JP6546836B2 - Method of manufacturing copper foil with carrier, method of manufacturing copper foil with carrier, laminate, method of manufacturing printed wiring board and method of manufacturing electronic device - Google Patents

Description

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

  Generally, a printed wiring board is manufactured through a process of forming a conductor pattern on a copper foil surface by etching after bonding an insulating substrate to a copper foil to form a copper-clad laminate. In recent years, with the miniaturization of electronic devices and the increase in needs for high performance, high density mounting of mounted components and high frequency of signals have progressed, and the conductor pattern has been miniaturized (fine pitched) or high frequency for printed wiring boards. Measures are required.

  Recently, copper foils with a thickness of 9 μm or less, and further 5 μm or less are required in response to finer pitches, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Since the substrate is easily broken at times and wrinkles are easily generated, a copper foil with a carrier has been developed, in which a thick metal foil is used as a carrier and an ultrathin copper layer is electrodeposited via a peeling layer. After bonding the surface of the ultrathin copper layer to the insulating substrate and thermocompression bonding, the carrier is peeled off through the peeling layer. After forming a circuit pattern with a resist on the exposed ultrathin copper layer, a predetermined circuit is formed (see Patent Document 1 and the like).

WO 2004/005588

  The copper foil with a carrier is used by bonding the surface of the ultrathin copper layer to the insulating substrate and thermocompression bonding (heating press) as described above, and then peeling off and removing the carrier. At this time, if there is variation in the peel strength of the carrier, it will be difficult to peel off the ultra thin copper layer uniformly, for example, in a portion where the peel strength is higher than the periphery, there is a risk that holes may be formed in the ultra thin copper layer during the peeling. is there.

  Then, this invention makes it a subject to provide the manufacturing method of the copper foil with a carrier which can suppress the dispersion | variation in peeling strength favorably.

  As a result of intensive studies, the present inventors peeled an extremely thin copper layer from the carrier in a copper foil with a carrier in which the intermediate layer contains chromium, and performed depth direction analysis by TOF-SIMS on the surface of the carrier on the intermediate layer side. It has been found that, by controlling the secondary ion detection intensity on the outermost surface, the maximum intensity, and the position thereof on the outermost surface of the spectrum of Cr 2 O 4, it is possible to well suppress the variation in the peeling strength. In addition, in a copper foil with a carrier in which the intermediate layer contains nickel and chromium, when the ultrathin copper layer is peeled off from the carrier and the surface on the intermediate layer side of the carrier is subjected to depth direction analysis by TOF-SIMS, It has been found that, by controlling the maximum value of the secondary ion detection intensity and the position thereof, it is possible to well suppress the variation of the peeling strength.

The present invention has been completed on the basis of the above findings, and in one aspect, it is a copper foil with a carrier comprising a carrier, an intermediate layer and an ultrathin copper layer in this order, the intermediate layer containing chromium, and the electrode When the thin copper layer is peeled off from the carrier, and the surface on the intermediate layer side of the carrier is analyzed in the depth direction by TOF-SIMS, the secondary ion detection intensity of the outermost surface is 0.1 × 10 10 for the spectrum of Cr 2 O 4 Carrier-Bearing Copper which has ^{4 to} 2.0 × 10 ⁴ and a maximum intensity of 0.2 to 2.0 nm from the surface and a maximum intensity of 0.5 × 10 ^{4 to} 2.5 × 10 ⁴ It is a foil.

  In one embodiment, the copper foil with a carrier according to the present invention peels off the ultrathin copper layer from the carrier, and when analyzing the direction of depth by TOF-SIMS on the surface on the intermediate layer side of the carrier, the spectrum of Cr2O4 The ratio Cr—O / Cr—OH of the maximum intensity Cr—O to the maximum intensity Cr—OH of the spectrum of CrO 4 H is 0.8 or more.

In another embodiment of the copper foil with carrier of the present invention, the Cr adhesion amount of the intermediate layer is 5 to 100 μg / dm ² .

  Another aspect of the present invention is a method for producing a carrier-provided copper foil provided with a carrier, an intermediate layer having a chromate treatment layer, and an ultrathin copper layer in this order, and having a chromate treatment layer on the carrier. An intermediate layer forming step of forming an intermediate layer, a step of removing water on the surface of the intermediate layer formed on the carrier, and forming the ultrathin copper layer on the intermediate layer after the water removal It is a manufacturing method of the copper foil with a carrier of this invention including the ultra-thin copper layer formation process.

  Another aspect of the present invention is a method for producing a carrier-provided copper foil provided with a carrier, an intermediate layer having a chromate treatment layer, and an ultrathin copper layer in this order, and having a chromate treatment layer on the carrier. An intermediate layer forming step of forming an intermediate layer, a heating step of drying the surface of the intermediate layer formed on the carrier after removing water on the surface at 30 to 100 ° C. for 1 to 300 seconds, and It is a manufacturing method of the copper foil with a carrier of this invention including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on the intermediate | middle layer after drying.

  In one embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heating step, the intermediate layer is heated at 40 to 90 ° C. for 3 to 90 seconds after water on the surface is removed.

In another embodiment, the method for producing a copper foil with a carrier according to the present invention further includes a surface treatment layer forming step of performing the following treatment (1), (2) or (3) on the ultrathin copper layer. .
(1) Forming a roughened layer
(2) forming at least one layer selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer,
(3) After the roughening treatment layer is formed, one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer are formed.

In still another aspect of the present invention, there is provided a copper foil with a carrier comprising, in this order, a carrier, an intermediate layer, and an ultrathin copper layer, the intermediate layer comprising nickel and chromium, and the ultrathin copper layer being the carrier. When the surface of the carrier on the side of the intermediate layer is subjected to depth direction analysis by TOF-SIMS, the maximum value of secondary ion detection intensity is present at 0.5 to 5.0 nm from the surface with respect to the spectrum of NiO 2 It is a copper foil with a carrier whose maximum strength is 0.5 × 10 ^{4 to} 3.0 × 10 ⁴ .

In one embodiment still another copper foil with carrier of the present invention, Ni deposition amount is 100~40000μg / dm ^2, Cr deposition amount of the intermediate layer is a 5~100μg / dm ^2.

  According to still another aspect of the present invention, there is provided a method of producing a copper foil with a carrier comprising, in this order, a carrier, an intermediate layer having a Ni plating layer and a chromate treatment layer, and a very thin copper layer. Forming an Ni plating layer, forming an intermediate layer forming the chromate treatment layer, removing the surface moisture from the intermediate layer formed on the carrier, and an intermediate after removing the moisture It is a manufacturing method of the copper foil with a carrier of this invention including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on a layer.

