KR20150135523A - Copper foil with carrier, printed circuit board, copper clad laminated sheet, electronic device, and printed circuit board fabrication method - Google Patents

Abstract

Provided is a copper foil with a carrier which is excellent in laser hole forming property of an ultra-thin copper layer and is suitable for manufacturing a high-density integrated circuit board. When the carrier-coated copper foil having the carrier, the intermediate layer and the ultra-thin copper layer in this order was heated at 220 캜 for 2 hours and then the ultra-thin copper layer was peeled off according to JIS C 6471, A copper foil with a carrier having a surface roughness Sz of 1.40 탆 or more and 4.05 탆 or less on an intermediate layer side of an ultra thin copper layer to be measured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper-clad laminate, a copper clad laminate, a copper clad laminate, a copper clad laminate, a copper clad laminate, a copper clad laminate,

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

The printed wiring board is generally manufactured through a step of bonding an insulating substrate to a copper foil to form a copper clad laminate, and then forming a conductor pattern on the copper foil surface by etching. In recent years, along with an increase in the demand for miniaturization and high performance of electronic apparatuses, mounting of high-density mounting parts and high frequency signals have been progressed, and conductor patterns (finer pitch) and high frequency response have been required for printed wiring boards.

In response to the fine pitching, a copper foil having a thickness of 9 占 퐉 or less and further having a thickness of 5 占 퐉 or less is required in recent years. However, such a copper foil with a very thin foil has low mechanical strength and is cracked, wrinkled A copper foil with a carrier in which a thin metal foil is used as a carrier and an extremely thin copper layer is electrodeposited with a release layer interposed therebetween has appeared. The surface of the ultra-thin copper layer is bonded to an insulating substrate, and after thermocompression bonding, the carrier is peeled off through the peeling layer. After a circuit pattern is formed with a resist on the exposed ultra thin copper layer, a predetermined circuit is formed.

Here, the surface of the ultra-thin copper layer of the copper foil with a carrier, which is the adhesion surface to the resin, mainly has a sufficient peel strength between the ultra-thin copper layer and the resin substrate and the peel strength thereof is high temperature heating, It is required to be sufficiently maintained even after the treatment or the like. As a method of increasing the peeling strength between the ultra-thin copper layer and the resin substrate, a method of attaching a large amount of roughened particles on the ultra-thin copper layer having a generally increased profile (irregularity and roughness) of the surface is typical .

However, when a very thin copper layer having such a profile (irregularity and roughness) is used for a semiconductor package substrate which needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles remain in circuit etching, And the like.

For this reason, in WO 2004/005888 (Patent Document 1), it has been attempted to use a copper foil with a carrier which does not carry out the roughening treatment on the surface of the ultra-thin copper layer as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate . The adhesion (peel strength) between the ultra-thin copper layer and the resin not subjected to such roughening treatment tends to be lowered as compared with a general copper foil for a printed wiring board due to its low profile (unevenness, roughness and roughness). Therefore, further improvement is required for the copper foil with a carrier.

Japanese Unexamined Patent Application Publication No. 2007-007937 (Patent Document 2) and Japanese Unexamined Patent Publication (Kokai) No. 2010-006071 (Patent Document 3) disclose a method for manufacturing a thin copper foil with a carrier on the surface of a polyimide- Forming a Ni layer and / or a Ni alloy layer, forming a chromate layer, forming a Cr layer and / or a Cr alloy layer, forming a Ni layer and a chromate layer, forming a Ni layer and a Cr layer . By forming these surface treatment layers, the adhesion strength between the polyimide-based resin substrate and the ultra-thin copper foil with a carrier is obtained without harmony treatment or by reducing (fineness) the degree of roughening treatment. It is also described that surface treatment with a silane coupling agent or rust-preventive treatment is performed.

WO2004 / 005588 Japanese Patent Application Laid-Open No. 2007-007937 Japanese Laid-Open Patent Publication No. 2010-006071 Japanese Patent Publication No. 3261119

In the development of the copper foil with a carrier, the prior art has focused on securing the peeling strength between the ultra-thin copper layer and the resin substrate. Therefore, a copper foil with a carrier suitable for high-density packaging of a printed wiring board has not yet been sufficiently examined, and there is still room for improvement.

In order to increase the density of the integrated circuit 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 generally used. In addition, a method for forming a fine circuit accompanied with a pitch reduction is a method of forming a wiring circuit on an ultra-thin copper layer and then etching the ultra-thin copper layer with an etchant of sulfuric acid-hydrogen peroxide system (MSAP: Modified-Semi -Additive-Process) is used, the laser hole forming property of the ultra-thin copper layer is an important item in manufacturing a high-density integrated circuit board. The laser pore formability of the ultra-thin copper layer greatly affects the design and productivity of the integrated circuit because it relates to conditions such as hole diameter precision and laser output. Japanese Patent Publication No. 3261119 (Patent Document 4) discloses a copper clad laminate having good laser hole forming property. However, according to the study of the present inventor, there is still room for improvement in terms of etching property.

Therefore, an object of the present invention is to provide a copper foil with a carrier which is excellent in laser hole forming property of an ultra-thin copper layer and is suitable for manufacturing a high-density integrated circuit board.

In order to achieve the above object, the inventor of the present invention has conducted intensive studies and, as a result, has found that the surface roughness measured by a laser microscope on the peeling side of an ultra-thin copper layer when a very thin copper layer is peeled off from a copper- Is extremely effective in improving the laser hole forming property of the ultra-thin copper layer.

In one aspect of the present invention, there is provided a carrier-coated copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the carrier-coated copper foil is heated at 220 캜 for 2 hours, Wherein the surface roughness Sz of the extremely thin copper layer measured by a laser microscope on the side of the intermediate layer when the copper layer is peeled is not less than 1.40 mu m and not more than 4.05 mu m.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off in accordance with JIS C 6471, And the standard deviation of the surface roughness Sz of the intermediate layer side of the layer is 1.30 mu m or less.

In the copper foil with a carrier according to another embodiment of the present invention, when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, The standard deviation of the surface roughness Sz of the copper layer on the intermediate layer side is not less than 0.01 mu m and not more than 1.20 mu m.

In the copper foil with a carrier according to another embodiment of the present invention, when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, And the surface roughness Sz of the extremely thin copper layer on the side of the intermediate layer is 1.60 mu m or more and 3.70 mu m or less.

According to another aspect of the present invention, there is provided a carrier-coated copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order, wherein the carrier-coated copper foil is heated at 220 캜 for 2 hours, And the surface roughness Ra of the extremely thin copper layer measured by a laser microscope on the side of the intermediate layer when the ultra-thin copper layer is peeled is 0.14 mu m or more and 0.35 mu m or less.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, And the standard deviation of the surface roughness Ra of the copper layer on the side of the intermediate layer is 0.11 m or less.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, The standard deviation of the surface roughness Ra of the copper layer on the side of the intermediate layer is not less than 0.001 mu m and not more than 0.10 mu m.

According to another aspect of the present invention, there is provided a carrier-attached copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order,

Wherein the surface of the extremely thin copper layer measured by a laser microscope when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the extremely thin copper layer according to JIS C 6471 has a surface roughness Rz of 0.62 탆 or more And the standard deviation of the surface roughness Rz is 0.51 占 퐉 or less.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, The standard deviation of the surface roughness Rz of the copper layer on the intermediate layer side is not less than 0.01 mu m and not more than 0.48 mu m.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, The skewness Sku of the surface height distribution of the copper layer on the intermediate layer side is not less than 0.50 and not more than 3.70.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, The skew of the surface height distribution of the copper layer on the intermediate layer side is not less than 1.00 and not more than 3.60.

In another aspect of the copper foil with a carrier according to the present invention, the thickness of the carrier is 5 to 70 mu m.

The copper foil with a carrier according to another aspect of the present invention has a roughened treatment layer on the surface of the ultra-thin copper layer.

The copper foil with a carrier according to another aspect of the present invention is the copper foil with a carrier according to any one of the above aspects, wherein the roughened layer is formed of any one or any group selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc And a layer made of an alloy containing at least one kind of alloy.

