JP5746402B2 - Copper foil with carrier, copper-clad laminate, printed wiring board, electronic device, and method for manufacturing printed wiring board - Google Patents

Description

  The present invention relates to a carrier-attached copper foil, a copper-clad laminate, 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 resist on the exposed ultra-thin copper layer, the micro-thin copper layer is etched with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.

  Here, for the surface of the ultrathin copper layer of the copper foil with a carrier that becomes the adhesive surface with the resin, the peel strength between the ultrathin copper layer and the resin base material 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 ultra-thin 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. Therefore, sufficient examination has not yet been made on the etching property, and there is still room for improvement.

  As a result of intensive studies, the present inventors have determined that the amount of Ni deposited on the peel-side surface of the ultrathin copper layer when the ultrathin copper layer is peeled off from the copper foil with carrier that has been subjected to the predetermined heat treatment, and It has been found that a copper foil with a carrier having good etching properties can be provided by controlling the surface roughness Rz of the ultrathin copper layer measured using a stylus type roughness meter.

The present invention in one aspect has been completed on the basis of the above findings, the carrier and, an intermediate layer, a copper foil with carrier having an ultra-thin copper layer in this order, ultrathin copper layer of a copper carrier foil Forming a circuit on the side surface, forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier so that the circuit is buried, forming a circuit on the resin layer, the resin The step of peeling the carrier after forming a circuit on the layer, and the resin formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer after peeling the carrier A copper foil with a carrier used in a method of manufacturing a printed wiring board including a step of exposing a circuit buried in a layer, the intermediate layer contains Ni, and the copper foil with a carrier is heated at 220 ° C. for 2 hours After that, in accordance with JIS C 6471 And when peeling off the ultra-thin copper layer, the electrode deposition amount of Ni of the intermediate layer side surface of the thin copper layer is at 400 [mu] g / dm ² or less, a stylus-type roughness in compliance with JIS B0601-1982 A copper foil with a carrier in which the surface roughness Rz of the ultrathin copper layer measured using a dynamometer is 0.2 μm or more and 1.5 μm or less, and the standard deviation of the surface roughness Rz is 0.6 μm or less. is there.

Another aspect of the present invention is a copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, and a circuit is formed on the surface of the copper foil with a carrier on the ultrathin copper layer side. Forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier so as to bury the circuit, forming a circuit on the resin layer, forming a circuit on the resin layer And a circuit embedded in the resin layer formed on the surface of the ultra-thin copper layer by removing the ultra-thin copper layer after the carrier is peeled off Is a copper foil with a carrier used in a method for manufacturing a printed wiring board including a step of exposing the substrate, the intermediate layer contains Ni, and the copper foil with a carrier is heated at 220 ° C. for 2 hours, to JIS C 6471. The ultra-thin copper layer was peeled off according to Can, the electrode deposition amount of Ni of the intermediate layer side surface of the ultra-thin copper layer is at 400 [mu] g / dm ² or less, which is measured using a stylus-type roughness meter in conformity with JIS B0601-1982 It is a copper foil with a carrier whose surface roughness Rz of a thin copper layer is 0.2 micrometer or more and 1.0 micrometer or less.

In one embodiment, the copper foil with a carrier according to the present invention is obtained by heating the copper foil with a carrier at 220 ° C. for 2 hours, and then peeling off the ultra thin copper layer in accordance with JIS C 6471. The adhesion amount of Ni on the surface on the intermediate layer side is 5 μg / dm ² or more.

In another embodiment of the copper foil with a carrier according to the present invention, when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off, the intermediate layer side of the ultrathin copper layer is provided. The adhesion amount of Ni on the surface is 5 μg / dm ² or more and 300 μg / dm ² or less.

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer of the ultra thin copper layer is obtained when the ultra thin copper layer is peeled off after the copper foil with carrier is heated at 220 ° C. for 2 hours. The adhesion amount of Ni on the side surface is 5 μg / dm ² or more and 250 μg / dm ² or less.

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer of the ultra thin copper layer is obtained when the ultra thin copper layer is peeled off after the copper foil with carrier is heated at 220 ° C. for 2 hours. The adhesion amount of Ni on the side surface is 5 μg / dm ² or more and 200 μg / dm ² or less.

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer of the ultra thin copper layer is obtained when the ultra thin copper layer is peeled off after the copper foil with carrier is heated at 220 ° C. for 2 hours. The adhesion amount of Ni on the side surface is 5 μg / dm ² or more and 150 μg / dm ² or less.

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer of the ultra thin copper layer is obtained when the ultra thin copper layer is peeled off after the copper foil with carrier is heated at 220 ° C. for 2 hours. The adhesion amount of Ni on the side surface is 5 μg / dm ² or more and 100 μg / dm ² or less.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the ultrathin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is 0.2 μm. It is 1.0 μm or less.

  In yet another embodiment of the copper foil with a carrier according to the present invention, the surface roughness Rz of the ultrathin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is 0.2 μm. It is 0.6 μm or less.

In one embodiment copper foil yet another carrier of the present invention, Ni content of the intermediate layer is 100 [mu] g / dm ² or more 5000 [mu] g / dm ² or less.

  In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer has Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, an alloy thereof, and a water thereof. 1 type or 2 types or more selected from the group which consists of a Japanese thing, these oxides, and organic substance are included.

In still another embodiment of the copper foil with a carrier of the present invention, when the intermediate layer contains Cr, it contains 5 to 100 μg / dm ^{2 of} Cr, and when it contains Mo, 10 μg / dm of Mo. ² above 1000 [mu] g / dm ² contained less, containing case containing Co, a Co containing 10 [mu] g / dm ² or more 1000 [mu] g / dm ² or less, if it contains Zn, the Zn 1 [mu] g / dm ² or more 120 [mu] g / dm ² or less To do.

  In another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an organic substance in a thickness of 25 nm or more and 80 nm or less.

  In another embodiment of the copper foil with a carrier of the present invention, the organic substance is an organic substance composed of one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids.

  In another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.6 μm or less.

  In still another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.4 μm or less.

  In another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.2 μm or less.

  In another embodiment of the copper foil with a carrier of the present invention, the standard deviation of the surface roughness Rz is 0.1 μm or less.

  In another embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultrathin copper layer in this order on both sides of the carrier.

  In another embodiment of the copper foil with a carrier of the present invention, the carrier is formed of an electrolytic copper foil or a rolled copper foil.

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

  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 yet another embodiment of the copper foil with a carrier according to the present invention, a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane are formed on one surface or both surfaces of the ultrathin copper layer. It has 1 or more types of layers selected from the group which consists of a coupling 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 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 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 copper foil with carrier and the insulating substrate, after lamination to form a copper-clad laminate through a step of peeling the career of the copper foil with a carrier, then the semi-additive method, a subtractive method, by any of the methods of part Lee additive method or modified semi-additive method, It is a manufacturing method of a printed wiring board including the process of forming a circuit.

  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.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier which implement | achieves a favorable processing precision can be provided.

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. It is a schematic diagram which shows a drum-type foil conveyance system. It is a schematic diagram which shows a 99-fold folding method. It is a graph which shows the relationship between etching time and the thickness reduced by the etching. It is a schematic diagram which shows the measurement location of the sample sheet | seat in evaluation of the depth profile of carbon concentration by XPS measurement.

<Copper foil with carrier>
The copper foil with a carrier of this invention has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order. 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. Substrate epoxy resin, glass cloth / glass nonwoven fabric composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film, etc. Then, an ultrathin copper layer bonded to an insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCD film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or 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. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
Moreover, as electrolytic copper foil, it can produce with the following electrolyte solution composition and manufacturing conditions.
When electrolytic copper foil is manufactured under the following conditions, Rz in the TD on the copper foil surface (direction perpendicular to the traveling direction of the copper foil (width direction) in the copper foil manufacturing equipment) is small, and TD is 60 degrees. An electrolytic copper foil with high gloss can be obtained.
In addition, the remainder of the process liquid used for manufacture of the copper foil described in this specification, surface treatment of copper foil, plating of copper foil, etc. is water unless otherwise specified.
<Electrolyte composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound 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 In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.