  According to still another aspect of the present invention, there is provided a method of producing a copper foil with a carrier comprising, in this order, a carrier, an intermediate layer having a Ni plating layer and a chromate treatment layer, and a very thin copper layer. Forming an Ni plating layer, forming an intermediate layer forming a chromate-treated layer, and removing the surface moisture with respect to the intermediate layer formed on the carrier under conditions of 30 to 100 ° C. It is a manufacturing method of the copper foil with a carrier of the present invention including a heating step of drying for 300 seconds, and an ultrathin copper layer forming step of forming the ultrathin copper layer on the intermediate layer after the drying.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heating step, after removing moisture on the surface of the intermediate layer, at 40 to 90 ° C. for 3 to 90 seconds. Let it heat up.

In still another embodiment, the method for producing a copper foil with a carrier according to the present invention further includes a surface treatment layer forming step of performing the following treatment (1), (2) or (3) on the ultrathin copper layer. It is a manufacturing method of the copper foil with a carrier of this invention which contains.
(1) Forming a roughened layer
(2) forming at least one layer selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer,
(3) After the roughening treatment layer is formed, one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer are formed.

  In still another embodiment, the copper foil with carrier of the present invention has a roughened layer on either or both of the surface of the ultrathin copper layer and the surface of the carrier.

  The copper foil with a carrier according to the present invention is, in still another embodiment, one type selected from the group consisting of a heat-resistant layer, an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the roughening treatment layer. It has the above layers.

  The copper foil with a carrier according to the present invention is, in still another embodiment, one type selected from the group consisting of a heat-resistant layer, an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the ultrathin copper layer. It has the above layers.

  The copper foil with carrier according to the present invention, in still another embodiment, comprises a resin layer on the ultrathin copper layer.

  The copper foil with a carrier according to the present invention further includes a resin layer on the roughened layer in another embodiment.

  The copper foil with a carrier according to the present invention is, in still another embodiment, a resin layer on at least one layer selected from the group consisting of the heat-resistant layer, the rustproof layer, the chromate treatment layer and the silane coupling treatment layer. Equipped with

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

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

  The present invention, in still another aspect, is a laminate provided with the copper foil with a carrier of the present invention.

  According to still another aspect of the present invention, there is provided a laminate comprising the copper foil with carrier of the present invention and a resin, wherein a part or all of the end face of the copper foil with carrier is covered with the resin. It is.

  In still another aspect of the present invention, the copper foil with a carrier according to the present invention and the resin are two sets, and the ultrathin copper layer side surface of one of the two sets of copper foil with a carrier and the other carrier. It is a laminated body provided so that the ultrathin copper layer side surface of attached copper foil may be exposed, respectively.

  In still another aspect, the present invention is a method for producing a printed wiring board, which produces a printed wiring board using the copper foil with a carrier of the present invention.

  In still another aspect, the present invention is a method of manufacturing an electronic device, which manufactures an electronic device using the printed wiring board of the present invention.

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

  In still another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention, the copper foil with carrier such that the circuit is embedded. Forming a resin layer on the very thin copper layer side surface or the carrier side surface, forming a circuit on the resin layer, forming the circuit on the resin layer, the carrier or the very thin copper layer And peeling the carrier or the ultrathin copper layer, and then removing the ultrathin copper layer or the carrier to form the ultrathin copper layer surface or the carrier side surface. A method of manufacturing a printed wiring board, comprising the step of exposing a circuit embedded in the resin layer.

  In still another aspect of the present invention, the process of laminating the copper foil with carrier according to the present invention on the resin substrate from the carrier side, a circuit on the ultrathin copper layer side surface of the copper foil with carrier or the carrier side surface Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so as to embed the circuit, forming a circuit on the resin layer, the resin Peeling the carrier or the ultrathin copper layer after forming a circuit on the layer, and removing the ultrathin copper layer or the carrier after peeling the carrier or the ultrathin copper layer The method is a method for manufacturing a printed wiring board, including the step of exposing a circuit embedded in the resin layer, which is formed on the ultrathin copper layer side surface or the carrier side surface.

  In still another aspect of the present invention, the step of laminating the resin substrate and the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention, the resin substrate of the copper foil with carrier is laminated Providing the resin layer and the circuit two layers at least once on the ultrathin copper layer side surface opposite to the side or the carrier side surface, and after forming the resin layer and the circuit two layers, It is a manufacturing method of a printed wired board including the process of exfoliating the above-mentioned career or the above-mentioned ultra-thin copper layer from copper foil with a career.

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

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier which can suppress the dispersion | variation in peeling strength favorably, and its manufacturing method can be provided.

A to C are schematic views of the cross section of the wiring board in the steps up to circuit plating and resist removal, according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention. D to F are schematic views of a cross section of a wiring board in a process from resin and second layer copper foil lamination with carrier to laser drilling according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention It is. G to I are schematic views of a cross section of a wiring board in steps from via fill formation to first layer carrier peeling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to formation of bumps and copper pillars according to a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention. It is a graph which shows the spectrum of Cr2O4 when the depth direction analysis by TOF-SIMS of Example 1 and 2 is performed. It is a graph which shows the spectrum of CrO4H when the depth direction analysis by TOF-SIMS of Example 1 and 2 is performed. It is a graph which shows the relationship between the measurement position of Example 2, and peeling strength. It is a graph which shows the relationship between the measurement position of comparative example 1, and exfoliation intensity.

Embodiment 1
<Copper foil with carrier and its manufacturing method>
The copper foil with carrier according to the first embodiment of the present invention is a copper foil with carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, the intermediate layer containing chromium, and the ultrathin copper layer When the carrier is separated from the carrier and the surface on the intermediate layer side of the carrier is analyzed in the depth direction by TOF-SIMS, the secondary ion detection intensity of the outermost surface is 0.1 × 10 ⁴ to 2.2. 0 × 10 ⁴ and maximum intensity from 0.2 to 2.0 nm from the surface, maximum intensity 0.5 × 10 ^{4 to} 2.5 × 10 ⁴ . With such a configuration, the chromium surface is oxidized to have corrosion resistance and stable peel strength.

  When the ultrathin copper layer is peeled off from the carrier, and depth direction analysis is performed on the interlayer side surface of the carrier by TOF-SIMS, the maximum intensity of the spectrum of Cr2O4 and the maximum intensity of the spectrum of CrO4H The ratio of Cr-O / Cr-OH to Cr-OH is preferably 0.8 or more. With such a configuration, the hydroxide or hydrate on the chromium surface (the hydroxide or hydrate is considered to be detected as CrO 4 H in depth direction analysis by TOF-SIMS) is an oxide (oxidized The peel strength is stabilized by the fact that the object is considered to be detected as Cr 2 O 4 in the depth direction analysis by TOF-SIMS.

