CN105392297A - Method for manufacturing copper foil with carrier, method for manufacturing copper-clad laminate, method for manufacturing printed wiring board and method for manufacturing electronic device, and products thereof - Google Patents

Abstract

The invention provides a method for manufacturing copper foil with carrier. The method comprises the following heating and processing steps: a copper foil with a carrier comprises a carrier, a middle layer, a ultrathin copper layer and a surface processing layer comprising a silane coupling processing layer, the copper foil with the carrier is performed a heating process for 1 hour to 8 hours at the heating temperature of 100 DEG C to 220 DEG C, or a heating process for 1 hour to 6 hours at the heating temperature of 100 DEG C to 220 DEG C, or a heating process for 2 hour to 4 hours at the heating temperature of 160 DEG C to 220 DEG C.

Description

Manufacturing method of copper foil with carrier, manufacturing method of copper-clad laminated board, manufacturing method of printed wiring board, manufacturing method of electronic equipment and their products

technical field

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

Background technique

A printed wiring board is usually produced through a process of forming a conductor pattern on the copper foil surface by etching after bonding an insulating substrate and copper foil to form a copper-clad laminate. In recent years, with the miniaturization of electronic equipment and the increase in the demand for high performance, the high-density packaging of mounted parts and the high frequency of signals have been promoted, and the miniaturization of conductor patterns (narrow pitch) is required for printed wiring boards. ) or high-frequency response, etc.

Corresponding to the narrow pitch, copper foil with a thickness of 9 μm or less, and even a thickness of 5 μm or less has recently been required. However, such extremely thin copper foil has low mechanical strength and is prone to cracking or cracking during the manufacture of printed wiring boards. Therefore, a copper foil with a carrier is developed, which uses a thick metal foil as a carrier and deposits an extremely thin copper layer on it through a peeling layer. After bonding the surface of the ultra-thin copper layer to the insulating substrate and performing thermocompression bonding, the carrier is peeled and removed through the release layer. After forming a circuit pattern with a resist on the exposed ultra-thin copper layer, the ultra-thin copper layer is etched and removed with a sulfuric acid-hydrogen peroxide-based etchant (MSAP: Modified-Semi-Additive-Process) to form microscopic circuits.

Here, for the surface of the ultra-thin copper layer of the copper foil with a carrier to be the bonding surface with the resin, it is mainly required that the peel strength between the ultra-thin copper layer and the resin base material is sufficient, and the peel strength is high temperature heating, wet processing, welding, Chemical agent treatment etc. are also kept sufficient afterward. The method of improving the peel strength between the ultra-thin copper layer and the resin base material is generally represented by the method of attaching a large number of roughening particles to the ultra-thin copper layer after the surface contour (concave-convex, roughness) is enlarged superior.

However, even in printed wiring boards, if such an ultra-thin copper layer with a large outline (concave-convex, roughness) is used on a semiconductor package substrate required to form a particularly fine circuit pattern, undesired copper will remain during circuit etching. Necessary copper particles cause problems such as poor insulation between circuit patterns.

Therefore, WO2004/005588 (Patent Document 1) attempted to use a copper foil with a carrier that did not roughen the surface of the ultra-thin copper layer as a copper foil with a carrier for fine circuits including semiconductor package substrates. Due to its low profile (concave-convex, roughness, roughness), the adhesion (peel strength) of this ultra-thin copper layer without roughening treatment to resin is lower than that of general copper foil for printed wiring boards. tends to decrease. Therefore, further improvement of the copper foil with a carrier is required.

Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Laid-Open No. 2010-006071 (Patent Document 3), it is described that an ultra-thin copper foil with a carrier and a polyimide-based resin substrate On the contacting (adhering) surface, a Ni layer or/and Ni alloy layer, a chromate layer, a Cr layer or/and Cr alloy layer, a Ni layer and a chromate layer, a Ni layer and a Cr layer are provided. By providing these surface treatment layers, the adhesion strength between the polyimide-based resin substrate and the ultra-thin copper foil with a carrier can be obtained without roughening or by reducing the degree of roughening (micronization). strength. In addition, it is also described that surface treatment or antirust treatment is performed using a silane coupling agent.

[Patent Document 1] WO2004/005588

[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-007937

[Patent Document 3] Japanese Unexamined Patent Publication No. 2010-006071.

Contents of the invention

In the development of copper foil with a carrier, securing the peel strength between the ultra-thin copper layer and the resin substrate has been regarded as an important point until now. Therefore, the circuit formability of the ultra-thin copper layer has not yet been fully studied, and there is still room for improvement.

Forming a circuit on an ultra-thin copper layer is usually performed by removing the carrier after laminating the ultra-thin copper layer on a resin base, and then placing a photoresist with a specific pattern on the ultra-thin copper layer , using a specific etchant for etching to remove the copper layer not covered by the photoresist. After that, by removing the photoresist, a circuit with a desired conductor pattern is fabricated.

Here, when the etching process is performed with a specific etching solution, if the wettability of the ultra-thin copper layer and the resin substrate near the interface with the etching solution is poor, the wettability of the etching solution will be insufficient. In this case, non-uniform etching occurs in the vicinity of the interface with the resin substrate, resulting in poor circuit linearity. This invention provides the manufacturing method of the copper foil with a carrier favorable to the circuit formability of an ultra-thin copper layer. Moreover, the copper foil with a carrier favorable in the wettability of an etchant is provided.

The present invention completed on the basis of the above knowledge is, in one aspect, a method for producing copper foil with a carrier, which includes the following heat treatment step: The copper foil with a carrier of the surface treatment layer of the coupling treatment layer is subjected to a heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 8 hours, or a heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 6 hours , or heat treatment at a heating temperature of 160° C. to 220° C. for 2 hours to 4 hours.

In another aspect of the present invention, it is a method of manufacturing copper foil with a carrier, which includes the following heat treatment step: for the copper foil with a carrier sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, The heating rate until reaching the heating temperature is set to exceed 50°C/hour, and the heating temperature is 100°C to 220°C for 1 hour to 8 hours, or the heating temperature is 100°C to 220°C for 1 hour to 6 hours heat treatment, or heat treatment at a heating temperature of 160°C to 220°C for 2 hours to 4 hours.

In one Embodiment, the manufacturing method of the copper foil with a carrier which concerns on this invention WHEREIN: The said temperature increase rate in the said heat process is 200 degreeC/hour or less.

In another embodiment of the manufacturing method of the copper foil with a carrier of this invention, the tensile strength of the carrier measured at normal temperature after the said heat treatment process is 300 MPa or more.

In yet another embodiment of the manufacturing method of the copper foil with a carrier of this invention, in the said heat treatment process, it heat-processes in an inert gas atmosphere.

In still another embodiment, the manufacturing method of the copper foil with a carrier of this invention heat-processes in the state which wound the copper foil with a carrier in the metal hollow tube in the said heat treatment process.

In yet another embodiment of the method for producing copper foil with a carrier according to the present invention, in the heat treatment step, the tension at the time of winding the copper foil with a carrier into a metal hollow tube is 5 to 100 kgf/ m or 20 to 100kgf/m for heat treatment.

In yet another embodiment of the method for producing copper foil with a carrier according to the present invention, in the heat treatment step, while the copper foil with a carrier is wrapped in a metal hollow tube, heat is heated at a temperature of 0.01 to 600 The heat treatment was performed while rotating the above-mentioned hollow tube at a speed of rotation/hour.

In still another embodiment of the manufacturing method of the copper foil with a carrier which concerns on this invention, the copper foil with a carrier before the said heat process further has an intermediate|middle layer and an ultra-thin copper layer in this order on the surface by the said carrier side.

In yet another one Embodiment of the manufacturing method of the copper foil with a carrier which concerns on this invention, the copper foil with a carrier before the said heat process has a surface treatment layer further in the surface by the side of the said carrier.

In yet another one Embodiment of the manufacturing method of the copper foil with a carrier which concerns on this invention, the said surface treatment layer contains a roughening treatment layer.

In yet another embodiment of the method for producing copper foil with a carrier according to the present invention, the surface of the above-mentioned surface treatment layer that is a roughening treatment layer further has a layer selected from a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling layer. Processes one or more layers in a group of layers.

In yet another embodiment of the method for producing copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment has a surface selected from a roughening treatment layer, a heat-resistant layer, and a rust-proof layer on the surface of the above-mentioned ultra-thin copper layer. One or more layers in the group consisting of the chromate treatment layer and the silane coupling treatment layer are used as the surface treatment layer.

In yet another one Embodiment of the manufacturing method of the copper foil with a carrier which concerns on this invention, the copper foil with a carrier before the said heat process is equipped with a resin layer on the said surface treatment layer.

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

In still another aspect, this invention is the manufacturing method of a printed wiring board using the copper foil with a carrier obtained by the method of this invention.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

Copper foil with carrier and insulating substrate prepared by the method of the present invention;

Laminate the above-mentioned copper foil with carrier and insulating substrate; and

After laminating the above-mentioned copper foil with a carrier and an insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate,

Thereafter, a circuit is formed by any method of semi-additive method, subtractive method, partial additive method, or modified semi-additive method (Modified SemiAdditive).

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

Forming a circuit on the above-mentioned ultra-thin copper layer side surface or the above-mentioned carrier side surface of the copper foil with a carrier produced by the method of the present invention;

Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side so as to bury the circuit;

forming a circuit on the above-mentioned resin layer;

After forming a circuit on the above resin layer, peeling off the above carrier or the above ultra-thin copper layer; and

After peeling off the carrier, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer-side surface or the carrier-side surface buried in the resin layer.

This invention is another aspect. It is the manufacturing method of the electronic equipment using the printed wiring board manufactured by the method of this invention.

In still another aspect, this invention is copper foil with a carrier manufactured by the method of this invention.

In yet another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer including a silane coupling treatment layer, with the ultra-thin copper foil side on the horizontal plane Place the copper foil with the carrier (except those with the resin layer) with the surface treatment layer on the top, and use a pipette to drop 30 μL of sulfuric acid 24% by weight-hydrogen peroxide 15% by weight (the rest is water) ) composition of the etchant, after leaving the etchant for 30 seconds and wiping off the etchant, the difference between the maximum diameter and the minimum diameter of the trace of the etchant is 10 mm or less.

In yet another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer including a silane coupling treatment layer, with the ultra-thin copper foil side on the horizontal plane Place the copper foil with the carrier (except those with the resin layer) with the surface treatment layer on the top, and use a pipette to drop 30 μL of sulfuric acid 24% by weight-hydrogen peroxide 15% by weight (the rest is water) ) of the composition of the etching solution, after wiping off the etching solution after leaving it for 30 seconds, the maximum diameter of the trace of the etching solution is 25 mm or more.

In yet another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, and the surface treatment layer on the side of the ultra-thin copper foil is on the horizontal plane. Place copper foil with carrier (except those with resin layer) in the same way, and use a pipette to drop 30 μL of etching solution consisting of 24% by weight of sulfuric acid - 15% by weight of hydrogen peroxide (the rest is water) , after wiping off the etchant after standing for 30 seconds, the difference between the maximum diameter and the minimum diameter of the trace of the etchant is 10 mm or less.

In yet another aspect of the present invention, it is a copper foil with a carrier, which sequentially includes a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, and the surface treatment layer on the side of the ultra-thin copper foil is on the horizontal plane. Place copper foil with carrier (except those with resin layer) in the same way, and use a pipette to drop 30 μL of etching solution consisting of 24% by weight of sulfuric acid - 15% by weight of hydrogen peroxide (the rest is water) , After wiping off the etching solution after leaving it for 30 seconds, the maximum diameter of the trace of the etching solution is more than 25mm.

In yet another aspect of the copper foil with a carrier of the present invention, the difference between the maximum diameter and the minimum diameter of the trace of the etching solution is 5 mm or less.

In yet another aspect of the copper foil with a carrier of the present invention, the maximum diameter of the trace of the etching solution is 35 mm or more.

In still another aspect, this invention is a laminate manufactured using the copper foil with a carrier of this invention.

In still another aspect, the present invention is a laminate comprising the copper foil with a carrier of the present invention and a resin, wherein part or all of the end faces of the copper foil with a carrier are covered with the resin.

Still another aspect of the present invention is a laminate in which one copper foil with a carrier of the present invention is laminated on another copper foil with a carrier of the present invention from the carrier side or the surface treatment layer side. The above-mentioned carrier side or the above-mentioned surface treatment layer side is formed.

In one embodiment of the laminate of the present invention, the carrier-side surface or the surface-treated layer-side surface of the one copper foil with a carrier and the carrier-side surface or the surface-treated layer-side surface of the other copper foil with a carrier are If necessary, it can be constructed by direct lamination via an adhesive.