<Intermediate layer>
An intermediate layer containing Ni is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the 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 according to the present invention includes, in addition to Ni, Cr, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, these One or two or more selected from the group consisting of oxides and organic substances may be included. The intermediate layer may be a plurality of layers. The intermediate layer may be provided on both sides of the carrier.

  Further, for example, the intermediate layer is selected from a single metal layer made of Ni from the carrier side or an element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn. An alloy layer composed of one or more elements is formed, and selected from a group of elements composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can be configured by forming a layer made of a hydrate or oxide of one or more elements.

  An intermediate layer containing Ni is provided on one side or both sides of the carrier. The intermediate layer is formed by laminating any one layer of nickel or an alloy containing nickel on the carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. In addition, it is preferable that zinc is contained in any one layer of nickel or an alloy containing nickel and / or a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel may be an alloy composed of three or more elements. The chromium alloy is an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy may be an alloy composed of three or more elements. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be a chromate treatment layer. 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 pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

The intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy and nickel-cobalt alloy on the carrier, and any of zinc chromate treatment layer, pure chromate treatment layer and chromium plating layer. It is preferable that one kind of layer is laminated in this order, and the intermediate layer is constituted by laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer in this order on the carrier. More preferably, the nickel-zinc alloy layer and the pure chromate treatment layer or the zinc chromate treatment layer are laminated in this order. Since the adhesive force between nickel and copper is higher than the adhesive force between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and the chromate treatment layer. 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. Further, it is preferable to form a chromate treatment layer on the intermediate layer instead of chrome plating. Since chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper foil is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of ultrathin copper foil by electroplating is less likely to reduce pinholes. it can. Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  Among the intermediate layers, the chromate treatment layer is thinly present at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel off from the carrier before the laminating process on the insulating substrate, while after the laminating process on the insulating substrate It is preferable for obtaining the property that the ultrathin copper layer can be peeled from the carrier. When the chromate treatment layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the peelability is hardly improved, and the chromate treatment layer When the nickel layer or the nickel-containing alloy layer (for example, nickel-zinc alloy layer) and the ultrathin copper layer are directly laminated, the nickel amount in the nickel layer or the nickel-containing alloy layer (for example, nickel-zinc alloy layer) Accordingly, the peel strength is too strong or too weak to obtain an appropriate peel strength.

  Further, if the chromate treatment layer is present at the boundary between the carrier and the nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer), the intermediate layer is also peeled along with the peeling of the ultrathin copper layer, that is, the carrier. And the intermediate layer is undesirably peeled off. Such a situation may occur not only when the chromate treatment layer is provided at the interface with the carrier, but also when the amount of chromium is excessive even if the chromate treatment layer is provided at the interface with the ultrathin copper layer. This is because copper and nickel are likely to be in solid solution, so if they are in contact with each other, the adhesive force increases due to mutual diffusion and is difficult to peel off, while chromium and copper are less likely to dissolve and cause mutual diffusion. It is considered that the adhesion between the chromium and copper interface is weak and easy to peel off. Further, when the nickel amount in the intermediate layer is insufficient, there is only a very small amount of chromium between the carrier and the ultrathin copper layer, so that they are in close contact with each other and are difficult to peel off.

The intermediate nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. can do. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.
In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed.

Further, the amount of adhered 100~40000μg / dm ² of nickel in the intermediate layer, the adhesion amount of chromium 5~100μg / dm ^2, the amount of deposition of zinc is preferably 1~70μg / dm ^2. As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultra-thin copper layer, the intermediate layer is made of a metal species (Cr, Zn) that suppresses the diffusion of Ni to the ultra-thin copper layer side while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this point of view, Ni content of the intermediate layer is preferably from 100~40000μg / dm ^2, more preferably not less 200 [mu] g / dm ² or more 20000μg / dm ² or less, 500 [mu] g / dm ² or more 10000 / more preferably at dm ² or less, and even more preferably 700 [mu] g / dm ² or more 5000 [mu] g / dm ² or less. Further, Cr is preferably contained 5~100μg / dm ^2, more preferably not less 8 [mu] g / dm ² or more 50 [mu] g / dm ² or less, more preferably at 10 [mu] g / dm ² or more 40 [mu] g / dm ² or less, More preferably, it is 12 μg / dm ² or more and 30 μg / dm ² or less. Zn is preferably contained 1~70μg / dm ^2, more preferably not less 3 [mu] g / dm ² or more 30 [mu] g / dm ² or less, and even more preferably 5 [mu] g / dm ² or more 20 [mu] g / dm ² or less.

The intermediate layer of the carrier-attached copper foil of the present invention is formed by laminating a nickel layer on a carrier and an organic material layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, The adhesion amount of nickel in the intermediate layer may be 100 to 40,000 μg / dm ² . Further, the intermediate layer of the carrier-attached copper foil of the present invention is configured by laminating in order of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer on the carrier. The adhesion amount of nickel in the intermediate layer may be 100 to 40,000 μg / dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultrathin copper layer, a nitrogen-containing organic compound, a sulfur-containing organic compound that suppresses the diffusion of Ni to the ultrathin copper layer side while reducing the Ni adhesion amount of the intermediate layer and It is preferable that the intermediate layer includes an organic material layer containing any of carboxylic acids. From this point of view, Ni content of the intermediate layer is preferably from 100~40000μg / dm ^2, more preferably not less 200 [mu] g / dm ² or more 20000μg / dm ² or less, 300 [mu] g / dm ² or more 10000 / more preferably at dm ² or less, and even more preferably 500 [mu] g / dm ² or more 5000 [mu] g / dm ² or less. Moreover, BTA (benzotriazole), MBT (mercaptobenzothiazole), etc. are mentioned as an organic substance containing either the said nitrogen containing organic compound, sulfur containing organic compound, and carboxylic acid.

Moreover, as an organic substance which an intermediate | middle layer contains, it is preferable to use what consists of 1 type (s) or 2 or more types selected from a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. Among the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
The organic material is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
In addition, the thickness of organic substance can be measured as follows.

<Thickness of organic material in the intermediate layer>
After peeling off the ultrathin copper layer of the carrier-attached copper foil from the carrier, the surface of the exposed ultrathin copper layer on the intermediate layer side and the exposed surface of the intermediate layer side of the carrier are subjected to XPS measurement to create a depth profile. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth can be defined as B (nm), and the sum of A and B can be defined as the thickness (nm) of the organic substance in the intermediate layer.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )

  The method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil. The intermediate layer is formed on the carrier by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or showering, spraying method, dropping method and electrodeposition method on the surface on which the intermediate layer is to be formed. Etc., and there is no need to adopt a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of a concentration of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. in all the organic substances described above. The concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low. In addition, the organic substance thickness of an intermediate | middle layer tends to become large, so that the density | concentration of organic substance is high, and the contact time of the carrier to the solvent which dissolved the organic substance mentioned above is long. And when the organic substance thickness of an intermediate | middle layer is thick, it exists in the tendency for the effect of organic substance to suppress the spreading | diffusion to the ultra-thin copper layer side of Ni to become large.

  In addition, the intermediate layer is preferably configured by stacking nickel and molybdenum or cobalt or a molybdenum-cobalt alloy in this order on a carrier. Since the adhesion force between nickel and copper is higher than the adhesion force between molybdenum or cobalt and copper, when peeling the ultrathin copper layer, the interface between the ultrathin copper layer and molybdenum or cobalt or molybdenum-cobalt alloy It will come off. 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.

