JP6134569B2 - Copper foil with carrier, method for producing copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with a carrier, a printed wiring board, a printed circuit board, a copper clad laminate, and a method for producing 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 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. A common method of using a copper foil with a carrier is to bond the surface of an ultrathin copper layer to an insulating substrate, thermocompression bond, and then peel the carrier through a peeling layer.

  A general method for forming a fine circuit using a copper foil with a carrier is a method in which a wiring circuit is formed on an ultrathin copper layer, and then the ultrathin copper layer is removed by etching with a sulfuric acid-hydrogen peroxide-based etchant (MSAP: Modified-Semi-Additive-Process). Therefore, it is preferable that the ultrathin copper layer has a uniform thickness.

  Here, the foil thickness accuracy of electrolytic plating is greatly influenced by the distance between the anode and the cathode. A general method for forming an ultrathin copper layer is to form a release layer on a copper foil carrier (12 to 70 μm), and further form an ultrathin copper layer (0.5 to 10.0 μm) and roughened particles on the surface. To do. Regarding the processes after the formation of the copper foil carrier, conventionally, it has been carried out using a ninety-fold folding method that does not support the copper foil carrier with a drum as shown in FIG. 1 (Patent Document 1).

  On the other hand, for the surface of the ultra-thin copper layer of the carrier-attached copper foil that becomes the adhesive surface with the resin, the surface profile (mainly for the purpose of increasing the adhesive force between the ultra-thin copper layer and the resin substrate) A general method is to deposit a large amount of roughened particles on an ultrathin copper layer having a large unevenness and roughness.

  However, if a very thin copper layer with such a large profile (irregularity, roughness) is used on a semiconductor package substrate that needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles during circuit etching Even if copper remains or copper particles do not remain, the linearity of the circuit deteriorates, and problems such as poor insulation between circuit patterns occur.

JP 2000-309898 A

  However, since the thickness accuracy of the ultrathin copper layer formed by electrolytic plating is greatly affected by the distance between the anode and the cathode, there is no support by the drum to the copper foil carrier described in Patent Document 1. When the foil carrying method is used, it is difficult to make the distance between the electrodes constant due to the influence of the electrolytic solution, the foil carrying tension, and the like, and there is a problem that the variation in thickness becomes large. When a roughening process is performed on the surface of an ultrathin copper layer having a large thickness variation, the linearity of the circuit pattern is remarkably impaired, and problems such as an insulation failure between the circuit patterns occur.

  Then, this invention makes it a subject to provide the copper foil with a carrier with favorable adhesive force with an insulated substrate, and favorable etching property.

  In order to achieve the above object, the present inventor has made extensive studies, and improves the thickness accuracy of the ultrathin copper layer on the carrier, and smoothes the adhesion surface of the ultrathin copper layer with the insulating substrate, The present inventors have found that it is extremely effective in improving the adhesion force and etching property of an ultrathin copper layer with an insulating substrate.

The present invention has been completed on the basis of the above knowledge. In one aspect, a carrier, a release layer laminated on the carrier, an ultrathin copper layer laminated on the release layer, and an ultrathin copper layer are provided. A copper foil with a carrier provided with an adhesive layer with a laminated insulating substrate,
The ultrathin copper layer is a 10 cm square sheet, and the thickness accuracy when the average thickness measurement value calculated by the weight thickness method is W ₁₀ and the standard deviation is σ ₁₀ : P ₁₀ = 3σ ₁₀ × 100 / W ₁₀ and P ₁₀ is 3.0% or less,
In the adhesive layer of the ultra-thin copper layer with the insulating substrate, it is a copper foil with a carrier satisfying a roughness Rz of 1.5 μm or less measured with a contact type roughness meter in accordance with JIS B0601-1994.

  In another aspect of the present invention, by treating the surface of a long carrier conveyed in the length direction by a roll-to-roll conveyance method, the carrier, a release layer laminated on the carrier, A method of manufacturing a carrier-attached copper foil comprising an ultrathin copper layer laminated on a release layer, a step of forming a release layer on the surface of a carrier conveyed by a conveyance roll, and a conveyance roll And a step of forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the carrier on which the release layer is formed with a drum.

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

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier with favorable adhesive force with an insulated substrate and favorable etching property can be provided.

It is a schematic diagram which shows the conventional ninety-fold folding method. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 2 of this invention. It is a schematic diagram which shows the conveyance method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 3 of this invention. It is the schematic of the cross section of the width direction of the circuit pattern in an Example, and the outline of the calculation method of the etching factor (EF) using this schematic diagram.