In another embodiment of the laminate of the present invention, the carrier or the surface treatment layer of the one copper foil with a carrier is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier.

In yet another embodiment of the laminate of the present invention, part or all of the end faces of the laminate are covered with a resin.

This invention is another one side. It is a printed wiring board manufactured using the copper foil with a carrier of this invention.

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

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above-mentioned copper foil with carrier and insulating substrate; and

After laminating the above-mentioned copper foil with a carrier and an insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate,

Thereafter, a circuit is formed by any one of semi-additive method, subtractive method, partial additive method, or modified semi-additive method.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

A circuit is formed on the side surface of the above-mentioned ultra-thin copper layer or the surface of the above-mentioned carrier side of the copper foil with a carrier of the present invention;

Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side so as to bury the circuit;

After forming the above-mentioned resin layer, peeling off the above-mentioned carrier or the above-mentioned ultra-thin copper layer; and

After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer side surface or the carrier-side surface buried in the resin layer.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

A circuit is formed on the side surface of the above-mentioned ultra-thin copper layer or the surface of the above-mentioned carrier side of the copper foil with a carrier of the present invention;

Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side so as to bury the circuit;

forming a circuit on the above-mentioned resin layer;

After forming a circuit on the above resin layer, peeling off the above carrier or the above ultra-thin copper layer; and

After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer side surface or the carrier-side surface buried in the resin layer.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

The above-mentioned ultra-thin copper layer side surface or the above-mentioned carrier side surface of the copper foil with a carrier of the present invention is laminated with a resin substrate;

At least one resin layer and a circuit are provided on the side surface of the ultra-thin copper layer or the surface of the carrier side opposite to the side of the copper foil with carrier on which the resin substrate is laminated; and

After forming two layers of the said resin layer and a circuit, the said carrier or the said ultra-thin copper layer are peeled from the said copper foil with a carrier.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board, which includes the following steps:

The above-mentioned carrier-side surface of the copper foil with a carrier of the present invention is laminated with a resin substrate;

Provide at least two layers of a resin layer and a circuit on the surface of the ultra-thin copper layer side opposite to the side of the above-mentioned copper foil with a carrier on which the resin substrate is laminated; and

After forming two layers of the said resin layer and a circuit, the said ultra-thin copper layer is peeled from the said copper foil with a carrier.

According to this invention, the manufacturing method of the copper foil with a carrier favorable to the circuit formability of an ultra-thin copper layer can be provided. Moreover, the copper foil with a carrier favorable in the wettability of an etchant is provided.

Description of drawings

1A to 1C are cross sections of the printed wiring board in the steps from exposure-development to circuit plating-photoresist removal in a specific example of the method of manufacturing a printed wiring board using copper foil with a carrier according to the present invention. schematic diagram.

2D to 2F are the steps from the build-up resin and the second layer of copper foil with a carrier to the laser opening of the specific embodiment of the manufacturing method of the printed wiring board using the copper foil with a carrier of the present invention. Schematic diagram of a patch panel cutaway.

3G to 3I are cross-sectional diagrams of the wiring board in the steps from the formation of the through-hole filling to the peeling of the first layer carrier in the specific embodiment of the method of manufacturing the printed wiring board using the copper foil with carrier of the present invention. schematic diagram.

4J to 4K are schematic diagrams of a cross section of a wiring board in steps from flash etching to bump-copper pillar formation in a specific example of the method of manufacturing a printed wiring board using copper foil with a carrier according to the present invention.

FIG. 5 : is a top view photograph of the circuit, showing the method of measuring the difference (μm) between the maximum and minimum width of the lower end of the circuit observed from the top of the circuit in the experimental example.

detailed description

＜Manufacturing method of copper foil with carrier＞

As a usage form of the copper foil with a carrier provided with a carrier, an intermediate layer, and an ultra-thin copper layer in this order, first, the surface of the ultra-thin copper layer is bonded to an insulating substrate and thermocompression-bonded, and then the carrier is peeled off. Next, a photoresist with a specific pattern is placed on the ultra-thin copper layer that has been bonded to the insulating substrate. Next, etching is performed with a specific etchant to remove the ultra-thin copper layer not covered by the photoresist to form a target conductor pattern, for example, to produce a printed wiring board with a specific circuit. Here, when etching is performed with a specific etchant, if the wettability of the ultra-thin copper layer near the interface with the resin base material to the etchant is poor, the wetting range of the etchant becomes insufficient. In this case, uneven etching occurs in the vicinity of the interface with the resin substrate, resulting in poor circuit linearity.

On the other hand, in one aspect of the manufacturing method of the copper foil with a carrier of the present invention, after preparing the copper foil with a carrier sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer including a silane coupling treatment layer, This copper foil with a carrier is heat-processed at the heating temperature of 100 degreeC - 220 degreeC for 1 hour - 8 hours. In addition, the said 100 degreeC - 220 degreeC represent the ambient temperature in a heating apparatus. In this way, by performing heat treatment at a heating temperature of 100° C. to 220° C. for 1 hour to 8 hours, since the unreacted hydrogen groups in the silane coupling treatment layer undergo dehydration condensation reaction, the treatment layer will become stronger. In addition to improving the adhesion to the resin base material, it will also make the vicinity of the interface between the ultra-thin copper layer and the surface treatment layer, and in the case of a multi-layer surface treatment layer, the vicinity of the interface between the multilayers. The discontinuous part of the atomic composition is formed into a continuous atomic composition distribution by interdiffusion, so the wettability of the ultra-thin copper layer near the interface with the resin substrate becomes good for the etchant, and near the interface with the resin substrate Partial etching is uniform, and the circuit linearity of the ultra-thin copper layer becomes good. Furthermore, typically, the ultra-thin copper layer is mainly composed of copper. In addition, the surface treatment layer may have a roughening treatment layer and/or a heat-resistant layer and/or a rust-proof layer and/or a chromate treatment layer and a silane coupling treatment layer in this order, and these layers may be provided in any order. It is preferable that the roughening treatment layer mainly consists of an alloy, for example, a copper alloy, a nickel alloy, or a cobalt alloy. The roughening layer can also mainly consist of copper. The chromate treatment layer is preferably composed mainly of metal oxides. The silane coupling treatment layer is preferably composed of an organosilicon compound.

Usually, when the copper foil with a carrier is bonded to the resin substrate, heat-compression bonding at a temperature of 160 to 220°C is performed for about 50 to 120 minutes, so although the above-mentioned interdiffusion also proceeds to some extent , but depending on the conditions, there may be insufficient mutual diffusion. Therefore, by performing the above-mentioned heat treatment before bonding to the resin base material, the effect of improving the etching property and its uniformity can be made more reliable.

In addition, when Si is detected on the surface of the ultra-thin copper layer side of the copper foil with a carrier, the presence of the silane coupling treatment layer can be judged by surface analysis such as XPS.

In this heat treatment, when the temperature is less than 100° C. or the heating time is less than 1 hour, mutual diffusion in the vicinity of the interface between the respective treatment layers becomes insufficient. In addition, in this heat treatment, when the temperature exceeds 220°C or the heating time exceeds 8 hours, the peel strength between the carrier and the ultra-thin copper foil may change, or the grain growth of the ultra-thin copper layer may occur. Thereby reducing the mechanical strength and other problems. In this heat treatment step, it is preferable to carry out heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 6 hours, preferably to carry out heat treatment at a heating temperature of 120°C to 220°C for 1 hour to 6 hours, and more preferably It is preferable to perform heat treatment at a heating temperature of 160° C. to 220° C. for 2 hours to 4 hours.

In another aspect, the method of manufacturing copper foil with a carrier of the present invention includes a heat treatment step of heating the copper foil with a carrier sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer to the heating temperature. The rate of temperature increase up to this point was set to exceed 50° C./hour, and heat treatment was performed at a heating temperature of 100° C. to 220° C. for 1 hour to 8 hours. Here, the temperature increase rate is the temperature increase rate from the start of heating until reaching the heating temperature for the first time. When the rate of temperature increase is 50° C./hour or less, the productivity of the heat treatment may decrease, and since the time of the heat treatment is long, the surface of the copper foil with a carrier may be oxidized. Also, the rate of temperature increase is preferably 200° C./hour or less. When the temperature increase rate exceeds 200°C/hour, the degree of elongation may vary due to the difference in thermal expansion coefficient between the winding core and the copper foil with carrier, resulting in wrinkles. Moreover, when exceeding 200 degreeC/hour, the wettability of the copper foil with a carrier with respect to etchant may deteriorate. The reason for this is not clear, but it may be that the copper foil with a carrier expands violently, causing friction or misalignment between the surface treatment layer and the carrier that come into contact with the coil, or stress on the surface treatment layer. Concentration, this friction, displacement, stress concentration, etc. are related to generation of partial displacement in the surface treatment layer, and this displacement affects the diffusion state of elements in the surface treatment layer.

The temperature increase rate until reaching the heating temperature is more preferably 70°C/hour to 200°C/hour, still more preferably 100°C/hour to 200°C/hour, still more preferably 150°C/hour to 200°C/hour.

In the method for producing copper foil with a carrier of the present invention, in the heat treatment step, heating is preferably performed in an environment that does not contain gases such as oxygen and water vapor that may cause oxidation or deterioration of the surface of the carrier and the surface of the ultra-thin copper layer. For the treatment, for example, heat treatment is preferably performed in an inert gas atmosphere of helium, neon, argon, nitrogen, or a mixed gas thereof.

In the manufacturing method of the copper foil with a carrier of this invention, it is preferable to heat-process in the state which wound up the copper foil with a carrier in the said heat treatment process in the hollow tube made of metal. By heating the copper foil with a carrier wrapped in a metal hollow tube, it is possible to heat the copper foil with a carrier from the inside by passing air through the metal tube with good thermal conductivity. effective heat treatment. The metal hollow tube is not particularly limited, and is preferably made of carbon steel or stainless steel, for example, and its size may be 7 cm to 20 cm in outer diameter and 0.5 cm to 3.0 cm in thickness.

In the manufacturing method of the copper foil with a carrier of the present invention, in the above-mentioned heat treatment step, it is preferable to carry out the following heat treatment: the tension when the copper foil with a carrier is wound into a metal hollow tube is set to 5 to 5. 100kgf/m. This tension is the tension per unit width (width 1m) of the copper foil with a carrier. By setting this tension to 5 kgf/m or more, entrainment of oxygen can be suppressed, and oxidation of the copper foil with a carrier can be prevented. In addition, by setting the tension to 100 kgf/m or less, wrinkles generated at the time of winding can be prevented.

The tension is more preferably 10 kgf/m or more, more preferably 20 kgf/m or more, more preferably 20 to 100 kgf/m, still more preferably 20 to 50 kgf/m, still more preferably 20 to 30 kgf/m.

In the method for producing copper foil with a carrier according to the present invention, in the heat treatment step, it is preferable to rotate the copper foil with a carrier at 0.01 to 600 rotations/hour while wrapping the copper foil with a carrier in a hollow metal tube. The above hollow tube is rotated at a certain speed while heat treatment is performed. By performing heat treatment while rotating the hollow tube at a relatively low speed of 0.01 rotations/hour or more and 600 rotations/hour or less, oxygen trapped between the wound copper foil and copper foil can be removed , thereby preventing oxidation of the copper foil with a carrier during heat treatment. The rotation speed of the hollow tube is more preferably 0.01-180 rotations/hour, more preferably 0.01-120 rotations/hour, more preferably 0.01-70 rotations/hour, more preferably 1-70 rotations/hour.

In the manufacturing method of the copper foil with a carrier of this invention, it is preferable that the tensile strength of the carrier measured at normal temperature after the said heat treatment process is 300 MPa or more. The tensile strength of the carrier measured at normal temperature after the heat treatment step as described above is 300 MPa or more, and the rigidity when the ultra-thin copper layer functions as a carrier can be sufficiently maintained.

The tensile strength of the support is more preferably 350 MPa or more, still more preferably 380 MPa or more, more typically 350 to 500 MPa, and still more typically 380 to 450 MPa.

＜Copper foil with carrier＞

Hereinafter, unless otherwise specified, the embodiment of the copper foil with a carrier is described before the heat treatment of the present invention, but this embodiment is for the heat treatment (the copper foil with a carrier produced by the method of manufacturing the copper foil with a carrier of the present invention) Carrier copper foil) is also suitable.

The copper foil with a carrier of the present invention has a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer in this order. The use method of copper foil with carrier itself is well known in the industry. For example, the surface of the ultra-thin copper layer can be bonded to paper-based phenol resin, paper-based epoxy resin, synthetic fiber cloth-based epoxy resin, glass cloth- Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film and other insulating substrates After thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer adhered to the insulating substrate is etched into the target conductor pattern, and finally a printed wiring board is manufactured.

