JPWO2014136785A1 - Copper foil with carrier, copper-clad laminate using the same, printed wiring board, electronic device, and method for manufacturing printed wiring board - Google Patents

Abstract

A copper foil with a carrier suitable for fine pitch formation is provided. A carrier-attached copper foil provided with a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the ultrathin copper layer is Rz measured with a non-contact type roughness meter on at least one side Is a copper foil with a carrier of 0.5 μm or less.

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 can be reduced in roughness. And it discovered that the said copper foil with a carrier was very 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, wherein the ultrathin The copper layer surface is a copper foil with a carrier having an Rz of 0.5 μm or less measured with a non-contact roughness meter on at least one side.

  In one Embodiment of the copper foil with a carrier which concerns on this invention, Rz measured with the non-contact-type roughness meter of both surfaces is 0.5 micrometer or less as for the said ultra-thin copper layer surface.

  In 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 of 0.12 μm or less.

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

  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, wherein the ultrathin copper layer surface is at least one side non-coated. It is copper foil with a carrier whose Ra measured with the contact-type roughness meter is 0.12 micrometer or less.

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

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

  In yet 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, wherein the ultrathin copper layer surface is at least one side. It is a copper foil with a carrier whose Rt measured with the non-contact-type roughness meter is 1.0 micrometer or less.

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

  In still another embodiment of the carrier-attached copper foil according to the present invention, the carrier is formed of a film.

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

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

  In yet another embodiment of the carrier-attached copper foil according to the present invention, a roughening treatment layer is formed on at least one surface of the ultrathin copper layer surface.

  In still another embodiment of the carrier-attached copper foil according to the present invention, the roughening layer is any selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc. A layer composed of a simple substance, a layer composed of an alloy including at least one kind, or a layer comprising an alloy including at least one kind.

  In still another embodiment of the copper foil with a carrier according to the present invention, the surface of the ultrathin copper layer is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer. It has one or more layers.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the surface of the roughening treatment layer was selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. It has one or more layers.

  In another embodiment of the copper foil with a carrier according to the present invention, a resin layer is provided on the surface of the ultrathin copper layer.

  In another embodiment of the copper foil with a carrier according to the present invention, a resin layer is provided on the surface of the roughening treatment layer.

  In still another embodiment of the carrier-attached copper foil according to the present invention, the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the silane coupling-treated layer is provided. A resin layer is provided.

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

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

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

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

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

In another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention 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,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

In yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
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 Is the method.

  The carrier-attached copper foil according to the present invention is suitable for fine pitch formation. For example, wiring finer than the line / space = 15 μm / 15 μm, which was considered to be a limit that can be formed by the MSAP process, for example, line / space = 10 μm / It becomes possible to form a fine wiring of 10 μm.

It is an example of the structure of the copper foil with a carrier of this invention. 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 24,000. 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.

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

(In the above chemical formula, R ₁ and R ₂ are selected from 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 even more typically 25-50 μm. , More typically 25-38 μm.

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. As an intermediate | middle layer, it can be set as arbitrary intermediate | middle layers by dry-type surface treatment and wet surface treatment in copper foil with a carrier. For example, the intermediate layer is one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or an alloy thereof, a hydrate thereof, an oxide thereof, or an organic material. It is preferable to form with the layer containing. The intermediate layer may be composed of a plurality of layers.

  In one embodiment of the present invention, the intermediate layer is a single metal layer made of any one element of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al elements from the carrier side, Or, an alloy layer made of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, and Cr, Ni, Co, formed thereon It is comprised from the layer which consists of a hydrate or oxide of 1 or more elements selected from the element group of Fe, Mo, Ti, W, P, Cu, and Al.

  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 dry plating or electroplating (wet plating) using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, and copper cyanide. A copper sulfate bath is preferred because it is used in foil and copper foil can be formed at a high current density. 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>
On the surface of the ultrathin copper layer, a roughening treatment layer is provided by performing a roughening treatment, for example, for improving the adhesion to the insulating 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 a layer made of any single member selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer made of an alloy containing any one or more of them. It can be comprised with the layer containing the alloy containing any 1 type or more.

Further, after roughening treatment, secondary particles and tertiary particles and / or heat-resistant layer and / or rust preventive layer are formed with nickel, cobalt, copper, zinc alone or an alloy, and chromate treatment is performed on the surface. Treatment such as silane coupling treatment may be performed. 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.
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 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 Surface treatment described in 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 0.10 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.

<Resin layer>
Resin layer on ultrathin copper layer of copper foil with carrier of the present invention (surface treatment layer formed on ultrathin copper layer by surface treatment when ultrathin copper layer is surface-treated) May be provided. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive resin, that is, an adhesive, or an adhesive semi-cured (B stage state) insulating resin layer. 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. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, 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.