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

<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 drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

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

<Peeling layer>
A release layer is provided on one or both sides of the carrier. While the copper foil with a carrier is difficult to peel off the ultrathin copper layer from the carrier before the lamination step on the insulating substrate, it is preferable that the ultrathin copper layer can be peeled off from the carrier after the lamination step onto the insulating substrate. Therefore, the release layer is formed by laminating any one layer of nickel or an alloy containing nickel on the carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. Here, the alloy containing nickel includes nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel is an alloy made of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. It is preferable that The alloy containing nickel may be an alloy composed of three or more elements. A chromium alloy is an alloy containing chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy is an alloy made of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. It is preferable. The chromium alloy may be an alloy composed of three or more elements. Further, the peeling layer may be formed by stacking a nickel layer or an alloy layer containing nickel on a carrier and a layer containing any one or more of molybdenum, cobalt, molybdenum cobalt alloy, and molybdenum nickel alloy in this order. Good. The release layer may contain zinc. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be 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 pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.
The release layer is formed on the carrier by any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy, nickel-molybdenum alloy, zinc chromate treatment layer, pure chromate treatment layer, chromium It is preferable that any one of the plating layers is laminated in this order, and the peeling layer includes a nickel layer or an alloy layer containing nickel on the carrier, and at least a nitrogen-containing organic compound and a sulfur-containing layer. It is preferable that the organic layer containing either an organic compound or a carboxylic acid is laminated in that order. Further, the release layer is formed by laminating an organic layer containing at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer or an alloy layer containing nickel on the carrier. Is preferred. Since the adhesive force between nickel and copper is higher than the adhesive force between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and the chromate treatment layer. In addition, the nickel in the release layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Further, it is preferable to form a chromate treatment layer on the release layer instead of chrome plating. Since chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper layer is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of an ultrathin copper layer by electroplating is less likely and pinholes can be reduced. it can. Here, by forming a zinc chromate treatment layer as the chromate treatment layer, the resistance when forming an ultrathin copper layer by electroplating becomes lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to.

The organic material is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm. The release 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.

<Organic thickness of release layer>
After the ultrathin copper layer of the carrier-attached copper foil is peeled from the carrier, the depth profile is created by XPS measurement of the surface of the exposed ultrathin copper layer on the peeling layer side and the surface of the exposed carrier on the peeling layer side. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the peeling 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 peeling 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 release layer.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieved vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (SiO ₂ conversion)

  The method for using the organic substance contained in the release layer will be described below with reference to the method for forming the release layer on the carrier foil. The release layer is formed on the carrier by dissolving the above-described organic substance in a solvent and immersing the carrier in the solvent, or showering, spraying, dropping method and electrodeposition method on the surface on which the release 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. Note that the organic substance thickness of the release layer tends to increase as the concentration of the organic substance is higher and as the contact time of the carrier with the solvent in which the organic substance is dissolved is longer. And when the organic substance thickness of a peeling layer is thick, it exists in the tendency for the effect of organic substance to suppress the spreading | diffusion to the ultra-thin copper layer side of Ni.

  Also, if the carrier transport speed (line speed) at the time of forming the release layer is slowed and / or the current density in the plating process is lowered, the density of the nickel layer or alloy layer containing nickel and the density of organic matter tend to increase. is there. When the density of the nickel layer or the alloy layer containing nickel and the density of the organic matter increase, the nickel in the nickel layer or the alloy layer containing nickel becomes difficult to diffuse, and after peeling, after the desmear treatment under a predetermined condition, it is extremely thin. The amount of Ni on the surface of the copper layer can be controlled.

  In addition, the peeling layer is preferably formed by stacking nickel and molybdenum, cobalt, a molybdenum-cobalt alloy, or a molybdenum-nickel 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 ultrathin copper layer and molybdenum or cobalt or molybdenum-cobalt alloy or molybdenum-nickel It peels at the interface with the alloy. In addition, the nickel in the release layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer.

  The molybdenum described above may be an alloy containing molybdenum. Here, the alloy containing molybdenum includes molybdenum and one or more elements selected from the group consisting of cobalt, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Refers to the alloy containing. The alloy containing molybdenum is an alloy composed of molybdenum and one or more elements selected from the group consisting of cobalt, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. There may be. The cobalt described above may be an alloy containing cobalt. Here, the alloy containing cobalt includes cobalt and one or more elements selected from the group consisting of molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Refers to the alloy containing. The alloy containing cobalt is an alloy composed of cobalt and one or more elements selected from the group consisting of molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. It may be.

  Molybdenum-cobalt alloy is an element other than molybdenum and cobalt (for example, one or more elements selected from the group consisting of nickel, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium). May be included.

  Molybdenum or cobalt or molybdenum-cobalt alloy layer or molybdenum-nickel alloy layer must be thin at the interface of the ultrathin copper layer, but the ultrathin copper layer is peeled off from the carrier before the lamination process to the insulating substrate. On the other hand, it is preferable for obtaining the characteristic that the ultra-thin copper layer can be peeled off from the carrier after the stacking process on the insulating substrate. If a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer, the peelability may be hardly improved, and the molybdenum or cobalt or molybdenum-cobalt alloy layer Or when there is no molybdenum-nickel alloy layer and a nickel layer and an ultra-thin copper layer are laminated directly, the peel strength may be too strong or too weak depending on the amount of nickel in the nickel layer, and an appropriate peel strength may not be obtained. is there.