<Carrier>

The carrier that can be used in the present invention is typically metal foil or 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, insulating resin Available in the form of film, polyimide film, and 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. Usually, electrolytic copper foil is manufactured by electrolytically depositing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and rolled copper foil is manufactured by repeating plastic working and heat treatment with rolling rolls. As the material of copper foil, in addition to high-purity copper such as refined copper (JISH3100 alloy number C1100) or oxygen-free copper (JISH3100 alloy number C1020 or JISH3510 alloy number C1011), for example, Sn-doped copper, Ag-doped copper, added Copper alloys such as Cr, Zr, or Mg, and copper alloys such as Cason-based copper alloys to which Ni, Si, etc. have been added.

In addition, as electrolytic copper foil, it can manufacture using the following electrolytic solution composition and manufacturing conditions.

In addition, the remainder of the processing liquid used for the manufacture of copper foil described in this specification, the surface treatment of copper foil, the plating of copper foil, etc. is water unless otherwise specified.

＜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-mentioned amine compound, an amine compound of the following chemical formula can be used.

( _In this chemical _formula , R1 and R2 are selected from the group consisting of hydroxyalkyl, ether group, aryl group, aromatic substituted alkyl group, unsaturated hydrocarbon group, and alkyl group)

＜Manufacturing conditions＞

Current density: 70～100A/ ^dm2

Electrolyte temperature: 50～60℃

Electrolyte linear velocity: 3～5m/sec

Electrolysis time: 0.5 to 10 minutes

In addition, when the term "copper foil" is used alone in this specification, copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is not particularly limited, as long as it is appropriately adjusted to a thickness suitable for functioning as a carrier, for example, it can be set to 5 μm or more. However, if it is too thick, the production cost will increase, so it is usually preferably set to 35 μm or less. Therefore, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, more typically 18 to 35 μm. In addition, from the viewpoint of reducing raw material costs, it is preferable that the thickness of the carrier is 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, preferably 5 μm to 11 μm, and preferably 5 μm to 10 μm. In addition, when the thickness of the carrier is small, wrinkles are easily generated when the carrier passes through the foil. In order to prevent wrinkles, it is effective, for example, to smoothen the conveyance roller of the copper foil with carrier manufacturing apparatus, or to shorten the distance between the conveyance roller and the next conveyance roller. Moreover, when using the copper foil with a carrier by the embedding method (Enbedded Process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier must be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably from 18 μm to 300 μm, preferably from 25 μm to 150 μm, preferably from 35 μm to 100 μm, and even more preferably from 35 μm to 70 μm.

＜Middle layer＞

An intermediate layer is provided on the carrier. It is also possible to arrange other layers between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it has a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with carrier on the insulating substrate, and on the other hand The very thin copper layer can be stripped from the carrier after the step. For example, the intermediate layer of the copper foil with a carrier of the present invention may also contain materials selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys of these metals, hydrates of these metals, One or two or more of these metal oxides and organic compounds. In addition, the intermediate layer may be multilayered. Also, the intermediate layer may be provided on both surfaces of the carrier.

Also, for example, the intermediate layer can be constituted by forming an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. A single metal layer, or an alloy layer composed of one or two or more elements selected from the element group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn , forming a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or composed of Cr , Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn element group consisting of one or two or more elements in the alloy layer, or an alloy layer selected from Cr, Ni, Co, A layer composed of hydrates or oxides or organic substances of one or more elements in the element group consisting of Fe, Mo, Ti, W, P, Cu, Al, and Zn.

In addition, a Ni-containing intermediate layer may be provided on one or both surfaces of the carrier. The intermediate layer is preferably constituted by sequentially laminating any one layer of nickel or an alloy containing nickel, and one or more layers containing chromium, a chromium alloy, or an oxide of chromium on a carrier. Furthermore, it is preferable to contain zinc in the layer containing any one of nickel or an alloy containing nickel and/or any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the so-called nickel-containing alloy refers to nickel and one or more selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. alloys of elements. The nickel-containing alloy may be an alloy composed of three or more elements. In addition, the so-called chromium alloy refers to chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium. alloy. The chromium alloy may be an alloy composed of three or more elements. In addition, the layer containing any one or more of chromium, chromium alloy, and chromium oxide may be a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a solution containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer can also contain elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (also can be metal, alloy, oxide, nitride, sulfide, etc.) any form of matter). Specific examples of the chromate treatment layer include: a pure chromate treatment layer, a zinc chromate treatment layer, and the like. In the present invention, the chromate treatment layer treated with chromic anhydride or potassium dichromate aqueous solution is called pure chromate treatment layer. In addition, in the present invention, the chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc-chromate-treated layer.

In addition, the intermediate layer is preferably a layer in which any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, and nickel-cobalt alloy is sequentially laminated on the carrier, and a zinc chromate treatment layer and a pure chromate treatment layer , chrome-plated layer, and the intermediate layer is preferably formed by sequentially laminating a nickel layer or a nickel-zinc alloy layer, and a zinc chromate treatment layer on a carrier, or sequentially laminating nickel-zinc alloy layers. Zinc alloy layer, and pure chromate treatment layer or zinc chromate treatment layer. Since the adhesive force between nickel and copper is higher than that between chromium and copper, when the ultra-thin copper layer is peeled off, it is peeled at the interface between the ultra-thin copper layer and the chromate-treated layer. Also, nickel in the intermediate layer is expected to have a barrier effect to prevent the diffusion of copper components from the carrier to the ultra-thin copper layer. Also, it is preferable to form a chromate treatment layer without performing chrome plating on the intermediate layer. Chromium plating forms a dense chromium oxide layer on the surface, so when an ultra-thin copper foil is formed by electroplating, the resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so it is less likely to become a resistance when forming an ultra-thin copper foil by electroplating, and pinholes can be reduced. Here, by forming a zinc chromate layer as a chromate layer, the electrical resistance when an ultra-thin copper foil is formed by electroplating is lower than that of a normal chromate layer, and the occurrence of pinholes can be further suppressed.

When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the glossy surface from the viewpoint of reducing pinholes.

When the chromate-treated layer in the intermediate layer exists thinly at the interface of the ultra-thin copper layer, the ultra-thin copper layer will not be peeled off from the carrier before the step of laminating the insulating substrate. It is preferable because the ultra-thin copper layer can be peeled off from the carrier after the substrate is laminated. When no nickel layer or nickel-containing alloy layer (such as nickel-zinc alloy layer) is provided and the chromate treatment layer exists at the junction of the carrier and the ultra-thin copper layer, the peelability is hardly improved. When the nickel layer or nickel-containing alloy layer (such as nickel-zinc alloy layer) is directly laminated with the ultra-thin copper layer, the nickel layer or nickel-containing alloy layer (such as nickel-zinc alloy layer) ) The amount of nickel in the peel strength is too strong or too weak to obtain an appropriate peel strength.

Also, if the chromate treatment layer exists at the junction of the carrier and the nickel layer or nickel-containing alloy layer (such as nickel-zinc alloy layer), the intermediate layer will also be peeled off when the ultra-thin copper layer is peeled off, that is, between the carrier and the nickel-containing alloy layer. Since peeling occurred between the intermediate layers, it was unfavorable. This situation occurs not only when the chromate treatment layer is provided at the interface with the carrier, but also occurs when the chromate treatment layer is provided at the interface with the ultra-thin copper layer when the amount of chromium is too large. The reason for this is considered to be that since copper and nickel are easily solid-soluted, if they are brought into contact with each other, the adhesive force will be improved due to mutual diffusion, and it will become difficult to peel off. Diffusion, so the adhesion force at the interface between chromium and copper is weak and easy to peel off. Also, when the amount of nickel in the intermediate layer is insufficient, only a small amount of chromium exists between the carrier and the ultra-thin copper layer, so that both are closely bonded and it becomes difficult to peel off.

The nickel layer or nickel-containing alloy layer (e.g. nickel-zinc alloy layer) of the intermediate layer can be deposited, for example, by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Apply to form. From the viewpoint of cost, electroplating is preferable. Furthermore, when the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and dip plating.

In addition, the chromate treatment layer can be formed, for example, by electrolytic chromate or immersion chromate, etc., but since the concentration of chromium can be increased, the peel strength of the ultra-thin copper layer from the carrier becomes good, so it is preferably formed by electrolytic chromate. form.

The intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating a nickel layer and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid on a carrier. In addition, the intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on a carrier. . Moreover, BTA (benzotriazole), MBT (mercaptobenzothiazole), etc. are mentioned as an organic substance containing any one of this nitrogen-containing organic compound, sulfur-containing organic compound, and carboxylic acid.

Also, as the organic substance contained in the intermediate layer, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Among nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, nitrogen-containing organic compounds include nitrogen-containing organic compounds having substituents. As a specific nitrogen-containing organic compound, it is preferable to use triazole compounds with substituents, namely 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolyl Methyl) urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, etc.

As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazole thiol, and the like.

As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, among which oleic acid, linolenic acid, linolenic acid, and the like are preferably used.

The above organic matter is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm. The intermediate layer may also contain multiple (or more than one) organic substances mentioned above.

In addition, the thickness of an organic substance can be measured as follows.

＜Thickness of organic matter in the middle layer＞

After peeling the ultra-thin copper layer of the copper foil with a carrier from the carrier, XPS measurement was performed on the exposed interlayer-side surface of the ultra-thin copper layer and the exposed interlayer-side surface of the carrier to prepare a depth profile. Then, the depth from the intermediate layer side surface of the ultra-thin copper layer to the first carbon concentration of 3 at% or less can be defined as A (nm), and the depth from the intermediate layer side surface of the carrier to the first carbon concentration of 3 at% or less can be defined as A (nm). is B (nm), and the total of A and B is the thickness (nm) of the organic substance of the intermediate layer.

The operating conditions of XPS are shown below.

Device: XPS measuring device (ULVAC-PHI company, model 5600MC)

·Ultimate vacuum: 3.8× ^10-7 Pa

X-ray: monochromatic AlKα or non-monochromatic MgKα, X-ray output 300W, detection area 800μmφ, angle between sample and detector 45°

Ion beam: ion type Ar ⁺ , accelerating voltage 3kV, scanning area 3mm×3mm, sputtering rate 2.8nm/min (SiO ₂ conversion)

About the usage method of the organic substance contained in an intermediate layer, the method of forming an intermediate layer on a carrier foil is described and demonstrated below. Forming the intermediate layer on the carrier is carried out by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or by using a shower method, a spray method, a dripping method, and an electrodeposition method on the surface where the intermediate layer is to be formed. A specifically defined method is used. At this time, the concentration of the organic solvent in the solvent is preferably in the range of a concentration of 0.01 g/L to 30 g/L and a liquid temperature of 20 to 60° C. among all the above-mentioned organic substances. The concentration of the organic matter is not particularly limited, and there is no problem if the concentration is high or low. Furthermore, there is a tendency that the higher the concentration of the organic matter is, the longer the contact time of the carrier with the solvent in which the organic matter is dissolved, and the thickness of the organic matter in the intermediate layer becomes larger. In addition, when the thickness of the organic substance in the intermediate layer is thick, the effect of suppressing the diffusion of Ni to the side of the ultra-thin copper layer tends to be greater.

＜Extremely thin copper layer＞

An extremely thin copper layer is provided on the intermediate layer. It is also possible to arrange other layers between the intermediate layer and the very thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and sulfuric acid is preferable in terms of forming a copper layer at a high current density. copper bath. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, less than 12 μm. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, still more typically 1.5 to 5 μm, and still more typically 2 to 5 μm. Furthermore, an extremely thin copper layer can also be provided on both sides of the carrier.

＜Roughening treatment and other surface treatment＞

A roughened layer can be provided by roughening the surface of the ultra-thin copper layer, for example, to improve adhesion with an insulating substrate. The roughening treatment can be performed, for example, by forming roughening particles with copper or a copper alloy. Coarsening processing can also be made finer. The roughening treatment layer may be a layer composed of any single substance selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing any one or more thereof. In addition, after forming roughened particles with copper or a copper alloy, roughening treatment for providing secondary particles or tertiary particles may be further performed using simple substances or alloys of nickel, cobalt, copper, and zinc. Then, a heat-resistant layer and/or an anti-rust layer may be formed using simple substances or alloys of nickel, cobalt, copper, and zinc, and further treatments such as chromate treatment and silane coupling treatment may be performed on the surface. Alternatively, without roughening treatment, a heat-resistant layer or an anti-rust layer may be formed using nickel, cobalt, copper, zinc, or an alloy, and the surface may be further treated with chromate treatment, silane coupling treatment, or the like. That is to say, 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. One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer are formed on the surface of the copper layer. In addition, the above-mentioned heat-resistant layer, rust-proof layer, chromate-treated layer, and silane-coupling-treated layer may each be formed in multiple layers (for example, two or more layers, three or more layers, etc.). The so-called chromate treatment layer here may be the above-mentioned chromate treatment layer or other chromate treatment layers.

