JP2016145390A - Copper foil with carrier, laminate, printed wiring board and method for producing printed wiring board - Google Patents

Abstract

Provided is a copper foil with a carrier in which falling off of roughened particles in a roughened particle layer provided on the surface of the ultrathin copper layer is satisfactorily suppressed and the peel strength is good. A copper foil with a carrier having a carrier, an intermediate layer, an ultrathin copper layer, and a surface treatment layer including a roughening treatment layer in this order, and a diameter of roughening particles constituting the roughening treatment layer. The number of particles exceeding 1 μm is suppressed to 5 or less in the range of 10 μm square, and coarse particles having a diameter of 0.1 μm to 1 μm are present in the range of 500 to 3000 in the range of 10 μm square. Copper foil with carrier. [Selection] Figure 1

Description

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

  Printed wiring boards have made great progress over the last half century and are now used in almost all electronic devices. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. In particular, when an IC chip is mounted on a printed wiring board, a fine pitch of L (line) / S (space) = 20 μm / 20 μm or less is required.

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

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

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

JP 2006-022406 A

  In the manufacturing method of the printed wiring board using the carrier-attached copper foil as described above, generally, a foreign material on the surface of the copper foil with the carrier or the surface of the printed wiring board is used by using a cleaning roller made of a synthetic rubber having adhesiveness. May be removed. At this time, in order to improve the adhesion to the insulating resin, the roughened layer applied to the surface of the copper foil with carrier on the side of the ultrathin copper layer is suitable for miniaturization of wiring and high-frequency signal transmission as described above. Therefore, it is smooth and fine. For this reason, when the cleaning roller is applied, the fine roughened particles constituting the roughened layer fall off from the surface of the copper foil, and transfer and adhere as conductive foreign matters onto the cleaning roller. As described above, the conductive foreign matter adhering to the surface of the cleaning roller may move again to the original copper foil or printed wiring board surface if cleaning is continued. In such a case, the circuit is formed on the copper foil. Causes a short circuit.

  Accordingly, the present invention is to provide a copper foil with a carrier in which the falling off of the roughened particles in the roughened particle layer provided on the surface of the ultrathin copper layer is satisfactorily suppressed and the peel strength is good. And

  In order to achieve the above-mentioned object, the present inventors conducted extensive research and found that the diameter of the roughened particles constituting the roughened layer to be processed on the surface of the ultrathin copper layer of the carrier-added copper foil has a diameter. It has been found that the problem can be solved by suppressing the generation density of coarse particles exceeding 1 μm and controlling the density of coarse particles having a diameter of 0.1 μm or more and 1.0 μm or less.

  The present invention has been completed on the basis of the above knowledge, and in one aspect, a carrier-added copper foil having a surface treatment layer including a carrier, an intermediate layer, an ultrathin copper layer, and a roughening treatment layer in this order. Of the roughening particles constituting the roughening treatment layer, those having a diameter of more than 1 μm are suppressed to 5 or less in a 10 μm square range, and the roughening particles having a diameter of 0.1 μm to 1 μm are 10 μm. It is a copper foil with a carrier that exists at a density of 500 or more and 3000 or less in a four-way range.

  In one embodiment of the copper foil with a carrier of the present invention, the roughened particles constituting the roughened layer have a diameter of more than 1 μm and are suppressed to 2 or less in a 10 μm square and 0.1 μm. Roughened particles having a diameter of 1 μm or less are present at a density of 500 or more and 3000 or less in a 10 μm square range.

  In another embodiment of the copper foil with a carrier of the present invention, among the roughened particles constituting the roughened layer, those having a diameter exceeding 1 μm are suppressed to 2 or less in a 10 μm square, and 0 .Roughening particles having a diameter of 1 μm or more and 1 μm or less are present at a density of 2000 or more and 3000 or less in the range of 10 μm square.

  In still another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer has a thickness of 0.1 μm or more and 6 μm or less.

In still another embodiment of the copper foil with a carrier according to the present invention, the amount of adhesion per unit area of the surface treatment layer is 0.1 g / m ² or more and 5 g / m ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the adhesion amount per unit area of the surface treatment layer is 0.8 g / m ² or more and 1.5 g / m ² or less.