  In addition, if the molybdenum, cobalt, molybdenum-cobalt alloy layer or molybdenum-nickel alloy layer is present at the boundary between the carrier and the nickel layer, the peeling layer may also be peeled off when the ultrathin copper layer is peeled off, that is, Since peeling occurs between the carrier and the peeling layer, it may not be preferable. Such a situation is not only when the molybdenum or cobalt or molybdenum-cobalt alloy layer or molybdenum-nickel alloy layer is provided at the interface with the carrier, but also with molybdenum or cobalt or molybdenum-cobalt alloy at the interface with the ultrathin copper layer. Even if a layer or a molybdenum-nickel alloy layer is provided, it may occur if the amount of molybdenum or cobalt is too large. This is because copper and nickel are likely to be in solid solution, so if they are in contact with each other, the adhesive force increases due to mutual diffusion and it is difficult to peel off, while molybdenum or cobalt and copper are less likely to dissolve and mutual diffusion. This is considered to be because the adhesive force is weak at the interface between the molybdenum or cobalt or molybdenum-cobalt alloy layer and copper and is easily peeled off. In addition, when the amount of nickel in the release layer is insufficient, there is only a small amount of molybdenum or cobalt between the carrier and the ultrathin copper layer, so that both may be in close contact and difficult to peel off.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the release layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 2-5 μm. For this reason, the adhesion layer of the ultra-thin copper layer with the insulating substrate includes Ni, Mo, Ti, Zn, Co, V, Sn, Mn, W, P, Fe and Cr alone, or Ni, Mo, Ti, It is preferable that an alloy, oxide, or hydrated oxide containing at least one of Zn, Co, V, Sn, Mn, W, P, Fe, and Cr is present. In addition, an intermediate layer made of a simple metal or alloy, and a simple metal or oxide of Cr, or an oxide or hydrated oxide, laminated in order from the surface of the ultra-thin copper layer on the adhesive layer with the ultra-thin copper layer insulating substrate The surface layer has a Cr deposition amount of 10 to 200 μg / dm ² , and the intermediate layer has Ni, Mo, Ti, Zn, Co, V, Sn, Mn, W, P, Fe, and Cr. The structure containing at least any one of these may be sufficient. Moreover, you may perform the process of forming a contact bonding layer with an ultra-thin copper layer insulation board | substrate by forming a surface treatment layer in the ultra-thin copper layer surface by dry plating. The adhesive layer may be composed of an intermediate layer on the surface of the ultrathin copper layer and an outermost layer on the intermediate layer.

The copper foil with a carrier according to the present invention has a roughness Rz measured in accordance with JIS B0601-1994 with a contact-type roughness meter in an adhesive layer with an ultrathin copper layer insulating substrate satisfying 1.5 μm or less. According to such a configuration, the adhesive force with the insulating substrate is good. The roughness Rz can be controlled by adjusting the surface roughness of the carrier and the formation conditions of the release layer, the ultrathin copper layer, and the adhesive layer.
The roughness Rz is preferably 1.0 μm or less, and more preferably 0.5 μm or less.

  The copper foil with a carrier according to the present invention can be manufactured by the carrying foil system shown in the following embodiments. FIG. 2 is a schematic diagram illustrating a foil handling method according to the method of manufacturing the copper foil with a carrier according to the first embodiment of the present invention. The manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention treats the surface of the elongate carrier conveyed in a length direction by a roll-to-roll conveyance system, a carrier, and on a carrier It is the method of manufacturing copper foil with a carrier provided with the peeling layer laminated | stacked on and the ultra-thin copper layer laminated | stacked on the peeling layer. The method for producing a copper foil with a carrier according to Embodiment 1 of the present invention includes a step of forming an ultrathin copper layer on the surface of the carrier by electrolytic plating while supporting the carrier conveyed by a conveyance roll with a drum, and a release layer. The process of forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the formed carrier with a drum, and the opposite side of the release layer of the ultrathin copper layer by electrolytic plating while supporting the carrier with a drum Forming an adhesive layer with an insulating substrate on the surface. In each step, the treatment surface of the carrier supported by the drum also serves as the cathode, and each electrolytic plating is performed in a plating solution between this drum and an anode provided so as to face the drum.

  In the present invention, in order to convey a long carrier by a roll-to-roll conveyance method, the carrier is conveyed while applying tension in the length direction of the carrier. The tension can be adjusted by applying torque by connecting each transport roll to a drive motor or the like. The carrier transport tension is preferably 0.01 to 0.2 kg / mm. When the conveyance tension is less than 0.01 kg / mm, the adhesion with the drum is weak, and it is difficult to form each layer in a desired thickness. Moreover, although it depends on the structure of the apparatus, problems such as slip are likely to occur, and further, winding of the carrier becomes loose, and problems such as winding slip are likely to occur. On the other hand, if the conveyance tension exceeds 0.2 kg / mm, wrinkles are likely to occur even if the carrier is slightly displaced, which is not preferable from the viewpoint of device management. In addition, the winding is hard, and winding wrinkles are likely to occur. The carrier transport tension is more preferably 0.02 to 0.1 kg / mm.