In another aspect of the present invention, the copper foil with a carrier has at least one layer selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the roughened treatment layer.

In another aspect of the present invention, the copper foil with a carrier has at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the ultra thin copper layer.

According to still another aspect of the present invention, there is provided a copper foil with a carrier, wherein the resin layer is provided on the extremely thin copper layer.

According to still another aspect of the present invention, there is provided a copper foil with a carrier, wherein a resin layer is provided on the roughening treatment layer.

The copper foil with a carrier according to another aspect of the present invention comprises a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the anticorrosive layer, the chromate treatment layer and the silane coupling treatment layer.

In another aspect, the present invention is a printed wiring board produced by using the copper foil with a carrier of the present invention.

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

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

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; A copper clad laminate is formed through a step of peeling off the carrier of the copper foil with a carrier, and thereafter a copper clad laminate is formed by any of a semi additive method, a subtractive method, a patty additive method, or a modified semi- And a step of forming a printed wiring board.

According to another aspect of the present invention, there is provided a method for manufacturing a copper foil with a carrier, comprising the steps of: forming a circuit on the ultra thin copper layer side surface of the copper foil with a carrier of the present invention; forming a resin layer on the ultra thin copper layer side surface of the carrier- 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 removing the ultra-thin copper layer after peeling off the carrier, And a step of exposing a circuit buried in the resin layer formed on the copper layer side surface.

According to the present invention, it is possible to provide a copper foil with a carrier which is excellent in laser hole forming property of an ultra-thin copper layer and is suitable for manufacturing a high-density integrated circuit board.

Fig. 1 schematically shows a cross-sectional view of a width direction of a circuit pattern in the embodiment and a calculation method of an etching factor EF using the schematic diagram.
Figs. 2A to 2C are schematic diagrams of a section of a wiring board in a process up to circuit plating and resist removal, relating to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.
3F to 3F are schematic views of a wiring board section in a process from the lamination of the resin and the second-layered copper foil with a carrier to the formation of a laser hole, relating to a concrete example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention .
4G to 4I are schematic views of a wiring board section in a process from the via fill formation to the carrier peeling of the first layer, relating to a concrete example of a production method of a printed wiring board using the copper foil with a carrier according to the present invention.
5A to 5K are schematic views of a wiring board section in a process from flash etching to bump-copper filler formation, according to a specific example of a method for producing a printed wiring board using the copper foil with a carrier according to the present invention.

<Copper with Carrier>

The copper foil with a carrier of the present invention comprises a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer. The method of using the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer may be coated with paper phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, A glass fiber nonwoven fabric composite epoxy resin, a glass fiber substrate epoxy resin, a polyester film, a polyimide film or the like, peeling the carrier after thermocompression bonding, and forming a very thin copper layer adhered to the insulating substrate And finally, a printed wiring board can be manufactured.

The carrier-coated copper foil of the present invention is characterized in that, on one side, the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the ultra-thin copper layer according to JIS C 6471, Side surface roughness Sz (10 point height of the surface) is controlled to be 1.40 탆 or more and 4.05 탆 or less. The carrier-bonded copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and the ultra-thin copper layer adhered to the insulating substrate is etched with a target conductor pattern to form a circuit. In this way, a printed wiring board is manufactured by forming the substrate into a multilayer structure. Here, in order to increase the density of the integrated circuit 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 a matter of course that it is difficult to form a laser hole in the ultra-thin copper layer. If the laser hole is excessively large or too small, it causes various problems. As described above, the laser hole forming property of the ultra-thin copper layer is an important characteristic that greatly affects the design and productivity of an integrated circuit because it relates to conditions such as hole diameter accuracy and laser output. In the present invention, the laser-hole-forming property of the extremely thin copper layer is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the extremely thin copper layer according to JIS C 6471, And the surface roughness Sz of the intermediate layer side of the layer is controlled to be 1.40 mu m or more and 4.05 mu m or less. If the surface roughness Sz of the ultra-thin copper layer measured by the laser microscope is less than 1.40 m, the surface roughness of the ultra-thin copper layer is insufficient and the laser absorbability at the time of hole formation is deteriorated, There arises a problem that even if it is formed, a small hole is formed. If the surface roughness Sz of the ultra-thin copper layer measured by the laser microscope exceeds 4.05 m, the surface roughness of the ultra-thin copper layer is too high and the laser absorbency during hole forming becomes excessive, There arises a problem that it becomes excessively large. The surface roughness Sz of the intermediate copper layer measured by the laser microscope is more preferably 1.60 mu m or more and 3.70 mu m or less, more preferably 1.80 mu m or more and 3.50 mu m or less, and still more preferably 2.40 mu m or more and 3.70 mu m or less . The above &quot; heating at 220 占 폚 for 2 hours &quot; shows a typical heating condition in the case where the copper foil with a carrier is bonded to an insulating substrate and thermocompression bonding is performed.

The carrier-coated copper foil of the present invention is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the ultra-thin copper layer in accordance with JIS C 6471, It is preferable that the standard deviation of the surface roughness Sz is controlled to be not more than 1.30 mu m. When the standard deviation Sz of the surface roughness Sz of the extremely thin copper layer measured by the laser microscope exceeds 1.30 mu m, the deviation of the laser pore diameter becomes large (i.e., the standard deviation becomes large) and the deviation of the etching factor becomes large The standard deviation becomes larger) may cause a problem. The standard deviation of the surface roughness Sz of the extremely thin copper layer measured by the laser microscope is more preferably 0.01 mu m or more and 1.20 mu m or less, still more preferably 0.05 mu m or more and 1.10 mu m or less, and more preferably 0.10 mu m or more and 1.00 mu m or less Mu m or less.

The carrier-coated copper foil of the present invention is characterized in that, in another aspect, the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off in accordance with JIS C 6471, And the surface roughness Ra (arithmetic mean roughness) on the side of the intermediate layer is controlled to be 0.14 mu m or more and 0.35 mu m or less. The carrier-bonded copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and the ultra-thin copper layer adhered to the insulating substrate is etched with a target conductor pattern to form a circuit. In this way, a printed wiring board is manufactured by forming the substrate into a multilayer structure. Here, in order to increase the density of the integrated circuit 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 a matter of course that it is difficult to form a laser hole in the ultra-thin copper layer. If the laser hole is excessively large or too small, it causes various problems. As described above, the laser hole forming property of the ultra-thin copper layer is an important characteristic that greatly affects the design and productivity of an integrated circuit because it relates to conditions such as hole diameter accuracy and laser output. In the present invention, the laser-hole-forming property of the extremely thin copper layer is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the extremely thin copper layer according to JIS C 6471, And the surface roughness Ra of the intermediate layer side of the layer is controlled to be not less than 0.14 mu m and not more than 0.35 mu m. If the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope is less than 0.14 탆, the surface roughness of the ultra-thin copper layer is insufficient and the laser absorbability at the time of hole formation is deteriorated, There arises a problem that even if it is formed, a small hole is formed. If the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope exceeds 0.35 mu m, the surface roughness of the ultra-thin copper layer is excessively high and the laser absorbency at the time of hole forming processing becomes excessive, There arises a problem that it becomes excessively large. The surface roughness Ra of the extremely thin copper layer measured by the laser microscope is preferably 0.16 mu m or more and 0.32 mu m or less, more preferably 0.18 mu m or more and 0.32 mu m or less, and still more preferably 0.20 mu m or more and 0.32 mu m or less . The surface roughness Ra of the intermediate copper layer of the ultra-thin copper layer measured by the laser microscope is preferably 0.14 mu m or more and 0.30 mu m or less. The above &quot; heating at 220 占 폚 for 2 hours &quot; shows a typical heating condition in the case where the copper foil with a carrier is bonded to an insulating substrate and thermocompression bonding is performed.