  The aforementioned nickel may be an alloy containing nickel. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The molybdenum described above may be an alloy containing molybdenum. Here, the alloy containing molybdenum is composed of molybdenum and one or more elements selected from the group consisting of cobalt, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The cobalt described above may be an alloy containing cobalt. Here, the alloy containing cobalt is made of cobalt and one or more elements selected from the group consisting of molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy.

Molybdenum-cobalt alloy is an element other than molybdenum and cobalt (for example, one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium). May be included.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  Among the intermediate layers, the molybdenum or cobalt or molybdenum-cobalt alloy layer is thinly present at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel off from the carrier before the lamination process to the insulating substrate, while the insulating substrate It is preferable for obtaining the property that the ultrathin copper layer can be peeled off from the carrier after the lamination step. If a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer, the peelability may be hardly improved, and the molybdenum or cobalt or molybdenum-cobalt alloy layer When the nickel layer and the ultrathin copper layer are directly laminated, the peel strength may be too strong or too weak depending on the amount of nickel in the nickel layer, and an appropriate peel strength may not be obtained.

  In addition, if the molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the nickel layer, the intermediate layer may be additionally peeled off when the ultrathin copper layer is peeled off, that is, between the carrier and the intermediate layer. May cause undesirable peeling. Such a situation is not only when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the carrier, but also when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the ultrathin copper layer. This can occur if the amount of molybdenum or cobalt is too high. This is because copper and nickel are likely to be in solid solution, so if they are in contact with each other, the adhesive force increases due to mutual diffusion and it is difficult to peel off, while molybdenum or cobalt and copper are less likely to dissolve and mutual diffusion. This is considered to be because the adhesive force is weak at the interface between the molybdenum or cobalt or molybdenum-cobalt alloy layer and copper and is easily peeled off. Further, when the amount of nickel in the intermediate layer is insufficient, since only a small amount of molybdenum or cobalt is present between the carrier and the ultrathin copper layer, they may be in close contact and difficult to peel off.

  The intermediate layer nickel and cobalt or molybdenum-cobalt alloy can be formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Molybdenum can be formed only by dry plating such as CVD and PDV. Electroplating is preferable from the viewpoint of cost.

In the intermediate layer, the adhesion amount of nickel is preferably 100 to 40000 μg / dm ² , the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and the adhesion amount of cobalt is preferably 10 to 1000 μg / dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultrathin copper layer, the intermediate layer is made of a metal species (Co, Mo) that suppresses the diffusion of Ni to the ultrathin copper layer side while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this viewpoint, the amount of nickel deposited is preferably to 100~40000μg / dm ^2, preferably to 200~20000μg / dm ^2, more preferably to 300~15000μg / dm ^2, 300~10000μg / Dm ² is more preferable. If included molybdenum in the intermediate layer, a molybdenum deposition amount is preferably set to 10~1000μg / dm ^2, the molybdenum deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably. If included cobalt in the intermediate layer, the cobalt coating weight is preferably set to 10~1000μg / dm ^2, cobalt deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² More preferably.

  As described above, the intermediate layer is plated for providing a molybdenum, cobalt, or molybdenum-cobalt alloy layer when nickel and molybdenum, cobalt, or a molybdenum-cobalt alloy are stacked in this order on a carrier. When the current density in the treatment is lowered and the carrier transport speed is lowered, the density of the molybdenum, cobalt, or molybdenum-cobalt alloy layer tends to increase. When the density of the layer containing molybdenum and / or cobalt increases, nickel in the nickel layer becomes difficult to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled.

  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.

When the copper foil with a carrier of the present invention is heated at 220 ° C. for 2 hours and then peeled off the ultrathin copper layer according to JIS C 6471, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is It is 5 μg / dm ² or more and 300 μg / dm ² or less. The copper foil with a carrier is bonded to an insulating substrate, the copper foil carrier is peeled off after thermocompression bonding, and the ultrathin copper layer bonded to the insulating substrate is etched into the intended conductor pattern. At this time, the surface of the ultrathin copper layer ( If the amount of Ni adhering to the surface opposite to the side bonded to the insulating substrate is large, the ultrathin copper layer is difficult to be etched, and it becomes difficult to form a fine pitch circuit. For this reason, the copper foil with a carrier of the present invention is controlled so that the Ni adhesion amount on the surface of the ultrathin copper layer after peeling is 300 μg / dm ² or less. When the Ni deposition amount exceeds 300 μg / dm ² , the ultra-thin copper layer is etched to form a finer wiring than L / S = 30 μm / 30 μm, for example, a fine wiring of L / S = 25 μm / 25 μm, for example L It becomes difficult to form fine wiring of / S = 20 μm / 20 μm, for example, fine wiring of L / S = 15 μm / 15 μm. The “heating at 220 ° C. for 2 hours” indicates a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.

If the amount of Ni deposited on the surface of the ultrathin copper layer after peeling as described above is too small, Cu in the copper foil carrier may diffuse to the ultrathin copper layer side. In such a case, the degree of bonding between the copper foil carrier and the ultrathin copper layer becomes too strong, and pinholes are easily generated in the ultrathin copper layer when the ultrathin copper layer is peeled off. Moreover, the adhesive force of resin and copper foil may deteriorate. For this reason, the adhesion amount of Ni is controlled to be 5 μg / dm ² or more. The Ni adhesion amount is preferably 5 μg / dm ² or more and 250 μg / dm ² or less, more preferably 5 μg / dm ² or more and 200 μg / dm ² or less.

Further, as described above, when the ultrathin copper layer is peeled off after the carrier-added copper foil is heated at 220 ° C. for 2 hours and the ultrathin copper layer is peeled off, the intermediate layer has an adhesion amount of Ni on the surface on the intermediate layer side. Is 300 μg / dm ² or less, in order to control the amount of Ni deposited on the surface of the ultrathin copper layer after peeling in this way, the Ni content in the intermediate layer is reduced and the Ni is on the side of the ultrathin copper layer. The intermediate layer needs to contain a metal species (Cr, Mo, Zn, etc.) or an organic substance that suppresses diffusion to the surface. From this point of view, Ni content of the intermediate layer is preferably at 100 [mu] g / dm ² or more 5000 [mu] g / dm ² or less, more preferably at 200 [mu] g / dm ² or more 4000μg / dm ² or less, 300 [mu] g / dm more preferably at ² or more 3000μg / dm ² or less, and even more preferably 400 [mu] g / dm ² or more 2000 [mu] g / dm ² or less. Moreover, as a metal seed | species which an intermediate | middle layer contains, 1 type, or 2 or more types selected from the group which consists of Cr, Mo, and Zn is preferable. When containing Cr is preferably contained 5~100μg / dm ² of Cr, it is more preferable to contain 5 [mu] g / dm ² or more 50 [mu] g / dm ² or less. When containing Mo is preferably contained 50 [mu] g / dm ² or more 1000 [mu] g / dm ² or less of Mo, and more preferably contains 70 [mu] g / dm ² or more 650μg / dm ² or less. When containing Zn is preferably contained 1 [mu] g / dm ² or more 120 [mu] g / dm ² or less of Zn, more preferably containing 2 [mu] g / dm ² or more 70 [mu] g / dm ² or less, 5 [mu] g / dm ² or more 50 [mu] g / dm ² It is more preferable to contain the following.

<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 the copper layer can be formed at a high current density. A copper sulfate bath is preferred. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 1-5 μm, even more typically 1.5-5 μm, and even more typically 2-5 μm. The ultra thin copper layer may be provided on both sides of the carrier. One or more selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on one surface or both surfaces of the ultrathin copper layer A layer may be provided or a surface treatment layer may be provided. The surface treatment layer may be one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer.