<Copper foil with carrier>
Thus, a carrier-attached copper foil including a carrier, a release layer laminated on the carrier, and an ultrathin copper layer laminated on the release layer is manufactured.
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, and an ultrathin copper layer in this order. 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.
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. 2-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. 2B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 2C, 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. 3D, 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. 3-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 3F, laser drilling is performed at a predetermined position of the resin layer to expose circuit plating and form a blind via.
Next, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 4-H, circuit plating is formed on the via fill as shown in FIGS. 2-B and 2-C.
Next, as shown to FIG. 4-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 5J, 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. 5K, 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. 4-H, and these circuits may be formed using 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.

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled.
(1) The color difference ΔE * ab based on JIS Z8730 on the surface of 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 is 45 or more.

  Here, the color differences ΔL, Δa, and Δb are respectively measured by a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ΔL: black and white, Δa: reddish green, Δb: yellow blue. ΔE * ab is expressed by the following formula using these color differences.

The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughened layer, the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolysis solution containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / Dm ² ), and the processing time can be shortened (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm ² ), and the processing time can be set long (20 to 40 seconds).

  When the color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, the contrast between the ultrathin copper layer and the circuit As a result, visibility is improved and circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

  When the color difference on the surface of the ultra-thin copper layer, roughened layer, heat-resistant layer, rust-proof layer, chromate-treated layer or silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear. , Visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 2-C, the circuit plating can be accurately formed at a predetermined position. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 5-J and 5-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

  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 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>
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 sputter layer having a thickness of 5 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.

Subsequently, the following roughening treatment 1, roughening treatment 2, heat treatment, chromate treatment, and silane coupling treatment were performed in this order on the surface of the 5 μm Cu sputter layer.
・ 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>
After forming a 5 μm Cu sputtered ultrathin copper layer on a polyimide film carrier in the same steps, methods and conditions as in Example 1, the heat treatment, chromate treatment and silane coupling treatment of Example 1 were performed in this order. went.

<Example 3>
After forming a 1 μm Cu sputtered layer on a polyimide carrier in the same steps, methods and conditions as in Example 1, subsequently, 2 μm by electrolytic plating on the Cu sputtered layer on a roll-to-roll type continuous plating line. The copper plating layer was formed, and an ultrathin copper layer having a total copper thickness of 3 μm was formed by electroplating under the following conditions to produce a copper foil with a carrier.
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 same roughening treatment 1, roughening treatment 2, heat treatment, chromate treatment, and silane coupling treatment in this order. .

<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 3. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 1 were performed in this order.

<Example 5>
Instead of the polyimide carrier of Example 4, 1 μm in the same steps, methods and conditions as in Example 4 for rolled copper foil (JX Nippon Mining & Metals Tough Pitch Copper (JIS H3100 alloy number C1100) foil 18 μm thickness) After forming the Cu sputtered layer, a 2 μm Cu plated layer was formed on the Cu sputtered layer by electrolytic plating on the roll-to-roll continuous plating line, and the total copper thickness was 3 μm. A layer was obtained. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 1 were performed in this order.

<Example 6>
Instead of the polyimide carrier of Example 4, after forming a 1 μm Cu sputter layer in the same steps, methods and conditions as Example 4 for electrolytic copper foil (JX Nippon Mining & Metals HLP foil 18 μm thickness), Subsequently, 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 1 were performed in this order.

<Example 7>
In place of the polyimide carrier of Example 4, an intermediate layer was formed in the same steps, methods and conditions as in Example 4 with respect to rolled copper foil (JX Nippon Mining & Metals Tough Pitch Copper (JIS H3100 alloy number C1100) foil 18 μm thick). Then, a 3 μm Cu plating layer was formed on the intermediate layer by electrolytic plating on the roll-to-roll-type continuous plating line under the same method and conditions as in Example 4, and the total copper thickness was A 3 μm ultra-thin copper layer was obtained. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 1 were performed in this order.

<Example 8>
Instead of the polyimide carrier of Example 4, 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, and then a roll -On a tow-roll type continuous plating line, a Cu plating layer having a thickness of 3 µm was formed on the intermediate layer by electrolytic plating, and an ultrathin copper layer having a total copper thickness of 3 µm was obtained. Next, the heat-resistant treatment, the chromate treatment, and the silane coupling treatment of Example 1 were performed in this order.

<Example 9>
In place of the polyimide carrier of Example 4, an intermediate layer was formed in the same steps, methods and conditions as in Example 4 with respect to rolled copper foil (JX Nippon Mining & Metals Tough Pitch Copper (JIS H3100 alloy number C1100) foil 18 μm thick). Then, a 3 μm Cu plating layer was formed on the intermediate layer by electrolytic plating on the roll-to-roll-type continuous plating line under the same method and conditions as in Example 4, and the total copper thickness was A 3 μm ultra-thin copper layer was obtained. Next, after performing the following roughening treatment 3, the heat resistance treatment, the chromate treatment, and the 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 10>
Instead of the polyimide carrier of Example 4, 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, and then a roll -On a tow-roll type continuous plating line, a Cu plating layer having a thickness of 3 µm was formed on the intermediate layer by electrolytic plating, and an ultrathin copper layer having a total copper thickness of 3 µm was obtained. Next, after performing the roughening treatment 3 of Example 9, the heat resistance treatment, the chromate treatment, and the silane coupling treatment of Example 1 were carried out in this order.