(Carrier)
Carrier of copper foil with carrier is typically metal foil or resin film, for example, copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil , An insulating resin film, a polyimide film, and an LCP film.
The carrier that can be used in the present invention is typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, an electrolytic copper foil is manufactured by electrolytically depositing copper on a drum of titanium or stainless steel from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating plastic working and heat treatment by rolling rolls. In addition to copper of high purity such as tough pitch copper (JIS H3100 alloy No. C1100) and oxygen free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011) as copper foil materials, for example, Sn containing copper, Ag containing copper, Cr It is also possible to use a copper alloy such as a copper alloy to which Zr, Mg or the like is added, or a Corson-based copper alloy to which Ni, Si or the like is added.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and can be, for example, 5 μm to 70 μm. However, if it is too thick, the production cost will increase, so in general, the thickness is preferably 35 μm or less. The thickness of the carrier is typically 8 μm or more and 70 μm or less, more typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less. Further, from the viewpoint of reducing the raw material cost, the thickness of the carrier is preferably small. Therefore, the thickness of the carrier is typically 5 μm to 35 μm, preferably 5 μm to 18 μm, preferably 5 μm to 12 μm, and preferably 5 μm to 11 μm, preferably 5 μm to 10 μm. It is below. In addition, when the thickness of a carrier is small, it is easy to generate a crease wrinkle at the time of passage of a carrier. In order to prevent the occurrence of creases and wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier or to shorten the distance between the transport roll and the transport roll next to the transport roll.

(Intermediate layer)
An intermediate layer is provided on one side or both sides of the carrier. Other layers may be provided between the carrier and the intermediate layer. The middle layer contains chromium. In addition, the intermediate layer may contain any one or more elements in the element group of Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al. In addition, the intermediate layer may be any one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or their alloys, or their hydrates, or their oxides, or organic substances. May be included. The middle layer may be composed of a plurality of layers. When the intermediate layer is composed of a plurality of layers, it is preferable that the layer closest to the very thin copper layer contains chromium. When the layer closest to the ultrathin copper layer contains chromium, the ultrathin copper layer is peeled from the carrier, and when the TOF-SIMS depth analysis is performed on the intermediate layer side surface of the carrier, the intermediate layer side of the carrier It becomes easy to control the secondary ion detection intensity of the Cr2O4 spectrum of the outermost surface, and it becomes easy to control so that the maximum intensity of the Cr2O4 spectrum exists at a position of 0.2 to 2.0 nm from the surface. This is to facilitate control of the value of the maximum intensity of the spectrum. The intermediate layer according to Embodiment 1 can be composed of a chromate-treated layer.

The example of the conditions of the said chromate process is shown below.
Chromium: 0.1 to 6.0 g / L
Zinc: 0 to 2.0 g / L
pH: 2.5 to 5.0
Liquid temperature: 25 to 60 ° C
Current density: 0.1 to 4 A / dm ²

It is preferable that the Cr adhesion amount in the intermediate layer is 5 to 100 μg / dm ² . By controlling the adhesion amount of chromium in this manner, the diffusion of copper between the carrier and the very thin copper layer at the time of pressure bonding of the substrate can be suppressed, and the variation in peel strength can be suppressed.
Cr deposition amount in the intermediate layer is more preferably in the range of 8~50μg / dm ^2, more preferably in the range of 10~40μg / dm ^2, and even more preferably 12~30μg / dm ^2.

  After the formation of the intermediate layer, the water on the surface of the intermediate layer is removed, and an ultrathin copper layer forming step of forming an ultrathin copper layer described later on the intermediate layer after the water removal is performed. By removing the moisture on the surface of the intermediate layer, an oxide layer can be formed on the surface of chromium when the surface is exposed to the atmosphere, and variations in peel strength can be suppressed. Further, the surface of chromium is dried by removing the moisture on the surface, and the surface of the chromium layer is difficult to dissolve in the ultrathin copper plating solution, so that the variation in peel strength can be suppressed.

Alternatively, after the formation of the intermediate layer, after removing moisture on the surface of the intermediate layer, a heating step of drying at 30 to 100 ° C. for 1 to 300 seconds, and the ultrathin copper layer on the intermediate layer after the drying An ultra-thin copper layer forming step is performed. By removing the water on the surface of the intermediate layer and drying at 30 to 100 ° C. for 1 to 300 seconds, an oxide layer can be formed on the surface of chromium to suppress variations in peel strength. When the heating temperature exceeds 100 ° C., the oxide layer on the surface becomes too thick and the electrical resistance becomes high, and it becomes difficult to form a very thin copper layer by plating.
In the heating step, the intermediate layer may be heated at 40 to 90 ° C. for 3 to 90 seconds after removing moisture on the surface.

Second Embodiment
<Copper foil with carrier and its manufacturing method>
A copper foil with carrier according to a second embodiment of the present invention is a copper foil with carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the intermediate layer contains nickel and chromium, and the ultrathin copper When the layer is peeled off from the carrier and the surface on the intermediate layer side of the carrier is analyzed in the depth direction by TOF-SIMS, the maximum secondary ion detection intensity is 0.5 to 5 from the surface for the spectrum of NiO2. At a maximum intensity of 0.5 × 10 ^{4 to} 3.0 × 10 ⁴ . With such a configuration, variations in peel strength can be suppressed by forming an oxide layer on the surface of the Ni layer.

(Carrier)
The carrier of the copper foil with carrier according to the second embodiment can be formed in the same manner as the carrier of the copper foil with carrier according to the first embodiment described above.

(Intermediate layer)
The intermediate layer according to the second embodiment may have a Ni plating layer and a chromate treatment layer in this order.

The example of the formation conditions of the said Ni plating layer is shown below.
-Ni plating-
Nickel: 20 to 200 g / L
Boric acid: 5 to 60 g / L
pH: 2.0 to 4.5
Liquid temperature: 40 to 65 ° C
Current density: 0.5 to 10 A / dm ²

The example of the conditions of the said chromate process is shown below.
Chromium: 0.1 to 6.0 g / L
Zinc: 0 to 2.0 g / L
pH: 2.5 to 5.0
Liquid temperature: 25 to 60 ° C
Current density: 0.1 to 4 A / dm ²

Ni deposition amount in the intermediate layer, 100~40000μg / dm ^2, Cr deposition amount is preferably from 5~100μg / dm ^2. As described above, by controlling the adhesion amount of nickel and chromium, it becomes possible to control the amount of Ni on the surface of the ultrathin copper layer after peeling the ultrathin copper layer from the copper foil with carrier. As described above, in order to control the amount of Ni on the surface of the ultrathin copper layer after peeling, while reducing the amount of Ni attached to the intermediate layer, metal species (Cr which suppress the diffusion of Ni to the side of the ultrathin copper layer) Preferably, the intermediate layer contains From this point of view, Ni content of the intermediate layer is more preferably in the range of 200~20000μg / dm ^2, more preferably in the range of 500~10000μg / dm ^2, and even a 700~5000μg / dm ² More preferable. Further, Cr is more preferably in the range of 8~50μg / dm ^2, more preferably in the range of 10~40μg / dm ^2, and even more preferably 12~30μg / dm ^2. When the amount of Ni on the surface of the ultra-thin copper layer after peeling the ultra-thin copper layer from the copper foil with carrier is controlled, the effect of improving the etching properties (such as solubility and circuit shape) of the ultra-thin copper layer There is.