The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off in accordance with JIS C 6471, It is preferable that the standard deviation of the surface roughness Ra of the intermediate layer side is controlled so as to be 0.11 m or less. If the standard deviation of the surface roughness Ra of the extremely thin copper layer measured by the laser microscope is larger than 0.11 mu m, the deviation of the laser hole diameter becomes large (i.e., the standard deviation becomes large), and the deviation of the etching factor becomes large (I.e., the standard deviation becomes large). The standard deviation of the surface roughness Ra of the extremely thin copper layer measured by the laser microscope is preferably 0.001 탆 to 0.10 탆, more preferably 0.003 탆 to 0.09 탆, even more preferably 0.005 탆 or more More preferably 0.08 mu m or less, still more preferably 0.005 mu m or more and 0.06 mu m or less.

The carrier-coated copper foil of the present invention is characterized in that the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling the ultra-thin copper layer according to JIS C 6471, Is controlled so that the surface roughness Rz (10-point average roughness) of the intermediate layer side is 0.62 mu m or more and 1.59 mu m or less. The carrier-bonded copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and the ultra-thin copper layer adhered to the insulating substrate is etched with a target conductor pattern to form a circuit. In this way, a printed wiring board is manufactured by forming the substrate into a multilayer structure. Here, in order to increase the density of the integrated circuit 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 a matter of course that it is difficult to form a laser hole in the ultra-thin copper layer. If the laser hole is excessively large or too small, it causes various problems. As described above, the laser hole forming property of the ultra-thin copper layer is an important characteristic that greatly affects the design and productivity of an integrated circuit because it relates to conditions such as hole diameter accuracy and laser output. In the present invention, the laser-hole-forming property of the extremely thin copper layer is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the extremely thin copper layer according to JIS C 6471, And the surface roughness Rz of the intermediate layer side of the layer is controlled to be 0.62 mu m or more and 1.59 mu m or less. When the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope is less than 0.62 mu m, the surface roughness of the ultra-thin copper layer is insufficient and the laser absorbability at the time of hole forming processing becomes poor, There arises a problem that even if it is formed, a small hole is formed. When the surface roughness Rz of the extremely thin copper layer measured by the laser microscope is more than 1.59 mu m, the roughness of the surface of the ultra-thin copper layer is excessively large, and the laser absorbability at the time of hole forming processing becomes excessive, There arises a problem that it becomes excessively large. The surface roughness Rz of the intermediate copper layer measured by the laser microscope is preferably 0.70 탆 or more and 1.52 탆 or less, more preferably 0.80 탆 or more and 1.50 탆 or less, and still more preferably 0.90 탆 or more and 1.40 탆 or less . The surface roughness Rz of the intermediate copper layer of the ultra-thin copper layer measured by the laser microscope is more preferably 1.10 mu m or more and 1.50 mu m or less. The above &quot; heating at 220 占 폚 for 2 hours &quot; shows a typical heating condition in the case where the copper foil with a carrier is bonded to an insulating substrate and thermocompression bonding is performed.

The carrier-coated copper foil of the present invention is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the ultra-thin copper layer in accordance with JIS C 6471, Is controlled so that the standard deviation Rz of the surface roughness Rz is 0.51 m or less. If the standard deviation Rz of the surface roughness Rz of the extremely thin copper layer measured by the laser microscope exceeds 0.51 m, the deviation of the laser hole diameter becomes large (i.e., the standard deviation becomes large) and the deviation of the etching factor becomes large The standard deviation becomes large). The standard deviation of the surface roughness Rz of the extremely thin copper layer measured by the laser microscope is preferably 0.01 mu m or more and 0.48 mu m or less, more preferably 0.04 mu m or more and 0.40 mu m or less, still more preferably 0.04 mu m or more and 0.35 mu m or less More preferably 0.05 mu m or more and 0.20 mu m or less.

The carrier-coated copper foil of the present invention is obtained by heating the copper foil with a carrier at 220 캜 for 2 hours and then peeling the ultra-thin copper layer according to JIS C 6471, It is preferable that the height Sku (kurtosis) of the height distribution is controlled to be not less than 0.50 and not more than 3.70. When Sku is less than 0.50, the convex portion of the surface of the ultra-thin copper layer is flattened, so that the laser absorbability at the time of hole forming is deteriorated, holes are hardly formed, and even if they are formed, There is a possibility of occurrence. On the other hand, if it is larger than 3.70, the convex portion of the irregularities on the surface of the extremely thin copper layer becomes a sharp shape, and the energy of the laser is locally absorbed to cause a problem that the size of the actual hole becomes larger with respect to the irradiation diameter of the laser There is a concern. The carrier-coated copper foil of the present invention is characterized in that when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the surface height distribution More preferably controlled at not less than 1.00 and not more than 3.60, more preferably not less than 1.50 but not more than 3.30, still more preferably not less than 1.50 but not more than 3.20, more preferably not less than 1.50 but not more than 3.10 More preferably controlled, and more preferably controlled to be not less than 1.50 and not more than 3.00.

<Carrier>

The carrier that can be used in the present invention is typically a metal foil or a resin film, and examples thereof include a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, a foil, an iron alloy foil, a stainless steel foil, an aluminum foil, A resin film, a polyimide film, and an LCD film.

Carriers which can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is manufactured by repeating plastic working and heat treatment by a rolling roll. Examples of the material of the copper foil 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) , A copper alloy to which Zr or Mg is added, a copper alloy such as a Colson type copper alloy to which Ni and Si are added, or the like can be used. In the present specification, when the term &quot; copper foil &quot; is used singly, copper alloy foil is also included.

The thickness of the carrier which can be used in the present invention is not particularly limited, but may be suitably adjusted to a suitable thickness for fulfilling its role as a carrier. For example, it may be 5 占 퐉 or more. However, if the thickness is excessively large, the production cost becomes high, and therefore, it is generally preferable to be 35 m or less. Thus, the thickness of the carrier is typically from 8 to 70 microns, more typically from 12 to 70 microns, and more typically from 18 to 35 microns. From the viewpoint of reducing the raw material cost, it is preferable that the thickness of the carrier is small. Therefore, the thickness of the carrier is typically 5 mu m or more and 35 mu m or less, preferably 5 mu m or more and 18 mu m or less, preferably 5 mu m or more and 12 mu m or less, preferably 5 mu m or more and 11 mu m or less And preferably not less than 5 占 퐉 and not more than 10 占 퐉. Further, when the thickness of the carrier is small, folded wrinkles are likely to occur at the time of the passage of the carrier. It is effective to smooth the conveying roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the conveying roll and the next conveying roll in order to prevent the occurrence of folds.

The surface roughness Sz, Ra, Rz and their standard deviation and Sku of the intermediate layer side of the ultra-thin copper layer measured by the laser microscope of the present invention can be controlled by adjusting the surface shape of the carrier on the ultra-thin copper layer side. Hereinafter, a method of manufacturing a carrier according to the present invention will be described.

An example of the production conditions when the electrolytic copper foil is used as the carrier is shown below.

<Electrolyte Composition>

Copper: 90 ~ 110 g / ℓ

Sulfuric acid: 90 to 110 g / l

Chlorine: 50 to 100 ppm

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 to 30 ppm

Leveling second (amine compound): 10 to 30 ppm

The amine compound may be an amine compound of the following formula.

[Chemical Formula 1]

Wherein 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.

<Manufacturing Conditions>

Current density: 70 to 100 A / dm 2

Electrolyte temperature: 50 to 60 ° C

Electrolyte flux: 3 ~ 5 m / sec

Electrolysis time: 0.5 to 10 minutes

The surface roughness Sz, Ra, Rz and their standard deviation and Sku of the intermediate layer side of the ultra-thin copper layer are controlled by adjusting the surface shape of the carrier on the ultra-thin copper layer side. The following methods (1) to (3) can be used to adjust the surface morphology of the carrier on the extremely shallow copper layer side. In addition, as shown in Table 2, the shape of the surface of the ultra-thin copper layer side of the carrier and the shape of the surface of the carrier-side extremely thin copper layer become close to each other. Therefore, by adjusting the shape of the surface of the ultra-thin copper layer side of the carrier, it is possible to obtain an ultra-thin copper foil with a carrier having the shape of the desired surface of the ultra thin copper layer of the carrier.