In the present invention, the “surface roughness of the ultrathin copper layer” means the surface roughness of the ultrathin copper layer, or the surface treatment layer surface when various surface treatments such as roughening treatment are applied. Indicates the roughness of the outer surface. The ultrathin copper layer of the present invention has a surface roughness Rz (ten-point average roughness) measured by using a stylus-type roughness meter in accordance with JIS B0601-1982 in a range of 0.2 μm to 1.5 μm. is there. When the surface roughness Rz (ten-point average roughness) of the ultrathin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is less than 0.2 μm, the carrier-attached copper foil is resin When the carrier is peeled from the copper foil after being laminated, the copper foil is peeled off from the resin. Further, when the surface roughness Rz of the ultrathin copper layer measured using a stylus type roughness meter in accordance with JIS B0601-1982 is more than 1.5 μm, there arises a problem that the etching property is deteriorated.
The surface roughness Rz is more preferably 0.2 μm or more and 1.0 μm or less, more preferably 0.20 μm or more and 0.90 μm or less, more preferably 0.25 μm or more and 0.8 μm or less, and 0.28 μm or more and 0.7 μm. Hereinafter, 0.28 μm or more and 0.6 m or less is even more preferable.
In order to lower Rz, it is effective to lower Rz in the TD direction of the carrier and to increase the glossiness by 60 degrees. In addition, when roughening the surface of the ultrathin copper layer, the current density in the roughening treatment is increased and / or the roughening time is shortened and / or the roughening treatment is performed by copper alloy plating. It is effective to do.

The TD roughness (Rz) and glossiness of the surface of the carrier on the processing side before forming the intermediate layer are controlled as follows. Specifically, the TD surface roughness (Rz) of the copper foil before the surface treatment is preferably 0.20 to 1.30 μm, more preferably 0.20 to 1.00 μm, and more preferably 0.20 to 0. .90 μm, more preferably 0.20 to 0.80 μm, more preferably 0.20 to 0.60 μm, and more preferably 0.20 to 0.50 μm. As such a copper foil, rolling is performed by adjusting the oil film equivalent of the rolling oil (high gloss rolling), or rolling is performed by adjusting the surface roughness of the rolling roll (for example, a direction perpendicular to the circumferential direction of the roll) In this case, the arithmetic average roughness Ra (JIS B0601) on the surface of the rolling roll can be set to 0.01 to 0.25 μm, and when the value of the arithmetic average roughness Ra on the surface of the rolling roll is large, the copper foil The TD roughness (Rz) on the surface is large and the glossiness tends to be low, and when the arithmetic average roughness Ra on the surface of the rolling roll is small, the TD roughness (Rz) on the copper foil is small. , Or the glossiness tends to increase.) Alternatively, it can be produced by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution. Thus, by making the surface roughness (Rz) and glossiness of the TD of the copper foil before the treatment within the above and below ranges, the surface roughness (Rz) of the copper foil after the treatment can be easily controlled. Can do.
Moreover, it is preferable that 60 degree glossiness of TD is 150 to 910% of the copper foil before surface treatment, it is more preferable that it is 200 to 810%, and it is more preferable that it is 400 to 750%. If the 60 degree gloss of MD of the copper foil before the surface treatment is less than 150%, the TD roughness Rz of the copper foil surface may be larger than the case of 150% or more. There is a risk that it will be difficult to do.
High gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 10000 to 24000 or less.
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 10,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used.
Chemical polishing is performed over a long period of time using an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a concentration lower than usual.

Further, the surface of the ultrathin copper layer (also referred to as “surface-treated surface”) after being subjected to various surface treatments such as a roughening treatment has a surface roughness Rz measured using the stylus-type roughness meter. The standard deviation is preferably 0.6 μm or less. When the standard deviation of the surface roughness Rz of the ultra-thin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is more than 0.6 μm, there is a problem that variation in etching property becomes large. May occur. The standard deviation of the surface roughness Rz is more preferably 0.5 μm or less, still more preferably 0.4 μm or less, more preferably 0.3 μm or less, and 0.25 μm or less. Is more preferably 0.2 μm or less, more preferably 0.15 μm or less, and more preferably 0.1 μm or less. The lower limit of the standard deviation is not particularly limited, but is, for example, 0.001 μm or more, for example, 0.005 μm or more, for example, 0.01 μm or more.
In addition, when forming the surface treatment layer on the surface of the ultrathin copper layer, the surface roughness is maintained by keeping the distance between the copper foil with a carrier and the electrode (distance between the electrodes) more uniform than before. The standard deviation of Rz can be reduced.
As a method of keeping the distance (distance between the electrodes) closer to the electrode more uniform than before, a cathode drum is used as the cathode, or the distance between the transport rolls is reduced (for example, 200 to 500 mm) and the transport tension is reduced. For example, it may be higher than the conventional one (for example, 3 kgf / mm ² or more).

When adjusting the above-mentioned surface roughness by controlling the plating conditions for forming the ultrathin copper layer, electrolytic plating is used. In that case, the ultrathin copper layer is produced with the following electrolytic solution composition and manufacturing conditions. be able to. The surface roughness described above increases the electrolyte temperature during the formation of the ultrathin copper layer and / or increases the linear flow rate of the plating (electrolytic) solution and / or a predetermined leveling agent in the electrolyte. It can adjust by adding.
<Electrolyte composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound 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

On the other hand, when the surface roughness is adjusted by applying a roughening treatment to the surface of the ultrathin copper layer and providing a roughening treatment layer, the roughening treatment is performed by, for example, roughening particles with copper or a copper alloy. This can be done by forming. The roughening process may be fine. 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 one or more of them. Also good. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy.
When the roughening layer is provided, the surface roughness is a plating solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, molybdenum, zinc, arsenic, chromium and phosphorus. Can be adjusted by increasing the current density (for example, 38 to 60 A / dm ² ) and reducing the processing time (for example, 0.1 to 1.5 seconds).

For example, the copper-cobalt-nickel alloy plating as a roughening treatment for controlling the surface roughness described above is performed by electrolytic plating. Copper having an adhesion amount of 15 to 40 mg / dm ² -cobalt with 100 to 3000 μg / dm ² A ternary alloy layer such as −100 to 1500 μg / dm ² of nickel can be formed.

An example of a plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 38 to 55 A / dm ²
Plating time: 0.3 to 1.5 seconds, more preferably 0.3 to 1.3 seconds In addition, the above-mentioned surface roughness is an alloy plating layer containing Ni that is not roughened (for example, Ni—W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating), the concentration of Ni in the plating solution is set to at least twice that of other elements, and the current density is 0.1 to ^{2 A} / dm ^2. It can be adjusted by making it lower than before and making the plating time 20 seconds or longer (for example, 20 seconds to 40 seconds).

The carrier-attached copper foil may include one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the roughened layer.
Further, a heat-resistant layer and a rust-proof layer may be provided on the roughening-treated layer, a chromate-treated layer may be provided on the heat-resistant layer and the rust-proof layer, and a silane coupling treatment is provided on the chromate-treated layer A layer may be provided.
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.
Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on the carrier, and is selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the carrier. One or more layers may be provided. The roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer may be provided by using known methods, and according to the methods described in the present specification, claims and drawings. It may be provided. Providing one or more layers selected from the roughening treatment layer, heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer on the carrier is possible from the surface side having the roughening treatment layer, etc. When the substrate is laminated on a support such as a resin substrate, the carrier and the support are less likely to be peeled off.