<Comparative Example 1>
In place of the polyimide carrier of Example 1, electroplating was performed on a roll-toe-roll type continuous plating line on the shiny surface on the 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.

<Comparative Example 2>
Instead of the polyimide film carrier of Example 4, using electrolytic copper foil (JX Nippon Mining & Metals JTC foil 18 μm thickness), except that a 1 μm Cu sputter layer was formed on the shiny surface on the electrolytic copper foil, The same treatment as in Example 4 was performed.

2. Characteristic evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following method.
(Surface roughness)
For the carrier on which the intermediate layer is formed, the surface roughness of the intermediate layer (surface roughness on the intermediate layer forming side of the carrier) is determined using a non-contact type roughness measuring instrument (LEXT OLS4000 manufactured by Olympus). Measured according to JIS B0601-2001, and 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 JISB0601-2001 using a non-contact-type roughness measuring machine (OLYMPUS LEXT OLS4000), about Rz Was measured according to 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. Then, 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. Then, after plating up to a total copper thickness of 15 μm using copper sulfate plating (Cubrite 21 made by JCU), the dry film resist was peeled off with a peeling 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. The results are shown in Table 1.

(Evaluation results)
In each of Examples 1 to 10, Rz on at least one surface of the ultrathin copper layer surface was 0.5 μm or less, and finer wiring than line / space = 15 μm / 15 μm could be formed. In each of Examples 1 to 10, Ra on at least one surface of the ultrathin copper layer surface was 0.12 μm or less. In all of Examples 1 to 10, Rt of 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 exceeded 0.5 μm, and finer wiring than line / space = 15 μm / 15 μm could not be formed. 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.

Claims (27)

  A carrier-attached copper foil comprising a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the ultrathin copper layer is measured by an at least one non-contact roughness meter Rz Is a copper foil with a carrier of 0.5 μm or less.   2. The copper foil with a carrier according to claim 1, wherein the ultrathin copper layer surface has an Rz of 0.5 μm or less measured with a non-contact type roughness meter on both sides.   The copper foil with a carrier according to claim 1, wherein Ra of the ultrathin copper layer surface is 0.12 μm or less as measured by a non-contact type roughness meter.   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 provided with a carrier as a support, an intermediate layer, and an ultrathin copper layer in this order, and the surface of the ultrathin copper layer is measured by a non-contact type roughness meter on at least one side. Is a copper foil with a carrier of 0.12 μm or less.   The copper foil with a carrier according to claim 5, wherein Ra of the ultrathin copper layer surface measured by a non-contact type roughness meter on both sides is 0.12 μm or less.   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 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, and the surface of the ultrathin copper layer is measured by a non-contact type roughness meter on at least one side. Is a copper foil with a carrier of 1.0 μm or less.   9. The copper foil with a carrier according to claim 8, wherein the ultrathin copper layer surface has an Rt of 1.0 μm or less as measured with a non-contact roughness meter on both sides.   The copper foil with a carrier according to any one of claims 1 to 9, wherein the carrier is formed of a film.   The copper foil with a carrier according to any one of claims 1 to 10, 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 10, 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 10, wherein Rt of the surface on the intermediate layer side of the carrier is 1.0 µm or less.   The copper foil with a carrier as described in any one of Claims 1-13 in which the roughening process layer is formed in the at least single side | surface of the ultra-thin copper layer surface.   The roughening layer is a layer made of any single element 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. Or the copper foil with a carrier of Claim 14 which is a layer containing the alloy containing any 1 or more types.   In the surface of the said ultra-thin copper layer, it has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier of description.   The copper with a carrier according to claim 14 or 15, wherein the surface of the roughening layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate layer, and a silane coupling layer. Foil.   The copper foil with a carrier as described in any one of Claims 1-13 which equips the surface of the said ultra-thin copper layer with a resin layer.   The copper foil with a carrier according to claim 14 or 15, comprising a resin layer on a surface of the roughening treatment layer.   The copper foil with a carrier according to claim 16 or 17, comprising a resin layer on the surface of 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.   The copper foil with a carrier according to any one of claims 18 to 20, wherein the resin layer includes a dielectric. The copper foil with a carrier according to any one of claims 1 to 21, wherein a circuit finer than line / space = 15/15 µm can be formed by a semi-additive method using an ultrathin copper layer.
  The copper clad laminated board manufactured using the copper foil with a carrier as described in any one of Claims 1-22.   The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 1-22.   An electronic apparatus using the printed wiring board according to claim 24. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 22 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. The process of forming a circuit in the ultra-thin copper layer side surface of the copper foil with a carrier according to any one of claims 1 to 22,
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.

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