  In Embodiment 1, the release layer and the ultrathin copper layer are both formed by electrolytic plating while supporting the carrier with a drum, but the present invention is not limited to this. For example, as Embodiment 2, as shown in FIG. 3, the ultrathin copper layer may be formed by electrolytic plating using a ninety-fold folding method that does not support a conventional carrier by a drum. . As Embodiment 3, as shown in FIG. 4, the release layer may be formed by electroplating using a ninety-fold folding method that does not support a conventional carrier by a drum. However, since Embodiments 2 and 3 do not carry out all the steps by a foil carrying method using a drum as in Embodiment 1, compared with Embodiment 1, the distance between electrodes at the time of electrolytic plating is made constant. The thickness accuracy of the release layer and / or ultrathin copper layer is poor. In the case of electrolytic plating using the foil handling method by 99-fold, shorten the distance between the transport rolls, prevent the foil from shaking using a guide roll, etc. By making it double, the plate-thickness accuracy can be improved by stabilizing the distance between the anode and the cathode in electrolytic plating.

  In the present invention, as described above, the distance between the anode and the cathode in the electrolytic plating is stabilized by supporting the carrier with the drum. For this reason, the variation in the thickness of the layer to form is suppressed favorably, and it becomes possible to produce a copper foil with a carrier having an extremely thin copper layer with high thickness accuracy.

The copper foil with a carrier produced in this way is a 10 cm square sheet in an ultrathin copper layer, when the weight thickness measured value calculated by the weight thickness method is W ₁₀ and the standard deviation is σ _10. Thickness accuracy: When P ₁₀ = 3σ ₁₀ × 100 / W ₁₀ , P ₁₀ is 3.0% or less, and the thickness accuracy is very good. The lower limit is not particularly limited, but is, for example, 0.05% or more, 0.1% or more, or 0.2% or more.
Here, a method for measuring thickness accuracy by the weight-thickness method will be described. First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The ultrathin copper layer piece to be measured is a 10 cm square sheet punched out by a press. In order to investigate the weight-thickness accuracy, the average value W of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) for each level. _{10 and the} standard deviation σ ₁₀ are obtained. The formula for calculating the weight thickness accuracy is as follows.
Thickness accuracy P ₁₀ (%) = 3σ ₁₀ × 100 / W ₁₀
The repeatability of this measurement method is 0.2%.

The thus prepared copper foil with a carrier, in the ultra-thin copper layer, as 5cm square sheet, and the average value of the weight measured thickness value calculated by the weight thickness Method and W _3, the standard deviation was sigma ₅ Thickness accuracy when: When P ₅ = 3σ ₅ × 100 / W ₅ , it is preferable that P ₅ is 3.0% or less. The lower limit is not particularly limited, but is, for example, 0.05% or more, 0.2% or more, 0.7% or more, or 1.0% or more.
Here, a method for measuring thickness accuracy by the weight-thickness method will be described. First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer is peeled off, the weight of the carrier is measured again, and the difference between the former and the latter is defined as the weight of the ultrathin copper layer. The ultrathin copper layer piece to be measured is a 5 cm square sheet beaten with a press. In order to investigate the weight-thickness accuracy, the average value W of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) for each level. _{5 and the} standard deviation σ ₅ are obtained. The formula for calculating the weight thickness accuracy is as follows.
Thickness accuracy P ₅ (%) = 3σ ₅ × 100 / W ₅
The repeatability of this measurement method is 0.2%.

Moreover, the copper foil with a carrier produced in this way has a thickness accuracy when the average thickness measured by the four-probe method is T and the standard deviation is σ _{T in the} ultrathin copper layer: P _T = When 3σ _T × 100 / T, _PT is preferably 10.0% or less. The thickness accuracy _PT can also be obtained by the four-probe method. That is, first, after determining the thickness of the copper foil with carrier by measuring the thickness resistance with four probes, peel off the ultra-thin copper layer, again measure the thickness due to the thickness resistance of the carrier, the former and the latter Is defined as the thickness of the ultrathin copper layer. In order to investigate the thickness accuracy, measurements were made at intervals of 5 mm in the width direction for each level, and the average value T and standard deviation σ _T of the total 280 measurement points were obtained, and the thickness accuracy: P _T = 3σ _T × 100 / T is calculated. The 280 measurement points need not be collected in one row, and may be collected over a plurality of rows according to the width of the copper foil with a carrier.

  Also, a carrier-attached copper foil comprising a carrier and a peeling layer laminated on the carrier, and an ultra-thin copper layer laminated on the peeling layer is formed on the ultra-thin copper layer with a heat-resistant layer and a rust-proof layer. One or more surface treatment layers selected from the group consisting of a chromate treatment layer and a silane coupling treatment layer 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 is performed on the heat resistance layer and the rust prevention layer. A layer may be provided, and 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 insulating resin layer.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, and the like can be preferably used. .

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

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

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

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

  The thickness of the resin layer is preferably 0.1 to 80 μm.

