TWI526299B - Manufacturing method of supporting copper foil, printed wiring board, copper clad sheet, electronic machine and printed wiring board - Google Patents

Description

Carrier copper foil, printed wiring board, copper clad laminate, electronic device, and printed wiring board manufacturing method

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

The printed wiring board is usually produced by forming a copper-clad laminate after the copper foil and the insulating substrate are bonded to each other, and then etching the copper foil surface to form a conductor pattern. With the increase in the demand for miniaturization and high performance of electronic devices, high-density mounting of mounted components or high-frequency signals have been developed, and it has been required to miniaturize (finely pitch) or increase the conductor pattern on printed wiring boards. Frequency correspondence.

Corresponding to the fine pitch, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less has recently been required. However, such an extremely thin copper foil has low mechanical strength and is liable to be broken or wrinkled during the manufacture of a printed wiring board, so that A metal foil having a thickness is used as a carrier, and a copper foil with a carrier on which a very thin copper layer is plated with a release layer is interposed. After bonding the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, the carrier is peeled off by the release layer. A predetermined circuit is formed by forming a circuit pattern on the exposed ultra-thin copper layer by a resist.

Here, the surface of the ultra-thin copper layer which is the copper foil with a carrier which is the adhesive surface of the resin is required to have sufficient peeling strength of the ultra-thin copper layer and the resin substrate, and the peeling strength is heated even at a high temperature, and the wet treatment is performed. After welding, chemical treatment, etc., it is also fully maintained. As The method of increasing the peeling strength between the ultra-thin copper layer and the resin substrate is generally a method of attaching a large amount of roughened particles to an extremely thin copper layer having an increased surface profile (concavity and roughness).

However, in the printed wiring board, particularly for a semiconductor package substrate in which a fine circuit pattern needs to be formed, an extremely thin copper layer having such a large profile (concavity, roughness, roughness) is used, and it is not necessary to be left in the circuit etching. The copper particles cause problems such as poor insulation between circuit patterns.

Therefore, in WO2004/005588 (Patent Document 1), a copper foil with a carrier which is not subjected to roughening treatment on the surface of the ultra-thin copper layer is used as a carrier-attached copper foil for use as a fine circuit for a semiconductor package substrate. The adhesion (peeling strength) between the ultra-thin copper layer and the resin which are not subjected to the roughening treatment is affected by the lower profile (concavity, roughness, roughness), and the copper for the conventional printed wiring board. There is a tendency for the foil to decrease compared to the foil. Therefore, further improvement is required for the copper foil with a carrier.

In JP-A-2007-007937 (Patent Document 2), JP-A-2010-006071 (Patent Document 3) discloses a contact with a polyimide-based resin substrate in an ultra-thin copper foil with a carrier. On the (subsequent) surface, a Ni layer or/and a Ni alloy layer, a chromate layer, a Cr layer or/and a Cr alloy layer, a Ni layer and a chromate layer, and a Ni layer and a Cr layer are provided. By providing such a surface treatment layer, the adhesion strength between the polyimide film and the carrier-attached ultra-thin copper foil is obtained without performing the roughening treatment, or the degree of the roughening treatment (reduction) is required. Then the intensity. Further, surface treatment or rust prevention treatment using a decane coupling agent is also described.

Patent Document 1: WO2004/005588

Patent Document 2: Japanese Laid-Open Patent Publication No. 2007-007937

Patent Document 3: Japanese Laid-Open Patent Publication No. 2010-006071

Patent Document 4: Japanese Patent No. 3261119

In the development of the carrier-attached copper foil, the focus has been on ensuring the peel strength of the extremely thin copper layer and the resin substrate. Therefore, there has not been sufficient research on the copper foil with a carrier suitable for high-density mounting of a printed wiring board, 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 through which the inner layer and the outer layer are connected is generally used. Further, regarding the method of forming a fine circuit with a narrow pitch, a method of etching an extremely thin copper layer by a sulfuric acid-hydrogen peroxide-based etchant after forming a wiring circuit on an extremely thin copper layer (MSAP (Modified- Semi-Additive-Process (modified semi-additive process)), therefore, the laser opening of the ultra-thin copper layer is an important item in the production of a high-density integrated circuit substrate. Since the laser opening property of the extremely thin copper layer is related to the aperture precision and the laser output, the design and productivity of the integrated circuit are greatly affected. Japanese Laid-Open Patent Publication No. 3261119 (Patent Document 4) discloses a copper-clad laminate having excellent laser opening properties. However, according to research by the inventors of the present invention, there is still room for improvement in etchability.

Accordingly, an object of the present invention is to provide a copper foil with a carrier which is excellent in laser opening properties and which is suitable for producing a high-density integrated circuit board.

In order to achieve the above object, the inventors of the present invention conducted an intensive research and found that the surface roughness of the ultra-thin copper layer peeling side measured by a laser microscope when the ultra-thin copper layer was peeled off from the copper foil with a predetermined heat treatment was controlled. Degree is extremely effective for improving the laser opening of the ultra-thin copper layer.

In one aspect of the present invention, a copper foil with a carrier is provided with a carrier, an intermediate layer, and an extremely thin copper layer, and the copper foil of the carrier is heated at 220 ° C for 2 hours, and then stripped according to JIS C 6471. In the case of the ultra-thin copper layer, the surface roughness Sz of the ultra-thin copper layer measured on the intermediate layer side by a laser microscope is 1.40 μm or more and 4.05 μm or less.

In one embodiment of the copper foil with carrier of the present invention, the copper foil with the carrier is After heating at 220 ° C for 2 hours, when the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the standard deviation of the surface roughness Sz of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope was 1.30 μm or less.

In another embodiment, the copper foil with carrier of the present invention is used for the copper foil with carrier After heating at 220 ° C for 2 hours, when the ultra-thin copper layer is peeled according to JIS C 6471, the standard deviation of the surface roughness Sz of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope is 0.01 μm or more and 1.20 μm. the following.

In still another embodiment of the copper foil with carrier of the present invention, the copper carrier is provided After the foil was heated at 220 ° C for 2 hours, the ultra-thin copper layer was peeled off according to JIS C 6471, and the surface roughness Sz of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope was 1.60 μm or more and 3.70 μm or less.

In another aspect of the invention, a copper foil with a carrier is provided with a load in sequence. a body, an intermediate layer, and an ultra-thin copper layer, after the copper foil with the carrier is heated at 220 ° C for 2 hours, when the ultra-thin copper layer is peeled according to JIS C 6471, the ultra-thin copper layer is measured by a laser microscope. The surface roughness Ra of the intermediate layer side is 0.14 μm or more and 0.35 μm or less.

In another aspect of the copper foil with carrier of the present invention, the copper foil with the carrier is After heating at 220 ° C for 2 hours, when the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the standard deviation of the surface roughness Ra of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope was 0.11 μm or less.

In another aspect of the copper foil with carrier of the present invention, the copper foil with the carrier is After heating at 220 ° C for 2 hours, when 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 on the intermediate layer side measured by a laser microscope is 0.001 μm or more and 0.10 μm or less. .

In still another aspect of the present invention, a copper foil with a carrier is provided with a load in sequence. a body, an intermediate layer, and an ultra-thin copper layer, after the copper foil with the carrier is heated at 220 ° C for 2 hours, when the ultra-thin copper layer is peeled according to JIS C 6471, the ultra-thin copper layer is measured by a laser microscope. The surface roughness Rz on the intermediate layer side is 0.62 μm or more and 1.59 μm or less, and the standard deviation of the surface roughness Rz is 0.51 μm or less.

In still another aspect of the invention, the copper foil with a carrier is heated by the carrier copper foil at 220 ° C for 2 hours, and the pole is measured by a laser microscope when the ultra-thin copper layer is peeled according to JIS C 6471. The standard deviation of the surface roughness Rz of the thin copper layer on the intermediate layer side is 0.01 μm or more and 0.48 μm or less.

In still another aspect of the invention, the copper foil with a carrier is heated by the carrier copper foil at 220 ° C for 2 hours, and the pole is measured by a laser microscope when the ultra-thin copper layer is peeled according to JIS C 6471. The kurtosis Sku of the surface height distribution of the thin copper layer on the intermediate layer side is 0.50 or more and 3.70 or less.

