JP6329727B2 - Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with a carrier, a method for producing a copper foil with a carrier, a printed wiring board, a printed circuit board, a copper clad laminate, and a method for producing a printed wiring board, and in particular, a printed wiring board for fine patterns. The present invention relates to a carrier-attached copper foil, a method for producing a carrier-attached copper foil, a printed wiring board, a printed circuit board, a copper-clad laminate, and a method for producing a printed wiring board.

  Printed wiring boards have made great progress over the last half century and are now used in almost all electronic devices. 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. In particular, when an IC chip is mounted on a printed wiring board, a fine pitch of L (line) / S (space) = 20 μm / 20 μm or less is required.

  A printed wiring board is first manufactured as a copper clad laminate in which an insulating substrate mainly composed of a copper foil and a glass epoxy substrate, BT resin, polyimide film or the like is bonded. Bonding is performed by laminating an insulating substrate and a copper foil and applying heat and pressure (laminating method), or by applying a varnish that is a precursor of an insulating substrate material to a surface having a coating layer of copper foil, A heating / curing method (casting method) is used.

  Along with the fine pitch, the thickness of the copper foil used for the copper clad laminate is also 9 μm, and further, 5 μm or less. However, when the foil thickness is 9 μm or less, the handleability when forming a copper clad laminate by the above-described lamination method or casting method is extremely deteriorated. Therefore, a copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is formed on the metal foil via a release layer. It is a general method of using a copper foil with a carrier that the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded, and then the carrier is peeled off via the peeling layer.

  Conventionally, a diffusion prevention layer, a release layer, and an electrolytic copper plating are formed in this order on the surface of the carrier foil, and a Cr or Cr hydrated oxide layer is used as the release layer, and Ni, Co, Fe, Cr, Patent Document 1 discloses a method for maintaining good peelability after hot pressing by using a single element or alloy of Mo, Ta, Cu, Al, and P.

  Alternatively, it is known that the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P, alloys thereof, or hydrates thereof. Furthermore, it is described in Patent Documents 2 and 3 that it is effective to provide Ni, Fe or an alloy layer thereof on the base of the release layer in order to stabilize the peelability in a high temperature use environment such as a hot press. Has been.

JP 2006-022406 A JP 2010-006071 A JP 2007-007937 A

  In copper foil with carrier, the ultra-thin copper layer must not be easily peeled off from the carrier before the lamination process on the insulating substrate, while the carrier is easily removed from the ultra-thin copper layer after the lamination process on the insulating substrate. It is necessary to peel off. In addition, after peeling off the carrier from the ultra-thin copper layer after lamination, a circuit is formed on the ultra-thin copper layer by a semi-additive method, so that organic materials and metal and metal oxides that are difficult to etch are maintained in order to maintain good etching properties. It is necessary to reduce the amount of metal hydrated oxide present.

  Regarding Patent Document 1, the peelability after hot pressing is good, but the state of the ultrathin copper layer surface is not mentioned.

  Further, in the same patent document, it is described that the order of the diffusion prevention layer and the release layer may be either, but the examples described are all in the order of carrier foil, release layer, diffusion prevention layer, electrolytic copper plating, At the time of peeling, the peeling layer / diffusion prevention layer interface may peel off. If it becomes so, a diffusion prevention layer will remain on the surface of electrolytic copper plating (ultra-thin copper layer), and it will lead to the etching failure at the time of forming a circuit.

  In Patent Documents 2 and 3, there is no description that can be considered that characteristics such as peel strength between the carrier and the ultrathin copper layer are sufficiently examined, and there is still room for improvement.

  Therefore, the present invention has a high adhesion between the carrier and the ultrathin copper layer before the lamination process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper layer is extremely increased due to the lamination process to the insulation substrate. It is an object of the present invention to provide a copper foil with a carrier that does not decrease, can be easily peeled off at the carrier / ultra thin copper layer interface, and has an excellent etching property of the ultra thin copper layer.

  In order to achieve the above-mentioned object, the present inventor conducted extensive research, and after heat-pressing the carrier-attached copper foil to the substrate under predetermined conditions to peel off the carrier, the amount of Cr deposited on the peeling surface of the carrier is controlled. Thus, it was found that good etching properties can be obtained for the ultrathin copper layer. Also, with such a configuration, the adhesion between the carrier and the ultra-thin copper layer is high before the lamination process to the insulating substrate, while the adhesion between the carrier and the ultra-thin copper layer in the lamination process to the insulation substrate is extremely high. It has been found that there is no increase or decrease, and it can be easily peeled off at the carrier / ultra-thin copper layer interface.