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

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

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

  A printed circuit board is completed by mounting electronic components on the printed wiring board. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As the carrier, a long electrolytic copper foil having a thickness of 18 μm (JTC manufactured by JX Nippon Mining & Metals) was used. With respect to the shiny surface of the copper foil, each of the peeling layer and the ultrathin copper layer shown in Tables 1 to 3 was formed under the following conditions on a roll-to-roll-type continuous line under the following conditions. Here, Examples 1-3, 11-12, and Comparative Example 2 were produced by the method according to Embodiment 3 shown in FIG. 4 described above, and Examples 4-10, 13 and Comparative Examples 3-4. Is manufactured by the method according to the first embodiment shown in FIG. Further, Comparative Example 1 is manufactured by the conventional method shown in FIG. Moreover, Comparative Examples 5-6 are produced by the method according to Embodiment 2 shown in FIG.

(Peeling layer formation)
(A) Foil system by 99-fold ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treatment surface ・ Distance between electrodes (shown in Tables 1 and 3)
Electrolytic plating solution composition (NiSO ₄ : 100 to 300 g / L)
Electrolytic plating solution pH: 1.5 to 3.5
-Electroplating bath temperature: 40-60 ° C
-Current density of electroplating: 0.5 to 10 A / dm ²
-Electroplating time: 3-15 seconds-Copper foil carrier transport tension: 0.05 kg / mm
(B) Drum carrying method by drum ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes (shown in Tables 1 and 3)
Electrolytic plating solution composition (NiSO ₄ : 100 to 300 g / L)
Electrolytic plating solution pH: 1.5 to 3.5
-Electroplating bath temperature: 40-60 ° C
-Current density of electroplating: 0.5 to 10 A / dm ²
-Electroplating time: 3-15 seconds-Copper foil carrier transport tension: 0.05 kg / mm

(Ultra-thin copper layer formation)
(A) Foil system by 99-fold ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier treatment surface ・ Distance between electrodes (shown in Tables 1 and 3)
Electrolytic plating solution composition (Cu: 30 to 120 g / L, H ₂ SO ₄ : 30 to 100 g / L, Cl: 20 to 70 ppm)
-Electroplating bath temperature: 40-65 ° C
-Current density of electrolytic plating: 10 to 70 A / dm ²
-Copper foil carrier transport tension: 0.05 kg / mm
(B) Drum carrying method by drum ・ Anode: Insoluble electrode ・ Cathode: Copper foil carrier surface supported by drum of 100 cm in diameter ・ Distance between electrodes (shown in Tables 1 and 3)
Electrolytic plating solution composition (Cu: 30 to 120 g / L, H ₂ SO ₄ : 30 to 100 g / L, Cl: 20 to 70 ppm)
-Electroplating bath temperature: 40-65 ° C
-Current density of electrolytic plating: 10 to 70 A / dm ²
-Copper foil carrier transport tension: 0.05 kg / mm

  The release layer was formed according to the processing order described in the item “Peel layer formation method” in Tables 1 and 3. That is, for example, what is described as “Ni—Zn / pure chromate” indicates that “Ni—Zn” is first processed and then “pure chromate” is processed. In addition, in the item of “peeling layer forming method”, “Ni” means that pure nickel plating is performed, and “Ni—Zn” means that nickel zinc alloy plating is performed. "Pure chromate" means that pure chromate treatment was performed, and "Ni-Mo" means that nickel-molybdenum alloy plating was performed And “Mo—Co” means that molybdenum cobalt alloy plating was performed, and “zinc chromate” means that zinc chromate treatment was performed. “BTA treatment” means that the surface treatment was performed using benzotriazole, and “MBT treatment” means that mercaptobenzotriazole was used. Meaning that was subjected to a surface treatment. Each processing condition is shown below. In addition, when increasing the adhesion amount of each metal, set the current density higher and / or set the plating time longer and / or increase the concentration of each element in the plating solution. I did that. Also, when reducing the amount of each metal attached, set the current density low and / or set the plating time short and / or reduce the concentration of each element in the plating solution. I did that. The balance of the liquid composition such as a plating solution is water.

"Ni": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, luster Agents: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 4-6
(Liquid temperature) 55-65 degreeC
(Current density) 1 to 11 A / dm ²
(Energization time) 1 to 20 seconds

"Ni-Zn": Nickel zinc alloy plating In the above nickel plating formation conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the nickel plating solution, and the zinc concentration is in the range of 0.05 to 5 g / L. Adjusted to form a nickel zinc alloy plating.

"Ni-Mo": Nickel molybdenum alloy plating In the above nickel plating formation conditions, molybdenum in the form of sodium molybdate is added to the nickel plating solution, and the molybdenum concentration is adjusted in the range of 0.1 to 10 g / L. Nickel molybdenum alloy plating was formed.

"Pure chromate": Pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 2-4, 7-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

-"Zinc chromate": Zinc chromate treatment In the above electrolytic pure chromate treatment conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the solution, and the zinc concentration is adjusted in the range of 0.05 to 5 g / L. Chromate treatment was performed.

