JP2014208909A - Copper foil with a carrier, printed wiring board, copper-clad laminate, electronic apparatus and method for producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a carrier that allows good laser holing of ultra-thin copper layer and is suitable in the preparation of high density integrated circuit board.SOLUTION: A copper foil with a carrier comprising a carrier, an intermediate layer and an ultra-thin copper layer in this order, characterized in that when the copper foil with a carrier is heated at 220°C for 2 hours, followed by peeling off the ultra-thin copper layer in accordance with JIS C6471, the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured by a laser microscope is 0.62 μm or more and 1.59 μm or less and the standard deviation of the surface roughness Rz is 0.51 μm or less.

Description

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

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

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

  Here, for the surface of the ultrathin copper layer of the copper foil with a carrier that becomes the adhesive surface with the resin, the peel strength between the ultrathin copper layer and the resin base material is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like. As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.

  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 Will remain, causing problems such as poor insulation between circuit patterns.

  For this reason, in WO2004 / 005588 (Patent Document 1), a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. Therefore, the further improvement is calculated | required about copper foil with a carrier.

  Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-006071 (Patent Document 3), the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been. By providing these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultra-thin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.

WO2004 / 005588 JP 2007-007937 A JP 2010-006071 A Japanese Patent No. 3261119

  In the development of a copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the resin substrate. For this reason, a copper foil with a carrier suitable for high-density mounting of a printed wiring board has not yet been sufficiently studied, and there is still room for improvement.

  In order to increase the integrated circuit density of the printed wiring board, a method of forming a laser hole and connecting the inner layer and the outer layer through the hole is general. In addition, the fine circuit formation method accompanying the narrowing of the pitch is a method (MSAP: Modified-Semi) which forms a wiring circuit on an ultrathin copper layer and then etches and removes the ultrathin copper layer with a sulfuric acid-hydrogen peroxide etchant. -Additive-Process) is used, the laser holeability of the ultra-thin copper layer is an important item in fabricating high-density integrated circuit boards. The laser holeability of an ultra-thin copper layer greatly affects the design and productivity of integrated circuits because it relates to various conditions such as hole diameter accuracy and laser output. Japanese Patent No. 3261119 (Patent Document 4) describes a copper-clad laminate with good laser drillability, but according to the study of the present inventors, there is still room for improvement in terms of etching properties. is there.

  Accordingly, an object of the present invention is to provide a carrier-attached copper foil that has an excellent laser drillability of an ultrathin copper layer and is suitable for manufacturing a high-density integrated circuit board.

  In order to achieve the above object, the present inventor conducted extensive research and found that a laser microscope on the peeling side of the ultrathin copper layer when the ultrathin copper layer was peeled off from the copper foil with a carrier that had been subjected to a predetermined heat treatment. It was found that controlling the surface roughness measured by the method is extremely effective in improving the laser holeability of the ultrathin copper layer.

  The present invention has been completed on the basis of the above knowledge. In one aspect, the present invention is a copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order. When the ultra-thin copper layer is peeled off in accordance with JIS C 6471 after heating at ° C for 2 hours, the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured by a laser microscope is 0.62 μm. The copper foil with a carrier is 1.59 μm or less and the standard deviation of the surface roughness Rz is 0.51 μm or less.

  In one embodiment, the copper foil with carrier according to the present invention is measured with a laser microscope when the ultra thin copper layer is peeled off in accordance with JIS C 6471 after heating the copper foil with carrier at 220 ° C. for 2 hours. The surface roughness Rz of the ultrathin copper layer on the intermediate layer side is 0.70 μm or more and 1.52 μm or less.

  In another embodiment of the copper foil with a carrier according to the present invention, when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope The surface roughness Rz of the ultrathin copper layer measured on the intermediate layer side is 0.80 μm or more and 1.50 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-added copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. The surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with a microscope is 0.90 μm or more and 1.40 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-added copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. The surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with a microscope is 1.10 μm or more and 1.50 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-added copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. The standard deviation of the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with a microscope is 0.01 μm or more and 0.48 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-added copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. The standard deviation of the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with a microscope is 0.04 μm or more and 0.40 μm or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-added copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. The sharpness Sku of the surface height distribution on the intermediate layer side of the ultrathin copper layer measured with a microscope is 0.50 or more and 3.70 or less.

