JP6438208B2 - Copper foil with carrier, copper-clad laminate using the same, printed wiring board, electronic device, and method for manufacturing printed wiring board - Google Patents

Description

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

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After forming a circuit pattern with a resist on the exposed ultrathin copper layer, a fine circuit is formed by a technique (MSAP: Modified-Semi-Additive-Process) of etching and removing the ultrathin copper layer with a sulfuric acid-hydrogen peroxide-based etchant. Is formed.

  Here, for the surface of the ultra-thin copper layer of the copper foil with carrier, which becomes the adhesive surface with the resin, the peel strength between the ultra-thin copper layer and the resin substrate is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like. As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.

  However, if a very thin copper layer with such a large profile (irregularity, roughness) is used on a semiconductor package substrate that needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles during circuit etching Will remain, causing problems such as poor insulation between circuit patterns.

  For this reason, in WO2004 / 005588 (Patent Document 1), a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. Therefore, the further improvement is calculated | required about copper foil with a carrier.

  Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-006071 (Patent Document 3), the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been. By providing these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultrathin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.

WO2004 / 005588 JP 2007-007937 A JP 2010-006071 A

  In the development of a copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the resin substrate. For this reason, the fine pitch has not been sufficiently studied yet, and there is still room for improvement. Then, this invention makes it a subject to provide the copper foil with a carrier suitable for fine pitch formation. Specifically, it is an object to provide a copper foil with a carrier capable of forming finer wiring than L (line) / S (space) = 15 μm / 15 μm, which has been considered to be a limit that can be formed by conventional MSAP. And

  In order to achieve the above object, the present inventors have conducted extensive research and found that the surface of the ultrathin copper layer has a low roughness and that the thickness accuracy of the ultrathin copper layer is controlled. It was found to be extremely effective for fine pitch formation.

  The present invention has been completed on the basis of the above knowledge, and in one aspect, a carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and a weight thickness method The thickness accuracy of the ultra-thin copper layer measured in (1) is 3.0% or less, and the surface of the ultra-thin copper layer is a carrier whose Rz measured by a non-contact type roughness meter of at least one side is 0.5 μm or less. It is a copper foil.

  Another aspect of the present invention is a copper foil with a carrier provided with a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the ultrathin copper measured by a four-probe method The thickness accuracy of the layer is 10.0% or less, and the surface of the ultrathin copper layer is a copper foil with a carrier having an Rz of 0.5 μm or less as measured with a non-contact roughness meter on at least one side.

  In one embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer surface has an Rz measured by a non-contact type roughness meter on both sides of 0.5 μm or less.

  In another embodiment of the copper foil with a carrier of the present invention, the surface of the ultrathin copper layer has an Ra measured by a non-contact type roughness meter of 0.12 μm or less.

  In another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer surface has an Rt measured by a non-contact type roughness meter of 1.0 μm or less.

  Still another aspect of the present invention is a copper foil with a carrier provided with a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the ultrathin copper measured by a weight thickness method The thickness accuracy of the layer is 3.0% or less, and the surface of the ultrathin copper layer is a copper foil with a carrier having Ra of 0.12 μm or less measured with a non-contact type roughness meter on at least one side.

  In another aspect of the present invention, a carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, the ultrathin measured by a four-probe method. The thickness accuracy of the copper layer is 10.0% or less, and the surface of the ultrathin copper layer is a copper foil with a carrier whose Ra measured by a non-contact type roughness meter on at least one side is 0.12 μm or less.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the surface of the ultrathin copper layer has an Ra measured by a non-contact type roughness meter on both sides of 0.12 μm or less.

  In another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer surface has an Rt measured by a non-contact type roughness meter of 1.0 μm or less.

  Still another aspect of the present invention is a copper foil with a carrier provided with a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the ultrathin copper measured by a weight thickness method The thickness accuracy of the layer is 3.0% or less, and the surface of the ultrathin copper layer is a copper foil with a carrier having an Rt of 1.0 μm or less measured with a non-contact roughness meter on at least one side.

  In another aspect of the present invention, a carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, the ultrathin measured by a four-probe method. The thickness accuracy of the copper layer is 10.0% or less, and the surface of the ultrathin copper layer is a copper foil with a carrier having an Rt of 1.0 μm or less measured with a non-contact roughness meter on at least one side.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the surface of the ultrathin copper layer has an Rt of 1.0 μm or less measured with a non-contact type roughness meter on both sides.

  In another embodiment of the copper foil with a carrier of the present invention, the carrier is formed of a film.

  In another embodiment of the copper foil with a carrier of the present invention, Rz of the surface on the intermediate layer side of the carrier is 0.5 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, Ra of the surface on the intermediate layer side of the carrier is 0.12 μm or less.

  In another embodiment of the copper foil with a carrier of the present invention, Rt of the intermediate layer side surface of the carrier is 1.0 μm or less.

  In still another embodiment, the carrier-attached copper foil of the present invention has a roughened layer on at least one surface of the ultrathin copper layer and the carrier, or on both surfaces.

  In yet another embodiment of the copper foil with a carrier according to the present invention, a circuit finer than line / space = 15 μm / 15 μm can be formed by a semi-additive method using an ultrathin copper layer.

  In yet another embodiment of the carrier-attached copper foil of the present invention, the roughening layer is any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc. It is a layer made of a simple substance or an alloy containing any one or more or a layer containing an alloy containing any one or more.

  In yet another embodiment, the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. It has the above layers.

  In yet another embodiment of the copper foil with a carrier according to the present invention, a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a silane cup are provided on at least one surface of the ultrathin copper layer and the carrier, or both surfaces. It has 1 or more types of layers selected from the group which consists of a ring process layer.

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

  In yet another embodiment, the carrier-attached copper foil of the present invention includes a resin layer on the roughening treatment layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention is a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. Is provided.