The present invention has been completed based on the above knowledge, and in one aspect, a carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer The intermediate layer contains Cr, and an insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, in accordance with JIS C 6471. When the carrier is peeled off, the average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, and the standard deviation is σ. When the coefficient of variation of the Cr adhesion amount is X = σ × 100 / A, X satisfies 50% or less, and satisfies any one of the following (1) to (3): It is.
(1) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 1 to 40 μg / dm ² .
(2) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 20 μg / dm ² .
(3) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the surface on the intermediate layer side of the ultrathin copper layer is 5 to 15 μg / dm ² .

In one embodiment, the copper foil with a carrier according to the present invention is obtained by thermocompression bonding an insulating substrate to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in JIS C 6471. When the carrier was peeled off in accordance with the standard deviation, the average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer was measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction was defined as A. Is σ and the coefficient of variation of Cr adhesion is X = σ × 100 / A, X satisfies 20% or less .

In another aspect , the carrier-attached copper foil according to the present invention is a carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. The intermediate layer contains Cr, and when the carrier is peeled in accordance with JIS C 6471, the amount of Cr deposited on the intermediate layer side surface of the ultrathin copper layer is 10 points at intervals of 20 mm in the width direction and the longitudinal direction. Assuming that the average value when measured one by one is A ′, the standard deviation is σ ′, and the variation coefficient of Cr adhesion amount is X ′ = σ ′ × 100 / A ′, X ′ satisfies 80% or less, and It satisfies any one or more of (4) to (6), or satisfies any one or more of the following (4) to (6) and any one or more of (7) to (10) It is a copper foil with a carrier that satisfies the above.
(4) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 1 to 40 μg / dm ² .
(5) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 20 μg / dm ² .
(6) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The adhesion amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 15 μg / dm ² .
(7) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr adhesion amount is When X = σ × 100 / A, X satisfies 50% or less.
(8) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr adhesion amount is When X = σ × 100 / A, X satisfies 20% or less.
(9) When the carrier is peeled according to JIS C 6471, the amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 50 μg / dm ² or less.
(10) when in conformity with JIS C 6471 peeling the carrier, the amount of deposition of Cr remaining on the intermediate layer side surface of the ultra-thin copper layer is 1~30μg / dm ^2.

In yet another embodiment of the copper foil with a carrier according to the present invention, when the carrier is peeled in accordance with JIS C 6471, the adhesion amount of Ni on the intermediate layer side surface of the ultrathin copper layer is determined in the width direction. The average value when 10 points are measured at intervals of 20 mm in the longitudinal direction is A ″ , the standard deviation is σ ″, and the coefficient of variation of the Ni adhesion amount is X ″ = σ ″ × 100 / A ″. Then, X ″ satisfies 50% or less.

  In still another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is made of any one layer of nickel or an alloy containing nickel on the carrier, chromium, a chromium alloy, and an oxide of chromium. A layer including any one or more of them is formed by stacking in this order.

  In still another embodiment of the carrier-attached copper foil according to the present invention, the layer containing at least one of chromium, a chromium alloy, and a chromium oxide includes a chromate treatment layer.

  In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer contains zinc.

  In still another embodiment of the carrier-attached copper foil according to the present invention, the intermediate layer is any one layer of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy on the carrier, And any one of a zinc chromate treatment layer, a pure chromate treatment layer, and a chromium plating layer is laminated in this order.

In yet another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is formed by laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer in this order on the carrier. Or a nickel-zinc alloy layer and a pure chromate treatment layer or a zinc chromate treatment layer are laminated in this order, and the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm ^2. The adhesion amount of chromium is 5 to 100 μg / dm ² , and the adhesion amount of zinc is 1 to 70 μg / dm ² .

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer includes a nickel layer on the carrier, and an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. The amount of nickel deposited on the intermediate layer is 100 to 40000 μg / dm ² .

In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer includes an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on the carrier, and a nickel layer. The amount of nickel deposited on the intermediate layer is 100 to 40000 μg / dm ² .