(1) A soft etching treatment or a reverse electrolytic treatment is performed on a carrier having low light intensity and high gloss.

Specifically, for a carrier having a surface roughness Rz of 0.2 탆 to 0.6 탆, or a surface roughness Ra of 0.2 탆 to 0.6 탆, or a surface roughness Sz of 0.2 탆 to 0.6 탆 and a 60 캜 specular glossiness of 500% , Soft etching treatment (for example, an aqueous solution containing 5 to 15 vol% of sulfuric acid and 0.5 to 5.0 wt% of hydrogen peroxide, etching treatment at 10 to 30 ° C for 0.5 to 10 minutes), or reverse electrolytic treatment Polishing to form concavities and convexities).

The &quot; reverse electrolytic polishing &quot; is electrolytic polishing. Generally, electrolytic polishing is aimed at smoothing. Therefore, when electrolytic polishing is performed on the electrolytic copper foil, it is a common thinking method that the surface (roughened surface) opposite to the glossy surface is the target. However, in this case, electrolytic polishing is performed on the polished surface to form irregularities, so that the electrolytic polishing process, that is, the reverse electrolytic polishing process, which is contrary to the usual process, is performed. The dissolution amount of copper by the reverse electrolytic treatment is 2 to 20 g / m 2. The current density of the reverse electrolytic polishing treatment is set to 0.5 to 50 A / dm 2.

(2) A carrier is produced by rolling with a rolling roll treated with sandblast.

Specifically, a rolled copper foil is prepared as a carrier, and the rolled copper foil is subjected to finish cold rolling using a rolling roll whose surface is coarsened by sand blast. At this time, the rolling roll roughness Ra can be set to 0.39 to 0.42 mu m and the oil film equivalent to 29000 to 40000.

Here, the equivalent film equivalent is expressed by the following equation.

(Yielding pressure [kg / mm &lt; 2 &gt;]) of the material = {(rolling oil viscosity [cSt]) x (passing speed [mpm] + roll main speed [mpm])} }

The viscosity of the rolling oil [cSt] is the kinematic viscosity at 40 ° C.

In order to set the oil film equivalent to 29000 to 40000, a known method may be used, for example, by using high-viscosity rolling oil or by increasing the speed of the plate.

(3) A carrier is produced by a predetermined electrolytic condition.

Specifically, using a copper sulfate electrolytic solution (copper concentration: 80 to 120 g / l, sulfuric acid concentration 70 to 90 g / l) and high-concentration glue (glue concentration: 3 to 10 mass ppm) (75 to 110 A / dm 2) and a high line flow rate (3.7 to 5.0 m / sec).

<Middle layer>

An intermediate layer is formed on one side or both sides of the carrier. Another layer may be formed between the carrier and the intermediate layer. The intermediate layer used in the present invention has a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with a carrier to the insulating substrate, and the ultra-thin copper layer is peelable from the carrier after the laminating step to the insulating substrate Is not particularly limited. For example, the intermediate layer of the copper foil with a carrier according to the present invention may be formed of a material selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, One or two or more selected from the group consisting of The intermediate layer may be a plurality of layers.

For example, the intermediate layer may be a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Ni, Co, Fe, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, , Mo, Ti, W, P, Cu, Al and Zn to form a layer composed of a hydrate or an oxide of one or more elements selected from the group consisting of Mo, Ti, W, P, Cu, Al and Zn.

When the intermediate layer is formed only on one side, it is preferable to form a rust prevention layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is formed by a chromate treatment, a zinc chromate treatment or a plating treatment, it is considered that a part of the attached metal such as chromium or zinc may be composed of a hydrate or an oxide.

In addition, for example, the intermediate layer can be formed by stacking nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium in this order on a carrier. Since the adhesive force between nickel and copper is higher than the adhesion force between chrome and copper, it is peeled from the interface between the ultra-thin copper layer and chromium when the ultra-thin copper layer is peeled off. It is expected that the nickel in the intermediate layer has a barrier effect for preventing the copper component from diffusing from the carrier into the ultra-thin copper layer. The adhesion amount of nickel in the intermediate layer is preferably 100 μg / dm 2 to 40000 μg / dm 2, more preferably 100 μg / dm 2 to 4000 μg / dm 2, and still more preferably 100 μg / Dm 2 or more, more preferably 100 μg / dm 2 or more and less than 1000 μg / dm 2, and the adhesion amount of chromium in the intermediate layer is preferably 5 μg / dm 2 or more and 100 μg / dm 2 or less. When the intermediate layer is formed only on one side, it is preferable to form a rust prevention layer such as a Ni plating layer on the opposite side of the carrier.

<Ultra-thin copper layer>

And an ultra-thin copper layer is formed on the intermediate layer. Another layer may be formed between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamide or copper cyanide, and is used in a general electrolytic copper foil and can form a copper foil at a high current density. . The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 占 퐉 or less. Typically from 0.5 to 12 占 퐉, more typically from 1 to 5 占 퐉, more typically from 1.5 to 5 占 퐉, and more typically from 2 to 5 占 퐉. In addition, a very thin copper layer may be formed on both sides of the carrier.

&Lt; Hardening treatment and other surface treatment &gt;

The roughened layer may be formed on the surface of the ultra-thin copper layer by, for example, roughening the roughened layer to improve adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming coarse particles with copper or a copper alloy. The harmonic treatment may be fine. The roughening treatment layer may be a layer made of any one or more of alloys selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc. It is also possible to carry out a harmonizing treatment for forming secondary particles or tertiary particles with nickel, cobalt, copper, zinc alone, or an alloy of nickel, cobalt, zinc, or the like after the roughening particles are formed of copper or a copper alloy. Thereafter, a heat resistant layer or rustproof layer may be formed of a single body of nickel, cobalt, copper, zinc, or an alloy, or the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. A heat resistant layer or a rust preventive layer may be formed of a single body of nickel, cobalt, copper, zinc or an alloy, and the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. That is, 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 may be formed on the surface of the roughened treatment layer, , A chromate treatment layer and a silane coupling treatment layer may be formed. The heat resistant layer, rust preventive layer, chromate treatment layer and silane coupling treatment layer described above may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

For example, the copper-cobalt-nickel alloy plating as the roughening treatment is a copper-cobalt-nickel alloy plating having an adhesion amount of 15 to 40 mg / dm 2 and a copper-100 to 3000 μg / dm 2 of cobalt-100 to 1500 μg / Of ternary system alloy layer of nickel. When the Co deposition amount is less than 100 占 퐂 / dm2, the heat resistance is deteriorated and the etching property is sometimes deteriorated. When the Co adherence amount is more than 3000 占 퐂 / dm2, it is not preferable when the effect of magnetism is to be considered, and etching unevenness occurs, and the acid resistance and chemical resistance deteriorate in some cases. When the Ni adhesion amount is less than 100 占 퐂 / dm2, the heat resistance may be deteriorated. On the other hand, if the amount of Ni adhered exceeds 1500 / / dm 2, etching residues may increase. The preferred Co deposition amount is 1000 to 2500 占 퐂 / dm2, and the preferable nickel deposition amount is 500 to 1200 占 퐂 / dm2. Here, the term "etching unevenness" means that Co remains unmelted when etching with copper chloride, and the term "etching residue" means that Ni remains unmelted when subjected to alkali etching with ammonium chloride.

An example of a general bath and plating condition for forming such a ternary copper-cobalt-nickel alloy plating is as follows:

Plating bath composition: 10 to 20 g / l of Cu, 1 to 10 g / l of Co, 1 to 10 g / l of Ni

pH: 1-4

Temperature: 30 ~ 50 ℃

Current density D _k : 20 to 30 A / dm 2

Plating time: 1 to 5 seconds

In this way, a carrier-adhered copper foil having the carrier, the intermediate layer laminated on the carrier, and the ultra-thin copper layer laminated on the intermediate layer is produced. The method of using the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer may be coated with paper phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, A glass fiber nonwoven fabric composite epoxy resin, a glass fiber substrate epoxy resin, a polyester film, a polyimide film or the like, peeling off the carrier after thermocompression to form a copper clad laminate, , And finally a printed wiring board can be manufactured.