In addition, the above-mentioned silane coupling treatment layer is an essential component as described above in the manufacturing method of the copper foil with a carrier according to another aspect of the invention of the present application. The manufacturing method of copper foil is one that includes the following heat treatment step: For copper foil with a carrier sequentially equipped with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, the temperature increase rate until reaching the heating temperature is set to exceed 50 °C/hour, and then perform heat treatment at 100°C to 220°C for 1 hour to 8 hours.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and/or rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. , iron, tantalum group of more than one element layer, can also be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, A metal layer or an alloy layer composed of one or more elements in the group of silver, platinum group elements, iron, and tantalum. In addition, the heat-resistant layer and/or rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. Oxides, nitrides, and silicides of one or more elements in the group of , iron, and tantalum. In addition, the heat-resistant layer and/or the rust-proof layer may be a layer containing a nickel-zinc alloy. Also, the heat-resistant layer and/or the rust-proof layer may be a nickel-zinc alloy layer. The above-mentioned nickel-zinc alloy layer may contain 50 wt % to 99 wt % of nickel and 50 wt % to 1 wt % of zinc in addition to unavoidable impurities. The total deposition amount of zinc and nickel in the nickel-zinc alloy layer is 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . In addition, it is preferable that the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer has a ratio of nickel adhesion to zinc adhesion (=nickel adhesion/zinc adhesion) of 1.5-10. Also, the nickel deposition amount of the layer containing nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or rust-proof layer is a layer containing nickel-zinc alloy, when the inner wall of the through hole (throughhole) or via hole (viahole) comes into contact with the desmear (desmear) liquid, the copper foil and The interface of the resin substrate is difficult to be corroded by the desmear solution, and the adhesion between the copper foil and the resin substrate will be improved.

For example, the heat-resistant layer and/or the rust-proof layer can be a nickel or nickel alloy layer with an adhesion amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and an adhesion amount of 1 mg/m 2 m ² to 80mg/m ² , preferably 5mg/m ² to 40mg/m ² tin layers are sequentially laminated. The nickel alloy layer can also be made of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt any composition. Also, the total adhesion amount of nickel or nickel alloy and tin in the heat-resistant layer and/or rust-proof layer is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . In addition, the heat-resistant layer and/or the antirust layer are preferably [Ni deposition amount in nickel or nickel alloy]/[Sn deposition amount]=0.25-10, more preferably 0.33-3. Using the heat-resistant layer and/or the rust-proof layer will improve the peel strength of the circuit after the copper foil with a carrier is processed into a printed wiring board, the chemical resistance deterioration rate of the peel strength, and the like.

In addition, a well-known silane coupling agent can be used for the silane coupling agent used for a silane coupling process, For example, an amine type silane coupling agent, an epoxy type silane coupling agent, and a mercapto type silane coupling agent can be used. In addition, the silane coupling agent can also use vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane (γ-methacryloxypropyltrimethoxysilane), γ-glycidoxy Propyltrimethoxysilane (γ-glycidoxypropyltrimethoxysilane), 4-epoxypropylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-amino Propyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazine silane, γ- Mercaptopropyltrimethoxysilane, etc.

The above-mentioned silane coupling treatment layer can also be formed using silane coupling agents such as epoxy-based silanes, amine-based silanes, methacryloxy-based silanes, and mercapto-based silanes. In addition, such a silane coupling agent can also be used in mixture of 2 or more types. Among them, those formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

The so-called amine silane coupling agent here can also be selected from the group consisting of the following substances: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N-phenyl Vinylmethyl-2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethyl Oxysilane, Aminopropyltrimethoxysilane, N-Methylaminopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, N-(3-Propyloxy-2- Hydroxypropyl)-3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-( 2-aminoethyl-3-aminopropyl)trimethoxysilane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)silane, 6- (Aminohexylaminopropyl)trimethoxysilane, Aminophenyltrimethoxysilane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxy Silane, 3-aminopropyltri(methoxyethoxyethoxy)silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminodeca Monoalkyltrimethoxysilane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxy Silane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, N-methylamino Propyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, γ-amine N-3-(4-(3-aminopropoxy)butoxy)propyl -3-Aminopropyltrimethoxysilane.

The silane coupling treatment layer is preferably 0.05 mg/m ² to 200 mg/m ² in terms of silicon atoms, preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/m ² range. In the case of the said range, the adhesiveness of a base resin and a surface-treated copper foil can be further improved.

In addition, the surface treatment described in the following patent can be carried out on the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, anti-rust layer, silane coupling layer or chromate layer: International Publication No. WO2008/053878 , Japanese Patent Application No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, Japanese Patent Laid-Open No. 2013-19056.

Furthermore, one or both surfaces of the ultra-thin copper layer may be provided with one selected from the group consisting of a roughening treatment layer, a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer. The above layer may also be provided with a surface treatment layer. The surface treatment layer may be one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer.

In addition, the copper foil with a carrier may include one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the roughened layer.

Also, a heat-resistant layer and a rust-proof layer may be provided on the above-mentioned roughening treatment layer, a chromate treatment layer may be provided on the above-mentioned heat-resistant layer and the rust-proof layer, and a chromate treatment layer may be provided on the above-mentioned chromate treatment layer. Silane coupling treatment layer.

In addition, the copper foil with a carrier may be provided with a resin layer on the ultra-thin copper layer, the roughened layer, or the heat-resistant layer, rust-proof layer, chromate-treated layer, or silane-coupling-treated layer. The aforementioned resin layer may also be an insulating resin layer.

In addition, the copper foil with a carrier may have a roughening treatment layer on the carrier, and may also have one or more layers selected from the roughening treatment layer, heat-resistant layer, anti-rust layer, chromate treatment layer and silane coupling treatment layer on the support. Layers in the composed group. The above-mentioned roughening treatment layer, heat-resistant layer, antirust layer, chromate treatment layer and silane coupling treatment layer can be provided by known methods, and can also be provided by the methods described in the specification, claims, and drawings of this application. . When the carrier is laminated on a support such as a resin substrate from the surface side having the above-mentioned roughening treatment layer, etc., one or more layers selected from the above-mentioned roughening treatment layer, heat-resistant layer, rust-proof layer, chromium In the case of the salt-treated layer and the silane-coupling-treated layer, there is an advantage that the carrier and the support are not easily peeled off.

The above-mentioned resin layer may be an adhesive, or may be an insulating resin layer in a semi-cured state (B-stage state) for adhesion. The semi-cured state (B-stage state) includes a state in which the surface does not feel sticky even when touched with a finger, and the insulating resin layer can be stacked and stored, and further heat treatment causes a curing reaction.

In addition, the above-mentioned resin layer may contain a thermosetting resin, or may be a thermoplastic resin. Moreover, the said resin layer may contain a thermoplastic resin. The resin layer may contain known resins, resin hardeners, compounds, hardening accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, and the like. In addition, for the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, frame material, etc.) can be used. And/or the forming method and forming device of the resin layer are formed. 11-140281, Japanese Patent No. 3184485, 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, JP 2003-304068, JP 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004 -349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open 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 , JP 2006-257153, JP 2007-326923, JP 2008-111169, JP 5024930, International Publication No. WO2006/028207, JP 4828427, JP 2009-67029 No., International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Application No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

Also, the type of the above-mentioned resin layer is not particularly limited, and as preferable, for example, a resin containing one or more selected from the group of the following components: epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, Urethane resin, polyethersulfone (also known as polyethersulphone, polyethersulfone), polyethersulfone (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubbery resin, Polyamine, aromatic polyamine, polyamide-imide resin, rubber-modified epoxy resin, phenoxy resin, carboxy-modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide three Oxyzine resins, thermosetting polyphenylene ether resins, cyanate ester resins, anhydrides of carboxylic acids, anhydrides of polycarboxylic acids, linear polymers with crosslinkable functional groups, polyphenylene ether resins, 2,2 - Bis(4-cyanatophenyl)propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate Resin, siloxane-modified polyamide-imide resin, cyanoester resin, phosphazene-based resin, rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, benzene Oxygen, polymer epoxy resin, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin and cyanate resin.

Moreover, the above-mentioned epoxy resin type has two or more epoxy groups in a molecule|numerator, and if it can be used for electrical and electronic materials, it can use especially without a problem. Moreover, it is preferable that the said epoxy resin is an epoxy resin obtained by epoxidizing using the compound which has 2 or more glycidyl groups in a molecule|numerator. In addition, one or two or more selected from the group consisting of the following components can be used in combination: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy resin, phenolic novolak type epoxy resin, naphthalene type ring Oxygen resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, epoxypropylamine type epoxy resin, triglycidyl isocyanurate , N,N-Diglycidylaniline and other glycidylamine compounds, tetrahydrophthalate and other glycidyl ester compounds, phosphorus-containing epoxy resins, biphenyl epoxy resins, biphenyl epoxy resins, A phenol novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a tetraphenylethane type epoxy resin, or hydrogenated or halogenated forms of the above epoxy resins may be used.

A known phosphorus-containing epoxy resin can be used as the above-mentioned phosphorus-containing epoxy resin. In addition, the above-mentioned phosphorus-containing epoxy resin is preferably, for example, a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. form of epoxy resin.

(When the resin layer contains a dielectric (dielectric filler))

The resin layer may contain a dielectric (dielectric filler).

When a dielectric (dielectric filler) is contained in any of the above-mentioned resin layers or resin compositions, it can be used to form a capacitor layer to increase the capacitance of a capacitor circuit. The dielectric (dielectric filler) is made of BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly called PZT), PbLaTiO ₃ PbLaZrO (commonly called PLZT), SrBi ₂ Ta ₂ O ₉ (commonly called SBT) Dielectric powders such as composite oxides having a perovskite (Perovskite) structure.

The dielectric (dielectric filler) may also be powdery. When the dielectric (dielectric filler) is in powder form, the powder properties of the dielectric (dielectric filler) are preferably 0.01 μm to 3.0 μm in particle size, preferably 0.02 μm to 2.0 μm. scope. Furthermore, when using a scanning electron microscope (SEM) to take a photo of the dielectric body, when drawing a straight line on the particles of the dielectric body on the photo, the length of the straight line that crosses the particles of the dielectric body is the longest Particle length of the dielectric body is defined as the particle diameter of the dielectric body. And, the average value of the particle diameters of the dielectric body within the measurement field of view was defined as the particle size of the dielectric body.

Dissolve the resin and/or resin composition and/or compound contained in the above resin layer in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-formaldehyde Pyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N,N-dimethylformamide and other solvents to make a resin solution (resin varnish), and apply it to the above-mentioned copper foil with a carrier by, for example, a roll coating method. The surface on the side of the ultra-thin copper layer is then heat-dried if necessary to remove the solvent and become a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250°C, preferably 130 to 200°C. Solvents can be used to dissolve the composition of the above resin layer to make a resin with a resin solid content of 3wt% to 70wt%, preferably 3wt% to 60wt%, preferably 10wt% to 40wt%, more preferably 25wt% to 40wt%. liquid. Furthermore, from the viewpoint of atmosphere, it is best to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone at this stage. In addition, as a solvent, it is preferable to use the solvent whose boiling point is the range of 50 degreeC - 200 degreeC.

Moreover, it is preferable that the said resin layer is a semi-hardened resin film whose resin flow rate when measured based on MIL-P-13949G in MIL standard is the range of 5 % - 35 %.

In this application specification, the so-called resin flow rate refers to the MIL-P-13949G in the MIL standard, taking 4 pieces of 10 cm square samples from the surface-treated copper foil with a resin thickness of 55 μm, and making the 4 In the state where the sheet samples are overlapped (laminated body), the lamination was carried out under the conditions of a pressing temperature of 171°C, a pressing pressure of 14kgf/cm ² , and a pressing time of 10 minutes. According to the results obtained by measuring the resin outflow weight at this time, Value calculated based on number 1.

[mathematical formula 1]

The surface-treated copper foil (surface-treated copper foil with resin) provided with the above-mentioned resin layer is used in such a way that the resin layer is laminated on the base material, and the whole body is thermocompression bonded to thermally harden the resin layer, and then the resin layer is coated on the surface. When the copper foil is an ultra-thin copper layer with a carrier copper foil, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the middle layer side of the ultra-thin copper layer is exposed), which is different from the roughness of the surface-treated copper foil. A specific wiring pattern is formed on the surface opposite to the chemically treated side.