  After the formation of the intermediate layer, the water on the surface of the intermediate layer is removed, and an ultrathin copper layer forming step of forming an ultrathin copper layer described later on the intermediate layer after the water removal is performed. By removing the moisture on the surface of the intermediate layer, an oxide layer can be formed on the surface of chromium when the surface is exposed to the atmosphere, and variations in peel strength can be suppressed.

Alternatively, after the formation of the intermediate layer, after removing moisture on the surface of the intermediate layer, a heating step of drying at 30 to 100 ° C. for 1 to 300 seconds, and the ultrathin copper layer on the intermediate layer after the drying An ultra-thin copper layer forming step is performed. By removing the water on the surface of the intermediate layer and drying at 30 to 100 ° C. for 1 to 300 seconds, an oxide layer can be formed on the surface of chromium to suppress variations in peel strength. When the heating temperature exceeds 100 ° C., the oxide layer on the surface becomes too thick and the electrical resistance becomes high, and it becomes difficult to form a very thin copper layer by plating.
In the heating step, the intermediate layer may be heated at 40 to 90 ° C. for 3 to 90 seconds after removing moisture on the surface.

(Ultra-thin copper layer)
In Embodiments 1 and 2, after forming each of the intermediate layers, an ultrathin copper layer is formed as follows.
That is, in Embodiments 1 and 2, an extremely thin copper layer is formed on the dried intermediate layer. Other layers may be provided between the intermediate layer and the very thin copper layer. The extremely thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and copper layer formation at high current density is possible. Copper sulfate baths are preferred. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically 0.5 to 12 μm, more typically 1 to 5 μm, even more typically 1.5 to 5 μm, even more typically 2 to 5 μm. The ultrathin copper layer may be provided on both sides of the carrier.

Next, in the first and second embodiments, the surface treatment layer is formed by further performing the following treatment (1), (2) or (3) on the ultrathin copper layer.
(1) Forming a roughened layer
(2) forming at least one layer selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer,
(3) After the roughening treatment layer is formed, one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer are formed.
Hereinafter, the forms of the roughening treatment and other surface treatments will be described in detail.

(Roughening treatment and other surface treatment)
A roughening treatment layer may be provided on the surface of the ultrathin copper layer, for example, by performing a roughening treatment to improve adhesion with the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughened layer is a layer composed of an alloy containing any one or more selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt and zinc. Or the like. In addition, after roughening particles are formed of copper or copper alloy, roughening treatment may be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc, an alloy or the like. Thereafter, the heat-resistant layer or the rust-preventing layer may be formed of nickel, cobalt, copper, zinc singly or as an alloy or the like, and the surface may be further subjected to a treatment such as chromate treatment or silane coupling treatment. Alternatively, a heat-resistant layer or rustproof layer may be formed of nickel, cobalt, copper, zinc singly or as an alloy without roughening, and the surface may be further treated by chromate treatment, silane coupling treatment, etc. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. At least one layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. The above-mentioned heat-resistant layer, rust-preventive layer, chromate-treated layer, and silane coupling-treated layer may each be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).

For example, copper as a roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, deposition amount in the nickel-cobalt -100~1500μg / dm ² of copper -100~3000μg / dm ² of 15~40mg / dm ² It can be implemented to form such a ternary alloy layer. If the Co adhesion amount is less than 100 μg / dm ² , the heat resistance may be deteriorated and the etching property may be deteriorated. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into consideration, and etching stains may occur, and acid resistance and chemical resistance may be deteriorated. Heat resistance may worsen that Ni adhesion amount is less than 100 microgram / dm < ² >. On the other hand, when the Ni deposition amount exceeds 1500 μg / dm ² , the etching residue may increase. The preferred amount of Co deposition is 1000 to 2500 μg / dm ² , and the preferred amount of nickel deposition is 500 to 1200 μg / dm ² . Here, the etching stain means that Co does not dissolve when etched with copper chloride, and the etching residue means that Ni does not dissolve when alkaline etching is performed with ammonium chloride. It means that.

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

  In this way, a copper foil with carrier comprising the carrier, the intermediate layer laminated on the carrier, and the ultrathin copper layer laminated on the intermediate layer is manufactured. The method of using the copper foil with carrier itself is well known to those skilled in the art, for example, the surface of a very thin copper layer is a paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite Base material epoxy resin, glass cloth · glass non-woven fabric composite base material epoxy resin and glass cloth base material Epoxy resin, polyester film, polyimide film, etc. The ultrathin copper layer adhered to the substrate can be etched into the desired conductor pattern to finally produce a printed wiring board.

In addition, a copper foil with a carrier comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer comprises a roughened layer on the ultrathin copper layer It is also preferable that one or more layers selected from the group consisting of a heat resistant layer, an anticorrosive layer, a chromate treated layer and a silane coupling treated layer may be provided on the roughened layer.
In addition, a roughening treatment layer may be provided on the ultrathin copper layer, and a heat-resistant layer and an anticorrosion layer may be provided on the roughening treatment layer, and a chromate treatment on the heat-resistant layer and the anticorrosion layer A layer may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
Further, the copper foil with carrier is provided with a resin layer on the ultra-thin copper layer, on the roughening treatment layer, or on the heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer. It is good. The resin layer may be an insulating resin layer.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. Although the type is not particularly limited, for example, a resin containing an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, etc. can be mentioned as a suitable one. .

