JP2014172179A - Carrier-provided copper foil, method of producing carrier-provided copper foil, printed wiring board, printed circuit board, copper-clad laminate and method of producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide carrier-provided copper foil which has high adhesion between a carrier and ultrathin copper foil before a step of laminating on an insulated substrate, does not cause extreme increase or decrease of the adhesion between the carrier and the ultrathin copper foil in the step of laminating on the insulated substrate, allows easy peeling in the carrier/ultrathin copper foil boundary surface and has good etching properties of the ultrathin copper foil.SOLUTION: In carrier-provided copper foil, an intermediate layer contains Ni. When an insulated substrate is adhered to an ultrathin copper layer by thermal compression in the atmosphere in conditions of a pressure of 20 kgf/cmand a duration of 220°C×2 h; the carrier is peeled by the method of JIS C 6471; and the surface of the ultrathin copper layer on the intermediate layer side is removed to a depth of 0.1 μm by etching, the adhesion amount of Ni remaining in the ultrathin copper layer is 200 μg/dmor smaller.

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. A common method of using a copper foil with a carrier is to bond the surface of an ultrathin copper layer to an insulating substrate, thermocompression bond, and then peel the carrier through a 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 ultrathin copper foil must not be easily peeled off from the carrier before the lamination process on the insulating substrate, while the carrier from the ultrathin copper foil is easily peeled off after the lamination process on the insulation substrate. It is necessary to peel off. In addition, after peeling the carrier from the ultra-thin copper foil after lamination, a circuit is formed on the ultra-thin copper foil by a semi-additive method, so that organic substances 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 foil 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 the properties such as the peel strength between the carrier and the ultrathin copper foil 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 foil before the lamination process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper foil 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 deteriorate, can be easily peeled off at the carrier / ultra thin copper foil interface, and has an excellent etching property of the ultra thin copper foil.

  In order to achieve the above object, the present inventor conducted extensive research, and then thermally bonded the insulating substrate to the ultrathin copper layer under predetermined conditions, and after removing the ultrathin copper layer from the copper foil with carrier, etching was performed. It is possible to control the amount of Ni on the peeling side surface of the ultrathin copper layer when the ultrathin copper layer is removed from the surface on the intermediate layer side to a very shallow region of a depth of 0.1 μm. The present inventors have found that it is extremely effective for improving the peelability at the thin copper foil interface and the etching property of the ultrathin copper foil.

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 Ni, and the ultra-thin copper layer is thermocompression bonded to the insulating substrate in the air under conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, and conforms to JIS C 6471. When the carrier is peeled off and removed by etching from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm, the adhesion amount of Ni remaining on the ultrathin copper layer becomes 200 μg / dm ² or less. Copper foil with carrier.

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 conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in JIS C 6471. When the ultra-thin copper layer is peeled off in accordance with the removal from the surface on the intermediate layer side of the ultra-thin copper layer to a depth of 0.1 μm, the adhesion amount of Ni remaining on the ultra-thin copper layer is 1 to 150 μg / dm ² .

In another embodiment of the copper foil with a carrier according to the present invention, an insulating substrate is thermocompression bonded to the ultrathin copper layer under conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in JIS C When the ultra-thin copper layer is peeled off in accordance with 6471, the remaining Ni adheres to the ultra-thin copper layer when the ultra-thin copper layer is removed by etching from the surface on the intermediate layer side to a depth of 0.1 μm. The amount is 3 to 50 μg / dm ² .

In another embodiment of the copper foil with a carrier according to the present invention, an insulating substrate is thermocompression bonded to the ultra-thin copper layer under conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in JIS, When the carrier is peeled in accordance with C 6471, the amount of Ni remaining on the ultrathin copper layer is 5 to 400 μg / dm ² .

In another embodiment of the copper foil with a carrier according to the present invention, when the carrier is peeled from the ultrathin copper layer in accordance with JIS C 6471, the amount of Ni remaining on the ultrathin copper layer is 1 ˜400 μg / dm ² .