In still another aspect of the invention, the copper foil with a carrier is heated by the carrier copper foil at 220 ° C for 2 hours, and the pole is measured by a laser microscope when the ultra-thin copper layer is peeled according to JIS C 6471. The kurtosis Sku of the surface height distribution of the thin copper layer on the intermediate layer side is 1.00 or more and 3.60 or less.

In still another aspect of the copper foil with a carrier of the present invention, the carrier has a thickness of 5 to 70 μm.

In still another aspect, the copper foil with a carrier of the present invention has a roughened layer on the surface of the ultra-thin copper layer.

In still another aspect of the present invention, the roughened layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. A single layer or a layer comprising any one or more of these elements.

The copper foil with carrier of the present invention is in another aspect, in the form of the roughened layer The surface has one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer.

In still another aspect, the copper foil with a carrier of the present invention has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the ultra-thin copper layer. Layer.

In still another aspect of the copper foil with a carrier of the present invention, a resin layer is provided on the ultra-thin copper layer.

In still another aspect of the copper foil with a carrier of the present invention, a resin layer is provided on the roughened layer.

In still another aspect, the copper foil with a carrier of the present invention has a resin layer on the layer selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. .

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

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

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

According to still another aspect of the present invention, a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the insulating substrate; After the carrier copper foil is laminated with the insulating substrate, the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified half-addition A circuit is formed by any of the methods.

In still another aspect of the invention, a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; a method of burying the circuit to form a resin layer on a side surface of the ultra-thin copper layer of the copper foil with a carrier; forming a circuit on the resin layer; peeling off the carrier after forming a circuit on the resin layer; and stripping the carrier Thereafter, the ultra-thin copper layer is removed, whereby the circuit formed on the side surface of the ultra-thin copper layer and buried in the resin layer is exposed.

According to the present invention, it is possible to provide a copper foil with a carrier which is excellent in laser opening properties and which is suitable for producing a high-density integrated circuit substrate.

Fig. 1 is a schematic view showing a cross section of a width direction of a circuit pattern in the embodiment, and an outline of a calculation method of an etching factor (EF) using the schematic diagram.

2A to 2C are schematic views showing a cross section of the wiring board in the step of removing the resist from the plating circuit and the specific example of the method of manufacturing the printed wiring board with the copper foil with a carrier of the present invention.

FIG. 3D to FIG. 3F are schematic diagrams showing the cross section of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening using the printed wiring board with the carrier-attached copper foil of the present invention. .

4G to 4I are schematic views showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier, in the method of manufacturing the printed wiring board with the copper foil with a carrier of the present invention.

5J to 5K are schematic views showing a cross section of a wiring board in a step from flash etching to formation of a bump or a copper pillar in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention.

<With carrier copper foil>

The copper foil with a carrier of the present invention comprises a carrier, an intermediate layer laminated on the carrier, and an extremely thin copper layer laminated on the intermediate layer. The method of using the carrier copper foil itself is well known in the art. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass. Cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate on epoxy resin, polyester film, polyimide film, etc., and the carrier is peeled off after thermocompression bonding A very thin copper layer which is followed by an insulating substrate is etched into a target conductor pattern to finally produce a printed wiring board.

The copper foil with carrier of the present invention is in one aspect, and the copper foil with carrier is 220 ° C After heating for 2 hours, when the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the surface roughness Sz (10-point height of the surface) of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side was controlled to be 1.40 μm or more and 4.05 μm. the following. The carrier-attached copper foil is bonded to the insulating substrate, and the carrier is peeled off by thermocompression bonding, and the extremely thin copper layer next to the insulating substrate is etched into a target conductor pattern to form a circuit. The printed wiring board was produced by forming the substrate into a multilayer structure in the above manner. 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, if it is difficult to open the laser hole in the extremely thin copper layer, it is of course a problem, and if the laser hole is too large or too small, various problems are caused, and therefore it is necessary to form an appropriate size. As described above, the laser opening property of the ultra-thin copper layer is related to various conditions such as the aperture accuracy and the laser output, and is therefore an important characteristic that greatly affects the design and productivity of the integrated circuit. In the present invention, it was found that the laser opening property of the ultra-thin copper layer is improved by the following operation, that is, after the carrier copper foil is heated at 220 ° C for 2 hours, the ultra-thin copper layer is peeled off in accordance with JIS C 6471. In the meantime, the surface roughness Sz of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side is controlled to be 1.40 μm or more and 4.05 μm or less. If the surface roughness Sz of the ultra-thin copper layer measured by the laser microscope on the side of the intermediate layer is less than 1.40 μm, the following problem occurs: the roughness of the surface of the extremely thin copper layer is insufficient and the absorption of the laser during the hole processing is caused. The sex becomes worse and it becomes difficult to open the hole, even if the hole is opened, it becomes a smaller hole. Moreover, if the ultra-thin copper layer measured by the laser microscope has a surface roughness Sz of more than 4.05 on the side of the intermediate layer When μm, there is a problem that the roughness of the surface of the extremely thin copper layer is too large, and the absorption of the laser at the time of the opening processing becomes excessive, and the pore becomes excessive. The surface roughness Sz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 1.60 μm or more and 3.70 μm or less, preferably 1.80 μm or more and 3.50 μm or less, and more preferably 2.40 μm or more and 3.70 μm or less. . In the above, "heating at 220 ° C for 2 hours" is a typical heating condition in the case where the carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonded.

Moreover, the copper foil with carrier of the present invention preferably heats the copper foil with carrier at 220 ° C After 2 hours, when the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the standard deviation of the surface roughness Sz of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side was controlled to 1.30 μm or less. If the standard deviation of the surface roughness Sz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side exceeds 1.30 μm, there is an increase in the unevenness of the laser aperture (ie, an increase in the standard deviation) or an etching factor. The problem of uneven increase (ie, increased standard deviation). Further, the standard deviation of the surface roughness Sz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 0.01 μm or more and 1.20 μm or less, more preferably 0.05 μm or more and 1.10 μm or less, and particularly preferably 0.10. Μm or more and 1.00 μm or less.

The copper foil with carrier of the present invention is in another aspect, After heating at 220 ° C for 2 hours, when the ultra-thin copper layer was peeled off according to JIS C 6471, the surface roughness Ra (arithmetic mean roughness) of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side was controlled to be 0.14 μm or more and 0.35. Below μm. The carrier-attached copper foil is bonded to the insulating substrate, and the carrier is peeled off by thermocompression bonding, and the extremely thin copper layer next to the insulating substrate is etched into a target conductor pattern to form a circuit. The printed wiring board was produced by forming the substrate into a multilayer structure in the above manner. 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, if it is difficult to open the laser hole in the extremely thin copper layer, it is of course a problem, and if the laser hole is too large or too small, various problems are caused, and therefore it is necessary to form an appropriate size. Thus, the laser opening property of the extremely thin copper layer is related to various conditions such as the aperture accuracy and the laser output. It is an important feature that has a large impact on the design and productivity of the integrated circuit. In the present invention, it has been found that the laser opening property of the ultra-thin copper layer is improved by heating the carrier-attached copper foil at 220 ° C for 2 hours and then peeling off the above-mentioned ultra-thin copper layer in accordance with JIS C 6471. The surface roughness Ra of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side is controlled to be 0.14 μm or more and 0.35 μm or less. If the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is less than 0.14 μm, the following problem occurs: the roughness of the surface of the ultra-thin copper layer is insufficient and the laser absorption during the hole processing is performed. It becomes difficult to open the hole, and even if the hole is opened, it becomes a smaller hole. Further, if the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side exceeds 0.35 μm, the following problem occurs: the roughness of the surface of the ultra-thin copper layer is too large and the laser absorption during the hole processing Sex becomes excessive and the hole becomes too large. The surface roughness Ra of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side is preferably 0.16 μm or more and 0.32 μm or less, more preferably 0.18 μm or more and 0.32 μm or less, and still more preferably 0.20 μm or more and 0.32 μm or less. . Moreover, the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 0.14 μm or more and 0.30 μm or less. In addition, the above-mentioned "heating at 220 ° C for 2 hours" indicates typical heating conditions in the case where the carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonded.