When this resin-attached surface-treated copper foil is used, the number of sheets of prepreg material used at the time of manufacturing a multilayer printed wiring board can be reduced. Furthermore, it is possible to manufacture a copper-clad laminate even if the thickness of the resin layer is set to a thickness that ensures interlaminar insulation, or a prepreg material is not used at all. In addition, at this time, an insulating resin primer may be applied to the surface of the substrate to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination process is simplified, so it is economically advantageous, and there are advantages in that only the prepreg The thickness of the multilayer printed wiring board is reduced to about the thickness of the bulk material, and an extremely thin multilayer printed wiring board with a thickness of one layer of 100 μm or less can be produced.

The thickness of the resin layer is preferably 0.1 to 120 μm.

If the thickness of the resin layer is thinner than 0.1 μm, the adhesive force may decrease, and it is difficult to laminate the surface-treated copper foil with resin on the base material provided with the inner layer material without intervening the prepreg material. Ensure interlayer insulation between the inner layer material and the circuit. On the other hand, if the thickness of the resin layer is thicker than 120 μm, it may be difficult to form the resin layer with the target thickness in one coating step, and unnecessary material cost and number of steps are required, so it becomes economically disadvantageous. .

Furthermore, when using the surface-treated copper foil which has a resin layer for manufacture of an extremely thin multilayer printed wiring board, the thickness of the said resin layer shall be 0.1 micrometer - 5 micrometers, More preferably, it shall be 0.5 micrometer - 5 micrometers, More preferably, when it is 1 micrometer - 5 micrometers, since the thickness of a multilayer printed wiring board can be made small, it is preferable.

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

Furthermore, electronic equipment can be produced using the printed wiring board, electronic equipment can be produced using the printed circuit board on which the electronic components are mounted, and electronic equipment can be produced using the printed circuit board on which the electronic components are mounted. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier of this invention are shown.

One embodiment of the method of manufacturing a printed wiring board of the present invention includes the following steps: preparing the copper foil with a carrier and the insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; and making the ultra-thin copper layer After laminating the above-mentioned copper foil with carrier and the insulating substrate in such a way that the side of the carrier-attached copper foil is opposite to the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off to form a copper-clad laminate, and thereafter, by semi-additive method, Improve any one of semi-additive method, partial additive method and subtractive method to form a circuit. The insulating substrate can also be used as the entrance of the inner layer circuit.

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

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method includes the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by etching or plasma using a corrosive solution such as acid;

providing through-holes or/and blind holes on the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

An electroless plating layer is provided in the area containing the above resin and the above through holes or/and blind holes;

setting a photoresist on the electroless plating layer;

exposing the above-mentioned photoresist, and thereafter, removing the photoresist in the region where the circuit is formed;

An electrolytic plating layer is provided in the above-mentioned region where the circuit is formed where the above-mentioned photoresist is removed;

removing said photoresist; and

The electroless plating layer located in the region other than the above-mentioned region where the circuit is formed is removed by flash etching or the like.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

setting through holes or/and blind holes on the ultra-thin copper layer exposed by peeling off the above-mentioned carrier and the above-mentioned insulating resin substrate;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by etching or plasma using a corrosive solution such as acid;

An electroless plating layer is provided in a region containing the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching or the like, and the above-mentioned through hole or/and blind hole;

setting a photoresist on the electroless plating layer;

exposing the above-mentioned photoresist, and thereafter, removing the photoresist in the region where the circuit is formed;

An electrolytic plating layer is provided in the above-mentioned region where the circuit is formed where the above-mentioned photoresist is removed;

removing said photoresist; and

The electroless plating layer located in the region other than the above-mentioned region where the circuit is formed is removed by flash etching or the like.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

setting through holes or/and blind holes on the ultra-thin copper layer exposed by peeling off the above-mentioned carrier and the above-mentioned insulating resin substrate;

The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by etching or plasma using a corrosive solution such as acid;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

An electroless plating layer is provided in a region containing the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching or the like, and the above-mentioned through hole or/and blind hole;

setting a photoresist on the electroless plating layer;

exposing the above-mentioned photoresist, and thereafter, removing the photoresist in the region where the circuit is formed;

An electrolytic plating layer is provided in the above-mentioned region where the circuit is formed where the above-mentioned photoresist is removed;

removing said photoresist; and

The electroless plating layer located in the region other than the above-mentioned region where the circuit is formed is removed by flash etching or the like.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

The extremely thin copper layer exposed by peeling off the above-mentioned carrier is completely removed by etching or plasma using a corrosive solution such as acid;

providing an electroless plating layer on the surface of the above-mentioned resin exposed by removing the above-mentioned ultra-thin copper layer by etching;

setting a photoresist on the electroless plating layer;

exposing the above-mentioned photoresist, and thereafter, removing the photoresist in the region where the circuit is formed;

An electrolytic plating layer is provided in the above-mentioned region where the circuit is formed where the above-mentioned photoresist is removed;

removing said photoresist; and

The electroless plating layer and the ultra-thin copper layer located in regions other than the above-mentioned region where the circuit is formed are removed by flash etching or the like.

In the present invention, the so-called improved semi-additive method refers to laminating metal foil on the insulating layer, protecting the non-circuit forming part with photoresist, thickening the copper thickness of the circuit forming part by electrolytic plating, and removing the resist. A method in which a circuit is formed on an insulating layer by removing the metal foil other than the above-mentioned circuit formation part by (rapid) etching.

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the improved semi-additive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

Provide through holes or/and blind holes on the exposed ultra-thin copper layer and insulating substrate after peeling off the above-mentioned carrier;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

An electroless plating layer is provided in the above-mentioned area containing through holes or/and blind holes;

A photoresist is arranged on the surface of the extremely thin copper layer exposed by peeling off the above-mentioned carrier;

After the above-mentioned photoresist is provided, a circuit is formed by electrolytic plating;

removing said photoresist; and

The very thin copper layer exposed by removing the above photoresist is removed by flash etching.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the modified semi-additive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

setting a photoresist on the extremely thin copper layer exposed by peeling off the above-mentioned carrier;

exposing the above-mentioned photoresist, and thereafter, removing the photoresist in the region where the circuit is formed;

An electrolytic plating layer is provided in the above-mentioned region where the circuit is formed where the above-mentioned photoresist has been removed;

removing said photoresist; and

The extremely thin copper layer located in regions other than the above-mentioned region where the circuit is formed is removed by flash etching or the like.

In the present invention, the so-called partial addition method refers to providing catalytic nuclei on a substrate formed by setting a conductor layer, a substrate formed by passing through a through hole or a hole for an auxiliary hole as needed, and etching to form a conductor circuit. A method of manufacturing a printed wiring board by thickening through-holes or auxiliary holes, etc., by electroless plating (if necessary, further electrolytic plating) on the conductor circuit after providing solder resist or photoresist .

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the partial additive method includes the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

Provide through holes or/and blind holes on the exposed ultra-thin copper layer and insulating substrate after peeling off the above-mentioned carrier;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

Provide catalytic cores in the above-mentioned regions containing through holes or/and blind holes;

Etching resist is provided on the surface of the ultra-thin copper layer exposed by peeling off the above-mentioned carrier;

Exposing the etching resist to form a circuit pattern;

Removing the above-mentioned ultra-thin copper layer and the above-mentioned catalytic core by means of etching or plasma using a corrosive solution such as acid to form a circuit;

removing the above etching resist;

Solder resist or photoresist is provided on the surface of the above-mentioned insulating substrate exposed by removing the above-mentioned ultra-thin copper layer and the above-mentioned catalyst nucleus by etching or plasma using a corrosive solution such as acid; and

An electroless plating layer is provided in a region where the above-mentioned solder resist or photoresist 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, one embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method includes the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

Provide through holes or/and blind holes on the exposed ultra-thin copper layer and insulating substrate after peeling off the above-mentioned carrier;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

An electroless plating layer is provided in the above-mentioned area containing through holes or/and blind holes;

An electrolytic plating layer is provided on the surface of the above-mentioned electroless plating layer;

setting an etch resist on the surface of the above-mentioned electrolytic plating layer or/and the above-mentioned ultra-thin copper layer;

Exposing the etching resist to form a circuit pattern;

The above-mentioned ultra-thin copper layer, the above-mentioned electroless plating layer, and the above-mentioned electrolytic plating layer are removed by etching or plasma using a corrosive solution such as acid to form a circuit; and

The above etching resist is removed.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method comprises the following steps:

Prepare the copper foil with carrier and insulating substrate of the present invention;

Laminate the above copper foil with carrier and insulating substrate;

After laminating the above-mentioned copper foil with carrier and the insulating substrate, the carrier of the above-mentioned copper foil with carrier is peeled off;

Provide through holes or/and blind holes on the exposed ultra-thin copper layer and insulating substrate after peeling off the above-mentioned carrier;

Perform desmear treatment on the area containing the above-mentioned through holes or/and blind holes;

An electroless plating layer is provided in the above-mentioned area containing through holes or/and blind holes;

Forming a mask on the surface of the electroless plating layer;

An electrolytic plating layer is provided on the surface of the above-mentioned electroless plating layer that does not form a mask;

setting an etch resist on the surface of the above-mentioned electrolytic plating layer or/and the above-mentioned ultra-thin copper layer;

Exposing the etching resist to form a circuit pattern;

Removing the above-mentioned ultra-thin copper layer and the above-mentioned electroless plating layer by etching or plasma using a corrosive solution such as acid to form a circuit; and

The above etching resist is removed.

The step of providing through holes and/or blind holes and the subsequent step of removing smear may also be omitted.

The method for manufacturing a printed wiring board of the present invention may include the steps of forming a circuit on the surface treatment layer side surface or the carrier side surface of the copper foil with a carrier of the present invention, embedding the circuit in the A step of forming a resin layer on the surface treatment layer side surface of the above-mentioned copper foil with a carrier or a step of forming a circuit on the above-mentioned resin layer, and after forming a circuit on the above-mentioned resin layer, the above-mentioned carrier or the above-mentioned ultra-thin copper The step of layer peeling, and after peeling the above-mentioned carrier or the above-mentioned ultra-thin copper layer, by removing the above-mentioned ultra-thin copper layer or the above-mentioned carrier, the resin layer formed on the surface treatment layer side surface or the above-mentioned carrier side surface is buried. The steps of the circuit exposed. In addition, the method of manufacturing a printed wiring board may include the steps of forming a circuit on the surface treatment layer side surface or the carrier side surface of the copper foil with a carrier of the present invention, embedding the circuit on the above-mentioned The step of forming a resin layer on the surface treatment layer side surface of the copper foil with a carrier or the above-mentioned carrier-side surface, the step of peeling the above-mentioned carrier or the above-mentioned ultra-thin copper layer, and after peeling the above-mentioned carrier or the above-mentioned ultra-thin copper layer, removing the above-mentioned A step of exposing the circuit embedded in the resin layer formed on the side surface of the surface treatment layer or the surface of the carrier side by forming an ultra-thin copper layer or the carrier.

Here, the specific Example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, here, the copper foil with a carrier having an ultra-thin copper layer formed with a roughening treatment layer as a surface treatment layer is described as an example, but it is not limited to this, and the use of this surface treatment layer does not mean roughening treatment. Layered copper foil with a carrier can also be performed in the same manner as the following method for producing a printed wiring board.

First, as shown in FIG. 1A , a copper foil with a carrier (first layer) having an ultra-thin copper layer in which a roughened layer is formed on the surface is prepared.

Next, as shown in FIG. 1B , a resist is applied on the roughened layer of the ultra-thin copper layer, and exposure and development are performed to etch the resist into a specific shape.

Next, as shown in FIG. 1C , by removing the resist after the formation of the circuit plating layer, a circuit plating layer of a specific shape is formed.

Next, as shown in Fig. 2D, an embedding resin is placed on the ultra-thin copper layer to form a lamination resin layer in such a way as to cover the circuit plating layer (by burying the circuit plating layer), and then another carrier is attached from the ultra-thin copper layer side. Copper Foil (Layer 2).

Next, as shown in FIG. 2E , the carrier is peeled off from the second-layer copper foil with a carrier.

Next, as shown in FIG. 2F , laser drilling is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Next, as shown in Figure 3G, copper is buried in the blind vias to form a via fill.

Next, as shown in FIG. 3H , a circuit plating layer is formed on the through-hole filling in the manner shown in FIGS. 1-B and 1-C described above.