  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 comprises a nickel layer or an alloy layer containing nickel on the carrier, and a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. The organic layer is laminated in the order of any one of them, and the adhesion amount of nickel in 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. Or it is comprised by laminating | stacking in order of the alloy layer containing nickel, and the adhesion amount of nickel in the said intermediate | middle layer is 100-40000 microgram / 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 or more and 80 nm or less.

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 foil is high before the laminating process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper foil due to the laminating process to the insulating substrate is extremely increased. There can be provided a copper foil with a carrier that does not deteriorate, can be easily peeled off at the carrier / ultra thin copper foil interface, and has an excellent etching property of the ultra thin copper foil.

It is the schematic of the cross section of the width direction of the circuit pattern in an Example, and the outline of the calculation method of the etching factor (EF) using this schematic diagram.

<Copper foil with carrier>
The copper foil with a carrier of the present invention comprises a carrier, an intermediate layer containing Ni 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. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. 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 insulating substrate is thermocompression bonded to the ultrathin copper layer under predetermined conditions, the ultrathin copper layer is peeled off from the copper foil with carrier, and then etched to a depth of 0.1 μm from the surface on the intermediate layer side of the ultrathin copper layer When the amount of Ni on the peeling side surface of the ultrathin copper layer when removed is large, the ultrathin copper layer is difficult to be etched, and it becomes difficult to form a fine pitch circuit. For this reason, the copper foil with a carrier of the present invention is 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 is peeled off and removed by etching from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm, the adhesion amount of Ni remaining on the ultrathin copper layer is 200 μg / dm ² or less. is controlled to, preferably being controlled so that 1~150μg / dm ^2, preferably being controlled so that 3~50μg / dm ^2, the 3~45μg / dm ² Is preferably controlled to be 3 to 40 μg / dm ² , preferably controlled to be 5 to 30 μg / dm ^2, and is preferably 5 to 20 μg / dm ^2. dm ² It is preferable to be controlled in such a manner. After the carrier-attached copper foil is bonded to the insulating substrate and the carrier is peeled off after thermocompression bonding, foreign matter is removed from the exposed surface of the intermediate layer of the ultrathin copper layer and the adhesion of the etching resist in the subsequent etching process is improved. Therefore, a very shallow region from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm may be etched. At this time, if there is a large amount of Ni remaining on the surface on the intermediate layer side of the ultrathin copper layer after etching in a very shallow region having a depth of 0.1 μm, the subsequent ultrathin copper layer is intended. In the process of etching the conductor pattern, the ultrathin copper layer is hardly etched, and it is difficult to form a fine pitch circuit. The region is a region where Ni is most likely to accumulate in the ultrathin copper layer due to diffusion of Ni in the intermediate layer. In contrast, in the copper foil with a carrier of the present invention, the amount of Ni deposited on the surface of the ultrathin copper layer when the etching is removed from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm is controlled. ing. When the Ni adhesion amount exceeds 200 μg / dm ² , the ultra-thin copper layer is etched to form a wiring finer than L / S = 20 μm / 20 μm, for example, a fine wiring of L / S = 15 μm / 15 μm. May become difficult, and the etching property of the ultrathin copper foil may be poor. The above-mentioned “thermocompression bonding under the condition of 220 ° C. × 2 hours” indicates a typical heating condition in the case where the carrier-attached copper foil is bonded to the insulating substrate and thermocompression bonded. In addition, if the amount of Ni remaining on the surface of the intermediate layer side of the ultrathin copper layer after etching in a very shallow region of 0.1 μm depth is too small, the circuit formability deteriorates (the etching factor is small). There is a case.

An example of the etching conditions of “from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm” in the present invention is shown below.
(Etching conditions)
・ Etching solution: 20 vol% of SE-07 manufactured by Mitsubishi Gas Chemical (diluted stock solution 5 times with water, copper concentration 50 g / L)
・ Temperature: 35 ± 2 ℃
Spray pressure: 0.1 MPa (spraying is performed so that the etching solution hits the copper layer to be etched perpendicularly)
In addition, as the above-described etching conditions and etchant, any known etching conditions and etchants used for copper foil etching or soft etching can be used. However, an etching condition or an etchant that selectively removes only Ni by etching is not preferable. Also, etching conditions and etching solutions that selectively remove only elements other than Ni by etching are not preferable.