Moreover, the copper foil with carrier of the present invention preferably has the above-mentioned copper foil with a carrier at 220 ° C. After the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the standard deviation of the surface roughness Ra of the ultra-thin copper layer measured on the intermediate layer side by a laser microscope was controlled to be 0.11 μm or less. If the standard deviation of the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side exceeds 0.11 μm, there is an increase in the unevenness of the laser aperture (ie, an increase in the standard deviation) or etching. The problem of an increase in the unevenness of the factor (ie, an increase in the standard deviation). Further, the standard deviation of the surface roughness Ra of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 0.001 μm or more and 0.10 μm or less, more preferably 0.003 μm or more and 0.09 μm or less, and still more preferably It is 0.005 μm or more and 0.08 μm or less, and more preferably 0.005 μm or more and 0.06 μm or less.

In another aspect of the copper foil with carrier of the present invention, the copper foil with a carrier is After heating at 220 ° C for 2 hours, when the ultra-thin copper layer was peeled off according to JIS C 6471, the surface roughness Rz (ten-point average roughness) of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side was controlled to 0.62 μm or more. 1.59 μm or less. The carrier-attached copper foil is bonded to the insulating substrate, and the carrier is peeled off by thermocompression bonding, and the extremely thin copper layer next to the insulating substrate is etched into a target conductor pattern to form a circuit. The printed wiring board was produced by forming the substrate into a multilayer structure in the above manner. 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, if it is difficult to open the laser hole in the extremely thin copper layer, it is of course a problem, and if the laser hole is too large or too small, various problems are caused, and therefore it is necessary to form an appropriate size. As described above, the laser opening property of the ultra-thin copper layer is related to various conditions such as the aperture accuracy and the laser output, and is therefore an important characteristic that greatly affects the design and productivity of the integrated circuit. In the present invention, it has been found that the laser opening property of the ultra-thin copper layer is improved by heating the carrier-attached copper foil at 220 ° C for 2 hours and then peeling off the above-mentioned ultra-thin copper layer in accordance with JIS C 6471. The surface roughness Rz of the ultra-thin copper layer measured by a laser microscope on the intermediate layer side is controlled to be 0.62 μm or more and 1.59 μm or less. If the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the side of the intermediate layer is less than 0.62 μm, the following problem occurs: the roughness of the surface of the ultra-thin copper layer is insufficient and the laser absorption during the hole processing is performed. It becomes difficult to open the hole, and even if the hole is opened, it becomes a smaller hole. Further, if the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side exceeds 1.59 μm, the following problem occurs: the roughness of the surface of the ultra-thin copper layer is too large and the laser is used for the hole processing. The absorption becomes excessive and the pores become too large. The surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 0.70 μm or more and 1.52 μm or less, more preferably 0.80 μm or more and 1.50 μm or less, and still more preferably 0.90 μm or more and 1.40 μm or less. . Moreover, the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is more preferably 1.10 μm or more and 1.50 μm or less. In addition, the above-mentioned "heating at 220 ° C for 2 hours" indicates typical heating conditions in the case where the carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonded.

Further, in the copper foil with carrier of the present invention, the copper foil with a carrier is heated at 220 ° C. After the etch of the ultra-thin copper layer in accordance with JIS C 6471, the standard deviation of the surface roughness Rz of the ultra-thin copper layer measured on the intermediate layer side by a laser microscope is controlled to 0.51 μm or less. If the standard deviation of the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side exceeds 0.51 μm, the unevenness of the laser aperture (ie, the standard deviation is increased) or the etching factor is not generated. The problem of increasing (ie, increasing the standard deviation). Further, the standard deviation of the surface roughness Rz of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side is preferably 0.01 μm or more and 0.48 μm or less, more preferably 0.04 μm or more and 0.40 μm or less, and still more preferably 0.04 or less. The μm or more is 0.35 μm or less, and more preferably 0.05 μm or more and 0.20 μm or less.

Moreover, the copper foil with carrier of the present invention preferably heats the copper foil with carrier at 220 ° C After 2 hours, when the ultra-thin copper layer was peeled off in accordance with JIS C 6471, the kurtosis Sku (Kurtosis) of the surface height distribution of the ultra-thin copper layer measured by the laser microscope on the intermediate layer side was controlled to be 0.50 or more and 3.70 or less. If Sku does not reach 0.50, there is a problem that the shape of the convex portion on the surface of the extremely thin copper layer is flat, so that the laser absorbability at the time of opening processing is deteriorated, and it becomes difficult to open the hole, even if it is opened. The hole also becomes a smaller hole. Further, when the Sku is larger than 3.70, there is a problem that the convex portion of the uneven surface of the ultra-thin copper layer has a steep shape, and the energy of the laser is locally absorbed, and the actual irradiation angle with respect to the laser is actually The size of the hole becomes larger. The copper foil with a carrier of the present invention is more preferably a surface of an extremely thin copper layer measured on a middle layer side by a laser microscope when the copper foil with a carrier is heated at 220 ° C for 2 hours, and the ultra-thin copper layer is peeled according to JIS C 6471. The height distribution kurtosis Sku is controlled to be 1.00 or more and 3.60 or less, and more preferably controlled to 1.50 or more and 3.30 or less, and more preferably controlled to 1.50 or more and 3.20 or less, and more preferably controlled to 1.50 or more and 3.10 or less. The control is preferably 1.50 or more and 3.00 or less.

<carrier>

The carrier usable in the present invention is typically a metal foil or a resin film, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, A resin film, a polyimide film, or an LCD film is provided.

The carrier which can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath on a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy No. C1100) or oxygen-free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011), for example, Sn-doped copper or Ag-doped may be used. Copper, and a copper alloy to which a Cr alloy such as Cr, Zr, or Mg is added, or a Cason copper alloy to which Ni or Si is added. Further, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

There is no particular limitation on the thickness of the carrier that can be used in the present invention, as long as it is The thickness may be appropriately adjusted to suit the thickness of the carrier, and may be, for example, 5 μm or more. However, if the production cost is increased if it is too thick, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and still more typically 18 to 35 μm. Further, from the viewpoint of reducing the cost of raw materials, it is preferred that the thickness of the carrier be thin. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, more preferably 5 μm or more and 12 μm or less, still more preferably 5 μm or more and 11 μm or less, and still more preferably 5 μm or more and 10 μm or less. Furthermore, in the case where the thickness of the carrier is thin, creases are likely to occur when the carrier is passed through the foil. In order to prevent creases, it is effective to smooth the conveyance roller of the carrier copper foil manufacturing apparatus, for example, or to shorten the distance between the conveyance roller and the next conveyance roller.

The above-mentioned ultra-thin copper layer measured by a laser microscope of the present invention is on the middle layer side The surface roughness Sz, Ra, Rz and the standard deviation of these, and Sku can be controlled by adjusting the surface morphology of the extremely thin copper layer of the carrier. Hereinafter, a method of producing the carrier of the present invention will be described.

One of the production conditions when an electrolytic copper foil is used as a carrier is exemplified below.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

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

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

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

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

The surface roughness Sz, Ra, Rz of the ultra-thin copper layer on the intermediate layer side and the standard deviations thereof, and the Sku system are controlled by adjusting the surface morphology of the ultra-thin copper layer side of the carrier. As an adjustment of the surface form of the ultra-thin copper layer of the carrier, the following adjustment methods (1) to (3) are exemplified. Furthermore, as shown in Table 2, the shape of the side surface of the extremely thin copper layer of the carrier and the surface of the extremely thin copper layer on the side of the carrier The form is close to the form. Therefore, by adjusting the morphology of the side surface of the extremely thin copper layer of the carrier, the carrier-attached ultra-thin copper foil having the desired surface of the carrier-side ultra-thin copper layer can be obtained.

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

Specifically, the surface roughness Rz is 0.2 μm to 0.6 μm, or the surface roughness Ra is 0.2 μm to 0.6 μm, or the surface roughness Sz is 0.2 μm to 0.6 μm, and the 60-degree specular gloss is 500% or more. The carrier is subjected to a soft etching treatment (for example, an aqueous solution of 5 to 15 vol% of sulfuric acid, 0.5 to 5.0% by weight of hydrogen peroxide, an etching treatment at 10 to 30 ° C for 0.5 to 10 minutes) or a reverse electrolytic treatment (electrolysis of the shiny side) Grinding to form irregularities).