The carrier-coated copper foil having the carrier and the ultra-thin copper layer laminated on the intermediate layer and stacked on the carrier may have a roughened treatment layer on the ultra-thin copper layer. On the roughened treatment layer, A heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer may be provided.

It is also possible to provide a roughened treatment layer on the ultra-thin copper layer, a heat resistant layer and a rust preventive layer on the roughened treatment layer, a chromate treatment layer on the heat resistant layer and the rust preventive layer, A silane coupling treatment layer may be provided on the chromate treatment layer.

The carrier-coated copper foil may be provided with a resin layer on the extremely thin copper layer, on the roughened layer, or on the heat resistant layer, the anticorrosive layer, the chromate treatment layer, or the silane coupling treatment layer. 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 for bonding (B stage). The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface is touched with a finger, and a curing reaction occurs when subjected to heat treatment.

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The kind thereof is not particularly limited, but resins suitable for example include epoxy resins, polyimide resins, polyfunctional cyanate ester compounds, maleimide compounds, polyvinyl acetal resins, urethane resins and the like.

The resin layer may be formed of any of known resins, resin curing agents, compounds, curing accelerators, dielectrics (dielectrics including inorganic compounds and / or organic compounds, dielectrics including metal oxides), reaction catalysts, A polymer, a prepreg, a skeleton material, and the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP- , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, JP-A-2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A- 2004-82687, 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication No. 4178415, International Publication Japanese Patent Application Laid-Open Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207, Japanese Patent Application Laid-Open No. 2009-71817, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Patent Publication No. International Publication Nos. WO2008 / 114858, WO2009 / 008471, JP-A-2011-14727, WO009 / 001850, WO2009 / 145179, WO2011 / 068157, JP-A-2013-19056 (Resin, curing accelerator, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton, etc.) and / or a method of forming a resin layer and a forming apparatus .

These resins are dissolved in, for example, a solvent such as methyl ethyl ketone (MEK) or toluene to form a resin solution, which is then coated on the ultra thin copper layer, or on the heat resistant layer, rust preventive layer or the chromate coating layer, For example, by a roll coater method, and then, if necessary, heated and dried to remove the solvent to obtain a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

The resin-coated copper foil with the resin layer (resin-coated copper foil with a carrier) having the resin layer is superimposed on the base material and then thermally pressed to thermally cure the resin layer. Subsequently, the carrier is peeled, (Of course, the surface to be exposed is the surface of the intermediate layer side of the extremely thin copper layer), and is used as an embodiment of forming a predetermined wiring pattern there.

The use of the copper foil with a carrier to which the resin is adhered can reduce the number of prepreg materials used in manufacturing a multilayer printed wiring board. In addition, the copper clad laminate can be produced even if the thickness of the resin layer is set to a thickness sufficient for ensuring interlayer insulation or the prepreg material is not used at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is reduced, and the lamination step is simplified, which is economically advantageous. Further, the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is It is possible to produce an ultra-thin multilayer printed circuit board having a thickness of 100 m or less in one layer.

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

When the thickness of the resin layer is smaller than 0.1 占 퐉, the adhesive force is lowered, and when the copper foil with a carrier on which the resin is adhered is laminated on a substrate having an inner layer material without interposing the prepreg material, It may be difficult to ensure insulation.

On the other hand, if the thickness of the resin layer is made thicker than 80 占 퐉, it becomes difficult to form a resin layer having a desired thickness in one coating step, resulting in economical disadvantages because extra material cost and number of steps are involved. Further, since the formed resin layer is poor in flexibility, cracks and the like are liable to be generated at the time of handling, and excess resin flow occurs at the time of thermocompression bonding with the inner layer material, which may make it difficult to smoothly laminate.

Another type of product of the copper foil with a carrier on which the resin is adhered is a product layer on the extremely thin copper layer or on the heat resistant layer, the anticorrosive layer, the chromate treatment layer, or the silane coupling treatment layer, It is possible to produce a resin in the form of a copper foil on which a carrier is not present by peeling the carrier after it is semi-cured.

In addition, by mounting electronic parts on the printed wiring board, a printed circuit board is completed. In the present invention, the &quot; printed wiring board &quot; includes a printed wiring board, a printed circuit board, and a printed board on which the electronic parts are mounted.

An electronic apparatus may be manufactured using the printed wiring board, an electronic apparatus may be manufactured using a printed circuit board on which the electronic apparatus is mounted, and an electronic apparatus may be manufactured using the printed board on which the electronic apparatus is mounted . Hereinafter, several examples of the production process of a printed wiring board using the copper foil with a carrier according to the present invention are shown.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to the present invention; laminating the copper foil with a carrier and an insulating substrate; Is laminated so that the extremely thin copper side faces the insulating substrate and then the carrier of the copper foil with a carrier is peeled off to form a copper clad laminate. Thereafter, a semi-additive process, a modified semi-additive process, An additive method, and a subtractive method. It is also possible that the insulating substrate has an inner layer circuit inserted therein.

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 to form a pattern, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of the method for producing the printed wiring board according to the present invention using the semi-additive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

The step of peeling the carrier to remove the exposed ultra-thin copper layer by any method such as etching or plasma using a corrosive solution such as an acid,

Forming a through hole and / or a blind via in the exposed resin by removing the ultra-thin copper layer by etching;

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the resin and the through hole and / or the blind via,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the insulating resin substrate by peeling the carrier and exposing the ultra thin copper layer,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

The step of peeling the carrier to remove the exposed ultra-thin copper layer by any method such as etching or plasma using a corrosive solution such as an acid,

Removing the ultra-thin copper layer by etching or the like to form an electroless plating layer on a region including the exposed resin and the through hole and / or the blind via,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of forming a through hole and / or a blind via in the insulating resin substrate by peeling the carrier and exposing the ultra thin copper layer,

The step of peeling the carrier to remove the exposed ultra-thin copper layer by any method such as etching or plasma using a corrosive solution such as an acid,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

Removing the ultra-thin copper layer by etching or the like to form an electroless plating layer on a region including the exposed resin and the through hole and / or the blind via,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like

.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

The step of peeling the carrier to remove the exposed ultra-thin copper layer by any method such as etching or plasma using a corrosive solution such as an acid,

A step of forming an electroless plating layer on the exposed surface of the resin by removing the extremely thin copper layer by etching,

A step of forming a plating resist on the electroless plating layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like

.

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, a copper thickness is formed in the circuit forming portion by electrolytic plating, And a metal foil other than the circuit forming portion is removed by (flash) etching to form a circuit on the insulating layer.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in the exposed ultra thin copper layer and the insulating substrate,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

Peeling the carrier to form a plating resist on the surface of the exposed ultra-thin copper layer,

A step of forming a circuit by electrolytic plating after the plating resist is formed,

A step of removing the plating resist,

A step of removing the exposed ultra-thin copper layer by flash etching by removing the plating resist

.

In another embodiment of the method for producing a printed wiring board according to the present invention using a modified semi-additive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

Peeling the carrier to form a plating resist on the exposed ultra-thin copper layer,

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroplating layer in a region where the plating resist is removed,

A step of removing the plating resist,

A step of removing the electroless plating layer and the ultra-thin copper layer in regions other than the region where the circuit is formed by flash etching or the like

.

In the present invention, the palladium additive method is a method in which a catalyst core is provided on a substrate on which conductor layers are formed and, if necessary, punched holes for through-holes or via-holes, etched to form conductor circuits, Refers to a method for producing a printed wiring board by forming a solder resist or a plating resist as necessary and then forming a thickness on the conductor circuit by through an electroless plating process on a through hole or a via hole.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the palladium additive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in the exposed ultra thin copper layer and the insulating substrate,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

Providing a catalyst nucleus to a region including the through hole and / or the blind via,

Peeling the carrier to form an etching resist on the exposed ultra thin copper layer surface,

A step of exposing the etching resist to a circuit pattern,

Removing the ultra-thin copper layer and the catalyst core by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit;

A step of removing the etching resist,

Removing the ultra-thin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid to form a solder resist or a plating resist on the exposed surface of the insulating substrate;

A step of forming an electroless plating layer in a region where the solder resist or the plating resist is not formed

.