If the amount of Ni deposited on the surface of the ultrathin copper layer after peeling the ultrathin copper layer from the thermo-compressed copper foil with carrier as described above is too large, the ultrathin copper layer becomes difficult to be etched, and a fine pitch circuit is formed. It may be difficult to form. On the other hand, if the Ni adhesion amount is too small, the carrier Cu may diffuse toward the ultrathin copper layer. In such a case, the degree of bonding between the carrier and the ultrathin copper layer becomes too strong, and pinholes are likely to occur in the ultrathin copper layer when the ultrathin copper layer is peeled off. From this point of view, when the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in the atmosphere, and the carrier is peeled off in accordance with JIS C 6471 , is preferable to be controlled so that the amount of deposition of Ni remaining in the ultra-thin copper layer is 5~400μg / dm ^2, more preferably is controlled so that 5~350μg / dm ^2, more preferably it is controlled so that 6~300μg / dm ^2, more preferably is controlled so that 8~250μg / dm ^2, is controlled to be 8~200μg / dm ² More preferably, it is more preferably controlled to be 10 to 100 μg / dm ² .

Moreover, the copper foil with a carrier of the present invention remains in the ultrathin copper layer when the carrier is peeled off from the ultrathin copper layer in accordance with JIS C 6471 without thermocompression bonding with the insulating substrate as described above. It is preferable to control the adhesion amount of Ni to be 1 to 400 μg / dm ² . When the Ni deposition amount exceeds 400 μg / dm ² , the ultra-thin copper layer is etched to form wiring finer than L / S = 20 μm / 20 μm, for example, fine wiring with L / S = 15 μm / 15 μm It may be difficult to do so, and the etching property of the ultrathin copper foil may be poor. On the other hand, if the Ni adhesion amount is less than 1 μg / dm ² , the carrier Cu may diffuse toward the ultrathin copper layer. In such a case, the degree of bonding between the carrier and the ultrathin copper layer becomes too strong, and pinholes are likely to occur in the ultrathin copper layer when the ultrathin copper layer is peeled off. The Ni coating weight is more preferable to be controlled so that 2~350μg / dm ^2, more preferably is controlled so that 3~300μg / dm ^2, and 5~250μg / dm ² It is more preferable to control so that it may become, it is more preferable to control so that it may become 8-200 microgram / dm < ² >, and it is more preferable to control so that it may become 10-100 microgram / dm < ² >.

<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 Ni is provided on one side or both sides of the carrier. The intermediate layer is formed by laminating any one layer of nickel or an alloy containing nickel on the carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. In addition, it is preferable that zinc is contained in any one layer of nickel or an alloy containing nickel and / or a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel may be an alloy composed of three or more elements. The chromium alloy is an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy may be an alloy composed of three or more elements. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.
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 foil is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of ultrathin copper foil by electroplating is less likely to reduce pinholes. it can. Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  Among the intermediate layers, the chromate treatment layer is thinly present at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel off from the carrier before the laminating process on the insulating substrate, while after the laminating process on the insulating substrate It is preferable for obtaining the property that the ultrathin copper layer can be peeled from the carrier. 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, and if they are in contact with each other, the adhesive force increases due to mutual diffusion and is difficult to peel off. 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 toward the ultra-thin copper layer 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 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.
Further, when the carrier transport speed (line speed) at the time of forming the intermediate layer is lowered and / or the current density in the plating process is lowered, any one layer of nickel or an alloy containing nickel, and chromium, chromium The density of the layer containing at least one of an alloy and a chromium oxide tends to increase. When the density of any one layer of nickel or an alloy containing nickel and the layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium increases, any one of nickel or an alloy containing nickel This makes it difficult for nickel in this layer to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled.