Further, the above "reverse electrolytic polishing" is electrolytic polishing. In general, the electrolytic polishing is aimed at smoothing. Therefore, it is generally understood that when the electrolytic copper foil is subjected to electrolytic polishing, the surface (rough surface) opposite to the shiny surface is targeted. However, here, since the uneven surface is formed by electrolytic polishing of the shiny surface, it is an electrolytic polishing process which is the opposite of the usual, that is, a reverse electrolytic polishing process. Further, the amount of copper dissolved by the reverse electrolytic treatment is set to 2 to 20 g/m ² . Further, 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 calendering using a calendering calendering roll.

Specifically, a rolled copper foil is prepared as a carrier, and the rolled copper foil is subjected to cold rolling by final processing using a calender roll which is roughened by sandblasting. In this case, the calender roll roughness Ra = 0.39 to 0.42 μm and the oil film equivalent of 29000 to 40,000.

Here, the oil film equivalent is expressed by the following formula.

Oil film equivalent = {(calender oil viscosity [cSt]) × (passing plate speed [mpm] + roll peripheral speed [mpm])} / {(roller bite angle [rad]) × (material fall stress [kg / Mm ² ])}

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

In order to set the oil film equivalent to 29,000 to 40,000, a known method such as using a high-viscosity rolling oil or accelerating the speed of the sheet can be used.

(3) The carrier is produced by the prescribed electrolytic conditions.

Specifically, a copper sulfate electrolyte (copper concentration: 80 to 120 g/L, sulfuric acid concentration: 70 to 90 g/L) is used, and a high concentration gelatin (gelatin concentration: 3 to 10 mass ppm) is used as an additive at a high current density. (75~110A/dm ² ) and a high-line flow rate (3.7~5.0m/sec) to produce an electrolytic copper foil carrier.

<intermediate layer>

An intermediate layer is provided on one or both sides of the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and the insulating layer is insulated. After the lamination step of the substrate, the ultra-thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or more of these oxides and organic compounds. Also, the intermediate layer may be a plurality of layers.

Further, for example, the intermediate layer may be formed by forming an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, and thereon A layer composed of a hydrate or an oxide selected from one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed.

In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a nickel plating layer on the opposite side of the carrier. Further, in the case where the intermediate layer is provided by chromate treatment or zinc chromate treatment or plating treatment, it is considered that a part of the metal to which the chromium or zinc adheres is a hydrate or an oxide.

Further, for example, the intermediate layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, and chromium on a carrier. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer. Deposited mass of nickel of the intermediate layer is preferably 100μg / dm ² or more 40000μg / dm ² or less, more preferably 100μg / dm ² or more 4000μg / dm ² or less, and still more preferably 100μg / dm ² or more 2500μg / dm ² or less, More preferably, it is 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a nickel plating layer on the opposite side of the carrier.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may also be provided 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 sulfonate or copper cyanide, and can be used for a conventional electrolytic copper foil and forming a copper foil at a high current density. Preferably, it is a copper sulfate bath. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically, it is 0.5 to 12 μm, more typically 1 to 5 μm, still more typically 1.5 to 5 μm, and further typically 2 to 5 μm. Furthermore, an extremely thin copper layer can be provided on both sides of the carrier.

<Coarsening and other surface treatment>

On the surface of the ultra-thin copper layer, for example, in order to improve the adhesion to the insulating substrate, the roughening treatment layer may be provided by performing the roughening treatment. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening treatment can also be fine. The roughening treatment layer may also be composed of any element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing any one or more of these elements. Layers, etc. Further, after the roughened particles are formed of copper or a copper alloy, the secondary particles or the tertiary particles may be subjected to roughening treatment by a simple substance such as nickel, cobalt, copper or zinc or an alloy. Then, a heat-resistant layer or a rust-preventing layer can be formed by a simple substance such as nickel, cobalt, copper or zinc, or an alloy, and the surface can be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventing layer may be formed by a single substance or an alloy of nickel, cobalt, copper or zinc, and the surface may be subjected to chromate treatment or decane coupling. Processing. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be formed on the surface of the ultra-thin copper layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer are selected. Further, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, or the like).

For example, the copper-cobalt-nickel alloy plating as the roughening treatment can be formed by electrolytic plating to form a cobalt-100-3000 μg/cobalt of 100-3000 μg/dm ² as a deposition amount of 15 to 40 mg/dm ² / The implementation of the ternary alloy layer of nickel of dm ² is carried out. When the Co adhesion amount is less than 100 μg/dm ² , the heat resistance is deteriorated and the etching property is deteriorated. When the Co adhesion amount exceeds 3000 μg/dm ² , there is a case where the influence of the magnetic properties is considered to be unsatisfactory, etching stains are generated, and acid resistance and chemical resistance are deteriorated. If the Ni adhesion amount is less than 100 μg/dm ² , the heat resistance may be deteriorated. On the other hand, when the Ni adhesion amount exceeds 1500 μg/dm ² , there is a case where the etching residue increases. Preferably, the deposited mass of Co is 1000 ~ 2500μg / dm ^2, preferably of the deposited mass of nickel is 500 ~ 1200μg / dm ^2. Here, the term "etching stain" means that Co is not dissolved and remains in the case of etching with copper chloride, and the term "etching residue" means that when alkali etching is performed by ammonium chloride, Ni is not dissolved. Residual.

One of the usual plating baths and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows: plating bath composition: Cu 10-20 g/L, Co 1 10 g/L, Ni 1~10g/L

pH: 1~4

Temperature: 30~50°C

Current density D _k : 20~30A/dm ²

Plating time: 1~5 seconds

A carrier-attached copper foil having a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer was produced in the above manner. The method of using the carrier copper foil itself is As is well known in the art, for example, the surface of an extremely thin copper layer can be bonded to a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, a glass cloth-paper composite substrate epoxy resin, Glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate, such as epoxy resin, polyester film, polyimide film, etc., after hot pressing, peeling off the carrier to form a copper-clad laminate, The insulating substrate is then etched into a target conductor pattern by an extremely thin copper layer to finally produce a printed wiring board.

Further, it has a carrier, an intermediate layer laminated on the carrier, and a laminate on the intermediate layer The copper foil with a very thin copper layer may have a roughened layer on the ultra-thin copper layer, or may have more than one layer selected from the heat-resistant layer, the rust-proof layer, and the chromate layer on the roughened layer. The layer and the layer of the decane coupling treatment layer.

Further, the ultra-thin copper layer may be provided with a roughened layer, and the heat-treated layer and the rust-preventing layer may be provided on the roughened layer, and the chromate-treated layer may be provided on the heat-resistant layer or the rust-preventing layer. A decane coupling treatment layer is provided on the chromate treatment layer.

Further, the copper foil with a carrier may have a resin layer on the ultra-thin copper layer or the roughened layer or the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the decane coupling treatment layer. . The above resin layer may also be an insulating resin layer.

The above resin layer may be an adhesive or a semi-hardened state for subsequent use (B-stage) Section) of the insulating resin layer. In the semi-hardened state (B-stage state), even if the surface is in contact with the finger, there is no adhesive feeling, and the insulating resin layer can be stacked and stored, and if it is further subjected to heat treatment, a curing reaction occurs.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type thereof is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, a polyvinyl acetal resin, and an amine. A resin such as an ester resin.

The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (a dielectric containing an inorganic compound and/or an organic compound may be used, including Any dielectric body such as a metal oxide dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, or the like. In addition, the resin layer may be, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei. No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003 -304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060 No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153 Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, and Japanese Special Open 2009-6 No. 7029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471 Substances (resin, resin hardener, compound, etc.) described in Japanese Laid-Open Patent Publication No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, and Japanese Patent Publication No. 2013-19056 It is formed by a hardening accelerator, a dielectric body, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like, and/or a method of forming a resin layer, and a forming apparatus.

Dissolving the resins in a solvent such as methyl ethyl ketone (MEK) or toluene The resin liquid is applied to the ultra-thin copper layer, the heat-resistant layer, the rust-preventive layer, the chromate film layer, or the decane coupling agent layer by, for example, a roll coating method. Then, if necessary, heat drying is carried out to remove the solvent and set it to a B-stage state. Drying, for example, by using hot air drying The drying furnace can be used, and the drying temperature is preferably 100 to 250 ° C, preferably 130 to 200 ° C.