-BTA treatment: Surface treatment using benzotriazole (Liquid composition) Benzotriazole: 0.1 to 20 g / L
(PH) 2-5
(Liquid temperature) 20-40 ° C
(Immersion time) 5-30s

MBT treatment: surface treatment using mercaptobenzothiazole (Liquid composition) 2-mercaptobenzothiazole sodium: 0.1 to 20 g / L
(PH) 7-10
(Liquid temperature) 40-60 ° C
(Voltage) 1-5V
(Energization time) 1 to 30 seconds

"Mo-Co": Molybdenum cobalt alloy plating (Liquid composition) Cobalt sulfate: 10-200 g / L, Sodium molybdate: 5-200 g / L, Sodium citrate: 2-240 g / L
(PH) 2-5
(Liquid temperature) 10-70 ° C
(Current density) 0.5 to 10 A / dm ²
(Energization time) 1 to 20 seconds

  Moreover, formation of the layer (adhesive layer) on the surface opposite to the peeling layer of the ultrathin copper layer was performed according to the processing order described in the item “Adhesive layer forming method” in Tables 1 and 3. Each processing condition is shown below.

"Sputtering Ni": Ni plating by sputtering Ni: A nickel layer was formed using a sputtering target having a composition of 99 mass%.
Target: Ni: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

-"Sputtering Cr": Cr plating by sputtering Cr: A chromium layer was formed using a sputtering target having a composition of 99 mass%.
Target: Cr: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

“Sputtered Ti”: Ti plating by sputtering Ti: A Ti layer was formed using a sputtering target having a composition of 99 mass%.
Target: Ti: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Sputtered Mo": Mo plating by sputtering Mo: A Mo layer was formed using a sputtering target having a composition of 99 mass%.
Target: Mo: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Sputtered Ni-V": Ni-V plating by sputtering Ni-V: A Ni-V layer was formed using a sputtering target having a composition of 99 mass%.
Target: Ni: 92 mass%-V: 7 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

“Sputtered Ni—Mn”: Ni—Mn plating by sputtering Ni—Mn: A Ni—V layer was formed using a sputtering target having a composition of 99 mass%.
Target: Ni: 79 mass% -Mn: 20 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Ni": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, luster Agents: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 2-5
(Liquid temperature) 55-65 degreeC
(Current density) 1 to 11 A / dm ²
(Energization time) 1 to 20 seconds

- "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

-"Zinc chromate": Zinc chromate treatment In the above electrolytic pure chromate treatment conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the solution, and the zinc concentration is adjusted in the range of 0.05 to 5 g / L. Chromate treatment was performed.

"Pure chromate": Pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 2-4, 7-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

"Ni-Co": nickel cobalt alloy plating In the above nickel plating formation conditions, cobalt in the form of cobalt sulfate was added to the nickel plating solution, and the cobalt concentration was adjusted in the range of 0.1 to 10 g / L. Nickel cobalt alloy plating was formed.

"Ni-Mo": Nickel molybdenum alloy plating In the above nickel plating formation conditions, molybdenum in the form of sodium molybdate is added to the nickel plating solution, and the molybdenum concentration is adjusted in the range of 0.1 to 10 g / L. Nickel molybdenum alloy plating was formed.

"Ni-Zn": Nickel zinc alloy plating In the above nickel plating formation conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the nickel plating solution, and the zinc concentration is in the range of 0.05 to 5 g / L. Adjusted to form a nickel zinc alloy plating.

-"Ni-Sn": Nickel tin alloy plating In the above nickel plating formation conditions, tin in the form of sodium stannate is added to the nickel plating solution, and the tin concentration is adjusted in the range of 0.1 to 10 g / L. Nickel tin alloy plating was formed.

"Ni-W": Nickel tungsten alloy plating In the above nickel plating formation conditions, add tungsten in the form of sodium tungstate to the nickel plating solution, and adjust the tungsten concentration in the range of 0.1 to 10 g / L. Nickel tungsten alloy plating was formed.

"Ni-Fe": Nickel-iron alloy plating In the above nickel plating formation conditions, iron is added in the form of iron sulfate in the nickel plating solution, and the iron concentration is adjusted within the range of 0.1 to 10 g / L. Nickel iron alloy plating was formed.

"Ni-P": Nickel phosphorus alloy plating In the above nickel plating formation conditions, phosphorus is added in the form of phosphonic acid in the nickel plating solution, and the phosphorus concentration is adjusted in the range of 0.1 to 10 g / L. Nickel phosphorus alloy plating was formed.

・ Roughening treatment
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
Zn: 0 to 20 g / L
pH: 1-4
Temperature: 40-50 ° C
Current density Dk: 20 to 50 A / dm ²
Time: 1-10 seconds, chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5 A / dm ²
Time: 5-30 seconds

  Each evaluation was implemented with the following method about the copper foil with a carrier of the Example and comparative example which were obtained as mentioned above.

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

<Metal adhesion amount of adhesive layer>
The amount of nickel deposited was measured by ICP emission analysis after dissolving the sample in nitric acid with a concentration of 20% by mass. The amount of molybdenum deposited was measured by concentration of molybdenum, titanium, zinc, cobalt, vanadium, tin, manganese, tungsten, phosphorus, iron and chromium. It was measured by dissolving in 7% by mass hydrochloric acid and performing quantitative analysis by atomic absorption method.