The intermediate layer of the carrier-attached copper foil of the present invention is laminated in the order of a nickel layer or an alloy layer containing nickel, and an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on the carrier. The adhesion amount of nickel in the intermediate layer may be 100 to 40,000 μg / dm ² . The alloy containing nickel is an alloy 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. I mean. The alloy containing nickel may be an alloy composed of three or more elements. The alloy containing nickel may contain an element other than the elements described above. Moreover, the intermediate layer of the copper foil with a carrier of the present invention is an organic 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 or an alloy layer containing nickel. It is constituted by being laminated, and the adhesion amount of nickel in the intermediate layer may be 100 to 40,000 μg / dm ² . The alloy containing nickel is an alloy 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. I mean. The alloy containing nickel may be an alloy composed of three or more elements. The alloy containing nickel may contain an element other than the elements described above. 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 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, 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.
Moreover, if the carrier conveyance speed (line speed) at the time of forming the intermediate layer is slowed and / or the current density in the plating process is lowered, the density of the nickel layer or the alloy layer containing nickel and the density of organic matter tend to increase. It is in. When the density of the nickel layer or the alloy layer containing nickel and the density of the organic matter increase, the nickel in the nickel layer or the alloy layer containing nickel becomes difficult to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled. it can.
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 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. Refers to the alloy containing. The alloy containing nickel is an alloy 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. There may be. The molybdenum described above may be an alloy containing molybdenum. Here, the alloy containing molybdenum includes 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. Refers to the alloy containing. The alloy containing molybdenum is an alloy 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. There may be. The cobalt described above may be an alloy containing cobalt. Here, the alloy containing cobalt includes 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. Refers to the alloy containing. The alloy containing cobalt is an alloy composed 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. It may be.
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. When the intermediate layer contains both molybdenum and cobalt, the total adhesion amount of molybdenum and cobalt is preferably 10 to 1000 μg / dm ^2, and the total adhesion amount of molybdenum and cobalt is 20 to 600 μg. / Dm ² is preferable, and 30 to 400 μg / dm ² is more preferable.
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 conveyance speed (line 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 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 preventive layer, a chromate treated layer and a silane coupling treated layer may be formed on the surface of the roughened treated 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.

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

1. Manufacture of copper foil with carrier As a carrier, long electrolytic copper foil (JTC made by JX Nippon Mining & Metals Co., Ltd.) and rolled copper foil (Tough pitch copper foil JIS H3100 alloy number C1100 made by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 35 μm And an intermediate layer was formed on the surface. The formation of the intermediate layer was performed according to the processing order described in the item “Method for forming intermediate layer” in Table 1. That is, for example, what is described as “Ni / zinc chromate” indicates that “Ni” was first processed and then “Zinc chromate” was processed. In the “intermediate layer” item, “Ni” means that pure nickel plating was performed, and “Cr” means that pure chromium plating was performed. Meaning "Ni-Zn" means that nickel-zinc alloy plating was performed, and "Ni-Co" means that nickel-cobalt alloy plating was performed. , "Ni-W" means that nickel-tungsten alloy plating was performed, and "Ni-Sn" means that nickel-tin alloy plating was performed. “Mo—Co” means that molybdenum cobalt alloy plating was performed, and “sputtered Ni” means that Ni plating was formed by sputtering. “Cr” means that Cr plating was formed by sputtering, “Pure chromate” means pure chromate treatment, and “Zinc chromate”. Means that the zinc chromate treatment was performed, and “BTA treatment” means that the surface treatment was performed using benzotriazole, and “MBT treatment” is stated. Means that the surface treatment was performed using mercaptobenzotriazole. Each processing condition is shown below. In addition, when increasing the adhesion amount of Ni, Zn, Cr, Mo, Co, W, and Sn, setting the current density higher and / or setting the plating time longer, and / or The concentration of each element in the plating solution was increased. Moreover, when reducing the adhesion amount of Ni, Zn, Cr, Mo, Co, W, and Sn, setting the current density lower and / or setting the plating time short, and / or The concentration of each element in the plating solution was lowered. The balance of the liquid composition such as a plating solution is water.