A copper foil with a carrier (the carrier-attached copper foil with a resin) having the above resin layer It is used in such a manner that after the resin layer and the substrate are overlapped, the entire resin layer is thermocompression-bonded to thermally harden the resin layer, and then the carrier is peeled off to expose the ultra-thin copper layer (of course, the exposed portion is extremely thin). The copper layer is on the surface of the intermediate layer side, and a predetermined wiring pattern is formed thereon.

When the copper foil with a carrier with a resin is used, the number of sheets of the prepreg used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be set to such a thickness as to ensure interlayer insulation, or a copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

Furthermore, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step can be simplified, which is economically advantageous, and has the following advantages: only the thickness of the prepreg material The thickness of the multilayer printed wiring board to be manufactured is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

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

When the thickness of the resin layer is less than 0.1 μm, the adhesion force is lowered, and when the resin-attached copper foil with a resin is laminated on the substrate having the inner layer material without interposing the prepreg, it is difficult to secure the inner layer. The case of interlayer insulation between circuits of materials.

On the other hand, when the thickness of the resin layer is made thicker than 80 μm, it is difficult to form a resin layer having a desired thickness by one application step, and an additional material cost and a number of steps are required, which is disadvantageous in terms of economy. Further, since the resin layer formed is inferior in flexibility, there is a case where cracks or the like are likely to occur during handling, and excessive resin flow occurs during thermal compression bonding with the inner layer material, and it is difficult to smoothly laminate.

Further, as another form of the resin-attached copper foil with a resin, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the decane coupling treatment may be applied to the ultra-thin copper layer. The layer is coated with a resin layer to make it semi-hardened, and then The carrier was peeled off and produced in the form of a resin-attached copper foil in the absence of a carrier.

Further, the printed circuit is completed by mounting electronic components on the printed wiring board. board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.

Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using the printed circuit board on which the electronic component is mounted, and an electronic device can be produced using the printed circuit board on which the electronic component is mounted. Hereinafter, an example of a manufacturing procedure of a printed wiring board using the copper foil with a carrier of the present invention will be described.

In one embodiment of the method for producing a printed wiring board of the present invention, The following steps: preparing the copper foil and the insulating substrate with the carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; and laminating the copper foil and the insulating substrate with the ultra-thin copper layer side opposite to the insulating substrate Forming a copper-clad laminate by stripping the carrier with the carrier copper foil, and then forming a circuit by any of a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method . The insulating substrate may also be provided as an inner layer circuit.

In the present invention, the so-called semi-additive method refers to an insulating substrate or a copper foil seed layer. A method in which a thin conductor is electrolessly plated and a conductor pattern is formed by plating and etching after patterning.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate After laminating the carrier-attached copper foil and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the extremely thin copper layer exposed by peeling off the carrier is removed by etching or plasma etching using an acid or the like. Providing a through hole or/and a blind via to expose the resin by removing the ultra-thin copper layer by etching; Performing desmear treatment on the region including the perforation or/and the blind hole; providing an electroless plating layer on the resin and the region including the perforation or/and the blind hole; and providing a plating resistance on the electroless plating layer Exposing the plating resist to the above, and then removing the plating resist in the region where the circuit is formed; and providing an electrolytic plating layer in the region of the circuit forming the plating resist; and removing the plating resist Removal; the electroless plating layer located in the region outside the region where the circuit is formed is removed by rapid etching or the like.

Another method for manufacturing a printed wiring board of the present invention using a semi-additive method The embodiment includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and then peeling off the copper foil with the carrier a carrier; a very thin copper layer exposed to peel off the carrier; and the insulating resin substrate provided with perforations or/and blind vias; a desmear treatment of the region including the perforations or/and blind vias; etching solution by using an acid or the like Etching or plasma, etc., removing all of the ultra-thin copper layer exposed by peeling off the carrier; and removing the resin and the region including the perforation or/and blind vias by removing the ultra-thin copper layer by etching or the like An electroless plating layer is disposed; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resist in the region where the circuit is formed is removed; and the plating resistance is removed An electrolytic plating layer is disposed in the region where the circuit is formed; the plating resist is removed; and electroless plating is performed on the region outside the region where the circuit is formed by rapid etching or the like. Layer removal.

Another method for manufacturing a printed wiring board of the present invention using a semi-additive method The embodiment includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and then peeling off the copper foil with the carrier a carrier; a very thin copper layer exposed to peel off the carrier; and the insulating resin substrate are provided with perforations or/and blind via holes; and the carrier is peeled off by etching or plasma etching using an acid or the like The copper layer is completely removed; the desmear treatment is performed on the region including the perforation or/and the blind via; and the resin and the region including the perforation or/and the blind via are exposed by removing the ultra-thin copper layer by etching or the like. An electroless plating layer is disposed; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resist in the region where the circuit is formed is removed; and the plating resistance is removed An electrolytic plating layer is disposed in the region where the circuit is formed; the plating resist is removed; and electroless plating is performed on the region outside the region where the circuit is formed by rapid etching or the like. Layer removal.

Another method for manufacturing a printed wiring board of the present invention using a semi-additive method The embodiment includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and then peeling off the copper foil with the carrier a carrier; the ultra-thin copper layer exposed by peeling off the carrier is removed by etching or plasma etching using an acid or the like; and the surface of the resin exposed by removing the ultra-thin copper layer by etching is provided Electroless plating layer; a plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resist in the region where the circuit is formed is removed; and the circuit forming region is removed from the plating resist An electrolytic plating layer is provided; the plating resist is removed; and the electroless plating layer and the ultra-thin copper layer in the region outside the region where the circuit is formed are removed by rapid etching or the like.

In the present invention, the so-called modified semi-additive method refers to the following method: in the insulating layer The upper metal foil is coated with a resist to protect the non-circuit forming portion, the copper thickness of the circuit forming portion is increased by electrolytic plating, the resist is removed, and the metal other than the circuit forming portion is removed by (fast) etching. A foil is used to form an electrical circuit on the insulating layer.

Therefore, the manufacturer of the printed wiring board of the present invention using the modified semi-additive method In one embodiment of the present invention, the method further comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and peeling off the carrier a carrier of copper foil; a thin copper layer exposed to the carrier and a perforated or/and blind via hole; and a desmear treatment for the region including the perforation or/and the blind via; And an electroless plating layer is disposed in the region of the blind hole; a plating resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; after the plating resist is disposed, the circuit is formed by electrolytic plating; The resist is removed; the extremely thin copper layer exposed by removing the plating resist is removed by rapid etching.

A method of manufacturing a printed wiring board of the present invention using a modified semi-additive method In another embodiment, the method further comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; Carrier of foil; Providing a plating resist on the extremely thin copper layer exposed by peeling off the carrier; exposing the plating resist, and then removing the plating resist in the region where the circuit is formed; and removing the plating resist An electrolytic plating layer is provided in a region where the circuit is formed; the plating resist is removed; and the electroless plating layer and the ultra-thin copper layer in the region outside the region where the circuit is formed are removed by rapid etching or the like.

In the present invention, the partial addition method refers to a method of setting a conductor The catalyst substrate is provided on the substrate (the substrate formed by the hole for the perforation or the through hole as needed), and is etched to form a conductor circuit, and if necessary, a solder resist or a plating resist is provided, On the conductor circuit, a through hole, a through hole, or the like is thickened by an electroless plating process to manufacture a printed wiring board.

Therefore, the method of manufacturing the printed wiring board of the present invention using the partial addition method In one embodiment, the method further comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; laminating the copper foil with the carrier and the insulating substrate, and peeling off the copper carrier a carrier for the foil; a perforated or/and blind via provided in the extremely thin copper layer and the insulating substrate exposed to peel off the carrier; and a desmear treatment on the region including the perforation or/and the blind via; a region of the blind hole is provided with a catalyst core; an etching resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; and the etching resist is exposed to form a circuit pattern; etching or plasma is performed by etching the solution using an acid or the like And removing the ultra-thin copper layer and the catalyst core to form a circuit; removing the etching resist; removing the ultra-thin copper layer and the touch by etching or plasma etching using an acid or the like a solder resist or a plating resist is disposed on the surface of the insulating substrate exposed by the dielectric core; An electroless plating layer is provided in a region where the above-mentioned solder resist or plating resist is not provided.