  In another embodiment of the carrier-attached copper foil of the present invention, the resin layer is an adhesive resin.

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

  In yet another aspect, the present invention is a copper clad laminate produced using the carrier-attached copper foil of the present invention.

  In yet another aspect, the present invention is a printed wiring board manufactured using the carrier-attached copper foil of the present invention.

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

  In yet another aspect of the present invention, the step of preparing the copper foil with carrier and the insulating substrate of the present invention, the step of laminating the copper foil with carrier and the insulating substrate, the laminating of the copper foil with carrier and the insulating substrate. Later, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a circuit is formed by any of the semi-additive method, subtractive method, partly additive method, or modified semi-additive method It is a manufacturing method of a printed wiring board including the process to do.

  In still another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier of the present invention, the ultrathin copper layer of the copper foil with carrier so that the circuit is buried. A step of forming a resin layer on a side surface, a step of forming a circuit on the resin layer, a step of peeling the carrier after forming a circuit on the resin layer, and after peeling the carrier, It is a manufacturing method of a printed wiring board including the process of exposing the circuit buried in the resin layer formed in the ultra-thin copper layer side surface by removing the ultra-thin copper layer.

  In one embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is performed by laminating another copper foil with a carrier on the resin layer from the ultrathin copper layer side. In this step, the circuit is formed using a copper foil with a carrier bonded to a layer.

  In another embodiment of the method for producing a printed wiring board of the present invention, another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier of the present invention.

  In still another embodiment of the method for producing a printed wiring board of the present invention, the step of forming a circuit on the resin layer is any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Done by the method.

  In yet another embodiment of the method for producing a printed wiring board of the present invention, the copper foil with carrier for forming a circuit on the surface has a substrate or a resin layer on the surface of the carrier of the copper foil with carrier.

  It is possible to form a wiring finer than L / S = 20 μm / 20 μm, for example, a fine wiring of L / S = 15 μm / 15 μm, and the thickness of the ultrathin copper layer on the carrier is excellent. I will provide a.

It is an example of the structure of the copper foil with a carrier of this invention. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention. It is a schematic diagram which shows the carrying method based on the manufacturing method of the copper foil with a carrier which concerns on Embodiment 2 of this invention. It is a schematic diagram which shows the conventional ninety-fold folding method. It is the schematic of the cross section of the width direction of the circuit pattern in an Example, and the outline of the calculation method of the etching factor (EF) using this schematic diagram. AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

<Career>
As the carrier of the present invention, it is preferable to use a carrier whose Rz on the intermediate layer side surface is 0.5 μm or less. According to such a configuration, it becomes easy to control Rz of one surface or both surfaces of the intermediate layer formed on the carrier to 0.5 μm or less. Rz on the intermediate layer side surface of the carrier is more preferably 0.3 μm or less, and even more preferably 0.1 μm or less.
Moreover, it is preferable to use the carrier of the present invention in which Ra on the intermediate layer side surface is 0.12 μm or less. According to such a configuration, it becomes easy to control Ra on one surface or both surfaces of the intermediate layer formed on the carrier to 0.12 μm or less. Ra of the intermediate layer side surface of the carrier is more preferably 0.1 μm or less, still more preferably 0.08 μm or less, and even more preferably 0.05 μm or less.
Moreover, it is preferable to use the carrier of the present invention in which Rt on the intermediate layer side surface is 1.0 μm or less. According to such a configuration, it becomes easy to control Rt of one surface or both surfaces of the intermediate layer formed on the carrier to 1.0 μm or less. Rt of the intermediate layer side surface of the carrier is more preferably 0.5 μm or less, and even more preferably 0.3 μm or less.
As the carrier of the present invention, it is preferable to use a film such as a resin film, and it is particularly preferable to use a film having surface smoothness. As such a film carrier, in general, a heat resistant film that can withstand a thermal load during dry surface treatment, wet surface treatment, or laminating press during substrate production is preferable, and a polyimide film or the like can be used. .
The material used for the polyimide film is not particularly limited. For example, Ube Industries Upilex, DuPont / Toray DuPont Kapton, Kaneka Apical, etc. are marketed, and any polyimide film can be applied. Moreover, the film which can be used for the carrier of this invention is not limited to such a specific kind.
When using a polyimide film, the film surface can be subjected to plasma treatment to remove contaminants on the film surface and to modify the surface. Rz on the surface of the polyimide film after the plasma treatment depends on the difference in material and the difference in initial surface roughness, but Rz = 2.5 to 500 nm, Ra = 1 to 100 nm, or Rt = 5 It can adjust in the range of -800 nm. Moreover, by obtaining in advance the relationship between the plasma treatment conditions and the surface roughness, it is possible to obtain a polyimide film having a desired surface roughness by performing plasma treatment under predetermined conditions.

Moreover, a metal foil can be used as the carrier of the present invention. As the metal foil, copper foil, nickel foil, nickel alloy foil, aluminum foil, aluminum alloy foil, iron foil, iron alloy foil, zinc foil, zinc alloy foil, stainless steel foil and the like can be used. Moreover, a copper foil can be used as the carrier of the present invention. The copper foil is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020), for example, copper containing Sn, copper containing Ag, Cr, Zr, Mg, etc. A copper alloy such as an added copper alloy or a Corson copper alloy added with Ni, Si, or the like can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.
The rolled copper foil used as the carrier of the present invention can be produced by high gloss rolling.
High gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13,000 to 24000 or less. When the surface roughness (Rz) of the copper foil after the surface treatment is desired to be smaller (for example, Rz = 0.20 μm), the oil film equivalent defined by the following formula is set to 12000 to 24000 for high gloss rolling. To do.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 12000 to 24000, a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used.