  The resin layer may be any known resin, resin curing agent, compound, curing accelerator, dielectric (a dielectric including an inorganic compound and / or an organic compound, a dielectric including a metal oxide, etc. ), Reaction catalysts, crosslinking agents, polymers, prepregs, frameworks and the like. In addition, the resin layer may be formed of, for example, International Publication Number WO2008 / 004399, International Publication Number WO2008 / 053878, International Publication Number WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application No. 11-140281, Patent No. 3184485, International Publication Nos. WO 97/02728, Patent No. 3676375, JP-A 2000-43188, Patent No. 3612594, JP-A 2002-179772, JP-A 2002-359444, JP-A 2003-304068, JP 3992225, JP-A 2003 No. 249739, Patent No. 4136509, Japanese Patent No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent No. 20 Patent No. 5-53218, Patent No. 3949676, Patent No. 4178415, International Publication No. WO 2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Publication No. 2007-326923, Japanese Patent Publication No. 2008-111169, Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, Japanese Patent Application Publication No. 2009-67029, International Publication No. WO2006 / 134868, Patent No. 5046927, Japanese Patent Application Publication No. 2009-1730017, International Publication No. WO2007 / 105635, Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Application Publication No. 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, JP-A-2013-19056 (a resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeletal material, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

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

  The resin-coated copper foil (the resin-coated carrier-coated copper foil) having the resin layer is laminated on the resin layer and then the whole is thermocompression-bonded to thermally cure the resin layer, and then the carrier is peeled off. It is used in such a manner that a very thin copper layer is exposed (it is naturally the surface on the intermediate layer side of the very thin copper layer) and a predetermined wiring pattern is formed there.

  By using this copper foil with a carrier with resin, it is possible to reduce the number of used prepreg materials at the time of manufacturing a multilayer printed wiring board. In addition, it is possible to manufacture a copper-clad laminate even if the thickness of the resin layer is such that interlayer insulation can be secured or the prepreg material is not used at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the surface smoothness.

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

  The thickness of the resin layer is preferably 0.1 to 80 μm. When the thickness of the resin layer is smaller than 0.1 μm, the adhesive force is reduced, and the circuit of the inner layer material when the copper foil with a carrier with a resin is laminated on the base material provided with the inner layer material without interposing the prepreg material. It may be difficult to secure interlayer insulation between them.

  On the other hand, when the thickness of the resin layer is greater than 80 μm, it becomes difficult to form the resin layer of the desired thickness in one application step, which is economically disadvantageous because extra material cost and man-hours are required. Furthermore, since the formed resin layer is poor in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

  Furthermore, as another product form of the carrier-coated copper foil with resin, it is possible to form the above-mentioned ultra-thin copper layer, or the above-mentioned heat-resistant layer, anticorrosive layer, or the above chromate treated layer, or the above silane coupling treated layer After coating with a resin layer and bringing it into a semi-cured state, it is also possible to peel off the carrier and produce it in the form of a resin-coated copper foil without a carrier.

Furthermore, by mounting electronic components on the printed wiring board, the printed circuit board is completed. In the present invention, the term "printed wiring board" also includes a printed wiring board, a printed circuit board and a printed circuit board on which electronic components are thus mounted.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted The substrate may be used to manufacture an electronic device. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, with the carrier After laminating the copper foil and the insulating substrate so that the very thin copper layer side faces the insulating substrate, the carrier of the copper foil with carrier is removed to form a copper-clad laminate, and then the semi-additive method, modified semi Forming a circuit by any of an additive method, a partory additive method and a subtractive method. The insulating substrate may be one including an inner layer circuit.

  In the present invention, the semi-additive method refers to a method of performing thin electroless plating on an insulating substrate or a copper foil seed layer, forming a pattern, and then forming a conductor pattern using electroplating and etching.

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

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

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

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

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

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

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

  In the present invention, in the partly additive method, a catalyst core is provided on a substrate provided with a conductor layer, and a substrate provided with holes for through holes and via holes as necessary, and a conductor circuit is formed by etching. And a method of manufacturing a printed wiring board by providing a solder resist or a plating resist as necessary, and thickening the through holes, via holes, etc. on the conductor circuit by electroless plating.

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

  In the present invention, the subtractive method refers to a method in which an unnecessary portion of the copper foil on the copper clad laminate is selectively removed by etching or the like to form a conductor pattern.

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

In another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Forming a mask on the surface of the electroless plating layer;
Providing an electrolytic plating layer on the surface of the electroless plating layer where the mask is not formed;
Providing an etching resist on the surface of the electrolytic plating layer or / and the very thin copper layer;
Exposing the etching resist to form a circuit pattern;
Forming a circuit by removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as acid;
Removing the etching resist;
including.

  The step of providing through holes or / and blind vias and the subsequent desmear step may not be performed.

Here, a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. In addition, although the copper foil with a carrier which has the ultrathin copper layer in which the roughening process layer was formed is demonstrated to an example here, the carrier which has the ultrathin copper layer in which the roughening process layer is not formed not only in this is formed. Even when using the attached copper foil, the following method for producing a printed wiring board can be carried out similarly.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer by which the roughening process layer was formed in the surface is prepared.
Next, as shown to FIG. 1-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and image development are performed, and a resist is etched in a defined shape.
Next, as shown in FIG. 1C, plating for a circuit is formed, and then the resist is removed to form a circuit plating of a predetermined shape.
Next, as shown in Fig. 2-D, the embedded resin is provided on the ultrathin copper layer to cover the circuit plating (so that the circuit plating is buried), and the resin layer is laminated, and then another carrier is attached. Bond the copper foil (second layer) from the very thin copper layer side.
Next, as shown in FIG. 2E, the carrier is peeled off from the second layer of copper foil with carrier.
Next, as shown in FIG. 2F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind via.
Next, as shown in FIG. 3G, copper is buried in the blind vias to form a via fill.
Next, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIG. 1-B and FIG. 1-C.
Next, as shown in FIG. 3I, the carrier is peeled off from the first layer of copper foil with carrier.
Next, as shown in FIG. 4J, the ultrathin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with carrier of the present invention is produced.

  The other copper foil with carrier (second layer) may use the copper foil with carrier of the present invention, may use a conventional copper foil with carrier, and may further use a normal copper foil. Further, one or more layers of circuits may be further formed on the circuit of the second layer shown in FIG. 3H, and the circuit formation thereof may be carried out by the semi-additive method, the subtractive method, the partory additive method or the modified semi It may be carried out by any of the additive methods.

  According to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, for example, in the removal of the ultrathin copper layer by flash etching as shown in FIG. Then, the circuit plating is protected by the resin layer and its shape is maintained, thereby facilitating the formation of the fine circuit. In addition, since the circuit plating is protected by the resin layer, the migration resistance is improved and the conduction of the wiring of the circuit is well suppressed. For this reason, formation of a fine circuit becomes easy. In addition, as shown in Fig. 4-J and Fig. 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a concaved shape from the resin layer, so bumps are formed on the circuit plating. Further, copper pillars can be easily formed thereon, and the manufacturing efficiency is improved.