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

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier are provided with perforations or/and blind vias; a region of the blind hole is subjected to desmear treatment; an electroless plating layer is disposed on the region including the perforation or/and the blind hole; an electrolytic plating layer is disposed on the surface of the electroless plating layer; and the electrolytic plating layer or And an etching resistor is disposed on the surface of the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer and the above-mentioned non-existing layer are formed by etching or plasma etching using an acid or the like The electrolytic plating layer and the electrolytic plating layer are removed to form a circuit; and the etching resist is removed.

Another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After the copper foil with the carrier is laminated with the insulating substrate, the carrier with the carrier copper foil is peeled off; the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier are provided with perforations or/and blind holes; and the perforations or/and blinds are included The area of the hole is subjected to desmear treatment; an electroless plating layer is disposed on the region including the perforation or/and the blind hole; a mask is formed on the surface of the electroless plating layer; and the electroless plating is performed on the surface without the mask An electrolytic plating layer is disposed on the surface of the coating layer; Providing an etching resist on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; exposing the etching resist to form a circuit pattern; and using etching or plasma etching using an acid or the like The ultra-thin copper layer and the electroless plating layer are removed to form a circuit; the etching resist is removed.

The step of providing perforations or/and blind holes, and the subsequent desmear step may also be omitted.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail using the drawings. Here, the copper foil with a carrier having an ultra-thin copper layer in which a roughened layer is formed is described as an example, but the invention is not limited thereto, and even a very thin copper layer having a roughened layer is not used. The carrier copper foil is attached, and the manufacturing method of the following printed wiring board can also be performed similarly.

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

Then, as shown in FIG. 2-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a predetermined shape.

Then, as shown in FIG. 2-C, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a predetermined shape.

Then, as shown in FIG. 3-D, a resin layer is laminated on the ultra-thin copper layer by coating the circuit (in the form of a buried circuit plating), and then the resin layer is laminated on the side of the ultra-thin copper layer. A carrier copper foil (layer 2).

Then, as shown in Fig. 3-E, the carrier was peeled off from the carrier copper foil of the second layer.

Then, as shown in FIG. 3-F, a laser opening is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind hole.

Then, as shown in FIG. 4-G, copper is buried in the blind via to form a via fill.

Then, as shown in FIG. 4-H, circuit plating is formed on the via fill as in the above-described FIG. 2-B and FIG. 2-C.

Then, as shown in Fig. 4-I, the carrier was peeled off from the first layer of the carrier-attached copper foil.

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

Then, as shown in FIG. 5-K, a bump is formed on the circuit plating in the resin layer, and a copper pillar is formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in the above manner.

The above-mentioned other carrier copper foil (the second layer) can use the copper carrier of the present invention. As the foil, a conventional copper foil may be used, and a usual copper foil may be used. Further, in the circuit of the second layer shown in FIG. 4-H, a one-layer or a plurality of layers can be further formed, which can be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method performs such circuit formation.

By the method of manufacturing a printed wiring board as described above, since the circuit is plated The composition is embedded in the resin layer. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in, for example, FIG. 5-J, the circuit plating is protected by the resin layer, and the shape thereof is maintained, whereby the fine circuit is easily formed. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the wiring of the circuit is favorably suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIGS. 5-J and 5-K, the exposed surface of the circuit plating is recessed from the resin layer, so that it is easily formed on the circuit plating layer. The bumps, on the other hand, easily form copper pillars thereon, thereby improving manufacturing efficiency.

Further, a well-known resin or prepreg can be used as the resin. For example, BT (bis-s-butylene diimide III) can be used. Resin or prepreg as a glass cloth impregnated with BT resin, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resin layer and/or the resin and/or the prepreg described in the present specification can be used as the resin.

Further, the copper foil with a carrier used in the first layer may be on the surface of the copper foil with the carrier The surface has a substrate or a resin layer. By having the substrate or the resin layer, the copper foil with a carrier used in the first layer is supported, and wrinkles are less likely to be formed, so that productivity is improved. Further, as long as the substrate or the resin layer has an effect of supporting the copper foil with a carrier used in the first layer, all of the substrate or the resin layer can be used. For example, as the substrate or the resin layer, 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, or an inorganic compound described in the present specification can be used. Foil, plate of organic compound, foil of organic compound.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples of the invention, but the invention should not be construed as limited.

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

A titanium rotating cylinder is disposed in the electrolytic cell, and electrodes are disposed apart from each other by a distance between the electrodes. Then, in the electrolytic cell, electrolysis was carried out under the conditions of the carrier foil described in Table 1, copper was deposited on the surface of the rotating cylinder, and copper deposited on the surface of the rotating cylinder was peeled off, and an electrolytic copper foil having a thickness of 18 μm was continuously produced. It is set as a copper foil carrier. Further, regarding Examples 1, 2, 6, 8, 9, and 12, the thickness of the surface-treated copper foil carrier was 12 μm, 5 μm, 70 μm, 12 μm, 35 μm, and 35 μm, respectively. Further, in Comparative Example 3, a copper foil carrier having a thickness of 12 μm was used. With respect to Examples 1, 2, 6, 8, 9, and 12, the copper foil carrier was subjected to surface treatment under the conditions described in Table 1. Further, the electrolysis time is set to 0.5 to 2 minutes, and the electrolyte temperature is set to 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 surface (also referred to as a matte side or M surface) of the formed electrolytic copper foil, and a copper foil was used as an anode, and DC electrolysis treatment was performed to thereby obtain no copper foil. The glossy surface was subjected to a reverse electrolytic polishing treatment. In Example 2, copper was dissolved at 3 to 8 g/m ² , and in Example 8, copper was dissolved at 8 to 15 g/m ² . Further, the current density in the reverse electrolytic polishing treatment was 5 to 15 A/dm ^{2 in the second} embodiment and 16 to 25 A/dm ^{2 in the} eighth embodiment. The 60-degree specular gloss of the copper foil in the width direction is 13 to 40, and the 60-degree specular gloss of the copper foil in the longitudinal direction is 20 to 94. Further, 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 Denshoku Industries Co., Ltd. according to JIS Z8741.

Then, the intermediate layer was formed under the following conditions.

Electroplating was performed on a continuous roll to roll type of plating line under the following conditions, thereby forming a Ni layer having an adhesion amount of 4000 μg/dm ² .

‧Ni layer

Nickel sulfate: 250~300g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss: saccharin, butylene glycol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

After washing with water and pickling, the electrolytic chromate treatment was carried out on a roll-to-roll type continuous plating line under the following conditions, whereby a Cr layer having an adhesion amount of 11 μg/dm ² was adhered to the Ni layer.

‧ electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

After the intermediate layer was formed, electroplating was performed on the intermediate layer under the following conditions, thereby forming an extremely thin copper layer having a thickness of 1 to 10 μm, thereby forming a copper foil with a carrier.

‧ very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20 ~ 120g / L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

Further, in Examples 2 and 3, a roughening treatment layer, a heat-resistant treatment layer, a chromate layer, and a decane coupling treatment layer were further provided on the ultra-thin copper layer.

‧ roughening

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

pH: 1~4

Temperature: 40~50°C

Current density D _k : 20~30A/dm ²

Time: 1~5 seconds

Cu adhesion: 15~40mg/dm ²

Co adhesion: 100~3000μg/dm ²

Ni adhesion: 100~1000μg/dm ²

‧ heat treatment

Zn: 0~20g/L (excluding 0g/L)

Ni: 0~5g/L (excluding 0g/L)

pH: 3.5

Temperature: 40 ° C

Current density D _k : 0~1.7A/dm ²

Time: 1 second

Zn adhesion: 5~250μg/dm ²

Ni adhesion: 5~300μg/dm ²

‧Chromate treatment

K ₂ Cr ₂ O ₇

(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnO or ZnSO ₄ 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

Cr adhesion: 10~150μg/dm ²

‧decane coupling treatment

Vinyl triethoxy decane aqueous solution

(Vinyl triethoxy decane concentration: 0.1~1.4wt%)

pH: 4~5

Time: 5~30 seconds

(Embodiment 10)

A rolled copper foil (fine copper, JIS H3100 C1100) was prepared, and the calendered copper foil was subjected to cold rolling for final processing by calendering the surface of the calender roll. At this time, the calender roll roughness Ra was 0.39 to 0.42 μm, and the oil film equivalent was 35,000. Thereby, a copper foil carrier was obtained.

