JP6872947B2 - A method for manufacturing a copper foil with a carrier, a laminate, a method for manufacturing a copper foil with a carrier, a method for manufacturing a laminate, a method for manufacturing a printed wiring board, and a method for manufacturing an electronic device. - Google Patents

Description

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

A printed wiring board is generally manufactured through a process in which an insulating substrate is adhered to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. With the increasing needs for miniaturization and high performance of electronic devices in recent years, high-density mounting of mounted components and high-frequency signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequencies for printed wiring boards. Correspondence is required.

Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less are required in response to fine pitching. Such ultra-thin copper foils have low mechanical strength and are used to manufacture printed wiring boards. Since it is easy to tear or wrinkle at times, a copper foil with a carrier that uses a thick metal foil as a carrier and electrodeposits an ultrathin copper layer via a release layer has appeared. After the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded, the carrier is peeled off and removed via the peeling layer (Patent Document 1).

Japanese Unexamined Patent Publication No. 2004-169181

When peeling the ultrathin copper layer from the carrier, if the peeling strength is too high, the ultrathin copper layer may be damaged. Further, if the peel strength is too small, there is a possibility that the carrier and the ultrathin copper layer may be peeled off when handling the copper foil with a carrier in the manufacturing process of a printed wiring board or the like. Further, when the ultrathin copper layer is peeled from the carrier, if the peeling strength in the peeling direction varies, there is a possibility that the productivity of the printed wiring board or the like using the copper foil with the carrier deteriorates. Therefore, it is an object of the present invention to provide a copper foil with a carrier, which has good peel strength at the time of carrier peeling and whose peel strength variation is satisfactorily suppressed.

In order to achieve the above object, the present inventor has set the surface roughness Sp of the carrier on the ultrathin copper layer side measured by a laser microscope when the carrier is peeled off under predetermined conditions, and 16 points on the surface of the carrier. By controlling the standard deviation of the surface roughness Sp when measured so as to satisfy a predetermined condition, the peeling strength at the time of carrier peeling is good, and the variation in peeling strength is well suppressed. We have found that we can provide foil.

The present invention has been completed based on the above findings, and is a copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order on one side, and the copper foil with a carrier is used at 220 ° C. for 90 minutes. After heat-bonding to the insulating substrate, when the carrier is peeled off in accordance with JIS C 6471, the surface roughness of the surface of the carrier on the ultrathin copper layer side measured at 256 μm × 256 μm square with a laser microscope. A copper foil with a carrier having a sp of 0.1 μm or more and 3.5 μm or less and a standard deviation of surface roughness Sp of 0.8 μm or less when the surface of the carrier is measured at 16 points.

In one embodiment, the copper foil with a carrier of the present invention has a standard deviation of surface roughness Sp of 0.7 μm or less when the surface of the carrier is measured at 16 points.

In another embodiment, the copper foil with a carrier of the present invention has a standard deviation of surface roughness Sp of 0.6 μm or less when the surface of the carrier is measured at 16 points.

In yet another embodiment the copper foil with carrier of the present invention, Ni deposition amount of the intermediate layer is 100 [mu] g / dm ² or more 40000μg / dm ² or less.

In still another embodiment, the copper foil with a carrier of the present invention has a Cr adhesion amount of 1 μg / dm ² or more and 100 μg / dm ² or less in the intermediate layer.

In still another embodiment, the copper foil with a carrier of the present invention has a surface roughness Sz of 0.3 μm or more and 4.5 μm or less on the ultrathin copper layer side of the carrier, and 16 points on the surface of the carrier. The standard deviation of the surface roughness Sz when measured is 1.0 μm or less.

In still another embodiment, the copper foil with a carrier of the present invention has a surface roughness Rz of 0.1 μm or more on the ultrathin copper layer side of the carrier when measured on a surface perpendicular to the MD direction of the carrier. It is 2.2 μm or less, and the standard deviation of the surface roughness Rz when the surface of the carrier is measured at 16 points is 0.3 μm or less.

In still another embodiment, the copper foil with a carrier of the present invention has an ultrathin copper layer on one surface of the carrier, and the copper foil with a carrier of the present invention has an ultrathin copper layer side and the carrier side. On at least one surface or both surfaces, or when the carrier-attached copper foil of the present invention has ultrathin copper layers on both sides of the carrier, on the surface on the one or both ultrathin copper layer side. It has one or more layers selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer.

In still another embodiment, the copper foil with a carrier of the present invention is one or more selected from the group consisting of the roughening treatment layer, the heat resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer. A resin layer is provided on the layer.

In yet another embodiment of the copper foil with a carrier of the present invention, at least one of the rust preventive layer and the heat resistant layer contains one or more elements selected from nickel, cobalt, copper and zinc.

In still another embodiment, the copper foil with a carrier of the present invention includes a resin layer on the ultrathin copper layer.

In yet another embodiment of the copper foil with a carrier of the present invention, the resin layer contains a dielectric.

In another aspect, the present invention is a method for producing a copper foil with a carrier, which comprises a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the carrier is etched or the surface of the carrier is subjected to. A step of adjusting the surface roughness of the carrier by plating up copper and a step of providing the intermediate layer and the ultrathin copper layer on the etching or the plated up surface side of the carrier in this order. It is a manufacturing method of a copper foil with a carrier including.

In yet another aspect, the present invention is a method for producing a laminate using the carrier-attached copper foil of the present invention.

In yet another aspect, the present invention is a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

In still another aspect, the present invention is a laminate containing the carrier-attached copper foil of the present invention and a resin, and a part or all of the end faces of the carrier-attached copper foil is covered with the resin. Is.

In yet another aspect of the present invention, one carrier-attached copper foil of the present invention is attached to the carrier side or the ultra-thin copper layer side, and another carrier-attached copper foil of the present invention is attached to the carrier side or the ultra-thin copper foil. It is a laminated body laminated on the copper layer side.

In yet another aspect, the present invention is a method for manufacturing a printed wiring board using the laminate of the present invention.

In yet another aspect of the present invention, after a step of providing the laminate of the present invention with two layers of a resin layer and a circuit at least once, and forming the two layers of the resin layer and the circuit at least once. A method for manufacturing a printed wiring board, which comprises a step of peeling the ultrathin copper layer or the carrier from the carrier-attached copper foil of the laminate.

In still another aspect of the present invention, the step of preparing the carrier-attached copper foil and the insulating substrate of the present invention, the step of laminating the carrier-attached copper foil and the insulating substrate, and the carrier-attached copper foil and the insulating substrate are provided. After laminating, a copper-clad laminate is formed through a step of peeling off the carrier of the copper foil with a carrier, and then a circuit is formed by any of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. It is a manufacturing method of a printed wiring board including a step of forming.

In yet another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention, the step of forming the circuit on the carrier-side surface, the carrier-attached copper foil so that the circuit is buried. After the step of forming a resin layer on the surface on the ultrathin copper layer side or the surface on the carrier side, the step of peeling off the carrier or the ultrathin copper layer, and peeling off the carrier or the ultrathin copper layer, the said A method for manufacturing a printed wiring board, which comprises a step of exposing a circuit embedded in the resin layer formed on the surface on the ultrathin copper layer side or the surface on the carrier side by removing the ultrathin copper layer or the carrier. Is.

In still another aspect of the present invention, a step of laminating the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention with a resin substrate, and laminating with the resin substrate of the carrier-attached copper foil. A step of providing the two layers of the resin layer and the circuit at least once on the surface on the ultrathin copper layer side opposite to the side or the surface on the carrier side, and forming the two layers of the resin layer and the circuit at least once. A method for manufacturing a printed wiring board, which comprises a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier later.

In yet another aspect, the present invention is a method of manufacturing an electronic device using a printed wiring board manufactured by the method of manufacturing a printed wiring board of the present invention.

According to the present invention, it is possible to provide a copper foil with a carrier having good peel strength at the time of peeling the carrier and well suppressing variation in peel strength.