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 manufacturing a printed wiring board according to the present invention using the subtractive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention,

A step of laminating the copper foil with a carrier and an insulating substrate,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in the exposed ultra thin copper layer and the insulating substrate,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming an electroplating layer on the surface of the electroless plating layer,

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely thin copper layer, 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,

A step of removing the etching resist,

.

In another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method, 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,

A step of peeling the carrier of the carrier-coated copper foil after the carrier-coated copper foil and the insulating substrate are laminated,

A step of peeling the carrier to form a through hole and / or a blind via in the exposed ultra thin copper layer and the insulating substrate,

A step of performing a desmear treatment on an area including the through hole and / or the blind via,

A step of forming an electroless plating layer on a region including the through hole and / or the blind via,

A step of forming a mask on the surface of the electroless plating layer,

A step of forming an electroplating layer on the surface of the electroless plating layer where no mask is formed,

A step of forming an etching resist on the surface of the electrolytic plating layer and / or the ultra-thin copper layer,

A step of exposing the etching resist to a circuit pattern,

Removing the extremely 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,

A step of removing the etching resist,

.

The step of forming the through hole and / or the blind via, and the subsequent desmearing step may not be performed.

Here, specific examples of the method for producing a printed wiring board using the copper foil with a carrier according to the present invention will be described in detail with reference to the drawings. Although the copper foil with a carrier having an ultra-thin copper layer formed with a roughened treatment layer is described here as an example, the present invention is not limited to this, and a copper foil with a carrier having an ultra- A manufacturing method of a wiring board can be carried out.

First, as shown in Fig. 2-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened treatment layer formed on its surface is prepared.

Next, as shown in Fig. 2-B, a resist is coated on the roughened layer of the ultra-thin copper layer, and exposure and development are performed to etch the resist into a predetermined shape.

Next, as shown in Fig. 2-C, a circuit plating for a circuit is formed, and then the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in Fig. 3-D, a resin layer is formed on the extremely thin copper layer so as to cover the circuit plating (so that the circuit plating is buried), the resin layers are laminated, Is bonded from the ultra-thin copper layer side.

Next, as shown in Fig. 3-E, the carrier is separated from the second-layered copper foil with a carrier.

Next, as shown in Fig. 3-F, a laser hole is formed at a predetermined position of the resin layer, and the circuit plating is exposed to form a blind via.

Next, as shown in Fig. 4-G, copper is buried 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 in Fig. 4-I, the carrier is peeled from the first-layer copper foil with a carrier.

Next, as shown in Fig. 5-J, the extremely thin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Next, as shown in Fig. 5-K, bumps are formed on the circuit plating in the resin layer, and a copper filler is formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention is produced.

The copper foil with a carrier of the present invention may be used for the other copper foil with a carrier (second layer), or a conventional copper foil with a carrier may be used, or a conventional copper foil may be used. In addition, the circuit may be formed in a single layer or a plurality of layers on the second layer circuit shown in Fig. 4-H, and their circuit formation may be formed by a semiadditive method, a subtractive method, a pattern additive method, And a semi-additive method.

According to the above-described method for producing a printed wiring board, since the circuit plating is embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown in, for example, The circuit plating is protected by the resin layer and the shape thereof is maintained, thereby making it easy to form a fine circuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved and conduction of the circuit wiring is well suppressed. Therefore, formation of a fine circuit is facilitated. As shown in Figs. 5-J and 5-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes depressed from the resin layer, The copper filler is easily formed thereon, and the production efficiency is improved.

Known resins and prepregs can be used for the buried resin (resin). For example, glass poison prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in this specification can be used for the above-mentioned embedding resin (resin).

The carrier-coated copper foil used for the first layer may have a substrate or a resin layer on the surface of the carrier-coated copper foil. By having such a substrate or a resin layer, the carrier-adhered copper foil used for the first layer is supported and wrinkles are less likely to be generated, so that there is an advantage that productivity is improved. Further, any substrate or resin layer can be used for the substrate or resin layer as long as it has the effect of supporting the copper foil with a carrier used for the first layer. For example, the substrate or resin layer may be a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, A foil of an organic compound can be used.

Example

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples at all.

(Examples 1 to 9, 11, 12, and Comparative Examples 1 to 5)

In the electrolytic bath, a titanium-made rotary drum and electrodes were arranged with a gap between the drums around the drums. Next, the electrolytic cell was electrolyzed under the carrier foil manufacturing conditions shown in Table 1 to deposit copper on the surface of the rotary drum, to remove the copper precipitated on the surface of the rotary drum, Which was used as a copper foil carrier. In Examples 1, 2, 6, 8, 9 and 12, the thickness of the copper foil carrier after the surface treatment was 12 탆, 5 탆, 70 탆, 12 탆, 35 탆 and 35 탆, respectively. In Comparative Example 3, a copper foil carrier having a thickness of 12 占 퐉 was used. For Examples 1, 2, 6, 8, 9 and 12, the surface treatment was performed on the copper foil carrier under the conditions shown in Table 1. The electrolysis time was 0.5 to 2 minutes, and the electrolyte temperature was 40 to 60 ° C.

Here, the surface treatment of Examples 2 and 8 will be described. In Examples 2 and 8, a cathode was disposed on the deposition side (also referred to as a matte side or an M side) of the formed electrolytic copper foil, and a copper foil was used as an anode to perform an electrolytic treatment with a direct current, And the copper was dissolved in an amount of 3 to 8 g / m 2 in Example 2 and 8 to 15 g / m 2 in Example 8. The current density of the reverse electrolytic polishing treatment was 5 to 15 A / dm 2 in Example 2 and 16 to 25 A / dm 2 in Example 8. The mirror-polished degree at 60 degrees in the direction of the width of the copper foil was 13 to 40, and the polished degree at 60 degrees in the lengthwise direction of the copper foil was 20 to 94 degrees. In addition, the 60-degree specular gloss was measured at an incident angle of 60 degrees using a gloss meter Handy Gloss Meter PG-1 manufactured by Nippon Seisen Kogyo Co., Ltd. in accordance with JIS Z8741.

Subsequently, an intermediate layer was formed under the following conditions.

And electroplating with a roll-to-roll continuous plating line under the following conditions to form a Ni layer having an adhesion amount of 4000 / / d㎡.

Ni layer

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Sodium citrate: 15-30 g / l

Polishing agents: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 30 to 100 ppm

pH: 4 to 6

Bath temperature: 50 ~ 70 ℃

Current density: 3 ~ 15 A / dm2

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 to 10 g / l, zinc 0 to 5 g / l

pH: 3-4

Temperature: 50 to 60 ° C

Current density: 0.1 to 2.6 A / dm 2

Culm amount: 0.5 to 30 As / dm 2

After formation of the intermediate layer, an ultra-thin copper layer having a thickness of 1 to 10 占 퐉 was formed on the intermediate layer by electroplating under the following conditions to form a copper foil with a carrier.

· Ultra-thin copper layer

Copper concentration: 30 ~ 120 g / ℓ

H ₂ SO ₄ concentration: 20 to 120 g / ℓ

Electrolyte temperature: 20 ~ 80 ℃

Current density: 10 to 100 A / dm 2

In Examples 2 and 3, a roughening treatment layer, a heat-resistant treatment layer, a chromate layer and a silane coupling treatment layer were further formed on the extremely thin copper layer.