Moreover, an example of the manufacturing conditions of the electrolytic copper foil used as the carrier of the present invention is shown below.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100mg / L
Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 to 50 mg / L
Leveling agent 2 (dialkylamino group-containing polymer): 10 to 50 mg / L
As the dialkylamino group-containing polymer, for example, a dialkylamino group-containing polymer having the following chemical formula can be used.

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

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes Moreover, JX Nippon Mining & Metals HLP foil is mentioned as an electrolytic copper foil which can be used for this invention.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 25 μm or more. However, if it is too thick, the production cost becomes high, so it is generally preferable that the thickness is 50 μm or less. Thus, the thickness of the carrier is typically 12-300 μm, more typically 12-150 μm, even more typically 12-100 μm, and more typically 25-50 μm, More typically, it is 25 to 38 μm.

<Intermediate layer>
An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, From hydrates or oxides or organic substances of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can comprise by forming the layer which becomes.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co , Fe, Mo, Ti, W, P, Cu, Al, and Zn can be formed by forming an alloy layer made of one or more elements selected from the group of elements.
When the intermediate layer is provided only on 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 attached metal such as chromium and zinc may be hydrates or oxides.
Further, for example, the intermediate layer can be configured 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 peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents 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 Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.

  The intermediate layer is preferably composed of two layers of a metal layer or an alloy layer and an oxide layer formed thereon. In this case, the metal layer or alloy layer is formed in contact with the interface with the film carrier, and the oxide layer is formed in contact with the interface with the ultrathin copper layer.

  The intermediate layer can be obtained by dry surface treatment such as sputtering, CVD and PVD, or wet surface treatment such as electroplating, electroless plating and immersion plating.

<Ultrathin 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 ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. In addition, when forming an ultrathin copper layer by wet plating, an ultrathin copper layer is formed in a copper plating bath containing chlorine, an organic sulfur compound as a leveling agent, and an organic nitrogen compound as a leveling agent. There is a need. For example, the composition and plating conditions of a copper plating bath that can be used for wet plating in the present application are as follows.

Copper plating bath Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Cl concentration: 30-80 mg / L
Bis (3-sulfopropyl) disulfide disodium concentration: 10-50 mg / L
Dialkylamino group-containing polymer represented by the following structural formula: 10 to 50 mg / L

-Copper plating conditions Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²
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 0.5-12 μm, more typically 2-5 μm. The ultra thin copper layer may be provided on both sides of the carrier.

<Roughening treatment and other surface treatment>
A roughening treatment layer can be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve adhesion to the insulating substrate. Another layer may be provided between the ultrathin copper layer and the roughened layer.
Moreover, you may provide a roughening process layer by performing the roughening process on the surface of a carrier. According to such a configuration, when performing the process of laminating the copper foil with a carrier of the present invention on the resin substrate from the carrier side, the adhesion between the carrier and the resin substrate is improved, and in the manufacturing process of the printed wiring board, the carrier and It becomes difficult to peel off from the resin substrate.
The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment layer is preferably composed of fine particles from the viewpoint of fine pitch formation.
The roughening treatment layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or a layer made of an alloy containing at least one of them. It may be a layer containing an alloy containing more than seeds. Further, after forming roughened particles with copper or a copper alloy on the surface of the ultrathin copper layer and / or the carrier surface, further providing secondary particles or tertiary particles with a simple substance or alloy of nickel, cobalt, copper, zinc, etc. Can also be performed. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).
Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. 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. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. 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% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino 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 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, 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-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

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

  In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-1111169, 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, JP2013-19056A. be able to.

  The surface of the ultrathin copper layer after various surface treatments such as roughening treatment (in the present invention, when the surface of the ultrathin copper layer is subjected to various surface treatments such as roughening treatment, "The surface of the ultrathin copper layer" and "the surface of the ultrathin copper layer" mean the surface of the ultrathin copper layer after various surface treatments such as roughening treatment). It is extremely advantageous from the viewpoint of fine pitch formation that Rz (ten-point average roughness) is 0.5 μm or less when both surfaces are measured with a non-contact type roughness meter. Rz is preferably 0.3 μm or less, and more preferably 0.1 μm or less. However, if Rz is too small, the adhesive strength with the resin is reduced, and therefore it is necessary to select it appropriately in combination with the resin of the substrate to be used. The lower limit of Rz is not particularly required to be set. For example, Rz is 0.0001 μm or more, such as 0.0005 μm or more, such as 0.0010 μm or more, such as 0.005 μm or more, such as 0.007 μm or more.

  The surface of the ultra-thin copper layer after various surface treatments such as roughening treatment is Ra (arithmetic mean roughness) when measured with a non-contact type roughness meter on at least one side, preferably both sides, on another side. ) Is 0.12 μm or less from the viewpoint of fine pitch formation. Ra is preferably 0.1 μm or less, more preferably 0.08 μm or less, and even more preferably 0.05 μm or less. However, if Ra becomes too small, the adhesive strength with the resin is lowered, so that appropriate selection is required depending on the combination with the resin of the substrate to be used. The lower limit of Ra does not need to be set in particular. For example, Ra is 0.0001 μm or more, such as 0.0005 μm or more, such as 0.0010 μm or more, such as 0.005 μm or more, such as 0.007 μm or more.

  The surface of the ultrathin copper layer after being subjected to various surface treatments such as roughening treatment, on one other side, at least one side, preferably both sides when measured with a non-contact type roughness meter, Rt is 1.0 μm. The following is extremely advantageous from the viewpoint of fine pitch formation. Rt is preferably 0.5 μm or less, more preferably 0.3 μm or less. However, if Rt is too small, the adhesive strength with the resin is reduced, and therefore it is necessary to select it appropriately in combination with the resin of the substrate to be used. The lower limit of Rt need not be set, but for example, Rt is 0.0001 μm or more, such as 0.0005 μm or more, such as 0.0010 μm or more, such as 0.005 μm or more, such as 0.007 μm or more.