A to C are schematic views of a cross section of a wiring board in a process up to circuit plating and resist removal according to a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier of the present invention. D to F are schematic views of the cross section of the wiring board in the process from laminating the resin and the copper foil with the second layer carrier to laser drilling, which relates to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention. Is. GI is a schematic view of a cross section of a wiring board in a process from viafill formation to peeling of a carrier of the first layer, which relates to a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier of the present invention. J to K are schematic views of the cross section of the wiring board in the process from flash etching to the formation of bumps and copper pillars, which relates to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

<Copper foil with carrier>
The copper foil with a carrier of the present invention has a carrier, an intermediate layer, and an ultrathin copper layer in this order. Further, an intermediate layer and an ultrathin copper layer may be provided on one surface or both surfaces of the carrier, and further, the ultrathin copper layer on one surface and the carrier on the other surface or ultrathin copper on both surfaces may be provided. The layer may be subjected to surface treatment such as roughening treatment. The method of using the carrier-attached copper foil itself is well known to those skilled in the art. Base material Epoxy resin, glass cloth / glass non-woven composite base material Epoxy resin and glass cloth base material Epoxy resin, polyester film, polyimide film, liquid crystal polymer, fluororesin, etc. are attached to an insulating substrate or film, and the carrier is peeled off after thermal pressure bonding. , The ultra-thin copper layer adhered to the insulating substrate can be etched into a target conductor pattern, and finally a laminate (copper-clad laminate or the like) or a printed wiring board or the like can be manufactured.

The copper foil with a carrier of the present invention has a copper foil with a carrier thermocompression bonded to an insulating substrate at 220 ° C. for 90 minutes, and then when the carrier is peeled off in accordance with JIS C 6471, it is 256 μm × 256 μm with a laser microscope. The surface roughness Sp (maximum mountain height) of the surface of the carrier on the ultrathin copper layer side measured at the angle is 0.1 μm or more and 3.5 μm or less. Since the surface roughness Sp of the surface of the carrier on the ultrathin copper layer side is 0.1 μm or more, the carrier and the ultrathin copper layer are peeled off when handling the copper foil with a carrier in the manufacturing process of a printed wiring board or the like. It is possible to suppress the problem of being lost. Further, since the surface roughness Sp of the surface of the carrier on the ultrathin copper layer side is 3.5 μm or less, it is possible to prevent the ultrathin copper layer from being damaged when the carrier is peeled off. The surface roughness Sp of the surface of the carrier on the ultrathin copper layer side is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 2.5 μm or less, and 0.1 μm or more. It is more preferably 2.0 μm or less, and more preferably 0.1 μm or more and 1.5 μm or less.

In the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less. When the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less, the copper foil with a carrier can be obtained in which the variation in peel strength is suppressed. The standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is preferably 0.7 μm or less, more preferably 0.6 μm or less, and more preferably 0.5 μm or less.

When producing a copper foil with a carrier, the surface roughness of the side where the intermediate layer of the carrier is provided is roughened (Sp, Sz,) by etching the surface of the carrier or plating up the copper before providing the intermediate layer on the carrier. By controlling the average and standard deviation of Rz), it is possible to produce a copper foil with a carrier in which variations in peel strength are suppressed. In the copper foil with a carrier, after the carrier is peeled off, a hole is made in the surface of the ultrathin copper layer with a carbon dioxide gas laser, but if the laser absorption of the ultrathin copper layer is poor, the laser drilling property is adversely affected. In the present invention, in order to improve the laser drilling property, the surface of the ultrathin copper layer can be roughened by etching the surface on the side where the intermediate layer of the carrier is provided to control the roughness. On the other hand, there is also a usage method in which a carbon dioxide laser is not used to make holes. In that case, in order to improve the fine etching property of the ultrathin copper layer, there is a request to smooth the ultrathin copper layer and improve the foil thickness accuracy compared to the conventional one. There is also. Therefore, in the present invention, it is possible to smooth the carrier surface by plating up the surface on the side where the intermediate layer of the carrier is provided with a blunt copper plating solution.

The average value of the surface roughness Sp (maximum mountain height) when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is 0.1 μm or more and 3.5 μm or less, and the surface of the carrier is 16 points. The standard deviation of the surface roughness Sp when measured is preferably 0.8 μm or less. According to such a configuration, the variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Sp when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is more preferably 0.1 μm or more and 3.0 μm or less, and 0.1 μm or more and 2.5 μm or more. It is more preferably 0.1 μm or more, and more preferably 2.0 μm or less. Further, the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is more preferably 0.8 μm or less, more preferably 0.7 μm or less, and more preferably 0.6 μm or less. Is more preferable.

The average value of the surface roughness Sz (maximum height) when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is 0.3 μm or more and 4.5 μm or less, and the surface of the carrier is 16 points. The standard deviation of the surface roughness Sz when measured is preferably 1.0 μm or less. According to such a configuration, the variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Sz when the surface of the carrier on the ultrathin copper layer side of the carrier is measured at 16 points is more preferably 0.3 μm or more and 4.0 μm or less, and more preferably 0.3 μm or more and 3.5 μm or more. It is more preferably 0.3 μm or more, and more preferably 3.0 μm or less. Further, the standard deviation of the surface roughness Sz when the surface of the carrier is measured at 16 points is more preferably 0.8 μm or less, more preferably 0.7 μm or less, and more preferably 0.6 μm or less. Is more preferable.

Surface roughness when measuring the surface of the carrier in the direction (TD direction) perpendicular to the MD direction of the carrier (the direction in which the carrier is conveyed in the device for forming the ultrathin copper layer) when the surface of the carrier is measured at 16 points. The average value of Rz (10-point average roughness) is 0.1 μm or more and 2.2 μm or less, and the standard deviation of surface roughness Rz when the surface of the carrier is measured at 16 points is 0.3 μm or less. Is preferable. According to such a configuration, the variation in peel strength can be satisfactorily suppressed.
The average value of the surface roughness Rz when measuring 16 points on the surface of the carrier when measuring the surface in the direction perpendicular to the MD direction (TD direction) of the carrier is 0.1 μm or more and 1.8 μm or less. It is more preferably 0.1 μm or more and 2.0 μm or less, and more preferably 0.1 μm or more and 1.6 μm or less. Further, the standard deviation of the surface roughness Rz when the surface of the carrier is measured at 16 points is more preferably 0.25 μm or less, more preferably 0.20 μm or less, and 0.15 μm or less. Is more preferable.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foils, copper alloy foils, nickel foils, nickel alloy foils, iron foils, iron alloy foils, stainless steel foils, aluminum foils, aluminum. It is provided in the form of an alloy foil, an insulating resin film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin film, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyamide film, and a polyamideimide film. Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, an electrolytic copper foil is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, and a rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Copper foil materials include tough pitch copper (JIS H3100 alloy number C1100), oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), high-purity copper such as phosphorylated copper and electrolytic copper, as well as Sn, for example. Copper alloys such as copper containing copper, copper containing Ag, copper alloys to which Cr, Zr, Mg and the like are added, and Corson-based copper alloys to which Ni and Si and the like are added can also be used. Also, known copper alloys can be used. When the term "copper foil" is used alone in the present specification, it also includes a copper alloy foil.

The thickness of the carrier that can be used in the present invention is also not particularly limited, but may be appropriately adjusted to a thickness suitable for fulfilling the role as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost will increase, so it is generally preferable to set it to 35 μm or less. Therefore, the thickness of the carrier is typically 8 μm or more and 70 μm or less, more typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less. Further, from the viewpoint of reducing the raw material cost, it is preferable that the thickness of the carrier is small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, and preferably 5 μm or more and 10 μm or less. It is as follows. If the thickness of the carrier is small, creases are likely to occur when the carrier is passed through the foil. In order to prevent the occurrence of creases, it is effective, for example, to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. When a copper foil with a carrier is used in an embedding method (embedded process), which is one of the methods for manufacturing a printed wiring board, it is necessary that the carrier has high rigidity. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Is even more preferable.