· Harmonization

Cu: 10 to 20 g / l

Co: 1-10 g / l

Ni: 1 to 10 g / l

pH: 1-4

Temperature: 40 ~ 50 ℃

Current density Dk: 20 to 30 A / dm 2

Time: 1 to 5 seconds

Cu adhesion amount: 15 to 40 mg / dm 2

Co Coverage: 100 ~ 3000 ㎍ / d㎡

Ni deposition amount: 100 ~ 1000 / / d㎡

· Heat treatment

Zn: 0 to 20 g / l

Ni: 0 to 5 g / l

pH: 3.5

Temperature: 40 ° C

Current density Dk: 0 ~ 1.7 A / dm2

Time: 1 second

Zn deposition amount: 5 ~ 250 / / dm 2

Ni deposition amount: 5 ~ 300 / / 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 to 50 g / l

ZnO or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7 to 13

Bath temperature: 20 ~ 80 ℃

Current density 0.05 to 5 A / dm 2

Time: 5 ~ 30 seconds

Cr deposition amount: 10-150 / / dm 2

· Silane coupling treatment

Aqueous solution of vinyltriethoxysilane

(Vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)

pH: 4 to 5

Time: 5 ~ 30 seconds

(Example 10)

A rolled copper foil (tough pitch copper, JIS H3100 C1100) was prepared, and the rolled copper foil was subjected to finish cold rolling using a rolling roll having a surface blended with sand blast. At this time, the rolling roll roughness Ra was 0.39 to 0.42 占 퐉, and the oil film equivalent was 35,000. Thus, a copper foil carrier was obtained.

Subsequently, a carrier-adhered copper foil was prepared by forming an intermediate layer and an ultra-thin copper layer on the surface (matte surface) of the electrolytic copper foil in the same manner as in Example 1.

The copper foils with a carrier of the examples and comparative examples thus obtained were evaluated in the following manner.

&Lt; Thickness of ultra thin copper layer &

The thickness of the ultra-thin copper layer of the produced copper foil with a carrier was observed using a FIB-SIM (magnification: 10000 to 30000 times). The cross section of the ultra-thin copper layer was observed to measure five points at intervals of 30 占 퐉, and an average value was obtained.

&Lt; Surface roughness of ultra-thin copper layer &

(GHPL-832NX-A manufactured by Mitsubishi Gas Chemical Co., Ltd.) was subjected to a lamination press which was heated at 220 占 폚 for 2 hours. Thereafter, the copper foil carrier was peeled off from the copper foil carrier in accordance with JIS C 6471 8.1 Peel strength of copper foil 8.1.1 Kinds of test method (1) Method A (a method of peeling the copper foil in the 90 占 direction with respect to the copper foil removal surface) was peeled off, The copper layer was exposed. Next, various illuminations of the exposed surface of the ultra-thin copper layer were measured by the following procedure.

(1) Surface roughness of the intermediate layer side of the ultra-thin copper layer

The surface roughness Rz (laser) of the intermediate layer side of the ultra-thin copper layer was measured with a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus Corporation in accordance with JIS B0601-1994. Rz (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Rz (laser) was set as the value of Rz (laser). The standard deviation of the values of 10 points was calculated for Rz (laser).

The surface roughness Ra (laser) of the intermediate layer side of the ultra-thin copper layer was measured with a laser microscope OLS4000 manufactured by Olympus Corporation in accordance with JIS B0601-1994. Ra (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Ra (laser) was taken as the value of Ra (laser). The standard deviation of the values at 10 points was calculated for Ra (laser).

The surface roughness Sz (laser) of the intermediate layer side of the ultra-thin copper layer was measured with a laser microscope OLS4000 manufactured by Olympus Corporation in accordance with ISO25178. Sz (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Sz (laser) was taken as the value of Sz (laser). The standard deviation of the values of 10 points was calculated for Sz (laser).

In accordance with ISO 25178, the Sku on the surface of the intermediate layer side of the ultra-thin copper layer was measured with a laser microscope OLS4000 manufactured by Olympus Corporation.

(2) the surface roughness of the carrier on the side forming the ultra-thin copper layer

The surface roughness Rz (laser) of the carrier on the side where the ultra-thin copper layer was formed was measured with a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus, according to JIS B0601-1994. Rz (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Rz (laser) was set as the value of Rz (laser). The standard deviation of the values of 10 points was calculated for Rz (laser).

The surface roughness Ra (laser) of the carrier on the side where the ultra-thin copper layer was formed was measured with a laser microscope OLS4000 manufactured by Olympus Corporation according to JIS B0601-1994. Ra (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Ra (laser) was taken as the value of Ra (laser). The standard deviation of the values of Ra (laser) at 10 points was calculated.

The surface roughness Sz (laser) of the carrier on the side where the ultra-thin copper layer was formed was measured by a laser microscope OLS4000 manufactured by Olympus Corporation in accordance with ISO25178. Sz (laser) was arbitrarily measured at 10 points, and the average value of 10 points of the Sz (laser) was taken as the value of Sz (laser). The standard deviation of the values of 10 points was calculated for Sz (laser).

Further, according to ISO 25178, the Sku of the surface of the carrier on the side where the ultra-thin copper layer was formed was measured with a laser microscope OLS4000 manufactured by Olympus Corporation.

The above Rz and Ra were measured in the direction (TD) in the direction perpendicular to the rolling direction when the carrier is rolled copper foil under the condition of an evaluation length (reference length) of 257.9 占 퐉 and a cutoff value of zero in observation of the ultra- ) Or in the case where the carrier is an electrolytic copper foil, the respective values were obtained by measuring the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the electrolytic copper foil production apparatus. With respect to Sz and Sku described above, the values were obtained by performing measurements on the extremely thin copper layer and the carrier surface under the conditions of an evaluation area (reference area) of 66524 mu m and a cutoff value of zero. The measurement environment temperature of Sz, Rz, Ra, and Sku of the surface by laser microscope was set at 23 to 25 ° C. For Examples 1, 2, 6, 8, 9 and 12, Sz, Ra, Rz and Sku of the copper foil carrier after surface treatment were measured.

&Lt; Laser hole forming property &

Next, one shot was irradiated to the untreated surface (surface of the intermediate layer side of the extremely thin copper layer) of the extremely thin copper layer under the following condition, and the shape of the hole after irradiation was observed with a microscope, and measurement was carried out. In the table, as a "real number" of hole formation, it is tried to form a hole at twelve points to actually show how many (X) holes are formed (X / 12) Ratio "(%). The table also shows the average diameter of the holes formed at this time, the standard deviation of the diameter of the formed holes, and the average diameter / beam diameter. Further, the diameter of the hole was the minimum diameter of the circle surrounding the hole.

· Gas species: CO ₂

· Copper opening diameter (target): 80 μm diameter

· Beam shape: Top hat

Output: 2.40 W / 10 μs

Pulse width: 33 ㎲

· Number of shots: 1 Shot

Number of holes: 12 holes / area

<Etching Properties>

The copper foil with a carrier was attached to a polyimide substrate and hot-pressed at 220 캜 for 2 hours. Thereafter, the ultra-thin copper layer was peeled from the carrier. Subsequently, a photosensitive resist is coated on the surface of the extremely thin copper layer on the polyimide substrate, and then a circuit of 50 L / S = 5 mu m / 5 mu m width is printed by the exposure process to remove unnecessary portions of the copper layer The etching treatment was carried out under the following spray etching conditions.

(Spray etching conditions)

Etching solution: aqueous solution of ferric chloride (bohde degree: 40 degrees)

Temperature: 60 ° C

Spraying pressure: 2.0 MPa

Etching was continued to measure the time until the circuit top width became 4 탆, and the circuit bottom width (the length of the bottom side X) and etch factor at that time were evaluated. Assuming that the circuit is etched vertically, assuming that the distance between the waterline from the upper surface of the copper foil and the length of the sag from the intersection of the resin substrate is a, The ratio of the thickness a of the copper foil to the thickness b of the copper foil: b / a. In this case, the larger the value is, the larger the inclination angle means that the etching residue is not left and the elongation becomes smaller. Fig. 1 schematically shows a cross-sectional view of a width direction of a circuit pattern and a calculation method of 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. Further, a = (X (占 퐉) - 4 (占 퐉)) / 2 was calculated. The etch factor is obtained by measuring 12 points in the circuit and taking an average value. Thus, it is possible to easily determine whether the etching property is good or bad. In addition, by calculating the standard deviation of the etching factors of 12 points, it is possible to determine whether the circuit formed by etching is good or bad.