As described above, the surface of the ultrathin copper layer does not control the roughness of Rz, Ra, and Rt independently, but controls Rz and Ra, Ra and Rt, or Rz, Ra, and Rt. By doing so, it becomes possible to form a fine pitch more satisfactorily.
In the present invention, Rz on the surface of the ultrathin copper layer is measured with a non-contact type roughness meter in accordance with JIS B0601-1994, and roughness parameters of Ra and Rt are measured in accordance with JIS B0601-2001.

  In this way, the copper foil with a carrier according to the present invention in which the roughness of Rz, Ra and / or Rt on the surface of the ultrathin copper layer is controlled is suitable for fine pitch formation, for example, formed in the MSAP process. It is possible to form a wiring finer than the line / space = 15 μm / 15 μm, which has been considered as a limit, for example, a fine wiring of line / space = 10 μm / 10 μm.

<Copper foil with carrier>
An example of the structure of the copper foil with a carrier of the present invention is shown in FIG. The copper foil with a carrier of the present invention shown in FIG. 1 includes a film carrier, an intermediate layer formed on the film carrier, and an ultrathin copper layer formed on the intermediate layer. The ultrathin copper layer is composed of a sputtered copper layer formed by sputtering and an electrolytic copper layer formed by electrolytic plating. Further, the surface of the ultrathin copper layer after the carrier-attached copper foil is attached to the resin substrate from the ultrathin copper layer side and the carrier is peeled is distinguished between the peeled surface side and the resin surface side.

<Method for producing copper foil with carrier>
Next, the manufacturing method of the copper foil with a carrier which concerns on this invention is demonstrated. FIG. 2 is a schematic diagram illustrating a foil handling method according to the method of manufacturing the copper foil with a carrier according to the first embodiment of the present invention. The manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention processes the surface of the elongate carrier conveyed in a length direction by a roll-toe-roll conveyance system, a carrier, on a carrier This is a method for producing a carrier-attached copper foil comprising an intermediate layer laminated on the intermediate layer and an ultrathin copper layer laminated on the intermediate layer. The manufacturing method of the copper foil with a carrier which concerns on Embodiment 1 of this invention forms an ultra-thin copper layer on the carrier surface by electroplating, forming an intermediate | middle layer by sputtering on the carrier conveyed with a conveyance roll, and supporting with a drum. Form. Next, a surface treatment layer is formed on the surface of the ultrathin copper layer by electrolytic plating while supporting the carrier with a drum. In each step, the treatment surface of the carrier supported by the drum also serves as the cathode, and each electrolytic plating is performed in a plating solution between this drum and an anode provided so as to face the drum.

  In the present invention, in order to transport a long copper foil carrier by a roll-to-roll transport system, it is transported while applying tension in the length direction of the carrier. The tension can be adjusted by applying torque by connecting each transport roll to a drive motor or the like. The conveyance tension of the copper foil carrier is preferably 0.01 to 0.2 kg / mm. When the conveyance tension is less than 0.01 kg / mm, the adhesion with the drum is weak, and it is difficult to form each layer in a desired thickness. Moreover, although it depends on the structure of the apparatus, problems such as slip are likely to occur, and further, winding of the carrier becomes loose, and problems such as winding slip are likely to occur. On the other hand, if the transport tension is more than 0.2 kg / mm, wrinkles are likely to occur even with a slight displacement of the copper foil carrier, which is not preferable from the viewpoint of device management. In addition, the winding is hard, and winding wrinkles are likely to occur. The carrier transport tension is more preferably 0.02 to 0.1 kg / mm.

  In Embodiment 1, the ultrathin copper layer and the surface treatment layer are both formed by electrolytic plating while supporting the carrier with a drum, but the invention is not limited to this. For example, as Embodiment 2, as shown in FIG. 3, the surface treatment layer may be formed by electrolytic plating using a ninety-fold folding method that does not support a conventional copper foil carrier by a drum. Good. However, in the second embodiment, both steps are not performed by a foil carrying method using a drum as in the first embodiment. Therefore, compared to the first embodiment, the distance between the electrodes at the time of electrolytic plating is made constant. However, the thickness accuracy of the ultrathin copper layer and / or the surface treatment layer is inferior. FIG. 4 shows a method in which the ultrathin copper layer and the surface treatment layer are formed using a ninety-fold folding method that does not support a conventional copper foil carrier by a drum. In addition, in the case of the foil carrying method by the 99-fold, the carrying tension and the next carrying when the electroplating is performed by setting the carrying tension high (for example, 0.15 to 0.2 kg / mm). By making the distance from the roll shorter (for example, 500 to 1800 mm) than before, it is possible to manufacture a copper foil with a carrier with excellent thickness accuracy of the ultrathin copper layer and / or the surface treatment layer.

  In the present invention, as described above, the distance between the anode and the cathode in the electrolytic plating is stabilized by supporting the carrier with the drum. For this reason, the variation in the thickness of the layer to form is suppressed favorably, and it becomes possible to produce a copper foil with a carrier having an extremely thin copper layer with high thickness accuracy. Further, in the case of electrolytic plating using a 99-fold folding method, the distance between the conveying rolls is shortened, the guide rolls are used to prevent the shake of the foil, and the conveying tension is set to the usual 3 By making it 5 times, the plate-thickness accuracy can be improved by stabilizing the distance between the anode and the cathode in electrolytic plating.