The following is an example of manufacturing conditions when an electrolytic copper foil is used as a carrier.
<Electrolytic solution composition>
Copper: 90 g / L or more and 110 g / L or less Sulfuric acid: 90 g / L or more and 110 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3 sulfopropyl) disulfide): 10 ppm or more and 30 ppm or less Leveling agent 2 (Amine compound): 10 ppm or more and 30 ppm or less An amine compound having the following chemical formula can be used as the above amine compound.

Unless otherwise specified, the balance of the treatment liquid used for electrolysis, surface treatment, plating, etc. used in the present invention is water.

（上記化学式中、Ｒ₁及びＲ₂はヒドロキシアルキル基、エーテル基、アリール基、芳香族置換アルキル基、不飽和炭化水素基、アルキル基からなる一群から選ばれるものである。）

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

<Manufacturing conditions>
Current density: 70 A / dm ² or more and 100 A / dm ² or less Electrolyte temperature: 50 ° C or more and 60 ° C or less Electrolyte fluid linear velocity: 3 m / sec or more and 5 m / sec or less Electrolysis time: 0.5 minutes or more and 10 minutes or less

<Middle layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultra-thin copper layer is difficult to peel off from the carrier before the carrier-attached copper foil is laminated on the insulating substrate, while the ultra-thin copper layer is formed from the carrier after the carrier-attached bonding process. The structure is not particularly limited as long as it can be peeled off. For example, the intermediate layer of the carrier-attached copper foil of the present invention includes Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, and the like. It may contain one or more selected from the group consisting of organic substances. Further, the intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of a kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. Alternatively, an alloy layer composed of one or more elements selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed. A hydrate or oxide of one or more elements selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance. A layer composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, a single metal layer composed of a kind of element selected from the element group, or Cr, It can be configured by forming an alloy layer composed of one or more elements selected from the element group composed of Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn. ..

When the intermediate layer is provided on only one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the adhered metals such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be formed by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it will be peeled off at the interface between the ultrathin copper layer and chromium. Further, nickel in the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more It is preferably 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium adhered to the intermediate layer ^{is preferably 1 μg / dm 2} or more and 100 μg / dm ² or less, and 5 μg / dm ² or more and 100 μg / dm ² or less. More preferably.

<Ultra-thin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultrathin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil at high current density. A copper sulfate bath is preferable because it is possible to form a copper foil. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 μm or more and 12 μm or less, more typically 1 μm or more and 5 μm or less, more typically 1.5 μm or more and 4 μm or less, and more typically 2 μm or more and 3.5 μm or less. In addition, ultra-thin copper layers may be provided on both sides of the carrier.

<Roughening treatment and other surface treatments>
A roughening treatment layer may be provided on either one or both of the surface of the ultrathin copper layer and the surface of the carrier by, for example, roughening treatment for improving the adhesion to the insulating substrate. Good. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment may be fine. The roughened layer is a layer made of any simple 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 of them. May be good. Further, after forming the roughened particles with copper or a copper alloy, it is also possible to carry out a roughening treatment in which secondary particles or tertiary particles are further provided with a simple substance or an alloy of nickel, cobalt, copper or zinc. After that, a heat-resistant layer and / or a rust-preventive layer may be formed from a simple substance or alloy of nickel, cobalt, copper, zinc, etc., and the surface thereof may be further subjected to a treatment such as chromate treatment or silane coupling treatment. .. Alternatively, a heat-resistant layer and / or a rust-preventive layer is formed from a simple substance or alloy of nickel, cobalt, copper, zinc, etc. without roughening treatment, and the surface thereof is further subjected to treatments such as chromate treatment and silane coupling treatment. You may. That is, one or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, and the ultrathin copper layer may be formed. One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface. The heat-resistant layer, the rust preventive layer, the chromate-treated layer, and the silane coupling-treated layer may each be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).
Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, chromic acid, chromate or dichromate. The chromate-treated layer has any form of elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metals, alloys, oxides, nitrides, sulfides, etc.). May be included). Specific examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc, and the like. ..

By providing the roughening treatment layer on the surface opposite to the surface on the side where the ultrathin copper layer of the carrier is provided, the carrier is laminated on a support such as a resin substrate from the surface side having the roughening treatment layer. At that time, it has an advantage that the carrier and the resin substrate are hard to be peeled off. By further forming a surface-treated layer such as a heat-resistant layer on the ultra-thin copper layer or the surface-roughened layer of the carrier as described above, the ultra-thin copper layer or copper from the carrier can be formed on the resin substrate to be laminated. Diffusion of elements can be satisfactorily suppressed, and adhesion by thermocompression bonding at the time of laminating with a resin base material is improved.

As the heat-resistant layer and rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or rust-preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. It may be a layer containing one or more elements selected from, and may be nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements. It may be a metal layer or an alloy layer composed of one or more elements selected from the group of iron and tantalum. The heat-resistant layer and / or rust-preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. It may contain an oxide, a nitride, or a silicate containing one or more elements selected from the above. Further, the heat-resistant layer and / or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% or more and 99 wt% or less of nickel and 50 wt% or more and 1 wt% or less of zinc, excluding unavoidable impurities. Said nickel - total adhesion amount of the zinc and nickel-zinc alloy layer is 5 mg / m ² or more 1000 mg / m ² or less, preferably 10 mg / m ² or more 500 mg / m ² or less, preferably 20 mg / m ² or more 100 mg / m ² It may be as follows. Further, when the ratio of the amount of nickel adhered to the amount of zinc adhered to the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= amount of nickel adhered / amount of zinc adhered) is 1.5 or more and 10 or less. It is preferable to have. Further, the nickel - layer or the nickel containing zinc alloy - zinc deposition amount of nickel alloy layer is preferably 0.5 mg / m ² or more 500 mg / m ² or less, 1 mg / m ² or more 50 mg / m ² The following is more preferable. When the heat-resistant layer and / or the rust-preventive layer is a layer containing a nickel-zinc alloy, the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and / or the rust-preventive layer is a nickel or nickel alloy layer having an adhesion amount of 1 ^{mg / m 2} or more and 100 mg / m ² or less, preferably 5 mg / m ² or more and 50 mg / m ^{2 or less, and an adhesion amount of 1 mg / m / m.} A tin layer of m ² or more and 80 mg / m ² or less, preferably 5 mg / m ² or more and 40 mg / m ² or less may be sequentially laminated, and the nickel alloy layer may be nickel-molybdenum, nickel-zinc, or nickel. It may be composed of any one of a molybdenum-cobalt and a nickel-tin alloy. The heat-resistant layer and / or the rust-preventive layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m ² or more and 150 mg / m ² or less, and 10 mg / m ² or more and 70 mg / m ² or less. Is more preferable. Further, the heat-resistant layer and / or the rust preventive layer described above preferably have [nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 or more and 10 or less, and 0.33 or more and 3 or less. Is more preferable. When the heat-resistant layer and / or the rust-preventive layer is used, the peeling strength of the circuit after processing the copper foil with a carrier into a printed wiring board, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

A known silane coupling agent may be used as the silane coupling agent used to provide the silane coupling treatment layer, for example, an amino-based silane coupling agent, an epoxy-based silane coupling agent, or a mercapto-based silane coupling agent. Agents may be used. The silane coupling agent includes vinyltrimethoxysilane, vinylphenyltrimethoxylan, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazinesilane, You may use γ-mercaptopropyltrimethoxysilane or the like.

The silane coupling treatment layer may be formed using a known silane coupling agent, and may be formed using an epoxy-based silane, an amino-based silane, a methacryloxy-based silane, a mercapto-based silane, a vinyl-based silane, an imidazole-based silane, or a triazine-based silane. It may be formed by using a silane coupling agent such as silane. Two or more kinds of such silane coupling agents may be mixed and used. Of these, those formed by using an amino-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

The amino-based silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3-. Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3) −Acrylicoxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenetiltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) ) -3,3-Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxy) Silane, 3- (2-N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane , (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyl Trimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxy It may be selected from the group consisting of silane.