  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. 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. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 40251177, 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.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine tree Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in powder form, the powder characteristics of the dielectric (dielectric filler) are such that the particle size ranges from 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). The surface of the copper foil with a carrier is coated on the surface of the ultrathin copper layer by, for example, a roll coater method, and then heated and 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 composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. In a state in which the samples are stacked (laminated body), the values are calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of pressing at 171 ° C., pressing pressure of 14 kgf / cm 2 and pressing time of 10 minutes. is there.

  The surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the 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 120 μm.

When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength is reduced, and when this surface-treated copper foil with resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material 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 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the surface-treated copper foil having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.

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;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
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 for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is 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;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin 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
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is 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 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 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 an ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the partial additive method 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, on the conductor circuit, by performing a thickness by electroless plating treatment (further electrolytic plating treatment if necessary) on a through hole or via hole, It refers to a method of manufacturing a printed wiring board.

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. 1-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. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding 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. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-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. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention 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. 3H, 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.

  Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

The copper foil with a carrier according to the present invention has good etching properties because the surface roughness of the ultrathin copper layer is controlled, and the printed wiring board as described above, for example, as shown in FIG. In the process, fine pitching circuit plating can be formed with high accuracy. In addition, according to the method for manufacturing a printed wiring board as described above, circuit plating is embedded in a resin layer, and thus, for example, removal of an 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. 4-J and 4-K, when the ultra-thin 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. The embedding resin may include a thermosetting resin or a thermoplastic resin. The embedding resin may include a thermoplastic resin. The type of the embedded resin is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polyvinyl acetal resin, urethane resin, block copolymer polyimide resin, block copolymer Resin including polyimide resin, paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin and glass A cloth base epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer film, a fluororesin film, etc. can be mentioned as a suitable thing.

<Peel strength (N / m)>
The copper foil with a carrier of the present invention has an ultra-thin copper layer side as an insulating substrate, (1) normal temperature and normal pressure (normal state) and / or (2) atmospheric pressure at 20 kgf / cm ² at 220 ° C. After thermocompression bonding by heating for 2 hours and / or (3) thermocompression bonding by heating at 220 ° C. for 2 hours at a pressure of 20 kgf / cm ^{2 in the} atmosphere. After pasting, after heating twice at 180 ° C. for 1 hour under normal pressure (ie, under no pressure, under atmospheric pressure) in a nitrogen atmosphere, the carrier side was pulled with a tensile tester and JIS C 6471 Each peel strength when the ultrathin copper layer is peeled according to the above is preferably 2 to 100 N / m. If the peel strength is less than 2 N / m, the ultra-thin copper layer may peel from the carrier during the production of the printed wiring board. If it exceeds 100 N / m, an extra force is applied at the time of peeling. For example, in the above-described embedding method (embedded process), there is a risk of peeling at the interface between the embedding resin and the ultrathin copper layer. The peel strength is more preferably 2 to 50 N / m, and even more preferably 2 to 20 N / m.

  Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example.

1. Production of Copper Foil with Carrier A long electrolytic copper foil or rolled copper foil having the thicknesses shown in Tables 1, 3, and 5 was prepared as a carrier.
The electrolytic copper foil was manufactured under the conditions described in Tables 1, 3, and 5, or JTC foil manufactured by JX Nippon Mining & Metals was used.
The rolled copper foil was manufactured as follows. After manufacturing a predetermined copper ingot and performing hot rolling, annealing and cold rolling of a 300-800 degreeC continuous annealing line were repeated, and the rolled sheet of 1-2 mm thickness was obtained. This rolled plate was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thicknesses shown in Tables 1, 3, and 5 to obtain a copper foil. Tables 1, 3, and 5 show the rolling conditions (high gloss rolling or normal rolling, oil film equivalent) at this time. “High-gloss rolling” and “normal rolling” were carried out by performing the final cold rolling (cold rolling after the final recrystallization annealing) at the oil film equivalent values shown in Tables 1, 3, and 5, respectively. means. “Tough pitch copper” in Tables 1, 3 and 5 indicates tough pitch copper standardized in JIS H3100 C1100. “Oxygen-free copper” in Tables 1, 3, and 5 represents oxygen-free copper specified in JIS H3100 C1020. “Ppm” of the additive elements described in Tables 1, 3, and 5 indicates mass ppm. For example, “tough pitch copper + Ag 180 ppm” in the carrier type column of Tables 1, 3, and 5 means that 180 mass ppm of Ag is added to tough pitch copper.
An intermediate layer was formed by electroplating the glossy surface (shiny surface) of this copper foil with a roll-to-roll-type continuous plating line under the following conditions.

"Ni": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Boric acid: 15-25 g / L, Brightener: Saccharin Butynediol: 5 to 15 ppm, Sodium dodecyl sulfate: 55 to 75 ppm
(PH) 4-6
(Liquid temperature) 55-65 degreeC
(Current density) 1 to 11 A / dm ²
(Energization time) 1 to 20 seconds

- "Ni-Zn": in the formation conditions of the nickel-zinc alloy plating the nickel plating, was added in the form of zinc of zinc sulfate (ZnSO ₄₎ in the nickel plating solution, zinc concentration: 0.05-5 g / L range In this way, a nickel zinc alloy plating was formed.

- "Cr": chromium plating (liquid _{composition) CrO 3: 200~400g / L,} H 2 SO 4: 1.5~4g / L
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²
(Energization time) 1 to 20 seconds

"Chromate": Electrolytic pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 7-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

· "Zn- Chromate": In Zinc chromate treatment the electrolytic pure chromate treatment conditions, the addition of zinc in the form of zinc sulfate (ZnSO ₄₎ in the liquid zinc concentration was adjusted within the range of 0.05-5 g / L The zinc chromate treatment was performed.

"Ni-Mo": nickel molybdenum alloy plating (Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

“Organic”: Organic substance layer forming treatment An aqueous solution containing carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L and having a liquid temperature of 40 ° C. and a pH of 5 was showered and sprayed for 20 to 120 seconds.

"Co-Mo": Cobalt molybdenum alloy plating (Liquid composition) Co sulfate 50 g / dm ³ , Sodium molybdate dihydrate: 60 g / dm ³ , Sodium citrate 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

"Ni-P": Nickel phosphorus alloy plating (Liquid composition) Ni: 30 to 70 g / L, P: 0.2 to 1.2 g / L
(PH) 1.5-2.5
(Liquid temperature) 30-40 ° C
(Current density) 1.0-10.0 A / dm < ² >
(Energization time) 0.5-30 seconds

  Subsequently, on the roll-to-roll type continuous plating line, electroplating an ultrathin copper layer having the thickness described in Tables 1, 3, and 5 on the intermediate layer under the conditions shown in Tables 1, 3, and 5. The copper foil with a carrier was manufactured.

The surface of the ultrathin copper layer was subjected to surface treatment under the surface treatment conditions (surface treatments 1 to 3) shown in Tables 2, 4, and 6. Here, FIG. 5 shows a schematic diagram of an electroplating process using a drum carrying method for the surface treatment method. Moreover, the schematic diagram of the electroplating process using the foil carrying system by 99 folds is shown in FIG. In the examples and comparative examples in which the surface treatment method is described as “drum”, the surface treatments 1 to 3 were all treated with the “drum”. Similarly, in the examples and comparative examples described as “Ninety Folds”, the surface treatments 1 to 3 were all treated by “Ninety Folds”.
Moreover, about the copper foil with a carrier of Example 3, 5, 7, 10-18, the following heat treatment, chromate treatment, and silane coupling treatment were performed on the surface treatment layer.
Moreover, about Example 20, only the heat-resistant process was performed . It went only silane coupling treatment for real施例24. In Examples 1 and 26, chromate treatment and silane coupling treatment were performed in this order.