  In yet another embodiment, the carrier-attached copper foil according to the present invention is a laser, when the carrier-attached copper foil is heated at 220 ° C. for 2 hours, and then the ultrathin copper layer is peeled off according to JIS C 6471. The sharpness Sku of the surface height distribution on the intermediate layer side of the ultrathin copper layer measured with a microscope is 1.00 or more and 3.60 or less.

  In still another embodiment of the copper foil with a carrier according to the present invention, the carrier is formed of an electrolytic copper foil or a rolled copper foil.

  In another embodiment of the copper foil with a carrier according to the present invention, the thickness of the carrier is 5 to 70 μm.

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

  In still another embodiment of the copper foil with a carrier according to the present invention, the roughening treatment layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is the layer which consists of an alloy containing any one simple substance or any 1 type or more.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. Has more than seed layers.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. Has more than seed layers.

  In yet another embodiment, the carrier-attached copper foil according to the present invention comprises a resin layer on the ultrathin copper layer.

  In yet another embodiment, the copper foil with a carrier according to the present invention includes a resin layer on the roughening treatment layer.

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

  In yet another embodiment of the copper foil with a carrier according to the present invention, the resin layer is an adhesive resin.

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

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

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

  In 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.

  ADVANTAGE OF THE INVENTION According to this invention, the copper hole with a carrier suitable for preparation of the high-density integrated circuit board | substrate with the favorable laser drillability of an ultra-thin copper layer can be provided.

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

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

  The copper foil with a carrier of the present invention is an ultrathin copper layer measured with a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then peeled off in accordance with JIS C 6471. The surface roughness Rz (ten-point average roughness) on the intermediate layer side is controlled to be 0.62 μm or more and 1.59 μm or less. A carrier-attached copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and an ultrathin copper layer bonded to the insulating substrate is etched into a target conductor pattern to form a circuit. In this way, a printed wiring board is produced with a multi-layered substrate. Here, in order to increase the integrated circuit density of such a printed wiring board, a laser hole is formed, and the inner layer and the outer layer are connected through the hole. At this time, it is of course a problem that it is difficult to make a laser hole in an ultra-thin copper layer, and it is necessary to form the laser hole to an appropriate size to cause various problems even if it is too large or too small. There is. As described above, the laser holeability of the ultrathin copper layer is an important characteristic that greatly affects the design and productivity of the integrated circuit because it relates to various conditions such as hole diameter accuracy and laser output. In the present invention, the laser piercing property of this ultra-thin copper layer is measured with a laser microscope when the copper foil with carrier is heated at 220 ° C. for 2 hours and then peeled off in accordance with JIS C 6471. It has been found that the surface roughness Rz on the intermediate layer side of the ultrathin copper layer to be measured is improved by controlling it to 0.62 μm or more and 1.59 μm or less. If the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope is less than 0.62 μm, the surface roughness of the ultra-thin copper layer is insufficient and the laser in the drilling process Absorbability deteriorates, making it difficult to make a hole, and even if it is made a problem, it becomes a small hole. Moreover, when the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured by the laser microscope exceeds 1.59 μm, the surface roughness of the ultrathin copper layer is too large, and the laser during the drilling process As a result, there is a problem that the absorbability of water becomes excessive and the hole becomes too large. The surface roughness Rz of the ultrathin copper layer measured by the laser microscope is preferably 0.70 μm or more and 1.52 μm or less, more preferably 0.80 μm or more and 1.50 μm or less, and 0.90 μm or more and 1 More preferably, it is 40 μm or less. The surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is more preferably 1.10 μm or more and 1.50 μm or less. The “heating at 220 ° C. for 2 hours” indicates a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.