The silane coupling-treated layer has a silicon atom equivalent of 0.05 mg / m ² or more and 200 mg / m ² or less, preferably 0.15 mg / m ² or more and 20 mg / m ² or less, preferably 0.3 mg / m ² or more 2 It is desirable that it is provided in the range of 0.0 mg / m ^{2 or less.} In the case of the above range, the adhesion between the base material and the copper foil with a carrier can be further improved.

Further, on the surface of an ultrathin copper layer, a roughened treatment layer, a heat resistant layer, a rust preventive layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. WO2008 / 053878, JP-A-2008-11169, Patent No. 5024930. , International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, Japanese Patent Application Laid-Open No. 2013-19506. be able to.

Further, the copper foil with a carrier of the present invention has a resin layer on the ultrathin copper layer, the roughening treatment layer, the heat resistant layer, the rust prevention layer, the chromate treatment layer, or the silane coupling treatment layer. May be provided.

The resin layer may be an adhesive or an insulating resin layer in a semi-cured state (B stage) for adhesion. The semi-cured state (B stage) is a state in which the surface is not sticky even when touched with a finger, the insulating resin layers can be stacked and stored, and a curing reaction occurs when the surface is further heat-treated. including.

Further, the resin layer may contain a thermosetting resin or may be a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type is not particularly limited, but for example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymerimide compound, maleimide resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin. , Polyether sulfone (also called polyether sulfone, polyether sulfone), polyether sulfone (also called polyether sulfone, polyether sulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin , Polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid Anhydrous, polyvalent carboxylic acid anhydride, linear polymer with crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenolic compound, manganese naphthenate, 2 , 2-Bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinylbutyral, phenoxy , High molecular weight epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and resin containing at least one selected from the group of cyanoester resins can be mentioned as suitable ones.

Further, the epoxy resin can be used without any problem as long as it has two or more epoxy groups in the molecule and can be used for electrical / electronic material applications. Further, the epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber-modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glysidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenylnovolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type One or a mixture of two or more selected from the group of epoxy resins can be used, or a hydrogenated or halogenated product of the epoxy resin can be used.
As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferable.

Any dielectric such as a known resin, resin curing agent, compound, curing accelerator, or dielectric (dielectric containing an inorganic compound and / or an organic compound, or a dielectric containing a metal oxide) may be used for the resin layer. Good), reaction catalysts, cross-linking agents, polymers, prepregs, skeleton materials, etc. may be included. Further, the resin layer is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-14281, Patent No. 3184485, International Publication No. WO97 / 02728, Japanese Patent No. 3676375, Japanese Patent No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, Japanese Patent Application Laid-Open No. 2002-359444, Japanese Patent Application Laid-Open No. 2003-3004068, Japanese Patent No. 3992225, Japanese Patent Application Laid-Open No. 2003 -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82887, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. 2005-53218 No., Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Patent Application Laid-Open No. 2009-173017, International Publication No. WO2007 / 105635, Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication No. WO2009 / 00150, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, Japanese Patent Application Laid-Open No. 2013-19506 ( It may be formed using a resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a cross-linking agent, a polymer, a prepreg, a skeleton material, etc.) and / or a method for forming a resin layer and a forming apparatus.

These resins described above are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin liquid, which is then used on the ultrathin copper layer, the heat resistant layer, the rust preventive layer, the chromate film layer, or the chromate film layer. It is applied on a surface treatment layer containing a silane coupling agent layer or the like by, for example, a roll coater method, and then, if necessary, heat-dried to remove the solvent to bring it into a B stage state. For drying, for example, a hot air drying furnace may be used, and the drying temperature may be 100 ° C. or higher and 250 ° C. or lower, preferably 130 ° C. or higher and 200 ° C. or lower.

The copper foil with a carrier provided with the resin layer (copper foil with a carrier with a resin) is obtained by superimposing the resin layer on a base material and then heat-pressing the entire resin layer to heat-cure the resin layer, and then the copper foil with a carrier. If this is the case, the carrier is peeled off to expose the ultrathin copper layer (naturally, the surface on the intermediate layer side of the ultrathin copper layer is exposed), and a predetermined wiring pattern is formed on the ultrathin copper layer. Is used in the form of forming.

When this copper foil with a carrier with resin is used, the number of prepreg materials used in the manufacture of the multilayer printed wiring board can be reduced. Moreover, the thickness of the resin layer can be made thick enough to ensure interlayer insulation, and the copper-clad laminate can be manufactured without using any prepreg material. At this time, the surface of the base material can be undercoated with an insulating resin to further improve the smoothness of the surface.

When the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is manufactured. The thickness is reduced, and there is an advantage that an ultra-thin multilayer printed wiring board having a layer thickness of 100 μm or less can be manufactured.

The thickness of this resin layer is preferably 0.1 μm or more and 80 μm or less. When the thickness of the resin layer is thinner than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material is formed. It may be difficult to secure interlayer insulation between the two.

On the other hand, if the thickness of the resin layer is made thicker than 80 μm, it becomes difficult to form a resin layer having a target thickness in one coating step, which is economically disadvantageous because extra material costs and man-hours are required. Furthermore, since the formed resin layer is inferior in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.

Further, as another product form of the copper foil with a carrier with resin, it is on the surface treatment layer of the ultrathin copper layer, or the heat resistant layer, the rust preventive layer, the chromate treatment layer, or the silane coupling treatment. It is also possible to coat the layer with a resin layer to make it semi-cured, and then peel off the carrier to produce a copper foil with a resin in which no carrier exists.

A printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.
Further, the electronic device may be manufactured using the printed wiring board, the electronic device may be manufactured using the printed circuit board on which the electronic component is mounted, and the printed circuit board on which the electronic component is mounted may be manufactured. An electronic device may be manufactured using a substrate. The following are some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier according to the present invention.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, there is a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, and the step of laminating the copper foil with a carrier and the insulating substrate. After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling off the carrier of the copper foil with a carrier. The step of forming a circuit by any method of an additive method, a partly additive method and a subtractive method is included. The insulating substrate may have an inner layer circuit.

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

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

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

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

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

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

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention.
The process of laminating the copper foil with carrier and the insulating substrate,
A step of peeling off the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and an insulating substrate.
A step of providing through holes or / and blind vias in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier.
The step of performing desmear treatment on the region including the through hole and / and the blind via,
A step of providing an electroless plating layer on a region including the through holes and / and blind vias.
A step of providing a plating resist on the surface of an ultrathin copper layer exposed by peeling off the carrier,
A step of forming a circuit by electrolytic plating after providing the plating resist,
The step of removing the plating resist,
A step of removing the exposed ultrathin copper layer by removing the plating resist by flash etching.
including.

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

In the present invention, the partial additive method is a substrate in which a conductor layer is provided, and if necessary, a catalyst nucleus is provided on a substrate in which holes for through holes and via holes are formed, and a conductor circuit is formed by etching. The present invention refers to a method of manufacturing a printed wiring board by providing a solder resist or a plating resist as necessary and then thickening the through holes, via holes, etc. on the conductor circuit by electroless plating treatment.

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the partial additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention.
The process of laminating the copper foil with carrier and the insulating substrate,
A step of peeling off the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and an insulating substrate.
A step of providing through holes or / and blind vias in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier.
The step of performing desmear treatment on the region including the through hole and / and the blind via,
The step of imparting a catalyst nucleus to the region containing the through hole and / and the blind via,
A step of providing an etching resist on the surface of an ultrathin copper layer exposed by peeling off the carrier,
The step of exposing the etching resist to form a circuit pattern,
A step of forming a circuit by removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as acid.
The step of removing the etching resist,
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as acid.
A step of providing an electroless plating layer in a region where the solder resist or plating resist is not provided.
including.