Next, as shown in FIG. 3I , the carrier is peeled off from the first-layer copper foil with a carrier.

Next, as shown in FIG. 4J , the extremely thin copper layers on both surfaces are removed by rapid etching, so that the surface of the circuit plating layer in the resin layer is exposed.

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, the printed wiring board using the copper foil with a carrier of this invention was produced.

The said another copper foil with a carrier (2nd layer) can use the copper foil with a carrier of this invention, the conventional copper foil with a carrier can be used, and a normal copper foil can also be used. Also, one or more layers of circuits can be further formed on the second layer circuit shown in Figure 3H, by any method in semi-additive method, subtractive method, partial additive method or improved semi-additive method And form these circuits.

Moreover, the copper foil with a carrier used for the said 1st layer may have a board|substrate on the carrier side surface of this copper foil with a carrier. By having this substrate, the copper foil with a carrier used in the first layer is supported, and wrinkles are less likely to be generated, so there is an advantage that productivity improves. In addition, as long as the said board|substrate exhibits the effect of supporting the copper foil with a carrier used by the said 1st layer, all board|substrates can be used. For example, the carrier, prepreg, resin layer described in the specification of this application or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate can be used , a foil of an organic compound as the above-mentioned substrate.

The timing of forming the substrate on the side surface of the carrier is not particularly limited, but must be formed before the carrier is peeled off. In particular, it is preferably formed before the step of forming a resin layer on the surface of the copper foil with a carrier on the side of the ultra-thin copper layer, more preferably before the step of forming a circuit on the surface of the copper foil with a carrier on the side of the above-mentioned ultra-thin copper layer. form.

In addition, well-known resin and 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 embedding resin may contain a thermosetting resin or may be a thermoplastic resin. In addition, the embedding resin may contain a thermoplastic resin. The type of the embedding resin is not particularly limited, but examples of preferred ones include epoxy resins, polyimide resins, polyfunctional cyanate compounds, maleimide compounds, polyvinyl alcohol Resins including acetal resin, urethane resin, block copolymerized polyimide resin, block copolymerized polyimide resin, etc., or paper-based phenolic resin, paper-based epoxy resin, synthetic Fiber cloth base epoxy resin, glass cloth-paper composite base epoxy resin, glass cloth-glass non-woven composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, liquid crystal Polymer film, fluororesin film, etc.

In addition, the method for manufacturing a printed wiring board of the present invention may be a method for manufacturing a printed wiring board (coreless method) including the step of coating the surface on the side of the ultra-thin copper layer of the copper foil with a carrier of the present invention or A step of laminating the surface on the carrier side and the resin substrate; providing at least one resin layer and a circuit on the surface of the copper foil with a carrier opposite to the surface treatment layer layer laminated with the resin substrate or the surface of the carrier side The step of these two layers; and the step of peeling the above-mentioned carrier or the above-mentioned ultra-thin copper layer from the above-mentioned copper foil with a carrier after forming the two layers of the above-mentioned resin layer and the circuit. Regarding the above-mentioned coreless method, as a specific example, first, the surface treatment layer side surface or the carrier side surface of the copper foil with a carrier of the present invention is laminated with a resin substrate. Then, a resin layer is formed on the surface of the copper foil with a carrier opposite to the surface treatment layer side surface laminated with the resin substrate or the carrier side surface. Another copper foil with a carrier may be laminated from the carrier side or the surface treatment layer side to the resin layer formed on the carrier side surface or the surface treatment layer side surface. In this case, the following structure is adopted: centering on the resin substrate, on both sides of the above-mentioned resin substrate, in the order of carrier/intermediate layer/ultra-thin copper layer/surface treatment layer or in the order of surface treatment layer/ultra-thin copper layer/ Sequential lamination of interlayer/carrier copper foil with carrier. It is also possible to provide another resin layer on the surface treatment layer at both ends or the exposed surface of the carrier, further provide a copper layer or a metal layer, and then process the copper layer or metal layer to form a circuit. Furthermore, another resin layer may be provided on the above-mentioned circuit so as to bury the above-mentioned circuit. Moreover, formation of such a circuit and a resin layer may be performed once or more (build-up method). And, about the laminate (hereinafter also referred to as laminate B) formed as described above, the ultra-thin copper layer or the carrier of each copper foil with a carrier can be peeled off from the carrier or the ultra-thin copper layer to produce a coreless substrate. In addition, when making the above-mentioned coreless substrate, it is also possible to use two copper foils with a carrier to make the following surface treatment layer/ultra-thin copper layer/intermediate layer/carrier/carrier/intermediate layer/ultra-thin copper layer/surface treatment layer composition, or a laminate with a carrier/intermediate layer/extremely thin copper layer surface treatment layer/surface treatment layer/extremely thin copper layer/intermediate layer/carrier, or a laminated body with a carrier/intermediate layer/ A laminate composed of an ultra-thin copper layer/surface treatment layer/carrier/intermediate layer/ultra-thin copper layer/surface treatment layer is used as the center. The ultra-thin copper layer or the surface of the carrier on both sides of these laminates (hereinafter also referred to as laminate A) may be provided with one or more resin layers and two layers of circuits, and after one or more resin layers and circuits are provided. After two layers, the ultra-thin copper layer or the carrier of each copper foil with carrier is peeled off from the carrier or the ultra-thin copper layer to produce a coreless substrate. The above laminate is on the surface of the surface treatment layer, between the surface treatment layer and the ultra-thin copper layer, on the surface of the carrier, between the carrier and the carrier, between the surface treatment layer and the surface treatment layer, and between the ultra-thin copper layer and the carrier There may also be other layers. In addition, in this specification, "the surface of the surface treatment layer", "the surface on the side of the surface treatment layer", "the surface of the carrier", "the surface on the side of the carrier", "the surface of the carrier", "the surface of the laminate", "the layered "Body surface", when the surface treatment layer, the carrier, or the laminate has other layers on the surface of the surface treatment layer, the carrier, or the laminate, is a concept defined as the surface (the outermost surface) including the above-mentioned other layers. Also, the laminate preferably has a configuration of surface treatment layer/ultra-thin copper layer/intermediate layer/carrier/carrier/intermediate layer/ultra-thin copper layer/surface treatment layer. This is because, when a coreless substrate is produced using the above-mentioned laminate, since an extremely thin copper layer is disposed on the coreless substrate side, it is easy to form a circuit on the coreless substrate by using the modified semi-additive method. Also, because the ultra-thin copper layer is thin, it is easy to remove the ultra-thin copper layer, and after removing the ultra-thin copper layer, it is easy to form a circuit on the coreless substrate by using a semi-additive method.

In addition, in this specification, the "layered body" not specifically described as "layered body A" or "layered body B" means a layered body including at least the layered body A and the layered body B.

Furthermore, in the manufacturing method of the above-mentioned coreless substrate, by covering part or all of the end faces of the copper foil with a carrier or the laminate (laminate A) with a resin, when manufacturing a printed wiring board by the build-up method, It can prevent chemical solvents from infiltrating into the middle layer or between a piece of copper foil with a carrier and another copper foil with a carrier that constitute the laminate, and can prevent the separation of the ultra-thin copper layer and the carrier caused by the infiltration of chemical solvents or the carrier. Corrosion of copper foil can improve yield. Resins that can be used for the resin layer can be used as the “resin covering part or all of the end surface of the copper foil with a carrier” or “the resin covering part or all of the end surface of the laminate” used here. In addition, in the above-mentioned manufacturing method of the coreless substrate, when the copper foil with a carrier or the laminated body is planarly viewed, the laminated part of the copper foil with a carrier or the laminated body (the laminated part of the carrier and the ultra-thin copper layer, or a laminated portion of one sheet of copper foil with a carrier and the other sheet of copper foil with a carrier) may be covered with a resin or a prepreg. In addition, the laminated body (laminated body A) formed by the manufacturing method of the said coreless board|substrate may be comprised so that a pair of copper foil with a carrier may be contact|connected separably. In addition, when the above-mentioned copper foil with a carrier is viewed from above, the laminated part of the copper foil with a carrier or the laminate (the laminated part of the carrier and the ultra-thin copper layer, or one sheet of the carrier) may be covered with a resin or a prepreg. Copper foil and another laminated part with carrier copper foil) The whole outer periphery. With such a configuration, when the copper foil with a carrier or the laminated body is viewed from above, the laminated portion of the copper foil with a carrier or the laminated body is covered with resin or prepreg. It is collision in a direction transverse to the lamination direction, and as a result, the peeling of the carrier and the ultra-thin copper layer or copper foil with a carrier during operation can be reduced. In addition, by covering the outer periphery of the laminated part of the copper foil with a carrier or the laminated body with a resin or a prepreg, it is possible to prevent the interface of the chemical solvent from the above-mentioned laminated part in the chemical solvent treatment step. The infiltration can prevent the corrosion or erosion of the copper foil with the carrier. Furthermore, when separating a single copper foil with a carrier from a pair of copper foils with a carrier in a laminate, or when separating the carrier and copper foil (extremely thin copper layer) of the copper foil with a carrier, it is necessary to remove the used resin or copper foil by cutting or the like. Copper foil with a carrier covered by a prepreg or the laminated part of a laminate (a laminated part of a carrier and an ultra-thin copper layer, or a laminated part of one copper foil with a carrier and another copper foil with a carrier).

The copper foil with a carrier of the present invention may be laminated on the carrier side or the surface treatment layer side of another copper foil with a carrier of the present invention from the carrier side or the surface treatment layer side to form a laminate. In addition, the following laminate may be used: the carrier-side surface or the surface-treated layer-side surface of the one copper foil with a carrier and the carrier-side surface or the surface-treated layer-side surface of the other copper foil with a carrier, If necessary, it can be obtained by direct lamination with an adhesive. Moreover, you may join the carrier or the surface treatment layer of the said one copper foil with a carrier, and the carrier or the surface treatment layer of the said other copper foil with a carrier. In addition, part or all of the end faces of the laminate may be covered with resin.

Lamination of carriers can be performed by, for example, the following method other than simply overlapping.

(a) Metallurgical joining method: welding (arc welding, TIG (tungsteninertgas, tungsten-inert gas) welding, MIG (metalinertgas, metal-inert gas) welding, resistance welding, seam welding, spot welding), crimping (ultrasonic welding , friction stir welding), soldering;

(b) Mechanical joining methods: caulking, joints by rivets (joints by self-piercing riveting, joints by rivets), bookbinding machines;

(c) Physical bonding method: Adhesive, (double-sided) tape

By joining a part or all of one carrier and a part or all of another carrier using the above-mentioned joining method, it is possible to manufacture a laminate constituted by layering a carrier and another carrier so that the carriers are in detachable contact with each other. . If one carrier and another carrier are weakly connected, in the case of layering one carrier and another carrier, it is possible to separate one carrier from another carrier without removing the connecting part of one carrier and another carrier . In addition, in the case where one carrier is strongly connected to another carrier, one carrier and another carrier can be separated by cutting or removing chemical polishing (etching, etc.), mechanical polishing, etc. at the part where one carrier is connected to another carrier. carrier.

In addition, a printed wiring board can be manufactured by performing the steps of: providing the two layers of the resin layer and the circuit at least once in the laminated body constituted as described above; and forming the two layers of the resin layer and the circuit at least once. After layering, the step of peeling the above-mentioned ultra-thin copper layer or the carrier from the copper foil with a carrier of the above-mentioned laminate. Furthermore, two layers of a resin layer and a circuit may be provided on one surface or both surfaces of the laminate.

[Example]

Hereinafter, it demonstrates based on an experimental example. In addition, this experimental example is only an example, and is not limited to this example.

1. Manufacture of copper foil with carrier

Copper foil with a carrier was produced by the following procedure.

First, long electrodeposited copper foil or rolled copper foil having the thickness described in Table 1 was prepared as a carrier.

Electrodeposited copper foil was produced under the following conditions.

(Electrolytic Bath Composition)

Cu: 80～120g/L

_{H2SO4 :} 80～120g/L

Cl: 20～80mg/L

Varnish: 0.1～6.0mg/L

(electrolysis conditions)

Liquid temperature: 55～65℃

Current density: 100A/ ^dm2

Electrolyte flow rate: 1.5m/s

As for the rolled copper foil, in Examples 9 and 12, refined copper (refined copper specified in JISH3100C1100) was used, and in Examples 10 and 11, oxygen-free copper (oxygen-free copper specified in JISH3100C1020) was used. "Rolled copper foil (Ag 180 ppm)" in the column of the type of carrier in Table 1 means that 180 mass ppm of Ag was added to refined copper.

<Intermediate layer of the example>

An intermediate layer was formed by electroplating on a roll-to-roll type continuous plating line on the shiny surface of the above-mentioned copper foil under the following conditions.