The copper foil with a carrier thus prepared has an extremely thin copper layer thickness accuracy of 3.0% or less, preferably 2.0% or less, measured by the weight-thickness method, and the thickness accuracy is very good. ing. The lower limit is not particularly limited, but is, for example, 0.05% or more, 0.1% or more, or 0.2% or more.
Here, a method for measuring thickness accuracy by the weight-thickness method will be described. First, after measuring the weight of the copper foil carrier and the copper foil with carrier, peel off the ultrathin copper layer, measure the weight of the copper foil carrier again, and define the difference between the former and the latter as the weight of the ultrathin copper layer To do. The ultrathin copper layer piece to be measured is a 5 cm square sheet punched out with a press. In order to investigate the weight-thickness accuracy, the average value of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) Obtain the standard deviation (σ). In addition, the calculation formula of weight thickness accuracy shall be the following formula.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method is 0.2%.

Moreover, the copper foil with a carrier produced in this way has an extremely thin copper layer thickness accuracy of 10.0% or less, preferably 6.0% or less, as measured by the four-probe method, and has extremely high thickness accuracy. It is good. The lower limit is not particularly limited, but is, for example, 0.05% or more, 0.5% or more, 0.7% or more, or 1.0% or more.
Here, a method for measuring thickness accuracy by the four-probe method will be described. First, after determining the thickness of the copper foil carrier and the copper foil with carrier by measuring the thickness resistance with a four-point probe, peel off the ultra-thin copper layer and measure the thickness due to the thickness resistance of the copper foil carrier again. The difference between the former and the latter is defined as the thickness of the ultrathin copper layer. In order to investigate the thickness accuracy, measurements are made at intervals of 5 mm in the width direction for each level, and an average value and standard deviation (σ) of a total of 280 measurement points are obtained. The 280 measurement points do not need to be set in one row, and may be provided in a plurality of rows according to the width dimension of the copper foil with a carrier. In addition, the calculation formula of the thickness accuracy by four probes is the following formula.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method is 1.0%.

Further, the carrier-attached copper foil comprising a carrier and an ultra-thin copper layer laminated on the intermediate layer on the carrier comprises a roughening treatment layer on the ultra-thin copper layer. Alternatively, one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be provided on the roughening treatment layer.
Further, a roughening treatment layer may be provided on the ultrathin copper layer, a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer, and a chromate treatment is performed on the heat resistance layer and the rust prevention layer. A layer may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be. The resin layer may be an insulating resin layer.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, or the like can be given as a preferable one. .

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, 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. No. 5-53218, 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, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

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

  The copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompressed to thermally cure the resin layer, and then the carrier is peeled off. Thus, the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.

  If this resin-attached copper foil with a carrier is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

  In addition, 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 used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.

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

  When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the 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 It may be difficult to ensure interlayer insulation between the two.

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

  Furthermore, as another product form of this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer After coating with a resin layer and making it into a semi-cured state, the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.

  The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The printed wiring board can be finally manufactured by etching the ultrathin copper layer adhered to the substrate into a desired conductor pattern.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  In one embodiment of a method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier 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 the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain 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, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

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

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

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

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

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

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
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 core by a method such as etching or plasma using a corrosive solution such as an acid;
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 unnecessary portions of a copper foil on a copper clad laminate by etching or the like.

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

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 6-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 6B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 6C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 7-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), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 7-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 7-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 8G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 8H, circuit plating is formed on the via fill as shown in FIGS. 6B and 6C.
Next, as shown to FIG. 8-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 9-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. 9K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second-layer circuit shown in FIG. 8H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

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

  The copper foil with carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil carrier of the copper foil with carrier. By having the said board | substrate or resin layer, since the copper foil with a carrier used for the first layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. The substrate or the resin layer is not particularly limited as long as it has an effect of supporting the carrier-attached copper foil 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 described in this specification A plate or an organic compound foil can be used.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

1. Production of copper foil with carrier <Example 1: Examples 1, 5, 9, 13, and Comparative Example 3>
A polyimide film (Upilex-S film manufactured by Ube Industries, Ltd .; thickness: 35 μm) was set in a vacuum apparatus, and after vacuum evacuation, plasma treatment was performed using oxygen.
Subsequently, a Cr layer having a thickness of 10 nm was formed on one side of the plasma-treated film by Cr sputtering. Thereafter, the Cr sputtered layer was treated in a chamber in an oxygen gas atmosphere to form chromium oxide on the surface, thereby forming an intermediate layer.
Further, Cu was sputtered on the surface of the Cr intermediate layer to form a Cu sputtered layer having a thickness of 1 μm. The sputtering conditions were a discharge voltage of 500 V, a discharge current of 15 A, and a degree of vacuum of 5 × 10 ⁻² Pa in Ar gas using a Cu target. After forming the Cu sputter layer, the 2 μm Cu plating layer is formed on the Cu sputter layer by electroplating on the roll-to-roll continuous plating line, and the total copper thickness is 3 μm. Was formed by electroplating under the following conditions to produce a copper foil with a carrier. In Example 13, the thickness of the Cu sputter layer was 2.5 μm, the thickness of the Cu plating layer of electrolytic plating was 2.5 μm, and the total copper thickness was 5 μm.
Electrolytic Cu plating layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Cl concentration: 30-80 mg / L
Bis (3-sulfopropyl) disulfide disodium concentration: 10-50 mg / L
Dialkylamino group-containing polymer (weight average molecular weight 8500): 10 to 50 mg / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²
After forming the ultrathin copper layer, the surface of the ultrathin copper layer was then subjected to the following roughening treatment 1, roughening treatment 2, heat treatment, chromate treatment, and silane coupling treatment in this order.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, heat-resistant treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

<Example 2: Examples 2, 6, 10, 14 and Comparative Example 4>
An intermediate layer and an ultrathin copper layer were formed on the polyimide film carrier in the same steps, methods and conditions as in Example 1. In Example 14, the thickness of the Cu sputter layer was 1.0 μm, the thickness of the Cu plating layer of electrolytic plating was 1.0 μm, and the total copper thickness was 2 μm.
Subsequently, the following heat-resistant treatment, chromate treatment, and silane coupling treatment were performed on the surface of the ultrathin copper layer in this order.
・ Heat-resistant treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