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

Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method, the step of preparing the copper foil with a carrier and the insulating substrate according to the present invention.
The process of laminating the copper foil with carrier and the insulating substrate,
A step of peeling off the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and an insulating substrate.
A step of providing through holes or / and blind vias in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier.
The step of performing desmear treatment on the region including the through hole and / and the blind via,
A step of providing an electroless plating layer on a region including the through holes and / and blind vias.
A step of providing an electrolytic plating layer on the surface of the electroless plating layer,
A step of providing an etching resist on the surface of the electrolytic plating layer and / and the ultrathin copper layer,
The step of exposing the etching resist to form a circuit pattern,
A step of forming a circuit by removing the ultrathin copper layer, the electroless plating layer, and the electroplating layer by a method such as etching using a corrosive solution such as acid or plasma.
The step of removing the etching resist,
including.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention.
The process of laminating the copper foil with carrier and the insulating substrate,
A step of peeling off the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and an insulating substrate.
A step of providing through holes or / and blind vias in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier.
The step of performing desmear treatment on the region including the through hole and / and the blind via,
A step of providing an electroless plating layer on a region including the through holes and / and blind vias.
The step of forming a mask on the surface of the electroless plating layer,
A step of providing an electrolytic plating layer on the surface of the electroless plating layer on which a mask is not formed,
A step of providing an etching resist on the surface of the electrolytic plating layer and / and the ultrathin copper layer,
The step of exposing the etching resist to form a circuit pattern,
A step of forming a circuit by removing the ultrathin copper layer and the electroless plating layer by a method such as etching with a corrosive solution such as acid or plasma.
The step of removing the etching resist,
including.

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

Here, a specific example of a method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Although the description will be made here using a copper foil with a carrier in which a roughening treatment layer is formed on the surface of the ultrathin copper layer, a copper foil with a carrier in which a surface treatment layer such as a roughening treatment layer is not provided may also be used. good.
First, as shown in FIG. 1-A, a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened treatment layer formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 1-C, after forming the plating for the circuit, the resist is removed to form the circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), the resin layer is laminated, and then another carrier is attached. The copper foil (second layer) is adhered from the ultrathin copper layer side.
Next, as shown in FIG. 2-E, the carrier is peeled off from the second layer of copper foil with a carrier.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind via.
Next, as shown in FIG. 3-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown in FIG. 3-I, the carrier is peeled off from the first layer of copper foil with a carrier.
Next, as shown in FIG. 4-J, the ultrathin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 4-K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. In this way, a printed wiring board using the copper foil with a carrier of the present invention is produced.
In the above-mentioned method for manufacturing a printed wiring board, the "ultra-thin copper layer" is read as a carrier and the "carrier" is read as an ultra-thin copper layer to form a circuit on the surface of the copper foil with a carrier on the carrier side. It is also possible to embed a circuit with resin and manufacture a printed wiring board.

As the other copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, the conventional copper foil with a carrier may be used, or a normal copper foil may be used. Further, one layer or a plurality of layers may be further formed on the second layer circuit shown in FIG. 3-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method or a modified semi. It may be carried out by any method of the additive method.

According to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, for example, when removing the ultrathin copper layer by flash etching as shown in FIG. 4-J. In addition, the circuit plating is protected by the resin layer and its shape is maintained, which facilitates the formation of fine circuits. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved and the continuity of the circuit wiring is satisfactorily suppressed. Therefore, the formation of a fine circuit becomes easy. Further, as shown in FIGS. 4-J and 4-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a concave shape from the resin layer, so that bumps are formed on the circuit plating. Furthermore, copper pillars are easily formed on the copper pillars, and the manufacturing efficiency is improved.

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

Further, the copper foil with a carrier used in the first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having the substrate or the resin layer, the copper foil with a carrier used in the first layer is supported and wrinkles are less likely to occur, so that there is an advantage that productivity is improved. As the substrate or resin layer, any substrate or resin layer can be used as long as it has the effect of supporting the copper foil with a carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, which are described in the present specification, Foil of organic compound can be used.

Further, the method for manufacturing a printed wiring board of the present invention is a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing two layers of a resin layer and a circuit at least once on the surface of the copper layer side or the surface of the copper foil with a carrier on the side opposite to the surface of the carrier side, and forming the two layers of the resin layer and the circuit. After that, a method for manufacturing a printed wiring board (coreless method) including a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier may be used. As a specific example of the coreless method, first, a laminated body (copper-clad laminate, copper-clad) is obtained by laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate. (Also called a laminate) is manufactured. Then, a resin layer is formed on the surface of the ultrathin copper layer laminated with the resin substrate or the surface of the copper foil with a carrier on the side opposite to the surface on the carrier side. Another copper foil with a carrier may be laminated from the carrier side or the ultrathin copper layer side on the resin layer formed on the carrier side surface or the ultrathin copper layer side surface. Further, centering on the resin substrate or the resin or the prepreg, the carrier / intermediate layer / ultrathin copper layer or the ultrathin copper layer / intermediate layer / carrier is placed on the surface side of both the resin substrate or the resin or the prepreg in this order. It has a structure in which copper foils with carriers are laminated, or a structure in which "carrier / intermediate layer / ultrathin copper layer / resin substrate or resin or prepreg / carrier / intermediate layer / ultrathin copper layer" is laminated in this order. A laminate or a laminate having a structure in which "carrier / intermediate layer / ultrathin copper layer / resin substrate / carrier / intermediate layer / ultrathin copper layer" is laminated in this order or "ultrathin copper layer / intermediate layer / carrier / resin" A laminate having a structure in which the substrate / carrier / intermediate layer / ultrathin copper layer is laminated in this order may be used in the above-mentioned method for manufacturing a printed wiring board (coreless method). Then, another resin layer is provided on the exposed surfaces of the ultrathin copper layers or carriers at both ends of the laminate, and after further providing the copper layer or metal layer, the copper layer or metal layer is processed. A circuit may be formed. Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed once or more (build-up method). Then, with respect to the laminate formed in this manner (hereinafter, also referred to as laminate B), the ultrathin copper layer or carrier of the copper foil with a carrier is peeled from the carrier or the ultrathin copper layer to prepare a coreless substrate. be able to. In the production of the coreless substrate described above, two copper foils with carriers are used to form a laminate having an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultrathin copper layer structure described later. It has a structure of a carrier / intermediate layer / ultra-thin copper layer / ultra-thin copper layer / intermediate layer / carrier, and a structure of carrier / intermediate layer / ultra-thin copper layer / carrier / intermediate layer / ultra-thin copper layer. It is also possible to prepare a laminated body and use the laminated body as a center. Two layers of a resin layer and a circuit are provided at least once on the surface of the ultrathin copper layers or carriers on both sides of these laminates (hereinafter, also referred to as laminate A), and two layers of the resin layer and the circuit are provided at least once. Later, the ultrathin copper layer or carrier of each carrier-attached copper foil can be peeled off from the carrier or ultrathin copper layer to produce a coreless substrate. The above-mentioned laminates include the surface of the ultrathin copper layer, the surface of the carrier, between the carrier and the carrier, between the ultrathin copper layer and the ultrathin copper layer, and between the ultrathin copper layer and the carrier. It may have a layer. The other layer may be a resin substrate or a resin layer. In the present specification, "the surface of the ultrathin copper layer", "the surface of the ultrathin copper layer", "the surface of the ultrathin copper layer", "the surface of the carrier", "the surface of the carrier side", "the surface of the carrier", " The "surface of the laminate" and "surface of the laminate" refer to the ultrathin copper layer, the carrier, and the other layer when the laminate has other layers on the surface of the ultrathin copper layer, the carrier surface, and the surface of the laminate. The concept includes the surface (outermost surface) of. Further, the laminate preferably has a structure of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultrathin copper layer. This is because when a coreless substrate is produced using the laminate, an ultrathin copper layer is arranged on the coreless substrate side, so that it becomes easy to form a circuit on the coreless substrate by using the modified semi-additive method. Further, since the thickness of the ultrathin copper layer is thin, it is easy to remove the ultrathin copper layer, and it is easy to form a circuit on the coreless substrate by using the semi-additive method after removing the ultrathin copper layer. ..
In addition, in this specification, a "laminate body" which is not particularly described as "laminate body A" or "laminate body B" indicates a laminated body including at least a laminated body A and a laminated body B.