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

In still another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer includes at least one of a nickel layer or an alloy layer containing nickel and molybdenum, cobalt, and a molybdenum cobalt alloy on the carrier. It is constructed by stacking in the order of the layers to include,
The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm ² , and when molybdenum is included, the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and when cobalt is included, the adhesion amount of cobalt is 10 ˜1000 μg / dm ² .

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

  In yet another embodiment, the copper foil with a carrier according to the present invention has a roughening treatment layer on the surface of the ultrathin copper layer.

  In still another embodiment of the copper foil with a carrier according to 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. Or a layer made of an alloy containing one or more of them.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. Has more than seed layers.

  In still another embodiment, the carrier-attached copper foil according to the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. Has more than seed layers.

  In another aspect of the present invention, after forming any one layer of nickel or an alloy containing nickel on a carrier, a layer containing any one or more of chromium, a chromium alloy, or an oxide of chromium is formed. An intermediate in which zinc is contained in at least one layer of nickel or an alloy containing nickel, or a layer containing any one or more of chromium, a chromium alloy, or an oxide of chromium It is a manufacturing method of copper foil with a carrier including the process of forming a layer, and the process of forming an ultra-thin copper layer by electrolytic plating on the said intermediate | middle layer.

  In one embodiment of the method for manufacturing a copper foil with a carrier according to the present invention, after forming a plating layer containing nickel and zinc on a carrier, an intermediate layer is formed by forming a plating layer containing chromium or a chromate treatment layer. And a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer.

  In another embodiment of the method for producing a copper foil with a carrier according to the present invention, after forming a plating layer containing nickel on a carrier, a plating layer containing chromium and zinc or a zinc chromate treatment layer is formed. Forming an intermediate layer; and forming an ultrathin copper layer on the intermediate layer by electrolytic plating.

  In yet another embodiment of the method for producing a copper foil with a carrier according to the present invention, a plating layer containing nickel and zinc is formed on a carrier, and then a plating layer containing zinc and zinc or a zinc chromate treatment layer is formed. Thus, the method includes a step of forming an intermediate layer and a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating.

  In yet another embodiment of the method for producing a copper foil with a carrier according to the present invention, after forming a nickel plating layer on the carrier, an intermediate layer is formed by forming a zinc chromate treatment layer with electrolytic chromate. Alternatively, after forming a nickel-zinc alloy plating layer, a step of forming an intermediate layer by forming a pure chromate treatment layer or a zinc chromate treatment layer by electrolytic chromate, and an ultrathin copper layer by electrolytic plating on the intermediate layer Forming the step.

  In still another embodiment, the method for producing a copper foil with a carrier according to the present invention further includes a step of forming a roughened layer on the ultrathin copper layer.

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

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

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

  In yet another aspect 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 the lamination, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then the circuit is formed by any of the semi-additive method, the subtractive method, the partial additive method, or the modified semi-additive method. It is a manufacturing method of a printed wiring board including the process of forming.

  According to the present invention, the adhesion between the carrier and the ultrathin copper layer is high before the lamination process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper layer is extremely increased due to the lamination process to the insulation substrate. It is possible to provide a copper foil with a carrier that does not decrease, can be easily peeled off at the carrier / ultra thin copper layer interface, and has an excellent etching property of the ultra thin copper layer.

It is a graph which shows the relationship between etching time and the thickness reduced by the etching.

<Copper foil with carrier>
The copper foil with a carrier of the present invention includes a carrier, an intermediate layer containing Cr laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. The method of using the copper foil with carrier itself is well known to those skilled in the art. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. A copper layer is etched into the intended conductor pattern, and finally a printed wiring board, a printed circuit board, a copper clad laminate, or the like can be produced.

After the copper foil with carrier is bonded to the substrate by thermocompression bonding and the ultrathin copper layer is peeled off from the copper foil with carrier, if the amount of Cr remaining in the ultrathin copper layer is large, the etching property of the ultrathin copper layer Becomes defective. For this reason, the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in accordance with JIS C 6471. when peeling off the carrier, deposition amount of Cr remaining on the intermediate layer side surface of the ultra-thin copper layer are controlled such that the 1~40μg / dm ^2, so as to 5-20 pg / dm ² It is more preferable to be controlled, and it is more preferable to be controlled so as to be 5 to 15 μg / dm ² .