  In yet another embodiment of the copper foil with a carrier of the present invention, the 10-point average roughness Rz of the surface of the ultra thin copper layer of the copper foil with a carrier is 0.3 to 1.5 μm.

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

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

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

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

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

  In another embodiment, the copper foil with a carrier of the present invention includes a resin layer on the surface of the surface treatment layer.

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

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

  In another aspect, the present invention is a laminate manufactured using the copper foil with a carrier of the present invention.

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

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

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

  In still another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier of the present invention, the ultrathin copper layer of the copper foil with carrier so that the circuit is buried. A step of forming a resin layer on a side surface, a step of forming a circuit on the resin layer, a step of peeling the carrier after forming a circuit on the resin layer, and after peeling the carrier, It is a manufacturing method of a printed wiring board including the process of exposing the circuit buried in the resin layer formed in the ultra-thin copper layer side surface by removing the ultra-thin copper layer.

In yet another aspect of the present invention, the step of laminating the carrier-attached copper foil of the present invention on the resin substrate from the carrier side, the step of forming a circuit on the ultrathin copper layer side surface of the carrier-attached copper foil,
After forming the resin layer on the resin layer, forming the resin layer on the ultrathin copper layer side surface of the copper foil with carrier so that the circuit is buried, forming the circuit on the resin layer, The step of peeling the carrier and the circuit embedded in the resin layer formed on the surface of the ultra-thin copper layer by removing the ultra-thin copper layer after peeling the carrier are exposed. It is the manufacturing method of the printed wiring board including the process to make.

  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 two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer opposite to the side or the carrier side surface, and after forming the two layers of the resin layer and the circuit, It is a manufacturing method of a printed wiring board including the process of exfoliating the career or the ultra-thin copper layer from copper foil with a carrier.

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

  According to the present invention, it is possible to provide a copper foil with a carrier in which the falling off of the roughened particles in the roughened particle layer provided on the surface of the ultrathin copper layer is satisfactorily suppressed and the peel strength is good. .

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. The surface SEM observation photograph after the roughening process of the copper foil of Example 2 is shown. The surface SEM observation photograph after the roughening process of the copper foil of the comparative example 1 is shown. The SEM observation photograph of the omission roughening particle | grains on the adhesive sheet of the comparative example 1 is shown.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCD film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a titanium or stainless steel drum, 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. The carrier is preferably an electrolytic copper foil or a rolled copper foil because of its high electrical conductivity, and is more preferably an electrolytic copper foil because its manufacturing cost is low and the roughness of the carrier side surface is easier to control. preferable. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-300 μm, more typically 12-150 μm, more typically 12-70 μm, and more typically 18-35 μm.

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

Further, for example, the intermediate layer can be configured by laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more preferably less than 100 [mu] g / dm ² or more 1000μg / dm ^2, the adhesion amount of chromium is preferably 5 [mu] g / dm ² or more 500 [mu] g / dm ² or less in the intermediate layer, 5 [mu] g / dm ² or more 100 [mu] g / dm ² or less More preferably.

  The chromium-containing layer may be a chromium plating layer, a chromium alloy plating layer, or a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

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

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

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

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

Further, for example, the intermediate layer can be configured by stacking nickel and molybdenum, cobalt, or a molybdenum-cobalt alloy in this order on a carrier. Since the adhesion force between nickel and copper is higher than the adhesion force between molybdenum or cobalt and copper, when peeling the ultrathin copper layer, the interface between the ultrathin copper layer and molybdenum or cobalt or molybdenum-cobalt alloy It will come off. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer.
In the intermediate layer, the adhesion amount of nickel is 100 to 40000 μg / dm ² , the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and the adhesion amount of cobalt is 10 to 1000 μg / dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultrathin copper layer, the intermediate layer is made of a metal species (Co, Mo) that suppresses the diffusion of Ni toward the ultrathin copper layer while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this viewpoint, the amount of nickel deposited is preferably to 100~40000μg / dm ^2, preferably to 200~20000μg / dm ^2, more preferably to 300~15000μg / dm ^2, 300~10000μg / Dm ² is more preferable. If included molybdenum in the intermediate layer, a molybdenum deposition amount is preferably set to 10~1000μg / dm ^2, the molybdenum deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably. If included cobalt in the intermediate layer, the cobalt coating weight is preferably set to 10~1000μg / dm ^2, cobalt deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably.
As described above, the intermediate layer is plated for providing a molybdenum, cobalt, or molybdenum-cobalt alloy layer when nickel and molybdenum, cobalt, or a molybdenum-cobalt alloy are stacked in this order on a carrier. When the current density in the treatment is lowered and the carrier conveyance speed is lowered, the density of the molybdenum, cobalt, or molybdenum-cobalt alloy layer tends to increase. When the density of the layer containing molybdenum and / or cobalt increases, nickel in the nickel layer becomes difficult to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled.