·Ni layer

Nickel sulfate: 250～300g/L

Nickel chloride: 35～45g/L

Nickel acetate: 10～20g/L

Trisodium citrate: 15～30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50～70℃

Current density: ³ ～15A/dm2

Adhesion amount: 4000μg/dm ²

After water washing and pickling, a Cr layer with an adhesion amount of 10 μg/dm ² was deposited on the Ni layer by electrolytic chromate treatment on a roll-to-roll continuous plating line under the following conditions.

·Electrolytic chromate treatment

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

pH: 3~4

Liquid temperature: 50～60℃

Current density: 0.1～2.6A/ ^dm2

Coulomb quantity: 0.5～30As/dm ²

<Extremely thin copper layer of the example>

Next, an ultra-thin copper layer with a thickness of 3 μm was formed on the intermediate layer by electroplating under the following conditions on a roll-to-roll continuous plating line, thereby producing a copper foil with a carrier.

·Extremely thin copper layer

Copper concentration: 30～120g/L

H ₂ SO ₄ concentration: 20～120g/L

Electrolyte temperature: 20～80℃

Current density: ¹⁰ ～100A/dm2

<Surface treatment layer of the example>

The surface of the said ultra-thin copper layer was surface-treated by the following surface treatment conditions. Table 1 shows the layer constitution of the surface treatment layer formed by this surface treatment.

In some embodiments, one of Cu-W alloy plating, Cu-P alloy plating, and Cu-Co-Ni alloy plating is carried out on the surface of the above-mentioned ultra-thin copper layer under the following conditions: Apply as a roughening treatment.

・Cu－W alloy plating (Example 1, 2, 15, 16)

Liquid composition: Cu15g/liter, sulfuric acid 100g/liter, W5mg/liter

Temperature: 25°C

(The first stage)

Current density (D _k ): 90A/dm ²

Time: 1.5 seconds

(second stage)

Current density (D _k ): 20A/dm ²

Time: 3 seconds

·Cu－P alloy plating (Example 3, 4)

Liquid composition: Cu30g/liter, sulfuric acid 100g/liter, P500mg/liter

Temperature: 30°C

(The first stage)

Current density (D _k ): 140A/dm ²

Time: 0.6 seconds

(second stage)

Current density (D _k ): 20A/dm ²

Time: 2.0 seconds

·Cu－Co－Ni alloy plating (Example 5, 6, 14)

Liquid composition: Cu15g/liter, Co8g/liter, Ni8g/liter

pH: 1~3

Temperature: 40°C

(The first stage)

Current density (D _k ): 45A/dm ²

Time: 0.6 seconds

(second stage)

Current density (D _k ): 30A/dm ²

Time: 0.8 seconds

Next, at least one or more treatments selected from the following heat resistance treatment, rust prevention treatment, chromate treatment, and silane coupling treatment are sequentially performed. Wash the surface with water before performing each treatment.

・Heat-resistant treatment (formation of heat-resistant layer)

Liquid composition: Co1~8g/liter, Ni10~20g/liter

pH: 2~3

Temperature: 40°C

Current density (D _k ): 5A/dm ²

Time: 1.0 seconds

Anti-rust treatment (formation of anti-rust layer)

Liquid composition: Ni15～30g/liter, Zn1～10g/liter

pH: 2~4

Temperature: 40°C

Current density (D _k ): 5A/dm ²

Time: 1.0 seconds

・Electrolytic chromate treatment (formation of chromate treatment layer)

Liquid composition: K ₂ Cr ₂ O ₇ : 1-10g/liter, Zn: 0-5g/liter

pH: 2~4

Temperature: 40°C

Current density (D _k ): 1A/dm ²

Time: 1.0 seconds

・Silane coupling treatment (formation of silane coupling treatment layer)

After spraying 1.0% by volume of 3-glycidoxypropyltrimethoxysilane aqueous solution on the surface to be treated, the silane coupling agent coating treatment is carried out in an environment of 70°C to 200°C for more than 2 seconds. Dry to remove moisture from the surface.

・Resin layer (Example 13, 14, 15)

The coating of the resin layer is to apply the uncured resin on the surface of the ultra-thin copper layer using the gravure coating method, adjust the thickness of the resin coating film to 10 μm with a doctor blade, and volatilize the solvent in a dry environment at 200°C While hardening the resin component. In addition, as the resin used, epoxy resin (bisphenol A type epoxy resin manufactured by DIC Corporation) was used.

Furthermore, in Example 16, the above-mentioned roughening treatment (Cu-W alloy plating), heat-resistant layer, rust-proof layer, chromate treatment layer, Surface treatment of silane coupling treatment layer.

－Heat treatment－

Next, each copper foil with a carrier was heat-processed under the conditions described in Tables 2-4 in the nitrogen atmosphere which has a purity of 99.9% or more as heat processing. The temperature increase rates in Tables 2 to 4 are the temperature increase rates until reaching the temperature (heating temperature) described in the heat treatment conditions for the first time. The cooling time to normal temperature after the heat treatment is 1 to 6 hours.

Moreover, about Examples 1-16, it heat-processed in the state which wound up the copper foil with a carrier in the hollow tube (outer diameter 11cm, thickness 0.5cm) made of stainless steel.

Moreover, about Examples 1-16, the tension|tensile_strength at the time of winding up the said hollow tube was made into the setting described in Tables 2-4, respectively, and it heat-processed.

Moreover, the rotation speed of this hollow tube was set to the setting described in Tables 2-4, respectively, and it heat-processed.

2. Evaluation of copper foil with carrier

The following evaluation tests were performed for the copper foils with a carrier of Examples 1 to 16 produced in the above manner, before the heat treatment and after the heat treatment, respectively. The evaluation results are shown in Tables 2-4. Furthermore, regarding the description of the numbers of the experimental examples after heating in Tables 2 to 4, for example, "Example 1-1" to "Example 1-50" indicate that the sample before heating, that is, "Example 1", was heated. after the sample.

－Evaluation of wettability of etching solution－

Place the copper foil with carrier (except those with resin layer) on the horizontal plane with the surface treatment layer on the ultra-thin copper foil side on top, and drop 30 μL of sulfuric acid 24% by weight-peroxide to one part using a pipette. An etching solution having a hydrogen content of 15% by weight (the remainder being water) was left to stand for 30 seconds, and then the etching solution was wiped off. Since the sulfuric acid-hydrogen peroxide-based etchant increases the wetting while dissolving the surface treatment layer and the ultra-thin copper layer underlying it, it can be judged that if the trace of the droplet is close to a perfect circle, the etchant of the etchant near the surface The wettability is uniform, and if it is oval, it is uneven. In addition, the larger the maximum diameter of the droplet trace, the better the wetting of the etching solution, and it can be said that the removability by the etching solution is good.

· Wetting uniformity

Here, the maximum diameter and the minimum diameter of the trace of the droplet are measured, and if the difference between the maximum diameter and the minimum diameter is 10 mm or less, it is evaluated that the wettability of the etching solution is sufficiently uniform (Tables 2-4: Columns of wetting uniformity "◯"), and if it is 5 mm or less, it was evaluated as being more uniform (Tables 2 to 4: column "⊚" of wetting uniformity). Also, when the difference between the maximum diameter and the minimum diameter of the droplet traces was greater than 10 mm, it was evaluated that the wettability of the etchant was not uniform enough (Tables 2 to 4: "x" in the column of wettability uniformity). Here, "maximum wetting uniformity - minimum" in Tables 2 to 4 was calculated using "maximum diameter (mm) of trace of liquid droplet - minimum diameter (mm) of trace of liquid droplet".

· Wettability

The maximum diameter of the trace of the droplet was measured, and if the maximum diameter was 25 mm or more, it was evaluated as having good etching solution wettability (Tables 2-4: column "○" of wettability), and if it was 35 mm or more, it was evaluated as being More preferably good (Tables 2 to 4: column "⊚" of wettability). Moreover, when the maximum diameter was less than 25 mm, it evaluated that wettability of etchant was insufficient (Tables 2-4: column "x" of wettability). Here, the "maximum wettability diameter" in Tables 2 to 4 is defined as the "maximum diameter (mm) of the droplet trace".

In addition, in the above-mentioned evaluation of "uniformity of wetting" and "wettability", the minimum diameter of the circle surrounding the trace of the droplet is set as the "maximum diameter of the trace of the droplet", and the diameter of the droplet is The maximum diameter of the circles included in the trace is set to the "minimum diameter of the trace of the droplet".

－Evaluation of the tensile strength of the carrier－

The tensile strength of the carrier measured at normal temperature after the heat treatment step was measured in the following manner.

First, the carrier is peeled off with respect to the produced copper foil with a carrier. Next, the tensile strength (tensile strength) of this support was calculated|required by the tensile test based on JISZ2241.

－Evaluation of circuit line (circuit formability)－

After bonding the ultra-thin copper foil side with a carrier to the bismaleimide triazine resin prepreg by thermocompression bonding, the carrier is peeled off to remove it, and then, at L/S=21μm/ A patterned copper plating layer with a width of 21 μm was formed on the surface of the exposed ultra-thin copper layer in a 9 μm manner (the total thickness of the ultra-thin copper layer and the patterned copper plating layer was 16.5 μm), and then the patterned copper plating layer was formed under the following etching conditions Rapid etching is performed until a copper plated layer with a width of 12 to 15 μm is formed at the upper end of the circuit to form a circuit. Next, as shown in FIG. 5 , the difference (μm) between the maximum value and the minimum value of the width of the lower end of the circuit observed from the upper surface of the circuit was measured, and an average value obtained by measuring five locations was obtained. When the difference between the maximum value and the minimum value is 2 μm or less, it is judged that the linearity of the circuit is good, and the evaluation is ⊚. Also, when the difference between the maximum value and the minimum value exceeds 2 μm and is 4 μm or less, the evaluation is 0. Also, when the difference between the maximum value and the minimum value exceeds 4 μm, it is evaluated as x.

(etching conditions)

·Etching form: spray etching

Nozzle: solid cone type

·Spray pressure: 0.10MPa

·Etching solution temperature: 30°C

· Etching solution composition:

H ₂ O ₂ 18g/L

_{H2SO4 92g} /L

Cu8g/L

Additive: appropriate amount of FE-830IIW3C manufactured by JCU Co., Ltd.

- Observation of wrinkles -

The surface of the ultra-thin copper layer after the heat treatment of each experimental example was visually observed for the presence or absence of wrinkles in the range of length 5 m. If there are 0 spots where wrinkles with a length of 10 cm or more can be confirmed, then it is rated as ◎, when there is one spot, it is rated as 0, when there are two spots, it is rated as △, and when there are three or more spots, it is rated as ×.

－Oxidation degree－

For each experimental example, after the heat treatment, one roll was unrolled, and a sample having a length of 1 m in the second roll was observed visually. At this time, those whose discoloration area due to oxidation was 5% or less were evaluated as ◎, those whose discoloration area due to oxidation was more than 5% and less than 10% were evaluated as ○○, and those whose discoloration area due to oxidation exceeded 10% and less than 15% were evaluated as ◎. % or less was evaluated as 0, the area of discoloration due to oxidation was more than 15% and less than 20% was evaluated as △, and the area of discoloration due to oxidation was more than 20% was evaluated as x.

The test conditions and evaluation results are shown in Tables 1-4.

(Evaluation results)

Example 1-1 to Example 1-48, Example 2-1 to Example 2-3, Example 3-5 to Example 3-13, Example 4-1 to Example 16-1 have good circuit linearity (circuit formability) . Regarding Examples 1 to 4, Examples 7 to 10, and Examples 14 to 16, it was found that although the circuit linearity (circuit formability) was poor before heat treatment, the circuit linearity (circuit formability) was improved by appropriate heat treatment. sex) is improved.

Furthermore, regarding Example 1-1 to Example 1-48, Example 2-1 to Example 2-6, Example 3-5 to Example 3-13, Example 4-1 to Example 8-1, Example 11-1 and Example 16-1, the wettability of the etching solution was also good.

In Example 1-49, the temperature of the heat treatment was low, and the circuit linearity (circuit formability) was poor.

In Example 1-50, the heat treatment time was short, and the circuit linearity (circuit formability) was poor.

In Example 2-4, the heat treatment time was long, and the crystal grains were coarsened, resulting in poor circuit linearity (circuit formability).

In Examples 2-5 and 2-6, the heat treatment temperature was high, and the crystal grains were coarsened, resulting in poor circuit linearity (circuit formability).

In Examples 3-1 to 3-4, the heating rate of the heat treatment was small, and the circuit linearity (circuit formability) was poor.