Moreover, when the copper foil with a carrier is bonded to a substrate by thermocompression bonding and the ultrathin copper layer is peeled off from the copper foil with a carrier, the variation in the in-plane distribution of the amount of Cr deposited on the peeled surface of the ultrathin copper layer is large. In addition, the variation in the in-plane distribution of the etching property is increased, and the etching property of the ultrathin copper layer may be deteriorated. For this reason, the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in accordance with JIS C 6471. When the carrier was peeled off, the average value when the adhesion amount of Cr on the intermediate layer side surface of the ultra-thin copper layer was measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction was A, and the standard deviation was σ. The coefficient of variation in the amount of Cr adhesion: X = σ × 100 / A is used as an index of variation in the in-plane distribution of the Cr adhesion amount on the surface of the intermediate layer of the ultrathin copper layer, and by controlling this, the etching property It is preferable to control the in-plane distribution within a certain range, thereby improving the etching property of the ultrathin copper layer. In the present invention, the Cr adhesion amount variation coefficient: X is preferably controlled to satisfy 50% or less, and more preferably, X is controlled to satisfy 20% or less. The variation coefficient of Cr adhesion amount: X can be controlled by keeping the current density of Cr plating at the time of forming the intermediate layer low and controlling the adhesion amount at the conveyance speed. It is also effective to keep the parallelism between the carrier and the anode when forming the intermediate layer uniform.

It is also possible to control the amount of Cr remaining on the ultrathin copper layer when the ultrathin copper layer is peeled from the carrier-added copper foil without thermocompression bonding with the insulating substrate. It is preferable for improvement. From such a viewpoint, the copper foil with a carrier of the present invention has an adhesion amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer of 50 μg / dm ² when the carrier is peeled according to JIS C 6471. follows is preferable to be controlled so that, more preferably is controlled so that 1~30μg / dm ^2, more preferably is controlled so that 3~20μg / dm ² More preferably, it is controlled to be 5 to 15 μg / dm ² .

  In addition, it is also an etching aspect that suppresses the variation in the in-plane distribution of Cr adhesion on the peeled surface of the ultrathin copper layer when the ultrathin copper layer is peeled off from the carrier-attached copper foil without thermocompression bonding with the insulating substrate. It is preferable for suppressing variation in internal distribution. For this reason, the copper foil with a carrier of the present invention has an average value of A 'when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction. When the standard deviation is σ ′ and the variation coefficient of Cr adhesion amount is X ′ = σ ′ × 100 / A ′, it is preferable that X ′ is controlled to satisfy 80% or less, and satisfies 50% or less. It is more preferable to be controlled so that it is controlled to satisfy 20% or less.

<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. 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, for example, 12 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 12-70 μm, more typically 18-35 μm.

<Intermediate layer>
An intermediate layer containing Cr 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 chromate or dichromate. The chromate treatment layer may contain a metal such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. 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.
In addition, the intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy, zinc chromate treatment layer, pure chromate treatment layer, and chromium plating layer on the carrier. 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. It is more preferable that the nickel-zinc alloy layer and the pure chromate-treated layer or the zinc chromate-treated 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 layer 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 an ultrathin copper layer by electroplating is less likely and pinholes can be reduced. it can. Here, by forming a zinc chromate treatment layer as the chromate treatment layer, the resistance when forming an ultrathin copper layer by electroplating becomes 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. If a 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 If the nickel layer or 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 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.

  In addition, if the chromate treatment layer is present at the boundary between the carrier and the nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the intermediate layer is also peeled off along with the peeling of the ultrathin copper layer. 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.

Intermediate nickel layer or nickel-containing alloy layer (eg 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 nickel, 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 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 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.

<Strike plating>
An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 2-5 μm.

<Roughening treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. 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 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. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

<Printed wiring boards, printed circuit boards, and copper-clad laminates>
A copper clad laminate can be produced by attaching a copper foil with a carrier to the insulating resin plate from the ultrathin copper layer side, thermocompression bonding, and peeling the carrier. Thereafter, a copper circuit of a printed wiring board or a printed circuit board can be formed by etching the ultrathin copper layer portion. The insulating resin plate used here is not particularly limited as long as it has characteristics applicable to a printed wiring board or a printed circuit board. For example, a paper base phenolic resin, a paper base epoxy resin for rigid PWB, Use synthetic fiber cloth base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin, glass cloth base epoxy resin, etc., polyester film or polyimide film etc. for FPC Can be used. The printed wiring board, printed circuit board, and copper-clad laminate produced in this manner can be mounted on various electronic components that require high-density mounting of the mounted components.