In the above-mentioned method for manufacturing a coreless substrate, a printed wiring board is manufactured by a build-up method by covering a part or all of the end faces of the copper foil with a carrier or the above-mentioned laminate (including the laminate A) with a resin. In this case, it is possible to prevent the chemical solution from seeping between one carrier-attached copper foil and another carrier-attached copper foil constituting the intermediate layer or the laminate, and the ultra-thin copper layer due to the infiltration of the chemical solution. Separation of carriers and corrosion of copper foil with carriers can be prevented, and yield can be improved. As the "resin that covers a part or all of the end face of the copper foil with a carrier" or "the resin that covers a part or all of the end face of the laminate" used here, a resin that can be used for the resin layer or a known resin is used. Can be used. Further, in the above-mentioned method for manufacturing a coreless substrate, when the copper foil or laminate with a carrier is viewed in a plan view, the laminated portion of the copper foil or laminate with a carrier (the laminated portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery (a laminated portion of the copper foil with a carrier and another copper foil with a carrier) may be covered with a resin or a prepreg. Further, the laminated body (laminated body A) formed by the above-mentioned method for manufacturing a coreless substrate may be formed by contacting a pair of copper foils with carriers so as to be separable from each other. Further, when viewed in a plan view of the copper foil with a carrier, a laminated portion of the copper foil with a carrier or a laminated body (a laminated portion of a carrier and an ultrathin copper layer, or a copper foil with a carrier and another copper with a carrier). It may be covered with a resin or a prepreg over the entire outer periphery of the laminated portion (the laminated portion with the foil) or the entire surface of the laminated portion. Further, when viewed in a plan view, the resin or prepreg is preferably larger than the laminated portion of the copper foil or laminate or laminate with a carrier, and the resin or prepreg is laminated on both sides of the copper foil or laminate with a carrier and the carrier. It is preferable to use a laminated body having a structure in which the attached copper foil or the laminated body is bound (wrapped) with a resin or a prepreg. With such a configuration, when the copper foil or laminate with a carrier is viewed in a plan view, the laminated portion of the copper foil or laminate with a carrier is covered with resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the carrier from hitting from the lateral direction with respect to the laminating direction, and as a result, it is possible to reduce the peeling of the carrier and the ultrathin copper layer or the copper foil with the carrier during handling. Further, by covering the outer periphery of the laminated portion of the copper foil with a carrier or the laminated body with a resin or a prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated portion in the chemical solution treatment step as described above. , Corrosion and erosion of copper foil with carrier can be prevented. When separating one copper foil with a carrier from a pair of copper foils with a carrier of a laminated body, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), use a resin or a prepreg. The covered copper foil with carrier or the laminated part of the laminate (the laminated part of the carrier and the ultrathin copper layer, or the laminated part of one copper foil with carrier and another copper foil with carrier) is made of resin or If it is firmly adhered by a prepreg or the like, it may be necessary to remove the laminated portion or the like by cutting or the like.

The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention to form a laminate. Further, the carrier-side surface or the ultra-thin copper layer-side surface of the one carrier-attached copper foil and the carrier-side surface or the ultra-thin copper layer-side surface of the other carrier-attached copper foil are, if necessary. It may be a laminated body obtained by directly laminating through an adhesive. Further, the carrier or ultra-thin copper layer of the one carrier-attached copper foil may be bonded to the carrier or ultra-thin copper layer of the other carrier-attached copper foil. Here, the "bonding" also includes an embodiment in which the carrier or the ultrathin copper layer is bonded to each other via the surface-treated layer when the carrier or the ultrathin copper layer has the surface-treated layer. Further, a part or all of the end face of the laminated body may be covered with the resin.

Lamination of carriers, ultra-thin copper layers, carriers and ultra-thin copper layers, and carrier-attached copper foils can be performed by, for example, the following method, in addition to simply laminating.
(A) Metallic joining method: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, Friction stirring welding), brazing;
(B) Mechanical joining method: caulking, joining by rivets (joining by self-piercing rivets, joining by rivets), stitcher;
(C) Physical bonding method: Adhesive, (double-sided) adhesive tape

By joining a part or all of one carrier and a part or all of the other carrier or a part or all of the ultrathin copper layer by using the above-mentioned joining method, one carrier and the other carrier or pole It is possible to produce a laminated body formed by laminating thin copper layers and contacting the carriers with each other or the carriers and the ultrathin copper layer in a separable manner. When one carrier and the other carrier or ultrathin copper layer are weakly bonded and one carrier and the other carrier or ultrathin copper layer are laminated, one carrier and the other carrier or electrode are laminated. One carrier and the other carrier or ultrathin copper layer can be separated without removing the junction with the thin copper layer. When one carrier and the other carrier or ultra-thin copper layer are strongly bonded, the portion where one carrier and the other carrier or ultra-thin copper layer are bonded is cut or chemically polished (). One carrier can be separated from the other carrier or an ultrathin copper layer by removing the carrier by etching or the like or by mechanical polishing or the like.

Further, after forming the two layers of the resin layer and the circuit at least once in the laminated body configured as described above and forming the two layers of the resin layer and the circuit at least once, the laminated body is attached with a carrier. A printed wiring board having no core can be produced by carrying out a step of peeling the ultrathin copper layer or carrier from the copper foil. Two layers, a resin layer and a circuit, may be provided on one or both surfaces of the laminated body.
The resin substrate, resin layer, resin, and prepreg used in the above-mentioned laminate may be the resin layer described in the present specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in the present specification. Accelerators, dielectrics, reaction catalysts, cross-linking agents, polymers, prepregs, skeleton materials and the like may be included. The above-mentioned copper foil or laminate with a carrier may be smaller than the resin or prepreg or the resin substrate or the resin layer when viewed in a plan view.

The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base material phenol resin, a paper base material epoxy resin, or a synthetic fiber cloth base material for rigid PWB is used. Epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass non-woven composite base material epoxy resin, glass cloth base material epoxy resin, etc. are used, and polyester film, polyimide film, liquid crystal polymer (LCP) film for FPC. , Fluororesin, etc. can be used. When a liquid crystal polymer (LCP) film or a fluororesin film is used, the peel strength between the film and the copper foil with a carrier tends to be smaller than when a polyimide film is used. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, by covering the copper circuit with a coverlay after forming the copper circuit, the film and the copper circuit are less likely to be peeled off, and the peeling strength is lowered. It is possible to prevent the film from peeling off from the copper circuit.

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

-Method for producing carriers (Examples 1, 2, 4 and Comparative Examples 1 to 3)
A titanium rotary drum (electrolytic drum) was prepared. Next, the electrolytic drum and the electrodes were placed in the electrolytic cell at a predetermined distance between the poles around the drum. Next, electrolysis was performed in the electrolytic cell under the following conditions, and copper was deposited on the surface of the electrolytic drum while rotating the electrolytic drum.
<Electrolytic solution composition>
Copper: 80 g / L or more and 110 g / L or less Sulfuric acid: 70 g / L or more and 110 g / L or less Chlorine: 10 mass ppm or more and 100 mass ppm or less <Production conditions>
Current density: 50 A / dm ² or more and 200 A / dm ² or less Electrolyte temperature: 40 ° C or more and 70 ° C or less Electrolyte fluid linear velocity: 3 m / sec or more and 5 m / sec or less Electrolysis time: 0.5 minutes or more and 10 minutes or less Next, The copper deposited on the surface of the rotating electrolytic drum was stripped off to form a carrier.
The formation of the intermediate layer on the electrolytic copper foil, which will be described later, was carried out on the glossy surface side of the electrolytic copper foil.