  In addition, well-known resin and a prepreg can be used for embedding resin (resin). For example, a prepreg which is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. In addition, the resin layer and / or the resin and / or the prepreg described in the present specification can be used as the embedding resin (resin).

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

  Further, in the method for producing a printed wiring board of the present invention, a step of laminating the resin substrate and the surface on the very thin copper layer side or the carrier side of the copper foil with carrier of the present invention, ultrathin laminated with the resin substrate The process of providing two layers of a resin layer and a circuit at least once on the surface of copper foil with a carrier on the opposite side to the copper layer side surface or the said carrier side surface, and forming two layers of the said resin layer and a circuit It may be the manufacturing method (coreless construction method) of a printed wired board including the process of making the above-mentioned career or the ultra-thin copper layer exfoliate from the above-mentioned copper foil with a carrier after carrying out. About the said coreless construction method, first, the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention is laminated on a resin substrate. Thereafter, a resin layer is formed on the surface of the very thin copper layer side laminated on the resin substrate or the surface of the copper foil with carrier opposite to the surface on the carrier side. Another copper foil with a carrier may be laminated from the carrier side to the resin layer formed on the carrier side surface. In this case, a carrier / intermediate layer / very thin copper layer or copper foil with carrier is laminated in the order of carrier / intermediate layer / very thin copper layer or in the order of ultrathin copper layer / intermediate layer / carrier on both surface sides of the resin substrate with the resin substrate as the center. It has become. Thus, the copper foil with a carrier of the present invention can be used to manufacture a coreless printed wiring board. Another resin layer may be provided on the exposed surfaces of the ultrathin copper layers or carriers at both ends, and a copper layer may be provided, and then the copper layer may be processed to form a circuit. Furthermore, another resin layer may be provided on the circuit so as to embed the circuit. Moreover, you may provide formation of such a circuit and a resin layer once or more (build-up method). And about the laminated body formed in this way, the ultra-thin copper layer or carrier of each copper foil with a carrier can be peeled from a carrier or an ultra-thin copper layer, and a coreless board | substrate can be produced.

  In the method of manufacturing a coreless substrate described above, when a printed wiring board is manufactured by a build-up method, soaking of the chemical solution into the intermediate layer is performed by covering a part or all of the end face of the copper foil with carrier with resin. It is possible to prevent the separation of the very thin copper layer and the carrier due to the infiltration of the chemical solution, and the yield can be improved. As "resin which covers a part or all of the end face of copper foil with a carrier" used here, resin which can be used for a resin layer can be used. In order to separate the carrier and the ultrathin copper layer, it is necessary to cut off the portion of the end face of the copper foil with carrier covered with the resin. Further, in the method of manufacturing a coreless substrate described above, at least a part of the outer periphery of the laminated portion of the copper foil with carrier may be covered with a resin or a prepreg when viewed in plan in the copper foil with carrier. Moreover, the laminated body formed with the manufacturing method of the above-mentioned coreless board | substrate may make a pair of copper foil with a carrier contact mutually separably. Moreover, when it planarly views in the said copper foil with a carrier, it may be covered with resin or a prepreg over the whole outer periphery of the lamination | stacking part of copper foil with a carrier. With such a configuration, when the copper foil with carrier is viewed in plan, the laminated portion of the copper foil with carrier is covered with the resin or the prepreg, and the other members are in the lateral direction of this portion, that is, with respect to the laminating direction. As a result, it is possible to prevent contact from the direction from the side, and as a result, it is possible to reduce peeling of the copper foils with carrier during handling. In addition, by covering the outer periphery of the laminated portion of the carrier-attached copper foil with the resin or the prepreg so as not to expose, it is possible to prevent the chemical solution from entering the interface in the chemical treatment process as described above. It can prevent corrosion and erosion. When one copper foil with carrier is separated from a pair of copper foil with carrier, or when the copper foil of carrier with copper foil and the copper foil (very thin copper layer) are separated, they are covered with resin or prepreg. It is necessary to remove the laminated portion of the copper foil with carrier by cutting or the like.

  EXAMPLES The present invention will be described in more detail by the following examples of the present invention, but the present invention is not limited by these examples.

1. Production of Copper Foil with Carrier As a copper foil carrier of Examples 1 to 15 and Comparative Examples 1 and 2, a long electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metals Corporation) having a thickness of 18 μm was prepared. Moreover, as a copper foil carrier of Examples 16 to 21 and Comparative Example 3, a 17 μm-thick rolled copper foil (C1100 manufactured by JX Nippon Mining & Metals, Inc.) was prepared. This copper foil was cut into 150 mm × 55 mm, and a Ni plating and chromate treatment were performed on a shiny surface (shiny surface) to form an intermediate layer.

・ Ni plating Nickel: 20 to 200 g / L
Boric acid: 5 to 60 g / L
pH: 2.0 to 4.5
Liquid temperature: 40 to 65 ° C
Current density: 0.5 to 10 A / dm ²

Electrolytic chromate treatment Chromium: 0.1 to 6.0 g / L
Zinc: 0 to 2.0 g / L
pH: 2.5 to 5.0
Liquid temperature: 25 to 60 ° C
Current density: 0.1 to 4 A / dm ²

  Next, on the surface of the chromate-treated layer, cold air drying and drying after cold air drying were respectively performed under the conditions described in the table. In addition, in Comparative Examples 1 to 3, neither cold air drying nor drying after cold air drying was performed.

  Subsequently, an ultrathin copper layer having a thickness described in the table was electroplated (copper plating) on the intermediate layer under the following conditions to prepare a copper foil with carrier. When copper plating is performed, if the copper foil on which the intermediate layer is formed is immersed in the copper plating solution, the chromate layer is dissolved, and the peel strength is not stable. Therefore, a sample was produced by immersing in a copper plating solution after applying a current.

・ Copper plating Copper concentration: 90-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20 to 80 ° C
Current density: 10 to 70 A / dm ²

About these Examples and Comparative Examples, the following roughening treatment, rust prevention treatment, chromate treatment, and silane coupling treatment were all performed in this order on the surface of the ultrathin copper layer.
Roughing treatment Cu: 10 to 20 g / L
Co: 5 to 15 g / L
Ni: 5 to 15 g / L
pH: 1 to 4
Temperature: 40-50 ° C
Current density Dk: 40 to 50 A / dm ²
Time: 0.5 seconds to 2 seconds Cu adhesion amount: 15 to 40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²

・ Heat resistant treatment (Form heat resistant layer)
Liquid composition: Nickel 5 to 20 g / L, cobalt 1 to 8 g / L
pH: 2 to 3
Liquid temperature: 40 to 60 ° C
Current density: 5 to 20 A / dm ²
Coulomb amount: 10 to 20 As / dm ²

・ Chromate treatment (form a chromate treatment layer)
Liquid composition: Potassium dichromate 1 to 10 g / L, zinc 0 to 5 g / L
pH: 3 to 4
Liquid temperature: 50 to 60 ° C
Current density: 0 to ^{2 A} / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)

· Silane coupling treatment (forming a silane coupling treatment layer)
The silane coupling agent coating treatment was performed by spraying an aqueous solution of pH 7 to 8 at 60 ° C. containing 0.2 to 2% by mass of alkoxysilane.