<Method for manufacturing printed wiring board>
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, the carrier After laminating the attached 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, The method includes a step of forming a circuit by any one of the modified semi-additive method, the partly additive method, and the 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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

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

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
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.

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

1. Manufacture of copper foil with carrier As a copper foil carrier, a long electrolytic copper foil (JTC made by JX Nippon Mining & Metals) having a thickness of 35 μm and a rolled copper foil having a thickness of 33 μm (tough pitch copper foil made by JX Nippon Mining & Metals) JIS H3100 alloy number C1100) was prepared. On the shiny surface of this copper foil, an intermediate layer formation treatment was performed on the carrier surface with a roll-to-roll type continuous line under the following conditions. As the intermediate layer forming treatment, Ni plating treatment before treatment with the Cr-containing solution described in the table was performed, and subsequently, Cr-containing solution treatment was performed. The Ni plating treatment before Cr-containing solution treatment at this time is shown below. In addition, washing and pickling were performed between the processing steps on the carrier surface side and the ultrathin copper layer side.

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

Ni-Zn plating treatment conditions before Cr-containing solution treatment In the above-mentioned Ni plating formation conditions, zinc in the form of zinc sulfate (ZnSO ₄ ) was added to the Ni plating solution, and the zinc concentration was 0.05 to 5 g / L. The nickel zinc alloy plating was formed by adjusting the range.

Ni-W plating conditions before treatment with Cr-containing solution In the above Ni plating formation conditions, tungsten in the form of sodium tungstate was added to the Ni plating solution, and the tungsten concentration was adjusted in the range of 0.1 to 10 g / L. Nickel tungsten alloy plating was formed.

Conditions for Zn plating treatment before treatment with Cr-containing solution (Liquid composition) Zinc chloride: 70 to 95 g / L, Potassium chloride: 200 to 225 g / L, Sulfuric acid: 25 to 30 g / L
(PH) 4.5-5.5
(Liquid temperature) 20-35 ° C
(Current density) 0.5 to 5 A / dm ²
(Energization time) 1 to 20 seconds

Mo-Co plating treatment conditions before Cr-containing solution treatment In the above-mentioned Ni plating formation conditions, cobalt in the form of cobalt sulfate is added to the Ni plating solution, and the cobalt concentration is adjusted in the range of 0.1 to 10 g / L. Nickel cobalt alloy plating was formed.

Co plating conditions before treatment with Cr-containing solution (Liquid composition) Cobalt sulfate: 10 to 200 g / L, Sodium citrate: 2 to 240 g / L
(PH) 2-5
(Liquid temperature) 10-70 ° C
(Current density) 0.5 to 10 A / dm ²
(Energization time) 1 to 20 seconds

Ni-Sn plating conditions before treatment with Cr-containing solution In the above Ni plating formation conditions, tin in the form of sodium stannate is added to the Ni plating solution, and the tin concentration is adjusted in the range of 0.1 to 10 g / L. Thus, a nickel tin alloy plating was formed.

Cr plating treatment conditions before treatment with Cr-containing solution (Liquid composition) CrO ₃ : 200 to 400 g / L, H ₂ SO ₄ : 1.5 to ₄ g / L
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²
(Energization time) 1 to 20 seconds

Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 3 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

In Examples 2, 3, 7, and 11, the surface of the ultrathin copper layer was subjected to the following roughening treatment, rust prevention treatment, chromate treatment, and silane coupling treatment in this order.
・ Roughening treatment Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
Temperature: 40-50 ° C
Current density Dk: 20 to 30 A / dm ²
Time: 1 to 5 seconds Cu adhesion amount: 15 to 40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Rust prevention treatment Zn: 0-20g / L
Ni: 0 to 5 g / L
pH: 3.5
Temperature: 40 ° C
Current density Dk: 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment (zinc chromate treatment)
K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Time: 5-30 seconds

  When the intermediate layer is formed, the Cr adhesion amount variation coefficient: X and X ′ are controlled by keeping the current density of the chromate treatment low, controlling the adhesion amount by the conveyance speed, and adjusting the parallelism between the carrier and the anode. It was done by keeping it uniform.