  Moreover, the copper foil with a carrier of the present invention is the ultrathin film measured by a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled in accordance with JIS C 6471. The standard deviation of the surface roughness Rz on the intermediate layer side of the copper layer is controlled to be 0.51 μm or less. When the standard deviation of the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope exceeds 0.51 μm, the variation of the laser hole diameter becomes large (that is, the standard deviation becomes large) or etching. There arises a problem that the variation of the factor becomes large (that is, the standard deviation becomes large). Further, the standard deviation of the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is preferably 0.01 μm or more and 0.48 μm or less, and 0.04 μm or more and 0.40 μm or less. More preferably, it is 0.04 μm or more and 0.35 μm or less, and more preferably 0.05 μm or more and 0.20 μm or less.

  Moreover, the copper foil with a carrier of the present invention is an ultrathin copper measured by a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471. It is preferable that the degree of sharpness Sku (Cultosis) of the surface height distribution on the intermediate layer side of the layer is controlled to 0.50 or more and 3.70 or less. If the Sku is less than 0.50, the shape of the convex part on the surface of the ultra-thin copper layer will be flat, so that the laser absorbability during drilling will be poor and it will be difficult to drill holes. There is a possibility that the problem of becoming a small hole may occur. On the other hand, when it is larger than 3.70, the unevenness on the surface of the ultrathin copper layer has a sharp shape, the laser energy is absorbed locally, and the actual hole size is smaller than the laser irradiation diameter. There is a possibility that the problem of increasing will occur. The copper foil with a carrier of the present invention is an ultrathin copper layer measured with a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then peeled off in accordance with JIS C 6471. The sharpness Sku of the surface height distribution on the intermediate layer side is more preferably controlled to 1.00 or more and 3.60 or less, and even more preferably controlled to 1.50 or more and 3.30 or less, More preferably, it is controlled to 1.50 or more and 3.20 or less, more preferably 1.50 or more and 3.10 or less, and more preferably 1.50 or more and 3.00 or less. Even more preferably.

<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. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.
In addition, you may provide a roughening process layer in the surface on the opposite side to the surface in the side which provides the ultra-thin copper layer of a carrier. The said roughening process layer may be provided using a well-known method, and may be provided by the below-mentioned roughening process. Providing a roughened layer on the surface opposite to the surface on which the ultrathin copper layer of the carrier is provided, when laminating the carrier from the surface side having the roughened layer to a support such as a resin substrate, There is an advantage that the carrier and the resin substrate are hardly separated.

  The surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured by the laser microscope of the present invention can be controlled by adjusting the surface form of the ultrathin copper layer side of the carrier. Below, the manufacturing method of the carrier of this invention is demonstrated.

An example of manufacturing conditions when using electrolytic copper foil as a carrier is shown below.
<Electrolyte composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

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

  The surface roughness Rz on the intermediate layer side of the ultrathin copper layer and its standard deviation are controlled by adjusting the surface form of the carrier on the ultrathin copper layer side. Examples of the adjustment of the surface form of the carrier on the ultrathin copper layer side include the following adjustment methods (1) to (3). In addition, as shown in Table 2, the form of the ultrathin copper layer side surface of the carrier is close to the form of the carrier side ultrathin copper layer surface. Therefore, by adjusting the form of the surface of the carrier on the side of the ultrathin copper layer, an ultrathin copper foil with a carrier having the form of the surface of the desired carrier side ultrathin copper layer can be obtained.

(1) A soft etching process or a reverse electrolysis process is performed on a carrier having low roughness and high gloss.
Specifically, a soft etching treatment (for example, 5-15 vol% sulfuric acid, 0.1% hydrogen peroxide) is applied to a carrier having a surface roughness Rz of 0.2 μm to 0.6 μm and a 60 ° specular gloss of 500% or more. (Etching treatment for 0.5 to 10 minutes at 10 to 30 ° C. with an aqueous solution of 5 to 5.0 wt%) or reverse electrolysis treatment (treatment for forming unevenness by electrolytic polishing on the glossy surface).
The “reverse electropolishing” is electropolishing. In general, since electropolishing is intended for smoothing, if electropolishing is applied to an electrolytic copper foil, the normal idea is that the surface opposite to the glossy surface (rough surface) is the target. However, since the uneven surface is formed by electropolishing on the glossy surface here, the electropolishing process is the opposite of the normal one, that is, the reverse electropolishing process. The amount of copper dissolved by reverse electrolysis is ² to ²⁰ g / m ² . The current density of the reverse electrolytic polishing is a 0.5~50A / dm ^2.