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

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

・ Silane coupling treatment (forms a silane coupling treatment layer)
The silane coupling agent coating treatment was performed by spraying an aqueous solution having a pH of 7 to 8 and 60 ° C. containing 0.2 to 2% by mass of alkoxysilane.
The surface treatment plating baths are shown in Table 7, and the ultrathin copper layer formation plating baths are shown in Table 8.

2. Evaluation of copper foil with carrier Various evaluations were performed as follows for each sample of Examples and Comparative Examples prepared as described above.

・ Metal adhesion amount of the intermediate layer;
The amount of nickel adhered was measured by ICP emission analysis using an ICP emission spectrophotometer (model: SPS3100) manufactured by SII after dissolving the sample with nitric acid having a concentration of 20% by mass. Dissolved in hydrochloric acid with a concentration of 7% by mass at 100 ° C. and measured by quantitative analysis by atomic absorption spectrometry using a VARIAN atomic absorption spectrophotometer (model: AA240FS). The sample was dissolved in a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass), and was subjected to atomic absorption spectrometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. Measurement was performed by quantitative analysis. In addition, the measurement of the said nickel, zinc, chromium, and molybdenum adhesion amount was performed as follows. First, after peeling off the ultrathin copper layer from the copper foil with carrier, only the vicinity of the surface on the intermediate layer side of the ultrathin copper layer is dissolved (if the thickness of the ultrathin copper layer is 1.4 μm or more, If the thickness of the ultrathin copper layer is less than 1.4 μm, only 0.5 μm thickness is dissolved from the surface of the thin copper layer on the intermediate layer side. Only 20% is dissolved.), The adhesion amount of the surface of the ultrathin copper layer on the intermediate layer side is measured. Further, after peeling off the ultrathin copper layer, only the vicinity of the surface on the intermediate layer side of the carrier is dissolved (only the thickness of 0.5 μm from the surface is dissolved), and the amount of adhesion on the surface of the carrier on the intermediate layer side is measured. And the value which totaled the adhesion amount of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer and the adhesion amount of the surface by the side of the intermediate | middle layer of a carrier was made into the metal adhesion amount of an intermediate | middle layer.
When the sample is difficult to dissolve in nitric acid having a concentration of 20% by mass or hydrochloric acid having a concentration of 7% by mass, a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) After dissolving the sample, the amount of nickel, zinc and chromium deposited can be measured by the above-described method.
The “metal adhesion amount” means the metal adhesion amount (mass) per sample unit area (1 dm ² ).

-Organic layer thickness of the intermediate layer After peeling the ultra-thin copper layer of the copper foil with carrier from the carrier, the surface of the exposed ultra-thin copper layer on the intermediate layer side and the exposed surface of the intermediate layer side of the carrier are subjected to XPS measurement, A depth profile was created. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth was defined as B (nm), and the sum of A and B was defined as the thickness (nm) of the organic substance in the intermediate layer.
Note that the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In this example, the atomic concentration of the metal in the depth direction was measured at 0.28 nm (SiO ₂ equivalent) intervals (measured every 0.1 minutes by sputtering time).
In addition, the depth profile of the carbon concentration by the above XPS measurement is obtained from both ends in the long side direction of each sample sheet on the surface on the intermediate layer side of the exposed ultrathin copper layer and the surface on the intermediate layer side of the exposed carrier, respectively. A total of three locations, one in each region within 50 mm and one in a 50 mm × 50 mm region at the center, that is, the surface on the intermediate layer side of the exposed ultrathin copper layer and the intermediate layer side of the exposed carrier A total of six locations were created on the surface. FIG. 8 shows three measurement points on the surface on the intermediate layer side of the exposed ultrathin copper layer and three points on the surface on the intermediate layer side of the exposed carrier. Subsequently, from the depth profile created for each of the three regions on the exposed intermediate layer side surface of the exposed ultrathin copper layer and the exposed intermediate layer side of the carrier, on the intermediate layer side of the above described ultrathin copper layer, respectively. The depth A (nm) at which the carbon concentration first became 3 at% or less from the surface, and the depth B (nm) at which the carbon concentration first became 3 at% or less from the surface on the intermediate layer side of the carrier were calculated. The sum of the arithmetic average value of A (nm) and the arithmetic average value of B (nm) was defined as the thickness (nm) of the organic substance in the intermediate layer.
When the sample size is small, the above-mentioned region within 50 mm from both ends and the 50 mm × 50 mm region at the center may overlap.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )
XPS means X-ray photoelectron spectroscopy. In the present invention, it is assumed that an XPS measuring device (model 5600MC or an equivalent measuring device manufactured and sold by ULVAC-PHI) is used by ULVAC-PHI. If such a measuring device cannot be obtained, Other XPS measurements can be performed by setting the measurement interval of each element concentration in the depth direction to 0.10 to 0.30 nm (converted to SiO ₂ ) and the sputtering rate to 1.0 to 3.0 nm / min (converted to SiO ₂ ). An apparatus may be used.

-Ni adhesion amount on the surface of the ultra-thin copper layer;
The copper foil with a carrier was bonded to a BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on the ultrathin copper layer side and thermocompression bonded at 220 ° C. for 2 hours. Thereafter, the ultrathin copper layer was peeled off from the copper foil carrier in accordance with JIS C 6471 (Method A). Subsequently, the adhesion amount of Ni on the surface of the intermediate layer side of the ultra-thin copper layer was measured by dissolving the sample with nitric acid having a concentration of 20% by mass and using an ICP emission spectroscopic analyzer (model: SPS3100) manufactured by SII. Measured by luminescence analysis. In addition, when the surface of the ultrathin copper layer opposite to the surface on the intermediate layer side is treated with Ni, only the vicinity of the surface on the intermediate layer side of the ultrathin copper layer is dissolved (ultrathin copper layer). When the thickness of the copper layer is 1.4 μm or more, only 0.5 μm thickness is dissolved from the surface on the intermediate layer side of the ultrathin copper layer. When the thickness of the ultrathin copper layer is less than 1.4 μm, it is extremely thin. By dissolving only 20% of the thickness of the ultrathin copper layer from the surface on the intermediate layer side of the copper layer), it is possible to measure the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer.

・ Etching property;
The prepared copper foil with carrier and the base material (Mitsubishi Gas Chemical Co., Ltd .: GHPL-832NX-A, 0.05mm x 4 sheets) are laminated and heat-pressed at 220 ° C for 2 hours, and then the copper foil carrier is peeled off. The thin copper layer was exposed to a sample size of 250 × 250 mm ² . Adjust the amount of each thickness that can be etched to ultra-thin copper layer with sulfuric acid-peroxide aqueous solution (SE07 manufactured by Mitsubishi Gas Chemical Co., Ltd.). It carried out by. And the etching property of copper foil with a carrier was evaluated by the frequency | count of the etching required until resin was exposed to the whole surface. The etching conditions at this time are shown below.
(Etching conditions)
-As an etching solution, sulfuric acid-peroxide aqueous solution: 20 vol% of SE-07 manufactured by Mitsubishi Gas Chemical Co., Ltd. (diluted stock solution 5 times with water, copper concentration 18 g / L) was used.
The temperature of the etching solution was controlled at 35 ± 2 ° C.
Spray pressure: 0.1 MPa (spraying was performed so that the etching solution hits the copper layer to be etched perpendicularly)
Etching rate (etching equivalent amount): 0.3 μm / time (30 seconds per pass of etching machine)
The above sulfuric acid-peroxide aqueous solution: The amount that can be etched with respect to each ultrathin copper layer with SE-07 manufactured by Mitsubishi Gas Chemical Co., Ltd. is the entire surface of electrolytic copper foil JTC (thickness 35 μm) manufactured by JX Nippon Mining & Metals The relationship between the etching amount (decrease in the thickness of the copper layer) measured by the weight method of the electrolytic copper foil JTC and the etching time at that time is obtained by a graph as shown in FIG. The etching amount (reduction amount of the copper layer thickness) was estimated and obtained by the etching time actually taken in the examples and comparative examples.
The measuring method of the etching amount (decreasing amount of the copper layer thickness) was obtained by the following formula.
Etching amount (reduction amount of copper layer thickness) (μm) = (weight before etching (g)) − (weight after etching (g)) / (etching area (μm ² ) × copper density (g / μm ³⁾ ))
The density of copper was 8.96 g / cm ³ = 8.96 × 10 ⁻¹² g / μm ³ .
Specifically, the relationship between the equivalent thickness B of the ultrathin copper layer removed by etching B = etching time (seconds) × coefficient α (= 0.0336) is obtained, and thereby the ultrathin copper layer removed by etching from the etching time. The equivalent thickness B of the copper layer was determined. That is, for example, the equivalent thickness B = 5 μm of the ultrathin copper layer removed by etching means that the etching is performed by 5 μm ÷ coefficient α (= 0.0336) = 148.8 seconds.
Thus, the number of times of etching, the average of the number of times of etching, and the maximum value-minimum value of the number of times of etching were measured. Table 10 shows the criteria for determining the number of times of etching with respect to the thickness of the ultrathin copper layer and the criteria for determining the variation in the number of times of etching.