-Making method of carrier (Example 3)
A copper ingot having a composition of 1200 wtppm of Sn added to oxygen-free copper specified in JIS H3100 is manufactured, hot-rolled at 800 ° C. or higher and 900 ° C. or lower, and then annealed on a continuous annealing line at 300 ° C. or higher and 700 ° C. or lower. Cold rolling was repeated once to obtain a rolled plate having a thickness of 1 mm or more and 2 mm or less. This rolled plate is annealed and recrystallized on a continuous annealing line at 600 ° C. or higher and 800 ° C. or lower, and finally cold-rolled to a thickness of 7 μm or higher and 50 μm or lower with a reduction ratio of 95% or higher and 99.7% or lower, and rolled copper. A foil was produced and used as a carrier.

-Controlling the surface of the carrier on the intermediate layer side In Example 2 and Comparative Example 1, a part of the carrier surface is used for the carrier by etching the surface of the carrier under the following conditions before providing the intermediate layer on the carrier. Rougher than the surface of the raw foil.
(Etching conditions)
Liquid composition: Sodium persulfate 50 g / L or more and 150 g / L or less, Sodium hydrogen sulfate 5 g / L or more and 20 g / L or less, Sulfuric acid 60 g / L or more and 180 g / L or less Liquid temperature: 25 ° C or more and 40 ° C or less Immersion time: 10 s or more 120 s or less In addition, in Example 4 and Comparative Example 1, the roughness of the carrier surface was made into a carrier by plating up the surface of the carrier by a thickness of 1 μm or more and 3 μm or less under the following conditions before providing an intermediate layer on the carrier. It was controlled to be smoother than the surface of the raw foil used.
(Plating up condition)
Copper concentration: 30 g / L or more and 120 g / L or less H ₂ SO ₄ concentration: 20 g / L or more and 120 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3 sulfopropyl) disulfide): 10 ppm or more and 30 ppm or less Leveling agent 2 (amine compound): 10 ppm or more and 30 ppm or less An amine compound having the following chemical formula was used as the amine compound.

（上記化学式中、Ｒ1及びＲ2はヒドロキシアルキル基、エーテル基、アリール基、芳香族置換アルキル基、不飽和炭化水素基、アルキル基からなる一群から選ばれるものである。）
電解液温度：２０℃以上８０℃以下
電流密度：１０Ａ／ｄｍ²以上１００Ａ／ｄｍ²以下

(In the above chemical formula, R1 and R2 are selected from a group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group and an alkyl group.)
Electrolyte temperature: 20 ° C or higher and 80 ° C or lower Current density: 10 A / dm ² or higher 100 A / dm ² or lower

-Formation of intermediate layer Next, in Example 2 and Comparative Example 1, a nickel sputtered film having a thickness of 50 nm was formed and then electroplated with a roll-to-roll type continuous plating line to obtain a nickel sputtered film. A Cr layer having an adhesion amount of 11 μg / dm ² was adhered onto the surface by electrolytic chromate treatment under the following conditions.
-Electrolytic chromate treatment Liquid composition: Potassium dichromate 1 g / L or more and 10 g / L or less, Zinc 0 g / L or more and 5 g / L or less pH: 3 or more and 4 or less Liquid temperature: 50 ° C or more and 60 ° C or less Current density: 0.1A / dm ² or more 2.6A / dm ² or less coulombs: 0.5As / dm ² or more 30AS / dm ² or less

In Examples 1, 3 and 4, and Comparative Examples 2 and 3, a Ni layer having an adhesion amount ^{of 4000 μg / dm 2} was electroplated on a roll-toe-roll type continuous plating line under the following conditions as an intermediate layer. Was formed.

-Ni layer Nickel sulfate: 250 g / L or more and 300 g / L or less Nickel chloride: 35 g / L or more and 45 g / L or less Nickel acetate: 10 g / L or more and 20 g / L or less Trisodium citrate: 15 g / L or more and 30 g / L or less Glossy Agents: Saccharin, butinediol, etc. Sodium dodecyl sulfate: 30 ppm or more and 100 ppm or less pH: 4 or more and 6 or less Liquid temperature: 50 ° C or more and 70 ° C or less Current density: 3 A / dm ² or more and 15 A / dm ² or less

^{After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm 2} was continuously attached onto the Ni layer on a roll-to-roll type continuous plating line by electrolytic chromate treatment under the following conditions. ..
-Electrolytic chromate treatment Liquid composition: Potassium dichromate 1 g / L or more and 10 g / L or less, Zinc 0 g / L or more and 5 g / L or less pH: 3 or more and 4 or less Liquid temperature: 50 ° C or more and 60 ° C or less Current density: 0.1A / dm ² or more 2.6A / dm ² or less coulombs: 0.5As / dm ² or more 30AS / dm ² or less

-Formation of ultra-thin copper layer After the intermediate layer was formed, an ultra-thin copper layer having a thickness of 0.8 μm or more and 5 μm or less was electroplated on the intermediate layer under the following conditions to obtain a copper foil with a carrier.
-Ultra-thin copper layer Copper concentration: 30 g / L or more and 120 g / L or less H ₂ SO ₄ concentration: 20 g / L or more and 120 g / L or less Chlorine: 50 ppm or more and 100 ppm or less Leveling agent 1 (bis (3 sulfopropyl) disulfide) : 10 ppm or more and 30 ppm or less Leveling agent 2 (amine compound): 10 ppm or more and 30 ppm or less An amine compound having the following chemical formula was used as the amine compound.

（上記化学式中、Ｒ1及びＲ2はヒドロキシアルキル基、エーテル基、アリール基、芳香族置換アルキル基、不飽和炭化水素基、アルキル基からなる一群から選ばれるものである。）
電解液温度：２０℃以上８０℃以下
電流密度：１０Ａ／ｄｍ²以上１００Ａ／ｄｍ²以下

(In the above chemical formula, R1 and R2 are selected from a group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group and an alkyl group.)
Electrolyte temperature: 20 ° C or higher and 80 ° C or lower Current density: 10 A / dm ² or higher 100 A / dm ² or lower

Electrolyte temperature: 20 ° C or higher and 80 ° C or lower Current density: 10 A / dm ² or higher 100 A / dm ² or lower

-Formation of surface-treated layer Next, in Examples 1 and 2 and Comparative Examples 1 to 3, the ultrathin copper layer was further roughened under any of the following conditions as shown in Tables 1 to 3. A treatment layer was provided.
Roughing conditions Liquid composition Cu: 10 g / L or more and 20 g / L or less Co: 1 g / L or more and 10 g / L or less Ni: 1 g / L or more and 10 g / L or less pH: 1 or more and 4 or less Liquid temperature: 50 ° C or more and 60 ° C Current density Dk: 30A / dm ² or more and 40A / dm ² or less Time: 0.2 seconds or more and 1 second or less

In Examples 3 and 4, a heat-resistant treatment layer, a chromate layer, and a silane coupling treatment layer were provided on the roughening treatment layer under the following conditions.
・ Heat-resistant treatment Zn: 0 g / L or more and 20 g / L or less Ni: 0 g / L or more and 5 g / L or less pH: 3.5
Temperature: 40 ° C
Current density Dk: 0A / dm ² or more and 1.7A / dm ² or less Time: 1 second Zn adhesion amount: 5μg / dm ² or more 250μg / dm ² or less Ni adhesion amount: 5μg / dm ² or more and 300μg / dm ² or less ・ Chromate Processing K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO _3): 2g / L or more 10 g / L or less NaOH or KOH: 10 g / L or more 50 g / L or less ZnO or _{ZnSO 4 7H 2 O: 0.05g /} L or more 10 g / L or less pH: 7 or more and 13 or less Liquid temperature: 20 ° C or more and 80 ° C or less Current density 0.05A / dm ² or more and 5A / dm ² or less Time: 5 seconds or more and 30 seconds or less Cr adhesion amount: 10 μg / dm ² or more and 150 μg / dm ² Below ・ Silane coupling treatment Vinyl triethoxysilane aqueous solution (vinyl triethoxysilane concentration: 0.1 wt% or more and 1.4 wt% or less)
pH: 4 or more and 5 or less Time: 5 seconds or more and 30 seconds or less

Each evaluation of each sample of the copper foil with a carrier obtained as described above was carried out by the following method.
-Surface roughness Sp, Sz, Rz
After the sample was thermocompression bonded to the insulating substrate at 220 ° C. for 90 minutes, the carrier was peeled off in accordance with JIS C 6471, and the surface of the carrier on the ultrathin copper layer side was surfaced with a laser microscope at 256 μm × 256 μm square. Roughness Sp, Sz, and Rz were measured, respectively.
The surface roughness (Sp, Sz, Rz) of the carrier was 8 points at 15 mm intervals in the TD direction (described as N1 to N8 in Tables 1 to 3) and 8 points at 15 mm intervals in the MD direction (Table 1). ~ 3 described as N1 to N8), a total of 16 points were measured. In Examples 1, 3 and Comparative Example 3, the carriers were measured as they were. In Example 2 and Comparative Example 1, the carriers were etched and then measured. In Example 4 and Comparative Example 2, the carriers were plated up with a blunt copper plating solution and then measured.