(2) A carrier is manufactured by rolling with a rolling roll treated with sandblasting.
Specifically, a rolled copper foil is prepared as a carrier, and finish cold rolling is performed on the rolled copper foil using a rolling roll whose surface is roughened by sandblasting. At this time, rolling roll roughness Ra can be set to 0.39 to 0.42 μm, and an oil film equivalent of 29000 to 40000.
Here, the oil film equivalent is expressed by the following equation.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 29000 to 40000, a known method such as using highly viscous rolling oil or increasing the sheet passing speed may be used.

(3) A carrier is manufactured under predetermined electrolytic conditions.
Specifically, using a copper sulfate electrolyte (copper concentration: 80 to 120 g / L, sulfuric acid concentration 70 to 90 g / L), using a high concentration glue (Nikawa concentration: 3 to 10 mass ppm) as an additive, An electrolytic copper foil carrier is produced under conditions of high current density (75 to 110 A / dm ² ) and high linear flow rate (3.7 to 5.0 m / sec).

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

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

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

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

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

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

Further, the carrier-attached copper foil comprising a carrier and an ultra-thin copper layer laminated on the intermediate layer on the carrier comprises a roughening treatment layer on the ultra-thin copper layer. Alternatively, 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 provided on the roughening treatment layer.
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 may be a semi-cured (B stage) insulating resin layer 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, or the like can be given as a preferable one. .

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179722, 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.

  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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 2-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. 2B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 2C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 3D, an embedded 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. 3-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 3F, laser drilling is performed at a predetermined position of the resin layer to expose circuit plating and form a blind via.
Next, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 4-H, circuit plating is formed on the via fill as shown in FIGS. 2-B and 2-C.
Next, as shown to FIG. 4-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 5J, the ultrathin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 5K, 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. 4-H, and these circuits may be formed using a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  According to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, when removing the ultrathin copper layer by flash etching as shown in FIG. In addition, the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 5-J and 5-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

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

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

  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.

(Examples 1-9, 11 and Comparative Examples 1-6)
In the electrolytic cell, a titanium rotating drum and electrodes were arranged around the drum with a distance between the electrodes. Next, electrolysis is performed in the electrolytic cell under the carrier foil production conditions shown in Table 1, copper is deposited on the surface of the rotating drum, the copper deposited on the surface of the rotating drum is peeled off, and electrolysis with a thickness of 18 μm is continuously performed. A copper foil was produced and used as a copper foil carrier. In Examples 1, 2, 6, 8, and 9 and Comparative Example 6, the thickness of the copper foil carrier after the surface treatment was 12 μm, 5 μm, 70 μm, 12 μm, 35 μm, and 35 μm, respectively. Comparative Example 3 was a copper foil carrier having a thickness of 12 μm. For Examples 1, 2, 6, 8, and 9 and Comparative Example 6, the copper foil carrier was surface treated under the conditions described in Table 1. The electrolysis time was 0.5-2 minutes, and the electrolyte temperature was 40-60 ° C.
Here, the surface treatment of Examples 2 and 8 will be described. In Examples 2 and 8, a cathode is arranged on the deposition surface (also referred to as mat surface or M surface) side of the formed electrolytic copper foil, and the copper foil mat is subjected to electrolytic treatment by direct current using the copper foil as an anode. performs an inverse electrolytic polishing on the surface, copper eXAMPLE 2 in 3 to 8 g / m ^2, was 8~15g / m ² dissolved in example 8. The current density of the reverse electrolytic polishing Example 2 In 5~15A / dm ^2, was 16~25A / dm ² in Example 8. The 60 degree specular gloss in the copper foil width direction was 13 to 40, and the 60 degree specular gloss in the copper foil length direction was 20 to 94. The 60 ° specular gloss was measured at an incident angle of 60 ° using a gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741.