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

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is preferably 0.1 μm or more and 6 μm or less. According to such a configuration, the fine wiring formability is improved. The thickness of the ultrathin copper layer is more preferably from 0.1 μm to 3 μm, even more preferably from 0.2 μm to 1.5 μm, and even more preferably from 0.3 μm to 1.2 μm. preferable. Moreover, you may use the layer of the structure which can be used as an intermediate | middle layer for another layer.

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

<Copper foil with carrier>
The copper foil with a carrier of the present invention has a surface treatment layer including a carrier, an intermediate layer, an ultrathin copper layer, and a roughening treatment layer in this order. The method of using the copper foil with carrier itself is well known to those skilled in the art. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. A copper layer is etched into the intended conductor pattern, and finally a laminate (such as a copper clad laminate) or a printed wiring board can be produced.

  The roughening treatment layer in the surface treatment layer has roughening particles, and among the roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 5 or less in a 10 μm square range, and 0 It is controlled so that coarse particles having a diameter of 1 μm or more and 1 μm or less are present at a density of 500 or more and 3000 or less in a range of 10 μm square. Here, the diameter of the roughened particles indicates the minimum diameter of a circle surrounding the roughened particles. By such a structure, generation | occurrence | production of the powder | flour of the ultra-thin copper layer side surface of copper foil with a carrier is suppressed favorably. Of the roughened particles constituting the roughened layer, those having a diameter exceeding 1 μm are preferably 2 or less, more preferably 1 or less, and more preferably 0 in a 10 μm square range. Is more preferable. Moreover, it is preferable that the roughened particles having a diameter of 0.1 μm or more and 1 μm or less are present in a range of 2000 or more and 3000 or less, more preferably 2000 or more and 2800 or less in a range of 10 μm square. More preferably, it is present at a density of 2000 or more and 2500 or less.

Moreover, it is preferable that the adhesion amount per unit area of the surface treatment layer is 0.1 g / m ² or more and 5 g / m ² or less. By such a structure, generation | occurrence | production of the powder | flour of the ultra-thin copper layer side surface of copper foil with a carrier is suppressed more favorably. The adhesion amount per unit area of the surface treatment layer is more preferably 0.8 g / m ² or more and 1.5 g / m ² or less, and 0.9 g / m ² or more and 1.4 g / m ² or less. Even more preferably, it is 1 g / m ² or more and 1.2 g / m ² or less.

  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. The roughening treatment layer may be formed by using a sulfuric acid / copper sulfate electrolytic bath containing one or more selected from the group consisting of alkyl sulfate salts, tungsten and arsenic. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface of the roughened layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the layer. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.). These surface treatments hardly affect the surface roughness of the carrier and the ultrathin copper layer.

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

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

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

  The carrier-attached copper foil of the present invention preferably has a 10-point average roughness Rz of the surface of the ultrathin copper layer side of 0.3 to 1.5 μm. Moreover, it is more preferable that 10-point average roughness Rz of the ultrathin copper layer side surface of the copper foil with a carrier is 0.5 to 1.4 μm.

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

Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on the ultrathin copper layer, and the heat treatment layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer on the roughening treatment layer. One or more layers selected from the group may be provided.
Further, a roughening treatment layer may be provided on the ultrathin copper layer, a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer, and a chromate treatment layer may be provided on the heat resistance layer and the rust prevention layer. Alternatively, a silane coupling treatment layer may be provided on the chromate treatment layer.
The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. 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.

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

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

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

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in powder form, the powder characteristics of the dielectric (dielectric filler) are such that the particle size ranges from 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). The surface of the copper foil with a carrier is coated on the surface of the ultrathin copper layer by, for example, a roll coater method, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. In a state in which the samples are stacked (laminated body), the values are calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of pressing at 171 ° C., pressing pressure of 14 kgf / cm 2 and pressing time of 10 minutes. is there.

