rust prevention layer formation)
“Chromate”: Chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5-30 seconds

(Silane coupling treatment layer formation)
After spray-applying 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution, it was dried and heated in air at 100 to 200 ° C. for 0.1 to 10 seconds.

2. Evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following methods.

<Measurement of the thickness of the ultrathin copper layer>
After measuring the weight of the copper foil with the carrier, the carrier is peeled off, the weight of the carrier is measured, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer.
Sample size: 10 cm square sheet (10 cm square sheet punched with a press)
-Sample collection: Arbitrary three locations-The thickness of the ultrathin copper layer by the weight method of each sample was calculated by the following formula.
Thickness of ultrathin copper layer by weight method (μm) = {(weight of copper foil with carrier of 10 cm square sheet (g / 100 cm ² )) − (drawing ultrathin copper layer from copper foil with carrier of 10 cm square sheet) Carrier weight (g / 100 cm ² ))} / copper density (8.96 g / cm ³ ) × 0.01 (100 cm ² / cm ² ) × 10000 μm / cm after peeling
A precision balance capable of measuring up to 4 digits after the decimal point was used for measuring the weight of the sample. And the measured value of the obtained weight was used for the said calculation as it was.
-The arithmetic average value of the thickness of the ultrathin copper layer by three weight methods was made into the thickness of the ultrathin copper layer by the weight method.
Moreover, aswan IBA-200 was used for the precision balance, and Noguchi Press Co., Ltd. HAP-12 was used for the press.
In addition, when surface treatment layers, such as a roughening process layer, were formed on the ultra-thin copper layer, the said measurement was performed after forming the said surface treatment layer.

<Measurement of peel strength (normal peel strength)>
The ultrathin copper layer side surface of the copper foil with a carrier was attached to BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and thermocompression bonded at 220 ° C. for 2 hours at 15 kg / cm ² . Next, the carrier side was pulled with a tensile tester, and the peel strength when the carrier was peeled off in accordance with JIS C 6471 8.1 was measured.

<Tear pinhole>
The ultrathin copper layer side surface of the copper foil with a carrier was attached to BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and thermocompression bonded at 220 ° C. for 2 hours at 15 kg / cm ² . Next, the carrier side was turned up, and the carrier was peeled off from the copper foil with a carrier by a 90 ° peeling method in accordance with JIS C 6471 8.1. Subsequently, a consumer photographic backlight as a light source was placed on the BT resin side of the ultrathin copper layer remaining on the BT resin after the carrier was peeled off from the aforementioned copper foil with carrier. Then, the position of the pinhole (hole) which exists in an ultra-thin copper layer was specified by observing the ultra-thin copper layer surface on the opposite side to the above-mentioned side heat-pressed with BT resin. Thereafter, the above-described pinhole was photographed using a scanning electron microscope (SEM, model: S-4700, manufactured by Hitachi High-Technologies Corporation). And the area S of the pinhole in the obtained photograph and the perimeter L of the pinhole were measured using the image processing software (ImageJ ver.1.48v) of open software. The aforementioned image processing software can be obtained from the following website.
Website: https://imagej.nih.gov/ij/notes.html
And the circularity of the pinhole was calculated by the following formula.
Circularity = 4π × (area S) ÷ (peripheral length L) ²
And it was determined whether the circularity of the pinhole was 0.8 or less. Then, the number of holes (breaking pinholes) having a circularity of 0.8 or less was counted. The above measurement was performed on five samples having a size of 250 mm × 250 mm.
Then, the number of broken pinholes per unit area (m ² ) was calculated by the following formula.
Number of broken pinholes per unit area (m ² ) (number / m ² ) = total number of broken pinholes measured for 5 samples of size 250 mm × 250 mm / total surface area observed Area (5 sheets x 0.0625 m ² / sheet)
And the tear pinhole was evaluated according to the following criteria.
◎ (very good): 0 / m ²
○ (Good): 1 to 10 / m ²
X (defect): More than 10 / m ²
Table 1 shows the production conditions and evaluation results of Examples and Comparative Examples.