<Evaluation of thickness accuracy by weight thickness method A>
First, after measuring the weight of the copper foil with a carrier, the ultrathin copper layer was peeled off, the weight of the carrier was measured again, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. The ultra-thin copper layer piece to be measured was a 5 cm square sheet punched out with a press. In order to investigate the weight-thickness accuracy, the average value of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) A standard deviation (σ ₅ ) was determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = 3σ ₅ × 100 / weight Average value of thickness measurement values The repeatability of this measurement method was 0.2%.
Moreover, HF-400 by A & D Co., Ltd. was used for the weight scale, and HAP-12 by Noguchi Press Co., Ltd. was used for the press machine.

<Evaluation B of thickness accuracy by weight-thickness method>
First, after measuring the weight of the copper foil with a carrier, the ultrathin copper layer was peeled off, the weight of the carrier was measured again, and the difference between the former and the latter was defined as the weight of the ultrathin copper layer. The ultra-thin copper layer piece to be measured was a 10 cm square sheet punched out with a press. In order to investigate the weight-thickness accuracy, the average value of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) A standard deviation (σ ₁₀ ) was determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = 3σ ₁₀ × 100 / weight Average value of measured thickness values The repeatability of this measurement method was 0.2%.
Moreover, HF-400 made from A & D Co., Ltd. was used for the weight scale, and HAP-12 made by Noropress Co., Ltd. was used for the press machine.

<Evaluation of thickness accuracy by four-point probe method>
After obtaining the thickness of the copper foil with a carrier by measuring the thickness resistance with a four-point probe, peel off the ultrathin copper layer, measure the thickness due to the thickness resistance of the carrier again, and determine the difference between the former and the latter. It was defined as the thickness of the ultrathin copper layer. In order to investigate the thickness accuracy, an average value and a standard deviation (σ _T ) of a total of 280 measurement points at intervals of 5 mm in the width direction were obtained for each level. The formula for calculating the thickness accuracy by the four-probe is as follows.
Thickness accuracy (%) = 3σ _T × 100 / average value The repeatability of this measurement method was 1.0%.
In addition, CMI-700 manufactured by OXFORD INSTRUMENTS was used as the four probes.

<Etching property>
A copper foil with a carrier was attached to a polyimide substrate and heat-pressed at 220 ° C. for 2 hours, and then the ultrathin copper layer was peeled off from the carrier. Subsequently, after applying a photosensitive resist to the surface of the ultra-thin copper layer on the polyimide substrate, 50 L / S = 5 μm / 5 μm wide circuits are printed by an exposure process to remove unnecessary portions of the copper layer. The etching process was performed under the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, the time until the circuit top width reached 4 μm was measured, and the circuit bottom width (the length of the base X) and the etching factor at that time were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 5 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. The etching factor is obtained by measuring 12 points in the circuit and taking an average value. Thereby, the quality of etching property can be determined easily. Also, by calculating the standard deviation of the 12 etching factors, it is possible to determine whether the linearity of the circuit formed by etching is good or bad.
In the present invention, an etching factor of 5 or more is etching property: ◯, 2.5 or more and less than 5 is etching property: Δ, less than 2.5 or calculation is impossible or circuit formation is impossible. -. Moreover, it can be said that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. When the standard deviation of the etching factor was less than 0.5, the linearity was evaluated as ◯, when 0.5 to less than 1.0 was determined as the linearity: Δ, and 1.0 or more was determined as the linearity: x. Moreover, the etching property was similarly measured about each sample before thermocompression bonding with the said resin.

<Surface roughness>
A straight line was drawn vertically and horizontally at a pitch of 55 mm from each copper foil with a carrier (550 mm × 550 mm square), and 100 square regions of 55 mm × 55 mm were assigned to each. In accordance with JIS B0601-1994 in accordance with JIS B0601-1994, a contact type roughness measuring machine (contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory Ltd.) is used for each region. The surface roughness (Rz) of the ultrathin copper layer was measured under the measurement conditions, and the average value was obtained.
(Measurement condition)
Cut-off: 0.25mm
Standard length: 0.8mm
Measurement ambient temperature: 23-25 ° C

<Peel strength>
After bonding the adhesive layer with the insulating substrate of the copper foil with carrier to GHPL-830MBT (product name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under the conditions of 20 kgf / cm ² and 220 ° C. × 2 hours, Build-up was performed by copper plating until the thickness of the ultrathin copper layer was 12 μm. The ultrathin copper layer built up by the load cell was pulled and measured according to the 90 ° peeling method (JIS C 6471 8.1).
Test conditions and test results are shown in Tables 1-3.