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

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the thickness of the resin layer is such that interlayer insulation can be ensured or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board having a thickness of one layer of 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 500 μm, more preferably 0.1 to 300 μm, more preferably 0.1 to 200 μm, and preferably 0.1 to 120 μm. More preferred.

When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer having a desired thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the copper foil with a carrier having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.
When the resin layer includes a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness with the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, more preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. Moreover, it is preferable that the thickness of a semi-hardened resin layer is 3 micrometers-55 micrometers, it is preferable that they are 7 micrometers-55 micrometers, and it is more desirable that it is 15-115 micrometers. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 μm, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.

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

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

  Furthermore, 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

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

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

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

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled.
(1) The color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer or the silane coupling-treated layer is 45 or more.

  Here, the color differences ΔL, Δa, and Δb are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ΔL: black and white, Δa: reddish green, Δb: yellow blue. ΔE * ab is expressed by the following formula using these color differences.

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

  When the color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, the contrast between the ultrathin copper layer and the circuit As a result, visibility is improved and circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

  When the color difference on the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, rust-proof layer, chromate-treated layer or silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear. , Visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 2-C, the circuit plating can be accurately formed at a predetermined position. In addition, according to the method for manufacturing a printed wiring board as described above, circuit plating is embedded in a resin layer, and thus, for example, removal of an ultrathin copper layer by flash etching as shown in FIG. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

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

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

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

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

1. Production of Copper Foil with Carrier As Examples 1 to 7 and Comparative Examples 1 to 4, an electrolytic copper foil having a thickness of 18 μm (JTC foil manufactured by JX Nippon Mining & Metals Co., Ltd., Examples other than Example 5 and Comparative Examples) or rolled Copper foil (tough pitch copper foil JIS H3100 alloy number: C1100, Example 5 only) was used as a carrier, and an intermediate layer and an intermediate layer were formed on the carrier (when an electrolytic copper foil was used, an intermediate layer was formed on the glossy surface). An ultrathin copper layer was formed in this order to obtain a copper foil with a carrier having a thickness of 0.6 to 5 μm.

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

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

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

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

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

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

・ Ultra-thin copper layer formation Subsequently, on the continuous plating line of roll-toe-roll type, an ultra-thin copper layer with a thickness of 0.6 to 5 μm is formed on the intermediate layer by electroplating under the conditions shown below. And the copper foil with a carrier was manufactured.
Solution composition: copper concentration 30 to 120 g / L, sulfuric acid concentration 20~120g ^/ L, Cl -: 20~50 mass ppm, polyethylene glycol: 10 to 100 ppm by weight, bis (3-sulfopropyl) disulfide: 10 to 30 mass ppm , Thiourea: 10-50 ppm by mass
Liquid temperature: 20-80 degreeC
Current density: 10 to 100 A / dm ²

  Next, on the ultrathin copper layer side surface of the copper foil with carrier, any one of the roughening treatments (1) to (3) described in the table, or (1) and (3), (2) and (3 ) Were successively performed in this order, and each surface treatment of heat treatment, rust prevention treatment, and silane coupling agent coating was further performed. In Comparative Example 3, the roughening treatment was not performed. Each processing condition is shown below.

[Roughening treatment]
-Roughening treatment (1) (Examples 1 and 7, Comparative Example 1):
Electrolyte composition: Cu 25-40 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid 80-120 g / L
Liquid temperature: 20-40 degreeC
Current density: 80 to 120 A / dm ²
Current-carrying time: 0.5 to 1.5 seconds For prevention of falling off of roughened particles and improvement of peel strength on the carrier side surface or ultrathin copper layer side surface of the copper foil with carrier subjected to the above roughening treatment (1). Then, plating was performed in a copper electrolytic bath made of sulfuric acid / copper sulfate. The covering plating conditions are described below.
Liquid composition: copper concentration 20-40 g / L, sulfuric acid concentration 80-120 g / L
Liquid temperature: 20-40 degreeC
Current density: 1-15 A / dm ²
Energizing time: 1-3 seconds