Claims (46)

1. A method of manufacturing copper foil with a carrier, comprising the following heat treatment step: performing a heat treatment on a copper foil with a carrier sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer including a silane coupling treatment layer. Heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 8 hours, or heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 6 hours, or heat treatment at a heating temperature of 160°C to 2 hours to 4 hours Heat treatment at 220°C. 2. The manufacturing method of the copper foil with a carrier according to claim 1, wherein the tensile strength of the carrier measured at normal temperature after the heat treatment step is 300 MPa or more. 3. A method of manufacturing copper foil with a carrier, which comprises the following heat treatment step: for the copper foil with a carrier sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, the temperature of the copper foil with a carrier is increased until the heating temperature is reached. The speed is set to exceed 50°C/hour, and heat treatment is performed at a heating temperature of 100°C to 220°C for 1 hour to 8 hours, or heat treatment at a heating temperature of 100°C to 220°C for 1 hour to 6 hours, or 2 hours Heat treatment at a heating temperature of 160°C to 220°C for ~4 hours. 4. The manufacturing method of copper foil with a carrier according to claim 3, wherein the temperature increase rate in the heat treatment is 200° C./hour or less. 5. The manufacturing method of copper foil with a carrier according to claim 3, wherein the tensile strength of the carrier measured at normal temperature after the heat treatment step is 300 MPa or more. 6 . The manufacturing method of copper foil with a carrier according to claim 4 , wherein the tensile strength of the carrier measured at normal temperature after the heat treatment step is 300 MPa or more. The manufacturing method of the copper foil with a carrier in any one of Claims 1-6 which heat-processes in an inert gas atmosphere in the said heat treatment process. 8. The method of manufacturing copper foil with a carrier according to any one of claims 1 to 6, wherein, in the heat treatment step, the copper foil with a carrier is wrapped in a hollow metal tube under heat treatment. 9. The method of manufacturing copper foil with a carrier according to claim 8, wherein in the heat treatment step, the tension at the time of winding the copper foil with a carrier into a metal hollow tube is 5 to 100 kgf /m or 20~100kgf/m for heat treatment. 10. The method of manufacturing copper foil with a carrier according to claim 8, wherein, in the heat treatment step, while the copper foil with a carrier is wrapped in a metal hollow tube, the copper foil with a carrier is heated at a temperature of 0.01 to Heat treatment was performed while rotating the hollow tube at a speed of 600 revolutions/hour. 11. The method of manufacturing copper foil with a carrier according to claim 9, wherein, in the heat treatment step, while the copper foil with a carrier is wrapped in a metal hollow tube, the copper foil with a carrier is heated at a temperature of 0.01 to Heat treatment was performed while rotating the hollow tube at a speed of 600 revolutions/hour. 12. The method of manufacturing copper foil with a carrier according to any one of claims 1 to 6, wherein the copper foil with a carrier before the heat treatment further has an intermediate layer, an ultra-thin copper layer, and an ultra-thin copper layer on the surface of the carrier side in this order. layer. The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-6 with which the copper foil with a carrier before the said heat treatment further has a surface treatment layer on the surface by the side of the said carrier. The manufacturing method of the copper foil with a carrier in any one of Claims 1-6 whose said surface treatment layer contains a roughening treatment layer. 15. The method of manufacturing copper foil with a carrier according to claim 14, wherein the surface of the surface treatment layer which is a roughening treatment layer further has a surface selected from a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane treatment layer. Coupling deals with one or more layers in the group consisting of layers. 16. The method of manufacturing copper foil with a carrier according to any one of claims 1 to 6, wherein the copper foil with a carrier before the heat treatment has a surface selected from a roughened layer, a roughened layer, and a surface of the ultra-thin copper layer. One or more layers in the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane-coupling-treated layer are used as the surface treatment layer. The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-6 in which the copper foil with a carrier before the said heat process is equipped with a resin layer on the said surface treatment layer. The manufacturing method of a copper-clad laminated board using the copper foil with a carrier manufactured by the manufacturing method of the copper foil with a carrier as described in any one of Claims 1-17. The manufacturing method of a printed wiring board using the copper foil with a carrier manufactured by the manufacturing method of the copper foil with a carrier as described in any one of Claims 1-17. 20. A method of manufacturing a printed wiring board, comprising the steps of: preparing the copper foil with a carrier and the insulating substrate obtained by the manufacturing method of the copper foil with a carrier according to any one of claims 1 to 17; Laminate the above-mentioned copper foil with carrier and insulating substrate; and After laminating the above-mentioned copper foil with a carrier and an insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate, Thereafter, a circuit is formed by any one of semi-additive method, subtractive method, partial additive method, or modified semi-additive method. 21. A method of manufacturing a printed wiring board, comprising the steps of: A circuit is formed on the side surface of the ultra-thin copper layer or the side surface of the carrier of the copper foil with a carrier obtained by the method of manufacturing copper foil with a carrier according to any one of claims 1 to 17; Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side so as to bury the circuit; forming a circuit on the above-mentioned resin layer; After forming a circuit on the above resin layer, peeling off the above carrier or the above ultra-thin copper layer; and After peeling off the carrier, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer-side surface or the carrier-side surface buried in the resin layer. The manufacturing method of the electronic equipment which used the printed wiring board manufactured by the manufacturing method of the printed wiring board in any one of Claims 19-21. Copper foil with a carrier obtained by the manufacturing method of the copper foil with a carrier as described in any one of Claims 1-17. 24. A copper foil with a carrier, which sequentially comprises a carrier, an intermediate layer, an ultra-thin copper layer, and a surface-treated layer including a silane coupling treatment layer, in which the surface-treated layer on the ultra-thin copper foil side is on top of the horizontal plane To place the copper foil with a carrier, use a pipette to drop 30 μL of an etching solution consisting of 24% by weight of sulfuric acid - 15% by weight of hydrogen peroxide, and the rest of which is water, and wipe off the etching solution after leaving it for 30 seconds. The difference between the maximum diameter and the minimum diameter of the trace of etching liquid is 10 mm or less, and the above-mentioned copper foil with a carrier does not include the thing provided with the resin layer. 25. The copper foil with a carrier according to claim 24, which is sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer including a silane coupling treatment layer, and the surface treatment layer on the side of the ultra-thin copper foil on the horizontal plane Place the copper foil with the carrier on top of the layer, use a pipette to drip 30 μL of an etching solution consisting of 24% by weight sulfuric acid - 15% by weight hydrogen peroxide, and the rest is water, and wipe it off after 30 seconds. After the etchant is removed, the maximum diameter of the trace of the etchant is 25 mm or more, and the copper foil with a carrier does not include a resin layer. 26. A copper foil with a carrier, which sequentially comprises a carrier, an intermediate layer, an ultra-thin copper layer, and a surface-treated layer including a silane coupling treatment layer, in which the surface-treated layer on the side of the ultra-thin copper foil is on top of the horizontal plane To place the copper foil with a carrier, use a pipette to drop 30 μL of an etching solution consisting of 24% by weight of sulfuric acid - 15% by weight of hydrogen peroxide, and the rest of which is water, and wipe off the etching solution after leaving it for 30 seconds. The maximum diameter of the trace of an etchant is 25 mm or more, and the said copper foil with a carrier does not include the thing provided with the resin layer. 27. A copper foil with a carrier, which sequentially comprises a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, and the copper foil with a carrier is placed on a horizontal plane with the surface treatment layer on the side of the ultra-thin copper foil on top , use a pipette to drip 30 μL of an etching solution consisting of 24% by weight sulfuric acid - 15% by weight hydrogen peroxide, and the rest is water. After leaving it for 30 seconds and wiping off the etching solution, the maximum The difference between the diameter and the minimum diameter is 10 mm or less, and the above-mentioned copper foil with a carrier does not include those provided with a resin layer. 28. The copper foil with a carrier according to claim 27, which is sequentially provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer. Place the copper foil with carrier, and drop 30 μL of an etching solution consisting of 24% by weight sulfuric acid - 15% by weight hydrogen peroxide, and the rest of water to one part using a pipette. The maximum diameter of the trace of the liquid is 25 mm or more, and the above-mentioned copper foil with a carrier does not include a resin layer. 29. A copper foil with a carrier comprising a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer in this order, and placing the copper foil with a carrier on a horizontal plane with the surface treatment layer on the side of the ultra-thin copper foil on top , use a pipette to drip 30 μL of an etching solution consisting of 24% by weight sulfuric acid - 15% by weight hydrogen peroxide, and the rest is water. After leaving it for 30 seconds and wiping off the etching solution, the maximum The diameter is 25 mm or more, and the above-mentioned copper foil with a carrier does not include those provided with a resin layer. 30 . The copper foil with a carrier according to claim 24 , wherein the difference between the maximum diameter and the minimum diameter of the trace of the etching solution is 5 mm or less. 31 . 31. The copper foil with a carrier according to any one of claims 24 to 29, wherein the trace of the etching solution has a maximum diameter of 35 mm or more. 32. The copper foil with a carrier according to claim 30, wherein the trace of the etching solution has a maximum diameter of 35 mm or more. The laminated body manufactured using the copper foil with a carrier as described in any one of Claims 23-32. 34. A laminate comprising the copper foil with a carrier according to any one of claims 23 to 32 and a resin, wherein part or all of the end faces of the copper foil with a carrier are covered with the resin. 35. A laminate comprising the copper foil with a carrier according to any one of claims 23 to 32, which is laminated from the side of the carrier or the side of the surface treatment layer to any one of claims 23 to 32. The said carrier side or the said surface treatment layer side of the said copper foil with a carrier of 1st item is formed. 36. The laminate according to claim 35, wherein the carrier-side surface or the surface-treated layer-side surface of the one copper foil with a carrier is separated from the carrier-side surface or the surface treatment of the other copper foil with a carrier. The surface on the side of the layer is formed by direct lamination via an adhesive, if necessary. 37. The laminate according to claim 35, wherein the carrier or the surface treatment layer of the one copper foil with a carrier is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier. 38. The laminate according to claim 36, wherein the carrier or the surface treatment layer of the one copper foil with a carrier is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier. 39. The laminate according to any one of claims 33 to 38, wherein a part or all of the end faces of the laminate are covered with a resin. The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 23-32. 41. An electronic device manufactured using the printed wiring board according to claim 40. 42. A method of manufacturing a printed wiring board, comprising the steps of: Prepare the copper foil with carrier and insulating substrate according to any one of claims 23 to 32; Laminate the above-mentioned copper foil with carrier and insulating substrate; and After laminating the above-mentioned copper foil with a carrier and an insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with a carrier is performed to form a copper-clad laminate, Thereafter, a circuit is formed by any one of semi-additive method, subtractive method, partial additive method, or modified semi-additive method. 43. A method of manufacturing a printed wiring board, comprising the steps of: A circuit is formed on the side surface of the ultra-thin copper layer or the side surface of the carrier of the copper foil with a carrier according to any one of claims 23 to 32; Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with carrier or the surface of the carrier side so as to bury the circuit; After forming the above-mentioned resin layer, peeling off the above-mentioned carrier or the above-mentioned ultra-thin copper layer; and After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer side surface or the carrier-side surface buried in the resin layer. 44. A method of manufacturing a printed wiring board, comprising the steps of: A circuit is formed on the side surface of the ultra-thin copper layer or the side surface of the carrier of the copper foil with a carrier according to any one of claims 23 to 32; Forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side so as to bury the circuit; forming a circuit on the above-mentioned resin layer; After forming a circuit on the above resin layer, peeling off the above carrier or the above ultra-thin copper layer; and After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, thereby exposing the circuit formed on the ultra-thin copper layer side surface or the carrier-side surface buried in the resin layer. 45. A method of manufacturing a printed wiring board, comprising the steps of: Laminating the ultra-thin copper layer-side surface or the carrier-side surface of the copper foil with a carrier according to any one of claims 23 to 32 with a resin substrate; At least one resin layer and a circuit are provided on the side surface of the ultra-thin copper layer or the surface of the carrier side opposite to the side of the copper foil with carrier on which the resin substrate is laminated; and After forming two layers of the said resin layer and a circuit, the said carrier or the said ultra-thin copper layer are peeled from the said copper foil with a carrier. 46. A method of manufacturing a printed wiring board, comprising the steps of: Laminating the above-mentioned carrier-side surface of the copper foil with a carrier according to any one of claims 23 to 32 and a resin substrate; Provide at least two layers of a resin layer and a circuit on the surface of the ultra-thin copper layer side opposite to the side where the resin substrate is laminated of the above-mentioned copper foil with a carrier; and After forming two layers of the said resin layer and a circuit, the said ultra-thin copper layer is peeled from the said copper foil with a carrier.