Then, an intermediate layer and an ultra-thin copper layer were formed on the surface (matte side) of the electrodeposited copper foil in the same manner as in Example 1 to prepare a copper foil with a carrier.

Each of the evaluations of the copper foil with a carrier of the examples and the comparative examples obtained in the above manner was carried out by the following method.

<thickness of very thin copper layer>

The thickness of the extremely thin copper layer of the prepared carrier copper foil was observed using a FIB-SIM (Focused Ion Beam-Scanning Ion Microscope) (magnification: 10,000 to 30,000 times). Five spots were measured at intervals of 30 μm by observing the cross section of the extremely thin copper layer, and the average value was determined.

<Surface roughness of very thin copper layer>

The ultra-thin copper layer with a carrier and a substrate (manufactured by Mitsubishi Gas Chemical Co., Ltd., GHPL-832NX-A) were laminated and heated at 220 ° C for 2 hours, and then peeled off according to JIS C 6471 (1995, further The method of the foil is 8.1. The peeling strength of the copper foil is 8.1.1 Type of the test method (1) Method A (method of peeling off the copper foil with respect to the copper foil removal surface in the 90° direction)) The copper foil carrier is peeled off, and An extremely thin copper layer is exposed. Then, various roughnesses of the exposed faces of the extremely thin copper layers were measured by the following procedure.

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

According to JIS B0601-1994, the surface roughness Rz (laser) of the ultra-thin copper layer on the intermediate layer side was measured using a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus Corporation. 10 Rz (laser) is arbitrarily measured, and the average value of 10 points of the Rz (laser) is set to the value of Rz (laser). Further, the standard deviation of the values of 10 points was calculated for Rz (laser).

Further, according to JIS B0601-1994, the surface roughness Ra (laser) of the ultra-thin copper layer on the intermediate layer side was measured using a laser microscope OLS4000 manufactured by Olympus Corporation. Ten Ra (laser) were measured arbitrarily, and the average value of the ten points of the Ra (laser) was set to the value of Ra (laser). Further, the standard deviation of the values of 10 points was calculated for Ra (laser).

Further, according to ISO 25178, the surface roughness Sz (laser) of the ultra-thin copper layer on the intermediate layer side was measured using a laser microscope OLS4000 manufactured by Olympus Corporation. Measure 10 Sz (laser) arbitrarily, The average value of the 10 points of the Sz (laser) is set to the value of Sz (laser). Further, the standard deviation of the values of 10 points was calculated for Sz (laser).

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

(2) Surface roughness of the carrier forming the side of the extremely thin copper layer

According to JIS B0601-1994, the surface roughness Rz (laser) of the carrier forming the side of the extremely thin copper layer was measured using a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus Corporation. 10 Rz (laser) is arbitrarily measured, and the average value of 10 points of the Rz (laser) is set to the value of Rz (laser). Further, the standard deviation of the values of 10 points was calculated for Rz (laser).

Further, according to JIS B0601-1994, the surface roughness Ra (laser) of the carrier forming the side of the extremely thin copper layer was measured using a laser microscope OLS4000 manufactured by Olympus Corporation. Ten Ra (laser) were measured arbitrarily, and the average value of the ten points of the Ra (laser) was set to the value of Ra (laser). Further, the standard deviation of the values of Ra (laser) at 10 points was calculated.

Further, according to ISO 25178, the surface roughness Sz (laser) of the carrier forming the side of the extremely thin copper layer was measured using a laser microscope OLS4000 manufactured by Olympus Corporation. 10 Sz (laser) is arbitrarily measured, and the average value of 10 points of the Sz (laser) is set to the value of Sz (laser). Further, 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 forming the side of the extremely thin copper layer was measured using a laser microscope OLS4000 manufactured by Olympus Corporation.

Further, regarding the above-mentioned Rz and Ra, in the observation of the ultra-thin copper layer and the surface of the carrier, the evaluation length (reference length) of 257.9 μm and the cutoff value of zero are used in the case where the carrier is a rolled copper foil by calendering and calendering. The direction perpendicular to the direction (TD) is measured, or when the carrier is an electrolytic copper foil, the value is obtained by measuring the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the apparatus for manufacturing an electrolytic copper foil. Further, regarding the above-described Sz and Sku, the ultra-thin copper layer and the surface of the carrier were measured under the conditions of an evaluation area (reference area) of 66,524 μm ² and a cutoff value of zero, thereby obtaining values. The measurement ambient temperature of the surface of the laser microscope using Sz, Rz, Ra, and Sku was set to 23 to 25 °C. Further, regarding Examples 1, 2, 6, 8, 9, and 12, Sz, Ra, Rz, and Sku of the surface-treated copper foil carrier were measured.

<Laser hole opening>

Then, on the untreated surface of the ultra-thin copper layer (the ultra-thin copper layer on the side surface of the intermediate layer), one shot of the laser was irradiated under the following conditions, and the shape of the hole after the irradiation was observed with a microscope, and measurement was performed. . In the table, the "actual quantity" of the opening means that the opening is attempted at 12 positions and actually several (X) holes (X/12) are opened, thereby indicating the "ratio" of the hole opened at this time ( %). Further, the table also shows the average diameter of the pores generated at this time, the standard deviation of the diameter of the generated pores, and the average diameter/beam diameter. Furthermore, the diameter of the hole is set to the diameter of the smallest circle surrounding the hole.

‧Gas type: CO ₂

‧ Copper foil opening diameter (target): 80μm diameter

‧ Beam shape: top hat

‧ Output: 2.40W/10μs

‧ Pulse width: 33μs

‧Number of hair: 1 round

‧Number of openings: 12 holes/area

<etching property>

The copper foil with a carrier was attached to the polyimide substrate, and was pressure-bonded at 220 ° C for 2 hours, and then the ultra-thin copper layer was peeled off from the carrier. Then, after applying a photosensitive resist on the surface of the ultra-thin copper layer on the polyimide substrate, 50 circuits of L/S=5 μm/5 μm wide were printed by an exposure step, and subjected to the following spray etching conditions. The etching process of the unnecessary portion of the copper layer is removed.

(spray etching conditions)

Etching solution: aqueous solution of ferric chloride (Baume scale: 40 degrees)

Liquid temperature: 60 ° C

Spray pressure: 2.0MPa

The etching was continued, and the time until the top width of the circuit became 4 μm was measured, and the width of the bottom of the circuit (the length of the bottom side X) and the etching factor were evaluated. Regarding the etching factor, when etching is gradually widened (when a collapse occurs), it is assumed that the length of the collapse from the intersection of the perpendicular line from the upper surface of the copper foil and the resin substrate when the circuit is vertically etched is set. When a is a, the ratio of the a to the thickness b of the copper foil: b/a, the larger the value, the larger the inclination angle, the less the etching residue remains, and the smaller the collapse. Fig. 1 is a view showing a schematic cross section of a circuit pattern in the width direction and an outline of a calculation method of an etching factor using the schematic diagram. The X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. Furthermore, calculation was performed with a = (X (μm) - 4 (μm))/2. The etch factor represents 12 points in the measurement circuit and is averaged. Thereby, the merits of the etching property can be easily determined. Further, by calculating the standard deviation of the etching factor of 12 o'clock, the linearity of the circuit formed by etching can be determined.

In the present invention, an etching factor of 4 or more is evaluated as etchability: ○, and 2.5 or more and less than 4 are evaluated as etchability: Δ, and a circuit which is less than 2.5 or cannot be calculated or cannot be formed is evaluated as etchability: ×, Will not be peeled off and evaluated as etch:-. Further, it is considered that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. The standard deviation of the etching factor was less than 0.8 and it was judged as linearity: ○, 0.8 to less than 1.2 was judged to be linear: Δ, and 1.2 or more was judged to be linear: ×.

The test conditions and test results are shown in Tables 1-3.