-Roughening treatment (2) (Examples 5 and 6, Comparative Example 2):
Liquid composition: copper concentration 10-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid concentration 80-120 g / L
Liquid temperature: 15-30 degreeC
Current density: 60-100 A / dm ²
Energizing time: 1.0 to 1.5 seconds

A copper electrolytic bath made of sulfuric acid / copper sulfate is used on the carrier-side surface or ultrathin copper layer-side surface of the copper foil with carrier that has been subjected to the above-mentioned roughening treatment (2) in order to prevent falling off of the roughened particles and to improve the peel strength. Cover plating was performed. The covering plating conditions are described below.
Liquid composition: copper concentration 20-40 g / L, sulfuric acid concentration 80-120 g / L
Liquid temperature: 40-50 degreeC
Current density: 5-20 A / dm ²
Energizing time: 1-6 seconds

Roughening treatment (3) (Examples 1 to 5, Comparative Examples 1 and 4):
Liquid composition: copper concentration 10-20 g / L, cobalt concentration 1-10 g / L, nickel concentration 1-10 g / L
pH: 1-4
Liquid temperature: 30-50 degreeC
Current density: 30 to 70 A / dm ²
Energizing time: 0.1 to 1.0 seconds

If the current density of the roughening treatments (1), (2) and (3) is high, the frequency of abnormal precipitation increases and the number of particles having a size of 1 μm or more increases. This can also be seen by comparing Example 1 and Comparative Example 1, which will be described later, and Example 6 and Comparative Example 2.
Also in the roughening process (3), it is preferable to divide energization into a plurality of times and set the current density low. When the current density exceeds 70 A / dm ² , local current concentration occurs, and the coarse particle density exceeding 1 μm in diameter begins to increase rapidly, and the majority of other coarse particle diameters of 1 μm or less become too small. Therefore, the adhesion with the ultrathin copper layer is impaired, and it becomes easy to fall off. In that case, adhesion (peel strength) with the insulating resin also decreases. This can also be seen by comparing Examples 2 to 4 with Comparative Example 4.
In addition, the energization amount (product of current density and energization time) of the covering plating in the roughening treatments (1) and (2) is 50 to 90% with respect to the energization amount of the roughening treatment. It is preferable for preventing the above.

Co-Ni alloy plating and Zn-Ni alloy plating were performed on the surface of the ultrathin copper layer of the carrier-added copper foil subjected to the roughening treatment under the above conditions to form a heat-resistant layer. The plating conditions are described below.
Liquid composition: cobalt concentration 1-30 g / L, nickel concentration 1-30 g / L
pH: 1.0-3.5
Liquid temperature: 30-80 degreeC
Current density 1-10 A / dm ²
Energizing time: 1-10 seconds

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

[Rust prevention treatment]
・ Chromate treatment:
Liquid composition: potassium dichromate concentration 3-5 g / L, zinc concentration 0.1-1 g / L
Liquid temperature: 30-50 degreeC
Current density 0.1-3.0 A / dm ²
Energizing time: 1-10 seconds

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

2. Evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following method.
<Number of roughened particles>
Of the roughened particles constituting the roughened layer, those having a diameter of more than 1 μm are in the range of 10 μm square, and the number of roughened particles having a diameter of 0.1 μm to 1 μm in the range of 10 μm square are as follows: It measured by the method of. Using SEM photographs taken at 10000 times, the size and number of particles were counted. The method for measuring the size of the particles will be sent separately via email. One field of view was measured for an SEM photograph having a width of 12.7 μm and a length of 10.2 μm. The diameter of the roughened particles was the minimum diameter of a circle surrounding the roughened particles. Moreover, the roughening process particle | grains piled up were determined as one roughening process particle | grain, and let the diameter of the minimum circle surrounding the whole roughening process particle | grains stacked as the diameter of the said roughening process particle | grains piled up.

<Adhesion amount per unit area of surface treatment layer>
The adhesion amount per unit area of the surface treatment layer was measured by the following method.
The weight (1) of the copper foil with a carrier before 10 cm square roughening treatment and the weight (2) of the copper foil with a carrier after 10 cm square roughening treatment were respectively measured, and weight (1) -weight (2 ) To calculate the adhesion amount.