In the present invention, it is evaluated that the etching property is not less than 4 and the etching property is not less than 2.5, the etching property is not less than 2.5, . It can be said that the smaller the standard deviation of the etching factor is, the better the linearity of the circuit is. When the standard deviation of the etching factor was less than 0.8, the linearity was evaluated as O, the linearity was less than 0.8 to 1.2, and the linearity was 1.2.

Test conditions and test results are shown in Tables 1 to 3.

(Evaluation results)

In Examples 1 to 12, since the surface roughness Sz (laser) of the intermediate layer side of the extremely thin copper layer was 1.40 탆 or more and 4.05 탆 or less, laser hole forming property and etching property were good.

In Comparative Examples 1 and 5, since the surface roughness Sz (laser) of the intermediate layer side of the extremely thin copper layer was less than 1.40 탆, the laser hole forming property was poor.

In Comparative Examples 2 to 4, the surface roughness Sz (laser) on the side of the intermediate layer of the extremely thin copper layer exceeded 4.05 占 퐉, so that the etching property was poor.

In Examples 1 to 12, since the surface roughness Ra (laser) of the intermediate layer side of the extremely thin copper layer was 0.14 탆 or more and 0.35 탆 or less, laser hole forming property and etching property were good.

In Comparative Examples 1 and 5, since the surface roughness Ra (laser) of the intermediate layer side of the extremely thin copper layer was less than 0.14 탆, the laser hole forming property was poor.

In Comparative Examples 2 to 4, the surface roughness Ra (laser) on the side of the intermediate layer of the extremely thin copper layer exceeded 0.35 mu m, and thus the etching property was poor.

In Examples 1 to 12, since the surface roughness Rz (laser) of the intermediate layer side of the extremely thin copper layer was 0.62 탆 or more and 1.59 탆 or less and the standard deviation of the surface roughness Rz (laser) was 0.51 탆 or less, Laser hole forming property and etching property were good.

In Comparative Examples 1 and 5, since the surface roughness Rz (laser) of the intermediate layer side of the ultra-thin copper layer was all less than 0.62 mu m, the laser hole forming property was poor.

In Comparative Examples 2 to 4, since the surface roughness Rz (laser) on the side of the intermediate layer of the extremely thin copper layer exceeded 1.59 탆, the etching property was poor.

Claims (26)

A carrier-attached copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order,
The surface of the extremely thin copper layer measured by a laser microscope when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the ultra-thin copper layer according to JIS C 6471 has a surface roughness Sz of 1.40 탆 or more 4.05 탆 or less. The method according to claim 1,
The surface of the extremely thin copper layer measured by a laser microscope when the surface of the copper foil with a carrier is heated at 220 캜 for 2 hours and then peeling off the extremely thin copper layer according to JIS C 6471 is 0.14 탆 or more 0.35 탆 or less. A carrier-attached copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order,
The surface of the extremely thin copper layer measured by a laser microscope when the surface of the copper foil with a carrier is heated at 220 캜 for 2 hours and then peeling off the extremely thin copper layer according to JIS C 6471 is 0.14 탆 or more 0.35 탆 or less. 4. The method according to any one of claims 1 to 3,
Wherein the surface of the extremely thin copper layer measured by a laser microscope when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the extremely thin copper layer according to JIS C 6471 has a surface roughness Rz of 0.62 탆 or more 1.59 탆 or less, and the standard deviation of the surface roughness Rz is 0.51 탆 or less. A carrier-attached copper foil having a carrier, an intermediate layer and an ultra-thin copper layer in this order,
Wherein the surface of the extremely thin copper layer measured by a laser microscope when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the extremely thin copper layer according to JIS C 6471 has a surface roughness Rz of 0.62 탆 or more 1.59 탆 or less, and the standard deviation of the surface roughness Rz is 0.51 탆 or less. 6. The method according to any one of claims 1 to 5,
When the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the standard deviation of the surface roughness Sz of the ultra-thin copper layer measured by a laser microscope is 1.30 탆 or less, with a carrier. The method according to claim 6,
When the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the standard deviation of the surface roughness Sz of the ultra-thin copper layer measured by a laser microscope is Wherein the carrier-bonded copper foil is 0.01 占 퐉 or more and 1.20 占 퐉 or less. 8. The method according to any one of claims 1 to 7,
The surface of the extremely thin copper layer measured by a laser microscope when the carrier-coated copper foil is heated at 220 캜 for 2 hours and then peeling off the ultra-thin copper layer according to JIS C 6471 has a surface roughness Sz of 1.60 탆 or more 3.70 탆 or less, with a carrier. 9. The method according to any one of claims 1 to 8,
When the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the standard deviation of the surface roughness Ra of the ultra-thin copper layer measured by a laser microscope is 0.11 탆 or less. 10. The method of claim 9,
When the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the standard deviation of the surface roughness Ra of the ultra-thin copper layer measured by a laser microscope is 0.001 mu m or more and 0.10 mu m or less. 11. The method according to any one of claims 1 to 10,
When the carrier-coated copper foil was heated at 220 캜 for 2 hours and then the ultra-thin copper layer was peeled off according to JIS C 6471, the standard deviation of the surface roughness Rz of the ultra-thin copper layer measured by a laser microscope Wherein the copper foil is 0.01 占 퐉 or more and 0.48 占 퐉 or less. 12. The method according to any one of claims 1 to 11,
The copper foil with a carrier was heated at 220 占 폚 for 2 hours and then peeled off according to JIS C 6471 in accordance with JIS C 6471 and the sharpness of the surface height distribution of the extremely thin copper layer measured by a laser microscope Degree) Sku of not less than 0.50 but not more than 3.70. 13. The method of claim 12,
When the carrier-coated copper foil is heated at 220 캜 for 2 hours and then the ultra-thin copper layer is peeled off according to JIS C 6471, the skewness Sku of the surface height distribution of the ultra-thin copper layer measured by a laser microscope 1.00 or more and 3.60 or less. 14. The method according to any one of claims 1 to 13,
Wherein the carrier has a thickness of 5 to 70 占 퐉. 15. The method according to any one of claims 1 to 14,
And a roughened layer on the surface of the ultra-thin copper layer. 16. The method of claim 15,
Wherein the roughening treatment layer is a layer made of an alloy containing any one or more selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc, . 17. The method according to claim 15 or 16,
Wherein the surface of the roughening treatment 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. 15. The method according to any one of claims 1 to 14,
Wherein the ultra thin copper layer has at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the ultra thin copper layer. 15. The method according to any one of claims 1 to 14,
And a resin layer on the extremely thin copper layer. 17. The method according to claim 15 or 16,
And a resin layer on the roughening treatment layer. The method according to claim 17 or 18,
And a resin layer on at least one layer selected from the group consisting of the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. A printed wiring board produced by using the copper foil with a carrier according to any one of claims 1 to 21. A copper clad laminate produced by using the copper foil with a carrier according to any one of claims 1 to 21. An electronic device manufactured using the printed wiring board according to claim 22. A method for manufacturing a semiconductor device, comprising the steps of: preparing the copper foil with a carrier according to any one of claims 1 to 21 and an insulating substrate;
A step of laminating the copper foil with a carrier and an insulating substrate,
After the step of laminating the carrier-bonded copper foil with the insulating substrate and the step of peeling the carrier of the carrier-coated copper foil, a copper clad laminate is formed,
And then forming a circuit by any one of a semi-additive method, a subtractive method, a pattern additive method, and a modified semi-additive method. A process for producing a copper foil with a carrier according to any one of claims 1 to 21,
Forming a resin layer on the surface of the carrier-coated copper foil on the extremely thin copper layer side so that the circuit is buried,
A step of forming a circuit on the resin layer,
A step of forming a circuit on the resin layer and thereafter peeling the carrier,
A step of exposing a circuit buried in the resin layer formed on the surface of the extremely thin copper layer by removing the extremely thin copper layer after peeling the carrier,
And a step of forming the printed circuit board.

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