For Example 5, after forming Ni plating as an intermediate layer, a BTA film (organic film) was formed by the following organic agent layer forming process, and a Cr-containing solution process was further performed.
(Organic agent layer formation treatment)
An aqueous solution containing BTA at a concentration of 5 g / L and having a liquid temperature of 40 ° C. and pH 5 was sprayed by showering for 30 seconds.

After forming the intermediate layer, an ultrathin copper layer having a thickness of 1 to 10 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

2. Evaluation of Copper Foil with Carrier For the copper foil with carrier obtained as described above, each evaluation was performed by the following methods.

<Cr average transfer amount (Cr adhesion amount) and its coefficient of variation>
Copper foil with carrier, ultrathin copper layer side on a substrate of BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in air, pressure: 20 kgf / cm ² , 220 ° C. × 2 hours And bonded by thermocompression. Thereafter, the ultrathin copper layer was peeled off from the carrier in accordance with JIS C 6471 (Method A). Subsequently, the sample size is 200 to 2000 mm in width × 200 to 2000 mm in length, dissolved in hydrochloric acid having a concentration of 7% by mass, and quantitative analysis is performed by atomic absorption, whereby Cr on the peeled surface of the ultrathin copper layer is obtained. The amount of adhesion was measured. Further, with respect to the peeling surface of the ultrathin copper layer, the average value when measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of Cr adhesion amount: X = σ X100 / A was determined. Similarly, the variation coefficient of Cr adhesion amount: X ′ = σ ′ × 100 / A ′ was also measured for the ultrathin copper layer of the carrier-attached copper foil before being bonded to the resin substrate.

<Thickness of ultrathin copper layer>
The thickness of the ultrathin copper layer of the produced copper foil with carrier was measured by observing the cross section of the ultrathin copper layer using FIB-SIM (magnification: 10,000 to 30,000 times). In the cross section of the ultrathin copper layer, the thickness of the ultrathin copper layer was measured at five locations at intervals of 30 μm, and the average value was obtained. And the said average value was made into the thickness of an ultra-thin copper layer.

<Peel strength>
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 load cell, and the peel strength was measured according to the 90 ° peel method (JIS C 6471 8.1). Also, the peel strength was measured in the same manner for each sample before thermocompression bonding with the resin.

<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 x 2h, 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.), and etch the entire surface to a small etching machine (Small Half Etching Device No.K-07003, manufactured by Ninomiya System) It carried out by. The etching conditions at this time are shown below.
(Etching conditions)
As an etching solution, 20 vol% of sulfuric acid-peroxide aqueous solution: SE-07 manufactured by Mitsubishi Gas Chemical Co., Ltd. (diluted stock solution 15 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 Co., Ltd. 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 was obtained in the form of 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 (reduction 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 etchings, the average of the number of times of etching, and the maximum number of etchings−the minimum number of etchings were measured. The determination of the number of times of etching was “◎” when the number of times of etching was 9 or less, “◯” when the number of etching was 10 to 12, and “x” when 13 or more times. The determination of the variation in the number of etchings is as follows: “Maximum number of etchings−Minimum number of etchings of 1-2” is “◎”, 3-4 times is “◯”, and 5 times or more is “×”. did. When the thickness of the ultra-thin copper layer is 4 μm and 5 μm, the number of etchings is judged as “◎” when the number of etchings is 16 times or less, “○” when 17-20 times, and 20 times. The above was designated as “x”. The determination of the variation in the number of etchings is as follows: “Maximum number of etchings−Minimum number of etchings of 1 to 4” is “◎”, 4 to 6 is “O”, and 7 or more is “×”. did. In addition, when the thickness of the ultrathin copper layer is 10 m, the number of etchings is determined as “」 ”when the number of etchings is 75 times or less,“ ○ ”when the number of etchings is 75 to 85 times, and 86 times or more. The thing was made into "x". The determination of the variation in the number of etchings is as follows: “Maximum number of etchings−Minimum number of etchings 1-5” is “◎”, 5-8 times is “O”, and 9 times or more is “X”. did.
Moreover, the etching property was similarly measured about each sample before thermocompression bonding with the said resin.