<Example 3: Examples 3, 7, 11, 15 and Comparative Example 5>
In place of the polyimide carrier of Example 2, 1 μm of Cu was used in the same processes, methods and conditions as Example 2 for rolled copper foil (Tough pitch copper (JIS H3100 alloy number C1100) foil made by JIS H3100, 18 μm thick) manufactured by JX Nippon Mining & Metals. After forming the sputter layer, a 2 μm Cu plating layer is formed on the Cu sputter layer by electrolytic plating on a roll-to-roll type continuous plating line, and an ultrathin copper layer having a total copper thickness of 3 μm is formed. Obtained. In Example 15, the thickness of the Cu sputter layer was 0.2 μm, the thickness of the Cu plating layer of electrolytic plating was 0.8 μm, and the total copper thickness was 1 μm. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 2 were performed in this order.

<Example 4: Examples 4, 8, 12, 16 and Comparative Example 6>
Instead of the polyimide carrier of Example 2, after forming a 1 μm Cu sputtered layer on the electrolytic copper foil (JX Nippon Mining & Metals HLP foil 18 μm thickness) in the same process, method and conditions as Example 2, On a roll-to-roll type continuous plating line, a Cu plating layer having a thickness of 2 μm was formed on the Cu sputter layer by electrolytic plating to obtain an ultrathin copper layer having a total copper thickness of 3 μm. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 2 were performed in this order.

<Example 5: Example 17>
In place of the polyimide carrier of Example 2, an intermediate layer is formed by the same steps, methods and conditions as Example 2 on rolled copper foil (JX Nippon Mining & Metals Tough Pitch Copper (JIS H3100 alloy number C1100) foil 18 μm thick). Subsequently, on the roll-to-roll type continuous plating line, a Cu plating layer of 3 μm was formed by electrolytic plating on the intermediate layer under the same method and conditions as in Example 2, and the total copper thickness was 3 μm. A thin copper layer was obtained. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were performed in this order.

<Example 6: Example 18>
Instead of the polyimide carrier of Example 2, an intermediate layer was formed on electrolytic copper foil (JX Nippon Mining & Metals HLP foil 18 μm thick) in the same process, method and conditions as in Example 2, and then roll tow -On a roll-type continuous plating line, a Cu plating layer having a thickness of 3 µm was formed on the intermediate layer by electrolytic plating to obtain an ultrathin copper layer having a total copper thickness of 3 µm. Next, the heat-resistant treatment, chromate treatment, and silane coupling treatment of Example 1 were performed in this order.

<Example 7: Example 19>
In place of the polyimide carrier of Example 2, an intermediate layer is formed by the same steps, methods and conditions as Example 2 on rolled copper foil (JX Nippon Mining & Metals Tough Pitch Copper (JIS H3100 alloy number C1100) foil 18 μm thick). Subsequently, on the roll-to-roll type continuous plating line, a Cu plating layer of 3 μm was formed by electrolytic plating on the intermediate layer under the same method and conditions as in Example 2, and the total copper thickness was 3 μm. A thin copper layer was obtained. Next, after performing the following roughening treatment 3, the heat treatment, chromate treatment and silane coupling treatment of Example 1 were carried out in this order.
・ Roughening 3
(Liquid composition 3)
Cu: 10 to 20 g / L
Ni: 5-15 g / L
Co: 5 to 15 g / L
(Electroplating condition 3)
Temperature: 25-60 ° C
Current density: 35 to 55 A / dm ²
Roughening coulomb amount: 5-50 As / dm ²
Plating time: 0.1 to 1.4 seconds

<Example 8: Example 20>
Instead of the polyimide carrier of Example 2, an intermediate layer was formed on electrolytic copper foil (JX Nippon Mining & Metals HLP Foil 18 μm thick) in the same steps, methods and conditions as in Example 4, On the tow-roll type continuous plating line, a 3 μm Cu plating layer was formed on the intermediate layer by electrolytic plating to obtain an ultrathin copper layer having a total copper thickness of 3 μm. Next, after performing the roughening treatment 3 of Example 7, the heat resistance treatment, the chromate treatment, and the silane coupling treatment of Example 1 were carried out in this order.

<Example 9: Comparative example 1>
Instead of the polyimide carrier of Example 1, electroplating is performed on a roll-to-roll continuous plating line on the shiny surface on electrolytic copper foil (JX Nippon Mining & Metals JTC foil 18 μm thick) under the following conditions: As a result, a Ni layer having an adhesion amount of 4000 μg / dm ² was formed.

-Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm ² was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 A · s / dm ²
On a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 5-9 A / dm ²
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, heat-resistant treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

<Example 10: Comparative example 2>
Instead of the polyimide film carrier of Example 2, an electrolytic copper foil (JX Nippon Mining & Metals JTC foil 18 μm thick) was used, except that a 1 μm Cu sputter layer was formed on the shiny surface of the electrolytic copper foil. The same treatment as 2 was performed.

  Here, as shown in Table 1, Examples 1 to 4 are manufactured by the method according to Embodiment 2 shown in FIG. 3 described above, and Examples 5 to 15 are the embodiments shown in FIG. 2 described above. Example 16 and Comparative Examples 1 to 6 are manufactured by the conventional method shown in FIG. 4 described above. Here, in all of the ultrathin copper layer forming step and the surface treatment layer forming step, Comparative Examples 1 to 4 are a transport roll above the plating bath shown in FIG. 4 and a transport roll (dip roll) in the plating bath. The distance (that is, the height of the upper conveying roll with respect to the dip roll) was 2500 mm, whereas in Example 16, the distance was as short as 1700 mm. Furthermore, in all of the ultrathin copper layer forming step and the surface treatment layer forming step, in Example 16, the conveyance tension was made three times higher than those of Comparative Examples 1 to 3.