2. Evaluation of Carrier Attached Copper Foil Various evaluations were performed as follows for each of the samples of the examples and comparative examples produced as described above.

Metal adhesion amount of the intermediate layer The nickel adhesion amount is determined by dissolving the sample with nitric acid at a concentration of 20% by mass and measuring it by ICP emission analysis using an ICP emission spectrophotometer (type: SPS3100) manufactured by SII. The sample was dissolved in hydrochloric acid at a concentration of 7% by mass, and measured by atomic absorption spectrophotometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. In addition, the measurement of the said nickel and chromium adhesion amount was performed as follows. First, after peeling the ultrathin copper layer from the copper foil with a carrier, only the vicinity of the surface on the middle layer side of the ultrathin copper layer is dissolved (when the thickness of the ultrathin copper layer is 1.4 μm or more Only a 0.5 μm thickness is dissolved from the surface on the middle layer side of the thin copper layer. If the thickness of the ultra thin copper layer is less than 1.4 μm, the thickness of the very thin copper layer is from the surface on the middle layer side The amount of adhesion of the surface on the middle layer side of the ultrathin copper layer is measured. Further, after peeling off the ultrathin copper layer, only the vicinity of the surface on the intermediate layer side of the carrier is dissolved (only 0.5 μm thickness is dissolved from the surface), and the adhesion amount of the surface on the intermediate layer side of the carrier is measured. And the value which totaled the adhesion amount of the surface at the side of the middle layer of an ultra-thin copper layer and the adhesion amount of the surface at the side of the middle layer of a carrier was made into the metal adhesion amount of the middle layer. When nickel and / or chromium is not sufficiently dissolved in the above-mentioned acid, for example, a mixture of nitric acid and hydrochloric acid (nitric acid concentration: 20 mass%, hydrochloric acid concentration: 12 mass%), nickel and / or chromium After dissolving the sample using a dissolving acid or solution, the above-mentioned nickel coverage and / or chromium coverage can be measured.

・ Detection strength of secondary ion by TOF-SIMS depth direction analysis TOF-SIMS depth direction analysis using the following equipment on the intermediate layer side surface of the carrier exposed by peeling the ultrathin copper layer from the copper foil with carrier The secondary ions NiO2, CrO4H, and Cr2O4 generated during TOF-SIMS depth profile analysis were measured.
Device: TOF-SIMS 300 (manufactured by ION-TOF)
Primary ion source: Bi
Measurement mode: High mass resolution Measurement plane: Depth direction analysis (Sputtering rate was 0.03 to 0.10 nm / s.)
Measurement area: 100 μm square Negative ions were measured.

· Peeling strength after pressure bonding of the substrate After bonding the ultrathin copper layer side of the copper foil with carrier on the insulating substrate and performing pressure bonding in air at 30 kgf / cm ² and 220 ° C for 2 hours, peeling strength The tensile strength was measured by pulling the carrier side with a load cell, and in accordance with the 90 ° peeling method (JIS C 6471 8.1).

(Evaluation results)
In each of Examples 1 to 21, variation in peel strength was well suppressed.
In Comparative Examples 1 to 3, the variation in peel strength was poor.
The graph which shows the spectrum of Cr2O4 when performing the depth direction analysis by TOF-SIMS of Example 1 and 2 in FIG. 5 is shown. The graph which shows the spectrum of CrO4H when performing the depth direction analysis by TOF-SIMS of Example 1 and 2 in FIG. 6 is shown. The graph which shows the relationship of the measurement position of Example 2 and peeling strength in FIG. 7 is shown. The graph which shows the relationship between the measurement position of comparative example 1 and exfoliation intensity in Drawing 8 is shown.

Claims (32)