-Peeling strength The ultra-thin copper layer side is thermocompression bonded to the insulating substrate at 220 ° C. for 90 minutes at 1.5 MPa, and the sample is cut out by about 250 mm in the length direction and 50 mm in the width direction, and in the longitudinal direction (MD direction). The peel strength was measured by pulling under the following conditions. The peel strength was measured at intervals of 150 mm in the width direction, and each sample was measured 5 times (described as N1 to N5 in Tables 1 to 3).
-Measurement method: Method shown in JIS C 6471-Tension angle: 90 degrees-Speed: 50 mm / min
-Tension test equipment: Shimadzu Autograph Manufacturing conditions and evaluation results are shown in Tables 1 to 3.

(Evaluation results)
In Examples 1 to 4, the copper foil with a carrier was thermocompression-bonded to the insulating substrate at 220 ° C. for 90 minutes, and then the carrier was peeled off in accordance with JIS C 6471 with a laser microscope at 256 μm × 256 μm square. The surface roughness Sp of the measured carrier on the ultrathin copper layer side is 0.1 μm or more and 3.5 μm or less, and the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm. Therefore, a copper foil with a carrier was obtained in which the variation in the peeling strength of the carrier was satisfactorily suppressed.
In Comparative Examples 1, 2 and 3, since the standard deviation of the surface roughness Sp when the surface of the carrier was measured at 16 points exceeded 0.8 μm, the variation in the peel strength of the carrier was poor.

Claims (23)

A copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order.
The copper foil with a carrier is thermocompression-bonded to an insulating substrate at 220 ° C. for 90 minutes, and when the carrier is peeled off in accordance with JIS C 6471, the carrier is measured with a laser microscope at a size of 256 μm × 256 μm square. The surface roughness Sp on the ultrathin copper layer side is 0.1 μm or more and 3.5 μm or less, and the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.8 μm or less. Copper foil with carrier. The copper foil with a carrier according to claim 1, wherein the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.7 μm or less. The copper foil with a carrier according to claim 2, wherein the standard deviation of the surface roughness Sp when the surface of the carrier is measured at 16 points is 0.6 μm or less. The intermediate layer contains Ni
The intermediate layer copper foil with a carrier according to any one of claims 1 to 3 Ni deposition amount is 100 [mu] g / dm ² or more 40000μg / dm ² following. The intermediate layer contains Cr and contains Cr.
The copper foil with a carrier according to any one of claims 1 to 4, wherein the amount of Cr adhered to the intermediate layer is 1 μg / dm ² or more and 100 μg / dm ^{2 or less.} The surface roughness Sz on the ultrathin copper layer side of the carrier is 0.3 μm or more and 4.5 μm or less, and the standard deviation of the surface roughness Sz when the surface of the carrier is measured at 16 points is 1.0 μm or less. The copper foil with a carrier according to any one of claims 1 to 5. The surface roughness Rz on the ultrathin copper layer side of the carrier when measured on the surface perpendicular to the MD direction of the carrier is 0.1 μm or more and 2.2 μm or less, and the surface of the carrier is 16 points. The copper foil with a carrier according to any one of claims 1 to 6, wherein the standard deviation of the surface roughness Rz when measured is 0.3 μm or less. When the copper foil with a carrier according to any one of claims 1 to 7 has an ultrathin copper layer on one surface of the carrier, at least one surface of the ultrathin copper layer side and the carrier side, or , On both surfaces, or
When the copper foil with a carrier according to any one of claims 1 to 7 has an ultrathin copper layer on both surfaces of the carrier, the surface on the one or both ultrathin copper layer side surfaces.
The carrier according to any one of claims 1 to 7, which has one or more layers selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. Copper foil. The carrier according to claim 8, wherein a resin layer is provided on one or more layers selected from the group consisting of the roughening treatment layer, the heat resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. Copper foil. The copper foil with a carrier according to claim 8 or 9, wherein at least one of the rust preventive layer and the heat resistant layer contains one or more elements selected from nickel, cobalt, copper, and zinc. The copper foil with a carrier according to any one of claims 1 to 7, wherein a resin layer is provided on the ultrathin copper layer. The copper foil with a carrier according to claim 9 or 11, wherein the resin layer contains a dielectric. The method for producing a copper foil with a carrier according to any one of claims 1 to 12 , wherein a carrier, an intermediate layer, and an ultrathin copper layer are provided in this order.
A step of adjusting the surface roughness of the carrier by etching the surface of the carrier or plating up copper on the surface of the carrier.
A step of providing the intermediate layer and the ultrathin copper layer on the etched or plated surface side of the carrier in this order.
A method for manufacturing a copper foil with a carrier including. A method for producing a laminate using the copper foil with a carrier according to any one of claims 1 to 12. A method for manufacturing a printed wiring board using the copper foil with a carrier according to any one of claims 1 to 12. A laminate containing the carrier-attached copper foil and the resin according to any one of claims 1 to 12, wherein a part or all of the end faces of the carrier-attached copper foil is covered with the resin. .. The copper foil with a carrier according to any one of claims 1 to 12 is attached to the copper foil with a carrier according to any one of claims 1 to 12 from the carrier side or the ultrathin copper layer side. A laminate laminated on the carrier side or the ultrathin copper layer side of a copper foil. A method for manufacturing a printed wiring board using the laminate according to claim 16 or 17. A step of providing the laminate according to claim 16 or 17 with two layers of a resin layer and a circuit at least once, and
A method for producing a printed wiring board, which comprises a step of forming the resin layer and the two layers of a circuit at least once, and then peeling the ultrathin copper layer or the carrier from the carrier-attached copper foil of the laminate. The step of preparing the copper foil with a carrier and the insulating substrate according to any one of claims 1 to 12.
The process of laminating the copper foil with carrier and the insulating substrate,
After laminating the copper foil with a carrier and the insulating substrate, a copper-clad laminate is formed through a step of peeling off the carrier of the copper foil with a carrier.
Then, a method for manufacturing a printed wiring board, which comprises a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partial additive method, and a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 12.
A step of forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier so that the circuit is buried.
The step of peeling off the carrier or the ultrathin copper layer, and
After the carrier or the ultrathin copper layer is peeled off, the ultrathin copper layer or the carrier is removed, so that the carrier or the ultrathin copper layer is buried in the resin layer formed on the surface on the ultrathin copper layer side or the surface on the carrier side. A method of manufacturing a printed wiring board including a process of exposing a circuit. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 12 with a resin substrate.
A step of providing at least once two layers of a resin layer and a circuit on the surface on the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with a carrier or on the surface on the carrier side, and
A method for manufacturing a printed wiring board, which comprises a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit at least once. A method for manufacturing an electronic device using a printed wiring board manufactured by the method for manufacturing a printed wiring board according to any one of claims 15 and 18 to 22.

Images