2. Characteristic evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following method.

<Thickness of ultrathin copper layer and electrolytic copper plating layer>
The thicknesses of the ultrathin copper layer and the electrolytic copper plating layer of the produced copper foil with carrier were observed using FIB-SIM (magnification: 10,000 to 30000 times). By observing the cross sections of the ultrathin copper layer and the electrolytic copper plating layer, five points were measured at intervals of 30 μm, and the average value was obtained.

<Evaluation of thickness accuracy by weight-thickness method>
First, after measuring the weight of the support copper foil and ultrathin copper foil, peel off the ultrathin copper layer, measure the weight of the support copper foil again, and define the difference between the former and the latter as the weight of the ultrathin copper layer did. The ultra-thin copper layer piece to be measured was a 5 cm square sheet punched out with a press. In order to investigate the weight-thickness accuracy, the average value of the weight-thickness measurement values of the ultra-thin copper layer piece of 15 points in total, 5 points at equal intervals in the width direction and 3 points in the length direction (4 cm intervals) Standard deviation (σ) was determined. The formula for calculating the weight thickness accuracy was as follows.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method was 0.2%.
Moreover, HF-400 by A & D Co., Ltd. was used for the weight scale, and HAP-12 by Noguchi Press Co., Ltd. was used for the press machine.
The evaluation of the foil thickness uniformity is performed based on the thickness accuracy by the weight-thickness method. The thickness accuracy by the weight-thickness method is 3.00% or less as good, and the thickness accuracy greater than 3.00% is evaluated as bad. did.

<Evaluation of thickness accuracy by four-point probe method>
After determining the thickness of the supporting copper foil and the ultrathin copper foil by measuring the thickness resistance with four probes, peel off the ultrathin copper layer, and again measure the thickness due to the thickness resistance of the supporting copper foil, the former And the difference between the latter and the latter was defined as the thickness of the ultrathin copper layer. In order to investigate the thickness accuracy, an average value and a standard deviation (σ) of a total of 280 measurement points were obtained at intervals of 5 mm in the width direction for each level. The formula for calculating the thickness accuracy by the four-probe is as follows.
Thickness accuracy (%) = 3σ × 100 / average value The repeatability of this measurement method was 1.0%.
Moreover, OXFORDINSTRUMENTS CMI-700 was used for the four probes.

<Etching property>
A copper foil with a carrier was attached to a polyimide substrate and heat-pressed at 220 ° C. for 2 hours, and then the ultrathin copper layer was peeled off from the carrier. Subsequently, after applying a photosensitive resist to the surface of the ultra-thin copper layer on the polyimide substrate, 50 L / S = 5 μm / 5 μm wide circuits are printed by an exposure process to remove unnecessary portions of the copper layer. The etching process was performed under the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, the time until the circuit top width reached 4 μm was measured, and the circuit bottom width (the length of the base X) and the etching factor at that time were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 1 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. The etching factor is obtained by measuring 12 points in the circuit and taking an average value. Thereby, the quality of etching property can be determined easily. Also, by calculating the standard deviation of the 12 etching factors, it is possible to determine whether the linearity of the circuit formed by etching is good or bad.
In the present invention, an etching factor of 4 or more is etching property: ◯, 2.5 or more and less than 4 are etching property: Δ, less than 2.5 or calculation is impossible or circuit formation is impossible. -Evaluated. Moreover, it can be said that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. When the standard deviation of the etching factor was less than 0.8, the linearity was evaluated as ◯, when 0.8 to 1.2 or less was determined as the linearity: Δ, and 1.2 or more was determined as the linearity: x.

(Surface roughness)
For the carrier on which the intermediate layer is formed, the surface roughness of the intermediate layer (the surface roughness on the intermediate layer forming side of the carrier) is measured using a non-contact type roughness measuring instrument (LEXTOLS 4000 manufactured by Olympus). B0601-2001, Rz was measured according to JIS B0601-1994. Moreover, about the surface roughness of the intermediate | middle layer side and resin side of an ultra-thin copper layer, Ra and Rt are based on JIS B0601-2001 using a non-contact-type roughness measuring machine (the Olympus LEXTOLS4000), About Rz It measured based on JIS B0601-1994.
<Measurement conditions>
Cut-off: None Standard length: 257.9 μm
Reference area: 66524 μm ²
Measurement ambient temperature: 23-25 ° C

(Circuit formability)
Each copper foil with a carrier was laminated and pressed on an epoxy resin, and then the carrier was peeled and removed. 0.3 μm of the exposed ultrathin copper layer was removed by soft etching. Thereafter, after washing and drying, a dry film resist (manufactured by Hitachi Chemical Co., Ltd., trade name RY-3625) was laminated on the ultrathin copper layer. Exposure was performed at 15 mJ / cm ² , and liquid jet rocking was performed at 38 ° C. for 1 minute using a developer (sodium carbonate) to form resist patterns of various lines / spaces. Next, after plating up to a total copper thickness of 15 μm using copper sulfate plating (Cubrite 21 manufactured by JCU), the dry film resist was stripped with a stripping solution (sodium hydroxide). Thereafter, the ultrathin copper layer was etched away with a sulfuric acid-hydrogen peroxide etchant (CPE-800 manufactured by Mitsubishi Gas Chemical) to form various lines / spaces.
Test conditions and results are shown in Table 1.