Subsequently, an intermediate layer was formed under the following conditions.
An Ni layer having an adhesion amount of 4000 μg / dm ² was formed by electroplating on a roll-to-roll continuous plating line under the following conditions.

-Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm ² was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²

After the formation of the intermediate layer, an ultrathin copper layer having a thickness of 1 to 10 μm was formed on the intermediate layer by electroplating under the following conditions to obtain a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²
In Examples 2 and 3, a roughening layer, a heat-resistant layer, a chromate layer, and a silane coupling layer were further provided on the ultrathin copper layer.
・ Roughening treatment Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
Temperature: 40-50 ° C
Current density Dk: 20 to 30 A / dm ²
Time: 1 to 5 seconds Cu adhesion amount: 15 to 40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Heat-resistant treatment Zn: 0 to 20 g / L
Ni: 0 to 5 g / L
pH: 3.5
Temperature: 40 ° C
Current density Dk: 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Time: 5-30 seconds

(Example 10)
A rolled copper foil (tough pitch copper, JIS H3100 C1100) was prepared, and cold rolling was performed on the rolled copper foil using a rolling roll whose surface was roughened by sandblasting. At this time, the rolling roll roughness Ra was set to 0.39 to 0.42 μm, and the oil film equivalent was 35000. This obtained the copper foil carrier.
Then, the copper foil with a carrier was produced by forming an intermediate | middle layer and an ultra-thin copper layer on the surface (matte surface) of electrolytic copper foil like Example 1. FIG.

  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.

<Surface roughness of ultra-thin copper layer>
After carrying out the lamination press of heating at 220 degreeC with respect to the ultra-thin copper layer with a carrier and a base material (Mitsubishi Gas Chemical Co., Ltd. product: GHPL-832NX-A), a copper foil carrier is set to JIS C 6471 ( 1995, the method of peeling off the copper foil is 8.1. The peel strength of the copper foil 8.1.1 Type of test method (1) Method A (90 ° direction of the copper foil with respect to the copper foil removal surface) In accordance with (1), the ultrathin copper layer was exposed. Next, various roughnesses of the exposed surface of the ultrathin copper layer were measured by the following procedure.
(1) Surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer The surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer is measured according to Olympus laser microscope OLS4000 (LEXT) in accordance with JIS B0601-1994. (OLS 4000). Rz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Rz (laser) was defined as the Rz (laser) value. Moreover, the standard deviation of the value of 10 places was calculated about Rz (laser).
Furthermore, in accordance with ISO25178, the Sku of the surface on the intermediate layer side of the ultrathin copper layer was measured with a laser microscope OLS4000 manufactured by Olympus.
(2) Carrier surface roughness on the side on which the ultrathin copper layer is formed The carrier surface roughness Rz (laser) on the side on which the ultrathin copper layer is formed, in accordance with JIS B0601-1994, Olympus Corporation Measurement was performed with a laser microscope OLS4000. Rz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Rz (laser) was defined as the Rz (laser) value. Moreover, the standard deviation of the value of 10 places was calculated about Rz (laser).
Furthermore, in accordance with ISO25178, Sku on the surface of the carrier on the side on which the ultrathin copper layer was formed was measured with an Olympus laser microscope OLS4000.
In addition, about Rz and Sku, in the observation of the ultrathin copper layer and the carrier surface, the carrier has an evaluation length (reference length) of 257.9 μm, an evaluation area (reference area) of 66524 μm ² , and a cutoff value of zero. When it is a rolled copper foil, it is measured in a direction (TD) perpendicular to the rolling direction, or when the carrier is an electrolytic copper foil, a direction perpendicular to the traveling direction of the electrolytic copper foil in the electrolytic copper foil manufacturing apparatus (TD) ) To obtain the respective values. In addition, the measurement environmental temperature of the surface Rz and Sku by a laser microscope was 23-25 degreeC. In addition, about Example 1, 2, 6, 8, and 9 and the comparative example 6, Rz and Sku of the copper foil carrier after surface treatment were measured.