・ Evaluation of surface roughness;
(1) Surface roughness Rz of ultrathin copper layer
The surface roughness Rz (stylus) (ten-point average roughness) of the ultrathin copper layer is measured according to JIS B0601-1982, contact roughness meter Surfcorder SE-3C stylus roughness, manufactured by Kosaka Laboratory Ltd. Measured using a meter. Rz (stylus) was arbitrarily measured at 10 locations, and the average value of Rz (stylus) was defined as the value of Rz (stylus). Moreover, the standard deviation of 10 values was calculated for Rz (stylus).
(2) Surface roughness of the intermediate layer formation side surface of the carrier Surface roughness Rz (stylus) of the carrier in the TD direction of the surface of the intermediate layer formation side according to JIS B0601-1982 It was measured using a laboratory-made contact roughness meter Surfcorder SE-3C stylus roughness meter. Rz (stylus) was arbitrarily measured at 10 locations, and the average value of Rz (stylus) was defined as the value of Rz (stylus).

-Adhesion between ultrathin copper layer and embedded resin;
A resist was applied onto the roughened layer of the ultrathin copper layer of the copper foil with carrier, exposed and developed, and the resist was etched into a line shape. Next, after forming Cu plating for a circuit, the resist was removed to form a line-shaped circuit plating. Next, an embedding resin (BT resin (bismaleimide triazine resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.) was provided on the ultrathin copper layer so that the circuit plating was buried, and the resin layer was laminated. Subsequently, the carrier was tried to be peeled off at the interface with the ultrathin copper layer, and the number of times the carrier was peeled off at the interface between the resin layer and the ultrathin copper layer was measured. When the number of peelings at the interface between the resin layer and the ultrathin copper layer is 0 out of 10 times, “◎◎”, and when 1 time out of 10 times, “◎”, 2-3 times out of 10 times In the case of ◯, “◯” was given, and in the case of 4-5 times in 10 times, “Δ”, and in the case of 6 times in 10 times, “x”.

・ Glossiness in the TD direction of carrier on the intermediate layer forming surface (%)
The gloss meter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. conforming to JIS Z8741 is used, and the rolled copper foil is perpendicular to the rolling direction (the traveling direction of the copper foil during rolling, ie, the width direction). Glossiness (%) was measured at an incident angle of 60 degrees in the direction (TD). Moreover, about electrolytic copper foil, glossiness (%) was measured about the mat | matte surface at the incident angle of 60 degree | times of the direction (namely, width direction) (TD) orthogonal to the copper foil conveyance direction at the time of electrolytic treatment.

・ Peel strength (N / m)
Heat the copper foil with a carrier to the BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Crimped and pasted. Subsequently, the carrier side was pulled with a tensile tester, and the peel strength when the ultrathin copper layer was peeled off according to JIS C 6471 was measured. (The values are shown in the column of “220 ° C., after 2 h baking (N / m)” in Table 9.)
Further, after the heating at 220 ° C. for 2 hours, the heating was performed twice at 180 ° C. for 1 hour without applying pressure (under atmospheric pressure, that is, atmospheric pressure) in a nitrogen atmosphere. The peel strength of each sample was measured under the conditions. (The values are shown in the column of “After 180 ° C., 1 h × 2 times baking (N / m)” in Table 9.)
In addition, for each sample before thermocompression bonding with the above resin (normal temperature and normal pressure state, that is, normal state), the carrier side is pulled with a tensile tester after the adhesive tape is attached to the resin substrate from the ultrathin copper layer side. The peel strength when the ultrathin copper layer was peeled off in accordance with JIS C 6471 was measured. (The values are shown in the “Normal (N / m)” column of Table 9.)

(Evaluation results)
In Examples 1-21 and 24-35 , after heating the copper foil with a carrier at 220 ° C. for 2 hours, when the ultrathin copper layer was peeled off according to JIS C 6471, the intermediate layer of the ultrathin copper layer The adhesion amount of Ni on the side surface is 400 μg / dm ² or less, the surface roughness Rz of the ultrathin copper layer is 0.2 μm or more and 1.5 μm or less, and the standard deviation of the surface roughness Rz is 0. It was 6 μm or less, and at least the etching property was good.
In Comparative Examples 1 to 9, after heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface of the intermediate layer side of the ultrathin copper layer The adhesion amount of Ni is more than 400 μg / dm ² , or the surface roughness Rz of the ultrathin copper layer is less than 0.2 μm or more than 1.5 μm, or the standard deviation of the surface roughness Rz is 0.6 μm It was super, and at least the etching property was poor.

Claims (61)