<Thickness of organic material in the intermediate layer>
For each sample before thermocompression bonding with resin, after peeling the ultrathin copper layer of the carrier-attached copper foil from the carrier, the exposed surface of the intermediate layer side of the exposed ultrathin copper layer and the exposed surface of the intermediate layer side of the carrier Is measured by XPS, and a depth profile is 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. The larger the value of x, the deeper (farther) the measurement position of the metal atomic concentration is from the surface. 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 the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
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 )
As described above, as a result of measuring the organic material thickness of the intermediate layer, the organic material thickness of the intermediate layer of Example 5 was 39 nm.
The results are shown in Tables 1 and 2.

In each of Examples 2 to 13 and 18 to 27, the peelability at the ultrathin copper layer / carrier interface and the etchability of the ultrathin copper layer were good. In particular, in Examples 2 to 7, 9 to 11, and 13, the in-plane variation in the amount of Cr adhered was well suppressed, and thus the variation in the number of etchings was also well suppressed.
In Comparative Example 1, Cr was not contained in the intermediate layer, and the peelability at the ultrathin copper layer / carrier interface was poor.
In Comparative Examples 14 to 17, since the adhesion amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer was outside the range of 1 to 40 μg / dm ² , both of the peelability at the ultrathin copper layer / carrier interface and // The etching property of the ultrathin copper layer was poor.

Claims (28)

A carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer,
The intermediate layer includes Cr;
When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in the atmosphere, and the carrier is peeled off in accordance with JIS C 6471, the ultrathin copper layer The average value when the amount of Cr deposited on the intermediate layer side surface of the layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr deposited amount is X = σ When it is set to x100 / A, X is 50% or less, and the copper foil with a carrier which satisfy | fills any one or more of the following (1)-(3).
(1) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 1 to 40 μg / dm ² .
(2) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 20 μg / dm ² .
(3) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the surface on the intermediate layer side of the ultrathin copper layer is 5 to 15 μg / dm ² . When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in the atmosphere, and the carrier is peeled off in accordance with JIS C 6471, the ultrathin copper layer The average value when the amount of Cr deposited on the intermediate layer side surface of the layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr deposited amount is X = σ When × and 100 / a, the copper foil with carrier according to claim 1 in which X satisfies the following 20%. A carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer,
The intermediate layer includes Cr;
When the carrier was peeled off in accordance with JIS C 6471, the average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer was measured 10 points at intervals of 20 mm in the width direction and the longitudinal direction was A , Where the standard deviation is σ 'and the variation coefficient of Cr adhesion is X' = σ '× 100 / A', X 'satisfies 80% or less, and any of the following (4) to (6) A copper foil with a carrier that satisfies at least one of the above, or satisfies at least one of the following (4) to (6) and satisfies at least one of (7) to (10).
(4) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 1 to 40 μg / dm ² .
(5) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 20 μg / dm ² .
(6) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The adhesion amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 5 to 15 μg / dm ² .
(7) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr adhesion amount is When X = σ × 100 / A, X satisfies 50% or less.
(8) When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and the carrier is peeled off in accordance with JIS C 6471, The average value when the adhesion amount of Cr on the intermediate layer side surface of the ultrathin copper layer is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction is A, the standard deviation is σ, and the variation coefficient of the Cr adhesion amount is When X = σ × 100 / A, X satisfies 20% or less.
(9) When the carrier is peeled according to JIS C 6471, the amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 50 μg / dm ² or less.
(10) When the carrier is peeled in accordance with JIS C 6471, the amount of Cr remaining on the intermediate layer side surface of the ultrathin copper layer is 1 to 30 μg / dm ² . When the carrier was peeled off in accordance with JIS C 6471, the average value when the adhesion amount of Ni on the intermediate layer side surface of the ultrathin copper layer was measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction was A 'and the standard deviation sigma''and''When,X' the variation coefficient of the Ni deposition amount X '' = σ '' × 100 / a '' is as defined in claim 3 which satisfies the following 50% Copper foil with carrier. The intermediate layer is configured 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. The copper foil with a carrier as described in any one of Claims 1-4 . The copper foil with a carrier according to claim 5 , wherein the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide includes a chromate treatment layer. The said intermediate | middle layer is copper foil with a carrier as described in any one of Claims 1-6 containing zinc. The intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy, zinc chromate treatment layer, pure chromate treatment layer, and chromium plating layer on the carrier. The copper foil with a carrier according to any one of claims 1 to 7 , wherein one layer is laminated in this order. The intermediate layer is on the carrier,
A nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer are laminated in this order, or
A nickel-zinc alloy layer and a pure chromate treatment layer or a zinc chromate treatment layer are laminated in this order.
The amount of adhered 100~40000μg / dm ² of nickel in the intermediate layer, the adhesion amount of chromium 5~100μg / dm ^2, any one of claims 1-7 adhering amount of zinc is 1~70μg / dm ² The copper foil with a carrier according to the item . The intermediate layer is formed by laminating a nickel layer on the 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 copper foil with a carrier according to any one of claims 1 to 7 , wherein an adhesion amount of nickel in the intermediate layer is 100 to 40,000 µg / dm ² . The intermediate layer is configured by laminating an organic material layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on the carrier, and a nickel layer in this order.
The copper foil with a carrier according to any one of claims 1 to 7 , wherein an adhesion amount of nickel in the intermediate layer is 100 to 40,000 µg / dm ² . The copper foil with a carrier according to claim 10 or 11 , wherein the intermediate layer contains an organic substance in a thickness of 25 nm to 80 nm. The intermediate layer is formed by laminating a nickel layer or an alloy layer containing nickel on the carrier and a layer containing any one or more of molybdenum, cobalt, and a molybdenum cobalt alloy in this order.
The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm ² , and when molybdenum is included, the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and when cobalt is included, the adhesion amount of cobalt is 10 ~1000μg / dm ² copper foil with carrier according to any one of claims 1 to 7. The copper foil with a carrier according to any one of claims 1 to 13 , wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil. Copper foil with carrier according to any one of claims 1 to 14 having a roughened layer on the ultra-thin copper layer surface. 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 16. A copper foil with a carrier according to Item 15 . The copper with a carrier according to claim 15 or 16 , comprising at least one layer 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. Foil. On the surface of the ultra-thin copper layer, heat-resistant layer, the anticorrosive layer, any one of claim 1 to 14 having one or more layers selected from the group consisting of chromate treatment layer and a silane coupling treatment layer The copper foil with a carrier of description. On the carrier, after forming any one layer of nickel or an alloy containing nickel, forming a layer containing any one or more of chromium, a chromium alloy or an oxide of chromium, and at least the nickel or nickel A step of forming an intermediate layer containing zinc in any one layer of an alloy containing or any one of chromium, a chromium alloy, or a layer containing an oxide of chromium, and the intermediate method for producing a copper foil with carrier according to any one of claims 1 to 18, and forming a very thin copper layer by electrolytic plating on the layer. After forming a plating layer containing nickel and zinc on the carrier, forming an intermediate layer by forming a plating layer containing chromium or a chromate treatment layer, and an ultrathin copper layer by electrolytic plating on the intermediate layer method for producing a copper foil with carrier according to any one of claims 1 to 18 including the step of forming a. After forming a plating layer containing nickel on the carrier, a step of forming an intermediate layer by forming a plating layer containing chromium and zinc or a zinc chromate treatment layer, and ultrathin copper by electrolytic plating on the intermediate layer method for producing a copper foil with carrier according to any one of claims 1 to 18 including the step of forming the layer. After forming a plating layer containing nickel and zinc on the carrier, forming a plating layer containing chromium and zinc or a zinc chromate treatment layer, and forming an intermediate layer on the intermediate layer by electrolytic plating method for producing a copper foil with carrier according to any one of claims 1 to 18, and forming a thin copper layer. After forming a nickel plating layer on the carrier, an intermediate layer is formed by forming a zinc chromate treatment layer by electrolytic chromate, or after forming a nickel-zinc alloy plating layer, a pure chromate treatment layer by electrolytic chromate or forming an intermediate layer by forming a zinc chromate treatment layer, according to any one of claims 1 to 18, and forming a very thin copper layer by electrolytic plating on the middle layer The manufacturing method of copper foil with a carrier. Method for producing a copper foil with carrier according to any one of claims 19 to 23, further comprising the step of forming a roughened layer on the ultra-thin copper layer. Printed wiring board produced using the copper foil with carrier according to any one of claims 1 to 18. Printed circuit board produced using the copper foil with carrier according to any one of claims 1 to 18. Copper-clad laminate produced using the copper foil with carrier according to any one of claims 1 to 18. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 18 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.