In addition, the adhesion amount per unit area of the surface treatment layer can also be measured as follows.
<Thickness of ultrathin copper layer>
The thickness of the ultrathin copper layer of the produced copper foil with a carrier is observed using FIB-SIM (magnification: 10,000 to 30,000 times). By observing the cross section of the ultrathin copper layer, five points are measured at intervals of 30 μm and the average value is obtained.
<Calculation of weight B of ultrathin copper layer>
The weight B of the ultrathin copper layer is calculated by the following formula.
Weight B (g / cm ² ) of ultrathin copper layer = thickness (μm) of ultrathin copper layer × unit area (100 cm ² / cm ² ) × copper density (8.94 g / cm ³ ) × 10 ⁻⁴ ( cm / μm)
<Calculation of adhesion amount of surface treatment layer>
Adhesion amount of surface treatment layer (g / m ² ) = ((weight of “ultra thin copper layer + surface treatment layer” A (measured with a 10 cm square sample) (g / cm ² )) − weight of ultra thin copper layer B (g / cm ² )) × 10 ⁴ cm ² / m ²
<Measurement of Weight A of “Ultra Thin Copper Layer + Roughening Treatment Layer”>
The weight A of “ultra-thin copper layer + roughening treatment layer” of the prepared copper foil with carrier is measured as follows.
First, after measuring the weight of the copper foil with the carrier, the ultrathin copper layer with the roughening treatment layer was peeled off, the weight of the obtained carrier was measured, and the difference between the former and the latter was determined as “ultrathin copper layer + It was defined as the weight of the “roughened layer”. The ultrathin copper layer piece to be measured is a 10 cm square sheet punched out by a press.
The weighing machine uses HF-400 manufactured by A & D Co., Ltd., and the press machine uses HAP-12 manufactured by Noguchi Press Co., Ltd.

<10-point average roughness after surface treatment>
About the ultrathin copper layer side surface of the copper foil with a carrier after the surface treatment, using a contact type roughness meter Surfcoder SE-3C manufactured by Kosaka Laboratory Co., Ltd., ten-point average roughness Rz according to JIS B0601-1994 Was measured in the TD direction (lateral direction). A direction (TD, ie, width) perpendicular to the carrier traveling direction in the carrier manufacturing apparatus under the conditions of a measurement standard length of 0.8 mm, an evaluation length of 4 mm, a cut-off value of 0.25 mm, and a feed rate of 0.1 mm / second. Direction), the measurement position was changed 10 times, and the average value of the 10 measurements was taken as the value of the ten-point average roughness (Rz).

<Peel strength>
30 kgf / cm < ² > in air | atmosphere with respect to the resin base material (Mitsubishi Gas Chemical Co., Ltd. product: GHPL-832NX-A) from the ultra-thin copper layer side the copper foil with a carrier after the surface treatment of an Example and a comparative example. After laminating by heating at 220 ° C. for 2 hours, the carrier was peeled from the copper foil with carrier. Then, copper plating was performed on the intermediate layer side surface of the exposed ultrathin copper layer, and the total thickness of the ultrathin copper layer and the copper plating layer was 18 μm. Then, the ultrathin copper layer and the copper plating layer are JIS C 6471 (1995, the method of peeling the copper foil is 8.1. The peel strength of the copper foil 8.1.1 Types of test methods (1) It peeled according to the method A (The method of peeling a copper foil 90 degree direction with respect to a copper foil removal surface).) The peel strength in that case was measured.

<Dirt transfer sheet>
On the surface of the copper foil with a carrier on the side of the ultrathin copper layer, the transfer sheet contamination was evaluated by the following method.
-Collection area: area 250,000mm ² (width 250mm x length 1000mm)
・ Cleaning roller used for collection: Nanocleen roller manufactured by Teknek (Techneck Japan Ltd.) After cleaning the ultrathin copper layer side surface with the above collection roller, transfer sheet (transfer sheet model number: ARBS-1400) from the roller The powder was transferred to Subsequently, the transfer sheet was observed by using an optical microscope at a magnification of 500 times to observe roughened particles that were dropped, thereby evaluating the stain on the transfer sheet.
The stain on the transfer sheet was evaluated according to the following criteria.
A: Dropped roughened particles are not observed. O: Dropped roughened particles are hardly observed. (Diameter less than 1μm)
X: Dropped rough particles (diameter of 1 μm or more) were observed.
Test conditions and results are shown in Tables 1 and 2.