(Evaluation results)
Examples 1-13, the thickness accuracy were all calculated by weight Thickness Method: P ₁₀ is 3.0% or less, the surface opposite the release layer of the ultra-thin copper layer, JIS in contact roughness meter Since the roughness Rz measured in accordance with B0601-1994 was 1.5 μm or less, the adhesiveness and the etching property were good.
In Comparative Examples 1 and 5, since the foil thickness accuracy of the ultrathin copper layer was poor, the linearity of the circuit deteriorated.
In Comparative Example 2, since the Rz on the surface of the ultrathin copper layer was large, the etching factor was small and the linearity of the circuit was poor.
In Comparative Example 3, since the adhesion amount of the adhesive surface intermediate layer was large, the linearity of the circuit was deteriorated.
In Comparative Example 4, the amount of Cr adhering to the adhesion surface was large, so that the linearity of the circuit deteriorated.
In Comparative Example 6, since there was no treatment of the adhesive surface, the peel strength between the ultrathin copper layer and the insulating substrate was weak.

Claims (12)

A carrier-attached copper foil comprising a carrier, a release layer laminated on the carrier, an ultrathin copper layer laminated on the release layer, and an adhesive layer between the insulating substrate laminated on the ultrathin copper layer There,
The ultrathin copper layer is a 10 cm square sheet, and the thickness accuracy when the average thickness measurement value calculated by the weight thickness method is W ₁₀ and the standard deviation is σ ₁₀ : P ₁₀ = 3σ ₁₀ × 100 / W when I was _10, not more than P ₁₀ is 3.0%,
A copper foil with a carrier satisfying a roughness Rz of 1.5 μm or less measured with a contact-type roughness meter in accordance with JIS B0601-1994 in an adhesive layer with an insulating substrate of an ultrathin copper layer. The copper foil with a carrier of Claim 1 which satisfy | fills any one or more of the following (A) or (B).
(A) Thickness accuracy when the ultrathin copper layer is a 5 cm square sheet and the average value of weight thickness measurement values calculated by the weight thickness method is W ₅ and the standard deviation is σ ₅ : P ₅ = 3σ ₅ × When 100 / W ₅ is set, P ₅ is 3.0% or less.
(B) The thickness of the ultrathin copper layer measured by the four-probe method is T, and when the standard deviation is σ _T , the thickness accuracy is P _T = 3σ _T × 100 / T, P _T is 10.0% or less.   For the adhesive layer of the ultra-thin copper layer with the insulating substrate, Ni, Mo, Ti, Zn, Co, V, Sn, Mn, W, P, Fe and Cr alone, or Ni, Mo, Ti, Zn, The copper foil with a carrier according to claim 1 or 2, wherein an alloy containing at least one of Co, V, Sn, Mn, W, P, Fe, and Cr, or an oxide or a hydrated oxide is present. The adhesion layer of the ultrathin copper layer to the insulating substrate is an intermediate layer made of a single metal or an alloy, and a single metal of Cr, an oxide, or a hydrated oxide, which are laminated in order from the surface of the ultrathin copper layer. The surface layer is composed of 10 to 200 μg / dm ² of Cr.
The copper with a carrier according to any one of claims 1 to 3, wherein the intermediate layer includes at least one of Ni, Mo, Ti, Zn, Co, V, Sn, Mn, W, P, Fe, and Cr. Foil. The intermediate layer is composed of any one of Ni, Mo, Ti, Zn, and Co. The intermediate layer includes any one of Ni, Mo, Ti, Zn, and Co at 10 to 2000 μg / The copper foil with a carrier according to claim 4, wherein the copper foil is present in an amount of dm ² . The intermediate layer is composed of an alloy of at least any two of Ni, Mo, Zn, Co, V, Sn, Mn, W, P, and Fe, and the intermediate layer includes Ni, Mo, Zn, Co, The copper foil with a carrier according to claim 4, wherein any ^two of V, Sn, Mn, W, P, Fe and Cr are present in an adhesion amount of 10 to 2000 μg / dm ² .   The said intermediate | middle layer was comprised with Ni alloy which consists of Ni and any one of Mo, Zn, Co, V, Sn, Mn, W, P, Fe, Mn, and Cr. Copper foil with carrier. The copper foil with a carrier according to any one of claims 1 to 7, which satisfies any one of the following (C) to (E).
(C) The surface of the adhesive layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer.
(D) A resin layer is provided on the adhesive layer.
(E) The surface of the adhesive layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer, and the heat-resistant layer and the rust-proof layer A resin layer is provided on one or more layers selected from the group consisting of a layer, a chromate treatment layer, and a silane coupling treatment layer. By treating the surface of a long carrier conveyed in the length direction by the roll-to-roll conveyance method, the carrier, the release layer laminated on the carrier, and the ultrathin layer laminated on the release layer It is a method of manufacturing a copper foil with a carrier provided with a copper layer,
Forming a release layer on the surface of the carrier conveyed by the conveyance roll;
Forming an ultrathin copper layer on the surface of the release layer by electrolytic plating while supporting the carrier on which the release layer is transported by a transport roll with a drum;
The manufacturing method of the copper foil with a carrier in any one of Claims 1-8 containing these.   The method to manufacture a printed wiring board using the copper foil with a carrier in any one of Claims 1-8.   The method to manufacture a copper clad laminated board using the copper foil with a carrier in any one of Claims 1-8. Preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 8,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

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