(Evaluation results)
In each of Examples 1 to 18, the resin was laminated on the ultrathin copper layer side of the carrier-attached copper foil, and the carrier-attached copper foil and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ^2. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled off from the copper foil with a carrier by a 90 ° peeling method in accordance with C 6471 8.1 is 10 / m ² It was controlled as follows, and the generation of pinholes that occurred when the carrier was peeled off was successfully suppressed.
In each of Comparative Examples 1 to 9, a resin was laminated on the ultrathin copper layer side of the copper foil with carrier, and the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ^2. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled off from the copper foil with a carrier by a 90 ° peeling method in accordance with C 6471 8.1 is 10 / m ² Therefore, it was not possible to satisfactorily suppress the generation of pinholes that occurred during carrier peeling.

Claims (29)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. When the carrier is peeled from the carrier-attached copper foil by a compliant 90 ° peeling method, the number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer is 10 / m ² or less. Copper foil with carrier. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled from the copper foil with a carrier by a compliant 90 ° peeling method is 7 / m ² or less. The copper foil with a carrier according to claim 1. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. When the carrier is peeled from the carrier-attached copper foil by a compliant 90 ° peeling method, the number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer is 3.5 pieces / m ² or less. The copper foil with a carrier according to claim 2. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled off from the copper foil with carrier by a compliant 90 ° peeling method is 2 / m ² or less The copper foil with a carrier according to claim 3. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. When the carrier is peeled off from the copper foil with a carrier by a compliant 90 ° peeling method, the number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer is 1 / m ² or less. The copper foil with a carrier according to claim 4. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled off from the copper foil with carrier by a compliant 90 ° peeling method is 0.5 pieces / m ² or less. The copper foil with a carrier according to claim 5. After laminating a resin on the ultrathin copper layer side of the copper foil with carrier, the copper foil with carrier and the resin were thermocompression bonded at 220 ° C. for 2 hours under the condition of 15 kg / cm ² , and then in accordance with JIS C 6471 8.1. The number density of holes having a circularity of 0.8 or less generated in the ultrathin copper layer when the carrier is peeled off from the copper foil with a carrier by a compliant 90 ° peeling method is 0 / m ^2. Item 7. A copper foil with a carrier according to Item 6.   The peeling strength when peeling the said carrier from the said copper foil with a carrier by the 90 degree peeling method based on JISC6471 8.1 is 2-10 N / m, It is any one of Claims 1-7 Copper foil with carrier.   The thickness of the said ultra-thin copper layer is 1.6 micrometers or less, Copper foil with a carrier as described in any one of Claims 1-8.   The copper foil with a carrier according to claim 9, wherein the ultrathin copper layer has a thickness of 1.2 μm or less.   The copper foil with a carrier according to claim 10, wherein the ultrathin copper layer has a thickness of 1.0 μm or less.   The copper foil with a carrier according to claim 11, wherein the ultrathin copper layer has a thickness of 0.9 μm or less.   The copper foil with a carrier according to claim 1, wherein the ultrathin copper layer has a thickness of 0.05 μm or more. In the case where the copper foil with carrier has an ultrathin copper layer on one side of the carrier, at least one surface of the ultrathin copper layer side and the carrier side, or both surfaces, or
In the case where the copper foil with carrier has an ultrathin copper layer on both sides of the carrier, on the surface of the one or both ultrathin copper layers side,
14. With a carrier according to claim 1, comprising at least one layer selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer. Copper foil.   The copper foil with a carrier according to claim 14, 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 carrier-attached claim according to claim 14, further 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 as described in any one of Claims 1-12 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 16 or 17, wherein the resin layer includes a dielectric. Forming the intermediate layer on the carrier by electrolytic treatment with a current density of 0.5 A / dm ² or less;
The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-18 provided with the process of forming the said ultra-thin copper layer in the said intermediate layer side surface of the said carrier.   The method to manufacture a printed wiring board using the copper foil with a carrier as described in any one of Claims 1-18.   The method to manufacture a laminated body using the copper foil with a carrier as described in any one of Claims 1-18.   It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-18, 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 18, wherein the carrier-attached copper foil according to any one of claims 1 to 18 is attached 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 22 or 23. A step of providing at least once two layers of a resin layer and a circuit on the laminate according to claim 22 or 23; 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 18 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the copper foil carrier of the copper foil with carrier,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 18,
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 18 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 Claims 24-28.