(Evaluation results)
In Examples 1 to 7, it is possible to obtain a copper foil with a carrier in which the falling off of the roughened particles in the roughened particle layer provided on the surface of the ultrathin copper layer is well suppressed and the peel strength is good. ing.
On the other hand, all of Comparative Examples 1 to 4 had poor dropout of the roughened particles in the roughened particle layer provided on the surface of the ultrathin copper layer or had poor peel strength.
In FIG. 5, the surface SEM observation photograph after the roughening process of the copper foil of Example 2 is shown.
In FIG. 6, the surface SEM observation photograph after the roughening process of the copper foil of the comparative example 1 is shown.
In FIG. 7, the SEM observation photograph of the omission roughening particle | grains on the adhesive sheet of the comparative example 1 is shown.

Claims (23)

  A copper foil with a carrier having a carrier, an intermediate layer, an ultrathin copper layer, and a surface treatment layer including a roughening treatment layer in this order, and a diameter of 1 μm among the roughening particles constituting the roughening treatment layer. Exceeding is suppressed to 5 or less in the range of 10 μm square, and roughened particles having a diameter of 0.1 μm to 1 μm are present in the range of 500 to 3000 in the range of 10 μm square to 500 μm Foil.   Among the roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 2 or less in the range of 10 μm square, and roughening particles having a diameter of 0.1 μm to 1 μm are 10 μm square. The carrier-attached copper foil according to claim 1, wherein the copper foil is present in a density of 500 to 3000.   Among the roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 2 or less in the range of 10 μm square, and roughening particles having a diameter of 0.1 μm to 1 μm are 10 μm square. The copper foil with a carrier according to claim 2, wherein the copper foil exists in a range of 2000 to 3000 in a range.   The thickness of the said ultra-thin copper layer is 0.1 micrometer or more and 6 micrometers or less, Copper foil with a carrier as described in any one of Claims 1-3. The copper foil with a carrier according to any one of claims 1 to 4, wherein an adhesion amount per unit area of the surface treatment layer is 0.1 g / m ² or more and 5 g / m ² or less. The copper foil with a carrier according to claim 5, wherein an adhesion amount per unit area of the surface treatment layer is 0.8 g / m ² or more and 1.5 g / m ² or less.   The copper foil with a carrier according to any one of claims 1 to 6, wherein the 10-point average roughness Rz of the surface of the ultrathin copper layer of the copper foil with a carrier is 0.3 to 1.5 µm.   The copper foil with a carrier as described in any one of Claims 1-7 in which the roughening process layer is formed in the surface on the opposite side to the said ultra-thin copper layer of the said carrier.   The roughening layer formed on the surface of the ultrathin copper layer is selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or any one or more of them. The copper foil with a carrier as described in any one of Claims 1-8 which is a layer which consists of an alloy containing.   The copper foil with a carrier as described in any one of Claims 1-9 which equips the surface of the roughening process layer formed in the said ultra-thin copper layer surface with a resin layer.   The surface of the roughening treatment layer formed on the surface of the ultrathin copper layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier as described in any one of 1-9.   One or more layers selected from the group consisting of the heat-resistant layer, the rust preventive layer, the chromate treatment layer, and the silane coupling treatment layer provided on the surface of the roughening treatment layer formed on the surface of the ultrathin copper layer The copper foil with a carrier of Claim 11 provided with a resin layer on top.   The copper foil with a carrier according to any one of claims 1 to 12, wherein a resin layer is provided on the surface of the surface treatment layer.   The copper foil with a carrier according to any one of claims 10, 12 and 13, wherein the resin layer is an adhesive resin.   The copper foil with a carrier according to claim 10, wherein the resin layer is a semi-cured resin.   The laminated body manufactured using the copper foil with a carrier as described in any one of Claims 1-15.   It is a laminated body containing the copper foil with a carrier as described in any one of Claims 1-15, and resin, 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 printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-15. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 15 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
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 of the copper foil with a carrier according to any one of claims 1 to 15,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. A step of laminating the carrier-attached copper foil according to any one of claims 1 to 15 on a resin substrate from the carrier side,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. 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 15 and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. The step of laminating the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 15 and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method for producing a printed wiring board, comprising the step of peeling the carrier from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.