<Laser drillability>
Next, the untreated surface of the ultrathin copper layer was irradiated with one shot of laser under the following conditions, and the hole shape after irradiation was observed with a microscope to perform measurement. The table shows how many (X) holes were actually drilled by trying to drill holes at 12 points as “real numbers” (X / 12). "Percentage" (%) is shown. The table also shows the average diameter of the holes generated at this time, the standard deviation of the diameter of the generated holes, and the average diameter / beam diameter. The diameter of the hole was the diameter of the smallest circle surrounding the hole.
・ Gas type: CO ₂
Copper foil opening diameter (target): 80 μm diameter Beam shape: Top hat Output: 2.40 W / 10 μs
・ Pulse width: 33μs
・ Number of shots: 1 shot ・ Number of holes: 12 holes / area

<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. 1 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 4 or more is etching property: ◯, 2.5 or more and less than 4 are etching property: Δ, less than 2.5 or calculation is impossible or circuit formation is impossible. -Evaluated. 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 0.8, the linearity was evaluated as ◯, when 0.8 to 1.2 or less was determined as the linearity: Δ, and 1.2 or more was determined as the linearity: x.
Test conditions and test results are shown in Tables 1 and 2.

(Evaluation results)
In each of Examples 1 to 11, the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer is 0.62 μm or more and 1.59 μm or less, and the standard deviation of the surface roughness Rz (laser) is Since it was 0.51 μm or less, the laser drilling property and etching property were good.
In Comparative Examples 1 and 5, since the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer was less than 0.62 μm, the laser holeability was poor.
In Comparative Examples 2 to 4, since the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer exceeded 1.59 μm, the etching property was poor.
In Comparative Example 6, since the standard deviation of the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer exceeded 0.51 μm, the laser holeability was poor.

Claims (25)

A copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order,
After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope A copper foil with a carrier having a roughness Rz of 0.62 μm or more and 1.59 μm or less and a standard deviation of the surface roughness Rz of 0.51 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 1, wherein the roughness Rz is 0.70 μm or more and 1.52 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 2, wherein the roughness Rz is 0.80 μm or more and 1.50 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 3, wherein the roughness Rz is 0.90 μm or more and 1.40 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 3, wherein the roughness Rz is 1.10 μm or more and 1.50 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to any one of claims 1 to 5, wherein a standard deviation of the roughness Rz is 0.01 µm or more and 0.48 µm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 6, wherein the standard deviation of the roughness Rz is 0.04 μm or more and 0.40 μm or less.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The sharpness Sku of the height distribution is 0.50 or more and 3.70 or less, the copper foil with a carrier according to any one of claims 1 to 7.   After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope The copper foil with a carrier according to claim 8, wherein the height distribution sharpness Sku is 1.00 or more and 3.60 or less.   The copper foil with a carrier according to any one of claims 1 to 9, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil.   The thickness of the said carrier is 5-70 micrometers, Copper foil with a carrier as described in any one of Claims 1-10.   The copper foil with a carrier as described in any one of Claims 1-11 which has a roughening process layer in any one or both of the said ultra-thin copper layer surface and the surface of the said carrier.   The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. The copper foil with a carrier according to claim 12 which is a layer.   The copper with a carrier according to claim 12 or 13, wherein the surface of the roughened 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. Foil.   The surface of the ultra-thin copper layer has at least one layer selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier of description.   The copper foil with a carrier as described in any one of Claims 1-11 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 12 or 13, comprising a resin layer on the roughening treatment layer.   The copper foil with a carrier according to claim 14 or 15, comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.   The copper foil with a carrier according to any one of claims 16 to 18, wherein the resin layer is an adhesive resin.   The copper foil with a carrier according to any one of claims 16 to 19, wherein the resin layer is a semi-cured resin.   The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-20.   The copper clad laminated board manufactured using the copper foil with a carrier as described in any one of Claims 1-20.   The electronic device manufactured using the printed wiring board of Claim 21. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 20 and an insulating substrate,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. The process of forming a circuit in the ultra-thin copper layer side surface of the copper foil with a carrier according to any one of claims 1 to 20,
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.