(Evaluation results)
In each of Examples 1 to 20, the Rz of at least one surface of the ultrathin copper layer surface is 0.5 μm or less, and the thickness accuracy of the ultrathin copper layer measured by the weight-thickness method is 3.0% or less. The thickness accuracy of the ultra-thin copper layer measured by the four-probe method is 10.0% or less, and finer wiring than line / space = 15 μm / 15 μm can be formed, and the average etching factor Values and standard deviations were good values. In each of Examples 1 to 20, Ra on at least one surface of the ultrathin copper layer surface was 0.12 μm or less, and Rt on at least one surface of the ultrathin copper layer surface was 1.0 μm or less.
In Comparative Examples 1 and 2, Rz on both surfaces of the ultrathin copper layer exceeds 0.5 μm, and the thickness accuracy of the ultrathin copper layer measured by the weight thickness method exceeds 3.0%. The thickness accuracy of the ultra-thin copper layer measured by the four-probe method exceeds 10.0%, and it is impossible to form finer wiring than line / space = 15 μm / 15 μm, and the etching factor The average value and standard deviation were large. In Comparative Examples 1 and 2, Ra on both surfaces of the ultrathin copper layer exceeded 0.12 μm, and Rt on both surfaces of the ultrathin copper layer exceeded 1.0 μm. In Comparative Examples 3 to 6, the thickness accuracy of the ultrathin copper layer measured by the weight thickness method is greater than 3.0%, and the thickness accuracy of the ultrathin copper layer measured by the four probe method. Was larger than 10.0%, and the average value and standard deviation of the etching factor were large.

Claims (30)

A carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order,
The thickness accuracy of the ultra-thin copper layer measured by the weight-thickness method is 3.0% or less,
The ultra-thin copper layer surface is a copper foil with a carrier whose Ra measured by a non-contact roughness meter on at least one surface is 0.12 μm or less. A carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order,
The thickness accuracy of the ultrathin copper layer measured by the four-probe method is 10.0% or less,
The ultra-thin copper layer surface is a copper foil with a carrier whose Ra measured by a non-contact roughness meter on at least one surface is 0.12 μm or less. The ultra-thin copper layer surface, the copper foil with carrier according to claim 1 or 2 Ra measured by a non-contact type roughness meter duplex is less than 0.12 .mu.m. The copper foil with a carrier according to any one of claims 1 to 3 , wherein the ultrathin copper layer surface has an Rt measured by a non-contact type roughness meter of 1.0 µm or less. A carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order,
The thickness accuracy of the ultra-thin copper layer measured by the weight-thickness method is 3.0% or less,
The ultrathin copper layer surface is a copper foil with a carrier having an Rt of 1.0 μm or less measured with a non-contact roughness meter on at least one side. A carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order,
The thickness accuracy of the ultrathin copper layer measured by the four-probe method is 10.0% or less,
The ultrathin copper layer surface is a copper foil with a carrier having an Rt of 1.0 μm or less measured with a non-contact roughness meter on at least one side. The copper foil with a carrier according to claim 5 or 6 , wherein the ultrathin copper layer surface has an Rt measured by a non-contact roughness meter on both sides of 1.0 µm or less. The copper foil with a carrier according to any one of claims 1 to 7 , wherein the carrier is formed of a film. The copper foil with a carrier according to any one of claims 1 to 8 , wherein Rz of the surface on the intermediate layer side of the carrier is 0.5 µm or less. The copper foil with a carrier according to any one of claims 1 to 8 , wherein Ra of the surface on the intermediate layer side of the carrier is 0.12 µm or less. The copper foil with a carrier according to any one of claims 1 to 8 , wherein Rt of the surface on the intermediate layer side of the carrier is 1.0 µm or less. The ultra-thin copper layer and at least one surface of the carrier, or a copper foil with carrier according to any one of claims 1 to 11 on both surfaces with a roughened layer. The copper foil with a carrier according to any one of claims 1 to 12 , wherein a circuit finer than line / space = 15 µm / 15 µm can be formed by a semi-additive method using an ultrathin copper layer. The roughening treatment layer is a single layer selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer made of an alloy containing at least one of them. The copper foil with a carrier according to claim 12 , which is a layer containing an alloy containing one or more kinds. The copper with a carrier according to claim 12 or 14 , wherein the surface of the roughened layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. Foil. 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 are provided on at least one surface of the ultrathin copper layer and the carrier, or both surfaces. copper foil with carrier according to any one of claims 1 to 13 including. Copper foil with carrier according to any one of claims 1 to 13, comprising a resin layer on the ultra-thin copper layer. The copper foil with a carrier according to any one of claims 12 , 14 and 15 , comprising a resin layer on the roughening treatment layer. The copper foil with a carrier according to claim 15 or 16 , comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. Copper foil with carrier according to any one of the resin layer is an adhesive resin in which claims 17-19. The copper foil with a carrier according to any one of claims 17 to 20 , wherein the resin layer is a semi-cured resin. Copper-clad laminate produced using the copper foil with carrier according to any one of claims 1 to 21. Printed wiring board produced using the copper foil with carrier according to any one of claims 1 to 21. The electronic device manufactured using the printed wiring board of Claim 23 . A step of preparing the carrier-attached copper foil according to any one of claims 1 to 21 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Forming a circuit on the ultra-thin copper layer-side surface of the copper foil with carrier according to any one of claims 1 to 21
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. The step of forming a circuit on the resin layer includes attaching another carrier-attached copper foil on the resin layer from the ultrathin copper layer side, and using the carrier-attached copper foil attached to the resin layer to form the circuit. 27. The method for manufacturing a printed wiring board according to claim 26 , wherein the method is a forming step. The method for producing a printed wiring board according to claim 27 , wherein another carrier-attached copper foil to be bonded onto the resin layer is the carrier-attached copper foil according to any one of claims 1 to 21 . The print according to any one of claims 26 to 28 , wherein the step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, and a modified semi-additive method. A method for manufacturing a wiring board. The printed wiring board manufacturing method according to any one of claims 26 to 29 , wherein the copper foil with a carrier forming a circuit on the surface has a substrate or a resin layer on the surface of the carrier of the copper foil with the carrier.