A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
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 The copper foil with carrier used in the method,
The intermediate layer includes Ni;
After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is 400 μg / dm ² or less,
The surface roughness Rz of the ultrathin copper layer measured using a stylus type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less, and the standard deviation of the surface roughness Rz Is a copper foil with a carrier of 0.6 μm or less. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
Forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
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 The copper foil with carrier used in the method,
The intermediate layer includes Ni;
After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is 400 μg / dm ² or less,
The copper foil with a carrier whose surface roughness Rz of the said ultra-thin copper layer measured using a stylus-type roughness meter based on JIS B0601-1982 is 0.2 micrometer or more and 1.0 micrometer or less. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The intermediate layer includes Ni;
After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is 400 μg / dm ² or less,
The surface roughness Rz of the ultrathin copper layer measured using a stylus type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or more and 1.5 μm or less,
The copper foil with a carrier whose standard deviation of the said surface roughness Rz is 0.1 micrometer or less. A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The intermediate layer includes Ni;
After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is 400 μg / dm ² or less,
The surface roughness Rz of the ultrathin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or more and 1.0 μm or less,
The copper foil with a carrier whose standard deviation of the said surface roughness Rz is 0.1 micrometer or less. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is The copper foil with a carrier according to claim 1 or 2 , wherein the copper foil is 5 µg / dm ² or more. After the copper foil with carrier was heated at 220 ° C. for 2 hours and then the ultrathin copper layer was peeled off, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer was 5 μg / dm ² or more and 300 μg / copper foil with carrier according to any one of claims 1, 2, and 5 is dm ² or less. When the ultrathin copper layer is peeled off after heating the copper foil with carrier at 220 ° C. for 2 hours, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm ² or more and 250 μg / The copper foil with a carrier according to claim 6, which is dm ² or less. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm ² or more and 200 μg / The copper foil with a carrier according to claim 7, which is dm ² or less. After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm ² or more and 150 μg / The copper foil with a carrier according to claim 8, which is dm ² or less. After the copper foil with carrier was heated at 220 ° C. for 2 hours and then the ultrathin copper layer was peeled off, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer was 5 μg / dm ² or more and 100 μg / The copper foil with a carrier according to claim 9, which is dm ² or less. Claim 2 surface roughness Rz of the ultra-thin copper layer is measured using a stylus-type roughness meter in conformity with JIS B0601-1982 is 0.2μm or more 1.0μm or less, and 5 The copper foil with a carrier according to any one of 10 .   The copper with a carrier according to claim 11, wherein the surface roughness Rz of the ultrathin copper layer measured by using a stylus type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or more and 0.6 μm or less. Foil. The surface roughness Rz of the ultra-thin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is 0.42 µm or more, or any one of claims 1, 2, and 5-12 The copper foil with a carrier according to one item. The Ni content of the intermediate layer, 100 [mu] g / dm ² or more 40000μg / dm ² or less copper foil with carrier according to any one of claims 1, 2, and 5-13 is. The Ni content of the intermediate layer, copper foil with carrier according to 100 [mu] g / dm ² or more 5000 [mu] g / dm ² or less is claim 14. The intermediate layer is selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates, oxides, and organic matter. The copper foil with a carrier as described in any one of Claims 1, 2, and 5-15 containing 1 type, or 2 or more types. When the intermediate layer contains Cr, it contains 5 to 100 μg / dm ^{2 of} Cr. When it contains Mo, it contains 10 μg / dm ² or more and 1000 μg / dm ² or less of Mo. the 10 [mu] g / dm ² or more 1000 [mu] g / dm ² contain less, if it contains Zn, the Zn 1 [mu] g / dm ² or more 120 [mu] g / dm ² according to claim 1 containing less, and in any one of 5 to 16 The copper foil with a carrier of description.   The copper foil with a carrier according to claim 16 or 17, wherein the intermediate layer contains an organic substance in a thickness of 25 nm to 80 nm.   The said organic substance is an organic substance which consists of 1 type, or 2 or more types selected from a nitrogen-containing organic compound, a sulfur containing organic compound, and carboxylic acid, Copper foil with a carrier as described in any one of Claims 16-18. .   The copper foil with a carrier according to any one of claims 1, 2, and 5 to 19, wherein a standard deviation of the surface roughness Rz is 0.6 µm or less.   The copper foil with a carrier according to claim 20, wherein the standard deviation of the surface roughness Rz is 0.4 μm or less.   The copper foil with a carrier according to claim 21, wherein the standard deviation of the surface roughness Rz is 0.2 μm or less.   The copper foil with a carrier according to claim 22, wherein the standard deviation of the surface roughness Rz is 0.1 μm or less. The copper foil with a carrier as described in any one of Claims 1, 2, and 5-23 which has the said intermediate | middle layer and the said ultra-thin copper layer in this order on the both surfaces of the said carrier. The copper foil with a carrier as described in any one of Claims 1, 2, and 5-24 which has a roughening process layer in at least one surface of the said ultra-thin copper layer and the said carrier, or both surfaces.   The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing at least one kind. Item 26. A copper foil with a carrier according to Item 25.   27. Copper with a carrier according to claim 25 or 26, 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. The copper foil with a carrier as described in any one of Claims 1, 2, and 5-24 .   One or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on one surface or both surfaces of the ultrathin copper layer The copper foil with a carrier of Claim 24 which has these. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni deposited on the surface of the ultrathin copper layer on the intermediate layer side is 5 μg / dm ² It is the above, The copper foil with a carrier of Claim 3 or 4. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm. ² 300 μg / dm or more ² The copper foil with a carrier according to any one of claims 3, 4, and 30, which is the following. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm. ² 250 μg / dm or more ² The copper foil with a carrier according to claim 31, wherein: After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm. ² 200 μg / dm or more ² The copper foil with a carrier according to claim 32, which is the following. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm. ² 150 μg / dm or more ² The copper foil with a carrier according to claim 33, which is as follows. After heating the copper foil with carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer, the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 μg / dm. ² 100 μg / dm or more ² The copper foil with a carrier according to claim 34, wherein: The surface roughness Rz of the ultrathin copper layer measured using a stylus-type roughness meter in accordance with JIS B0601-1982 is 0.2 μm or more and 1.0 μm or less. 35. A copper foil with a carrier according to any one of 35. The copper with a carrier according to claim 36, wherein the surface roughness Rz of the ultrathin copper layer measured by using a stylus type roughness meter in accordance with JIS B0601-1982 is 0.2 µm or more and 0.6 µm or less. Foil. Any of the surface roughness Rz of the said ultra-thin copper layer measured using a stylus-type roughness meter based on JIS B0601-1982 is 0.42 micrometer or more, Either of 3, 4, and 30-37 The copper foil with a carrier according to one item. Ni content of the intermediate layer is 100 μg / dm ² 40000 μg / dm ² It is the following, The copper foil with a carrier as described in any one of Claim 3, 4, and 30-38. Ni content of the intermediate layer is 100 μg / dm ² 5000 μg / dm or more ² The copper foil with a carrier according to claim 39, wherein: The intermediate layer is selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates, oxides, and organic matter. The copper foil with a carrier as described in any one of Claims 3, 4, and 30-40 containing 1 type, or 2 or more types. When the intermediate layer contains Cr, Cr is 5 to 100 μg / dm. ² When it contains and contains Mo, Mo is 10 μg / dm. ² 1000 μg / dm or more ² In the case of containing Co and containing Co, 10 μg / dm of Co ² 1000 μg / dm or more ² In the case of containing Zn and containing Zn, 1 μg / dm of Zn ² 120 μg / dm or more ² The copper foil with a carrier as described in any one of Claim 3, 4 and 30-41 contained below. The copper foil with a carrier according to claim 41 or 42, wherein the intermediate layer contains an organic substance in a thickness of 25 nm to 80 nm. The said organic substance is an organic substance which consists of 1 type, or 2 or more types selected from a nitrogen-containing organic compound, a sulfur containing organic compound, and carboxylic acid, Copper foil with a carrier as described in any one of Claims 41-43. . The copper foil with a carrier as described in any one of Claim 3, 4 and 30-44 which has the said intermediate | middle layer and the said ultra-thin copper layer in this order on both surfaces of the said carrier. The copper foil with a carrier according to any one of claims 3, 4, and 30 to 45, which has a roughened layer on at least one surface of the ultrathin copper layer and the carrier, or on both surfaces. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing at least one kind. Item 46. The copper foil with carrier according to Item 46. The copper with a carrier according to claim 46 or 47, 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. The copper foil with a carrier as described in any one of Claims 3, 4, and 30-45 which it has. One or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on one surface or both surfaces of the ultrathin copper layer The copper foil with a carrier of Claim 45 which has these. The copper foil with a carrier according to any one of claims 3, 4, and 30 to 45 , comprising a resin layer on the ultrathin copper layer. The copper foil with a carrier according to any one of claims 46, 47 and 50 , comprising a resin layer on the roughening treatment layer. The carrier according to any one of claims 48 to 50 , wherein a resin layer is provided 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. Copper-clad laminate produced using the copper foil with carrier according to any one of claims 1 to 53. Printed wiring board produced using the copper foil with carrier according to any one of claims 1 to 53. An electronic device manufactured using the printed wiring board according to claim 55 . A step of preparing the carrier-attached copper foil according to any one of claims 3 and 4, and 30 to 53 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 1-50,
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. 59. The method for manufacturing a printed wiring board according to claim 58 , which is a forming step. 60. The printed circuit board according to claim 59 , 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 3, 4, and 30 to 53. Method. 61. The print according to any one of claims 58 to 60 , 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 partly additive method, or a modified semi-additive method. A method for manufacturing a wiring board.