A copper foil with a carrier comprising a carrier, an intermediate layer and an ultrathin copper layer in this order,
The intermediate layer contains chromium and
When the ultrathin copper layer is peeled off from the carrier, and depth direction analysis is performed on the intermediate layer side surface of the carrier by TOF-SIMS, the secondary ion detection intensity of the outermost surface is 0.1 for the spectrum of Cr 2 O 4 A carrier having a density of 10 ^{4 to} 2.0 × 10 ⁴ and a maximum intensity of 0.2 to 2.0 nm from the surface and a maximum intensity of 0.5 × 10 ^{4 to} 2.5 × 10 ⁴ Copper foil attached.   When the ultrathin copper layer is peeled off from the carrier, and depth direction analysis is performed on the interlayer side surface of the carrier by TOF-SIMS, the maximum intensity of the spectrum of Cr2O4 and the maximum intensity of the spectrum of CrO4H The copper foil with a carrier according to claim 1, wherein the ratio Cr-O / Cr-OH to Cr-OH is 0.8 or more. The copper foil with a carrier according to claim 1 or 2, wherein the Cr adhesion amount of the intermediate layer is 5 to 100 μg / dm ² . A carrier, an intermediate layer having a chromate-treated layer, and a method of producing a copper foil with a carrier comprising an ultrathin copper layer in this order,
An intermediate layer forming step of forming an intermediate layer having a chromate treatment layer on the carrier;
Removing moisture on the surface of the intermediate layer formed on the carrier;
The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-3 including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on the intermediate | middle layer after the said moisture removal. A carrier, an intermediate layer having a chromate-treated layer, and a method of producing a copper foil with a carrier comprising an ultrathin copper layer in this order,
An intermediate layer forming step of forming an intermediate layer having a chromate treatment layer on the carrier;
Heating the surface of the intermediate layer formed on the carrier after removing water on the surface and drying at 30 to 100 ° C. for 1 to 300 seconds;
The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-3 including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on the intermediate | middle layer after the said drying.   The manufacturing method of the copper foil with a carrier according to claim 5, wherein the intermediate layer is heated at a temperature of 40 to 90 ° C for 3 to 90 seconds after removing moisture on the surface in the heating step. The copper foil with a carrier according to any one of claims 4 to 6, further comprising a surface treatment layer forming step of performing the following treatment (1), (2) or (3) on the ultrathin copper layer: Production method.
(1) Forming a roughened layer
(2) forming at least one layer selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer,
(3) After the roughening treatment layer is formed, one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer are formed. A copper foil with a carrier comprising a carrier, an intermediate layer and an ultrathin copper layer in this order,
The intermediate layer contains nickel and chromium,
When the ultrathin copper layer is peeled from the carrier, and depth direction analysis is performed on the surface of the carrier on the side of the intermediate layer by TOF-SIMS, the maximum secondary ion detection intensity is 0 from the surface for the spectrum of NiO 2 The copper foil with a carrier which exists in a range of 0.5 to 5.0 nm and which has a maximum strength of 0.5 × 10 ^{4 to} 3.0 × 10 ⁴ . A copper foil with a carrier comprising a carrier, an intermediate layer and an ultrathin copper layer in this order,
The intermediate layer contains nickel and chromium,
When the ultrathin copper layer is peeled from the carrier, and depth direction analysis is performed on the surface of the carrier on the side of the intermediate layer by TOF-SIMS, the maximum secondary ion detection intensity is 0 from the surface for the spectrum of NiO 2 The carrier-incorporated copper foil according to any one of claims 1 to 3, which has a maximum intensity of 0.5 × 10 ^{4 to} 3.0 × 10 ⁴ and is present at 0.5 to 5.0 nm. The copper foil with carrier according to claim 8 or 9 Ni deposition amount is 100~40000μg / dm ^2, Cr deposition amount of the intermediate layer is 5~100μg / dm ^2. A carrier, an intermediate layer having a Ni plating layer and a chromate treatment layer, and a method of producing a copper foil with a carrier comprising an ultrathin copper layer in this order,
An intermediate layer forming step of forming the chromate-treated layer after forming a Ni plating layer on the carrier;
Removing moisture on the surface of the intermediate layer formed on the carrier;
The manufacturing method of the copper foil with a carrier as described in any one of Claims 8-10 including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on the intermediate layer after the said moisture removal. A carrier, an intermediate layer having a Ni plating layer and a chromate treatment layer, and a method of producing a copper foil with a carrier comprising an ultrathin copper layer in this order,
An intermediate layer forming step of forming a chromate-treated layer after forming a Ni plating layer on the carrier;
Heating the surface of the intermediate layer formed on the carrier after removing water on the surface and drying at 30 to 100 ° C. for 1 to 300 seconds;
The manufacturing method of the copper foil with a carrier as described in any one of Claims 8-10 including the ultra-thin copper layer formation process of forming the said ultra-thin copper layer on the intermediate layer after the said drying.   The method for producing a copper foil with a carrier according to claim 12, wherein the intermediate layer is heated at a temperature of 40 to 90 ° C for 3 to 90 seconds after removing moisture on the surface in the heating step. The copper foil with a carrier according to any one of claims 11 to 13, further comprising a surface treatment layer forming step of performing the following treatment (1), (2) or (3) on the ultrathin copper layer: Production method.
(1) Forming a roughened layer
(2) forming at least one layer selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer,
(3) After the roughening treatment layer is formed, one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer are formed.   The copper foil with a carrier as described in any one of Claims 1-3 and 8-10 which has a roughening process layer in any one or both of the said ultra-thin copper layer surface and the surface of the said carrier.   The copper foil with carrier according to claim 15, further comprising at least one layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. The method according to any one of claims 1 to 3 and 8 to 10, wherein the surface of the ultrathin copper layer has one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer and a silane coupling treatment layer. Copper foil with carrier according to any one of the items.
  The copper foil with a carrier according to any one of claims 1 to 3 and 8 to 10, wherein a resin layer is provided on the ultrathin copper layer.   The copper foil with carrier according to claim 15, wherein a resin layer is provided on the roughened layer.   The copper foil with a carrier according to claim 16 or 17, further comprising a resin layer on at least one layer selected from the group consisting of the heat-resistant layer, the rustproof layer, the chromate treatment layer and the silane coupling treatment layer.   The copper foil with carrier according to any one of claims 18 to 20, wherein the resin layer is a bonding resin.   The copper foil with carrier according to any one of claims 18 to 21, wherein the resin layer is a resin in a semi-cured state.   The laminated body provided with the copper foil with a carrier as described in any one of Claims 1-3, 8-10, and 15-22.   It is a laminated body containing copper foil with a carrier as described in any one of Claims 1-3, 8-10, and 15-22, and resin, Comprising: A part or all of the end surface of the copper foil with a carrier is the said Laminate covered with resin.   The copper foil with a carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22 and two sets of the resin, and the ultrathin copper foil of one of the two sets of the carrier-attached copper foil The laminated body provided so that the layer side surface and the ultra-thin copper layer side surface of the other copper foil with a carrier may be exposed, respectively.   The manufacturing method of the printed wiring board which manufactures a printed wiring board using copper foil with a carrier as described in any one of Claims 1-3, 8-10, and 15-22.   The manufacturing method of the electronic device which manufactures an electronic device using the printed wiring board of Claim 26. A step of preparing a copper foil with a carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22 and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier.
And then forming a circuit by any of a semi-additive method, a subtractive method, a partial additive method or a modified semi-additive method. A process of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is embedded;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling off the carrier or the ultrathin copper layer;
After peeling off the carrier or the ultrathin copper layer, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. Method of producing a printed wiring board including the step of exposing the circuit. A step of laminating the copper foil with carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22 from the carrier side to a resin substrate,
Forming a circuit on the ultra-thin copper layer side surface of the copper foil with carrier or the carrier side surface;
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is embedded;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling off the carrier or the ultrathin copper layer;
After peeling off the carrier or the ultrathin copper layer, the ultrathin copper layer or the carrier is removed to be buried in the resin layer formed on the ultrathin copper layer side surface or the carrier side surface. Method of producing a printed wiring board including the step of exposing the circuit. A step of laminating the resin substrate on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22,
Providing at least once two layers of a resin layer and a circuit on the very thin copper layer side surface opposite to the side laminated with the resin substrate of the copper foil with carrier or the carrier side surface;
The manufacturing method of the printed wiring board including the process of making the said carrier or the ultra-thin copper layer peel from the said copper foil with a carrier, after forming two layers of the said resin layer and a circuit. A step of laminating the carrier side surface of the copper foil with carrier according to any one of claims 1 to 3, 8 to 10 and 15 to 22 and a resin substrate,
Providing at least once two layers of a resin layer and a circuit on the very thin copper layer side surface opposite to the side laminated with the resin substrate of the copper foil with carrier;
The manufacturing method of the printed wiring board including the process of making the said carrier peel from the said copper foil with a carrier, after forming two layers of the said resin layer and a circuit.