(Evaluation results)

In the examples 1 to 12, since the surface roughness Sz (laser) of the ultra-thin copper layer on the intermediate layer side was 1.40 μm or more and 4.05 μm or less, the laser opening property and the etching property were good.

In Comparative Examples 1 and 5, the surface roughness Sz (laser) of the ultra-thin copper layer on the intermediate layer side did not reach 1.40 μm, and thus the laser opening property was poor.

In Comparative Examples 2 to 4, the surface roughness Sz (laser) of the ultra-thin copper layer on the intermediate layer side exceeded 4.05 μm, and thus the etching property was poor.

In addition, in the examples 1 to 12, since the surface roughness Ra (laser) of the ultra-thin copper layer on the intermediate layer side is 0.14 μm or more and 0.35 μm or less, the laser opening property and the etching property are good.

In Comparative Examples 1 and 5, the surface roughness Ra (laser) of the ultra-thin copper layer on the intermediate layer side was less than 0.14 μm, and thus the laser opening property was poor.

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

Further, in Examples 1 to 12, the surface roughness Rz (laser) of the ultra-thin copper layer on the intermediate layer side was 0.62 μm or more and 1.59 μm or less, and the standard deviation of the surface roughness Rz (laser) was 0.51. Since it is not more than μm, the laser opening property and etching property are good.

In Comparative Examples 1 and 5, the surface roughness Rz (laser) of the ultra-thin copper layer on the intermediate layer side was less than 0.62 μm, and thus the laser opening property was poor.

In Comparative Examples 2 to 4, the surface roughness Rz (laser) of the ultra-thin copper layer on the intermediate layer side exceeded 1.59 μm, and thus the etching property was poor.

Claims (32)

A carrier-attached copper foil is provided with a carrier, an intermediate layer, and an ultra-thin copper layer in this order. After the carrier copper foil is heated at 220 ° C for 2 hours, the laser is removed by peeling the ultra-thin copper layer according to JIS C 6471. The surface roughness Sz of the ultra-thin copper layer measured on the intermediate layer side measured by a microscope is 1.40 μm or more and 4.05 μm or less. The copper foil with a carrier according to the first aspect of the invention, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Sz of the thin copper layer on the intermediate layer side is 1.30 μm or less. The copper foil with a carrier according to claim 2, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Sz of the thin copper layer on the intermediate layer side is 0.01 μm or more and 1.20 μm or less. The copper foil with a carrier according to any one of claims 1 to 3, wherein after the copper foil of the carrier is heated at 220 ° C for 2 hours, the ultra-thin copper layer is peeled according to JIS C 6471 The surface roughness Sz of the ultra-thin copper layer measured on the intermediate layer side measured by a microscope is 1.60 μm or more and 3.70 μm or less. The copper foil with a carrier according to the first aspect of the invention, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The surface roughness Ra of the thin copper layer on the intermediate layer side is 0.14 μm or more and 0.35 μm or less. The copper foil with a carrier according to the first aspect of the invention, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Ra of the thin copper layer on the intermediate layer side is 0.11 μm or less. The carrier copper foil according to claim 6, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Ra of the thin copper layer on the intermediate layer side is 0.001 μm or more and 0.10 μm or less. The carrier copper foil according to claim 1 or 5, wherein after the copper foil of the carrier is heated at 220 ° C for 2 hours, the ultra-thin copper layer is peeled according to JIS C 6471, and measured by a laser microscope. The surface roughness Rz of the ultra-thin copper layer on the intermediate layer side is 0.62 μm or more and 1.59 μm or less, and the standard deviation of the surface roughness Rz is 0.51 μm or less. The copper foil with a carrier according to the eighth aspect of the invention, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Rz of the thin copper layer on the intermediate layer side is 0.01 μm or more and 0.48 μm or less. A carrier-attached copper foil is provided with a carrier, an intermediate layer, and an ultra-thin copper layer in this order. After the copper foil of the carrier is heated at 220 ° C for 2 hours, the ultra-thin copper layer is peeled off according to JIS C 6471. The surface roughness Ra of the ultra-thin copper layer measured on the intermediate layer side measured by a laser microscope is 0.14 μm or more and 0.35 μm or less. The carrier copper foil according to claim 10, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Ra of the thin copper layer on the intermediate layer side is 0.11 μm or less. The carrier-attached copper foil according to claim 11, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Ra of the thin copper layer on the intermediate layer side is 0.001 μm or more and 0.10 μm or less. The carrier copper foil according to any one of claims 10 to 12, wherein After the carrier copper foil was heated at 220 ° C for 2 hours, when the ultra-thin copper layer was peeled according to JIS C 6471, the surface roughness Rz of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope was 0.62 μm or more and 1.59. Below μm, and the standard deviation of the surface roughness Rz is 0.51 μm or less. The carrier copper foil according to claim 13 of the invention, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Rz of the thin copper layer on the intermediate layer side is 0.01 μm or more and 0.48 μm or less. A copper foil with a carrier, which is provided with a carrier, an intermediate layer, and an ultra-thin copper layer in this order. After the copper foil of the carrier is heated at 220 ° C for 2 hours, the ultra-thin copper layer is stripped according to JIS C 6471. The surface roughness Rz of the ultra-thin copper layer measured on the intermediate layer side measured by a microscope is 0.62 μm or more and 1.59 μm or less, and the standard deviation of the surface roughness Rz is 0.51 μm or less. The copper foil with carrier of claim 15 wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The standard deviation of the surface roughness Rz of the thin copper layer on the intermediate layer side is 0.01 μm or more and 0.48 μm or less. The copper foil with carrier according to any one of claims 1 to 3, 5 to 7, 10 to 12, 15 and 16, wherein the copper foil of the carrier is heated at 220 ° C for 2 hours, according to JIS When C 6471 peels off the ultra-thin copper layer, the kurtosis Sku of the surface height distribution of the ultra-thin copper layer on the intermediate layer side measured by a laser microscope is 0.50 or more and 3.70 or less. The copper foil with a carrier according to claim 17, wherein the electrode copper foil is heated at 220 ° C for 2 hours, and the pole thin copper layer is peeled according to JIS C 6471, and the pole is measured by a laser microscope. The kurtosis Sku of the surface height distribution of the thin copper layer on the intermediate layer side is 1.00 or more and 3.60 or less. The carrier copper foil according to any one of claims 1 to 3, 5 to 7, 10 to 12, 15 and 16, wherein the carrier has a thickness of 5 to 70 μm. The copper foil with a carrier according to any one of claims 1 to 3, 5 to 7, 10 to 12, 15 and 16, wherein the surface of the ultra-thin copper layer has a roughened layer. The carrier copper foil according to claim 20, wherein the roughening layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc. A single layer or a layer comprising any one or more of these elements. The carrier-attached copper foil according to claim 20, wherein the surface of the roughened layer has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Layer. The carrier copper foil according to any one of claims 1 to 3, 5 to 7, 10 to 12, 15 and 16, wherein the surface of the ultra-thin copper layer has a heat-resistant layer and a rust-proof layer. One or more layers of the group consisting of a chromate treatment layer and a decane coupling treatment layer. A copper foil with a carrier according to any one of claims 1 to 3, 5 to 7, 10 to 12, 15 and 16, wherein a resin layer is provided on the ultra-thin copper layer. The carrier-attached copper foil according to claim 20, wherein a resin layer is provided on the roughened layer. The carrier-attached copper foil according to claim 22, wherein the resin layer is provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. . The carrier-attached copper foil according to claim 23, wherein the resin layer is provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. . A printed wiring board manufactured by using the carrier copper foil of any one of claims 1 to 27. A copper clad laminate produced by using the carrier copper foil of any one of claims 1 to 27. An electronic machine manufactured using a printed wiring board of claim 28 of the patent application. A method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate and an insulating substrate according to any one of claims 1 to 27; laminating the copper foil with the insulating substrate; After laminating the carrier copper foil and the insulating substrate, the copper-clad laminate is formed by stripping the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified semi-additive A circuit is formed by any of the methods. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier of any one of claims 1 to 27; a side surface of the ultra-thin copper layer of the carrier copper foil is formed with a resin layer; a circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and after the carrier is peeled off, the ultra-thin copper is removed The layer is thereby exposed to the circuit formed on the side surface of the ultra-thin copper layer and buried in the resin layer.