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

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

"Ni-Co": Nickel-cobalt alloy plating In the above nickel-plating formation conditions, cobalt in the form of cobalt sulfate is added to the nickel plating solution, and the cobalt concentration is adjusted in the range of 0.1 to 10 g / L. Nickel cobalt alloy plating was formed.

"Ni-W": Nickel tungsten alloy plating In the above nickel plating formation conditions, add tungsten in the form of sodium tungstate to the nickel plating solution and adjust the tungsten concentration in the range of 0.1 to 10 g / L. Nickel tungsten alloy plating was formed.

"Ni-Mo": nickel molybdenum alloy plating In the above nickel plating formation conditions, molybdenum in the form of sodium molybdate is added to the nickel plating solution, and the molybdenum concentration is adjusted in the range of 0.1 to 10 g / L. Nickel molybdenum alloy plating was formed.

-"Ni-Sn": Nickel tin alloy plating In the above nickel plating formation conditions, tin in the form of sodium stannate is added to the nickel plating solution, and the tin concentration is adjusted in the range of 0.1 to 10 g / L. Nickel tin alloy plating was formed.

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

"Pure chromate": Pure chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L
(PH) 2-4, 7-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

-"Zinc chromate": Zinc chromate treatment In the above electrolytic pure chromate treatment conditions, zinc in the form of zinc sulfate (ZnSO ₄ ) is added to the solution, and the zinc concentration is adjusted in the range of 0.05 to 5 g / L. Zinc chromate treatment was performed.

-BTA treatment: rust prevention treatment using benzotriazole (Liquid composition) Benzotriazole: 0.1-20 g / L
(PH) 2-5
(Liquid temperature) 20-40 ° C
(Immersion time) 5-30s

MBT treatment: Rust prevention treatment using mercaptobenzothiazole (Liquid composition) 2-Mercaptobenzothiazole sodium: 0.1 to 20 g / L
(PH) 7-10
(Liquid temperature) 40-60 ° C
(Voltage) 1-5V
(Energization time) 1 to 30 seconds

"Sputtering Ni": Ni plating by sputtering Ni: A nickel layer was formed using a sputtering target having a composition of 99 mass%.
Target: Ni: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

-"Sputtering Cr": Cr plating by sputtering Cr: A chromium layer was formed using a sputtering target having a composition of 99 mass%.
Target: Cr: 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Mo-Co": Molybdenum cobalt alloy plating (Liquid composition) Cobalt sulfate: 10-200 g / L, Sodium molybdate: 5-200 g / L, Sodium citrate: 2-240 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

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 The copper foil with carrier obtained as described above was evaluated by the following methods.
<Metal adhesion amount of intermediate layer>
The amount of nickel deposited was measured by ICP emission analysis after dissolving the sample in nitric acid with a concentration of 20% by mass. The amount of zinc, chromium, molybdenum and cobalt deposited was dissolved in hydrochloric acid with a concentration of 7% by mass and the atomic absorption method was used. It was measured by performing quantitative analysis. The nickel, zinc, chromium, molybdenum and cobalt adhesion amounts were measured as follows. First, after peeling the ultrathin copper layer from the carrier-attached copper foil, only the vicinity of the surface on the intermediate layer side of the ultrathin copper layer is dissolved (for example, only 0.5 μm thickness from the surface is dissolved), The amount of adhesion on the surface on the intermediate layer side is measured. In addition, after peeling off the ultrathin copper layer, only the vicinity of the surface on the intermediate layer side of the carrier is dissolved (for example, only 0.5 μm thickness from the surface is dissolved), and the amount of adhesion on the surface of the carrier on the intermediate layer side is measured. . And the value which totaled the adhesion amount of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer and the adhesion amount of the surface by the side of the intermediate | middle layer of a carrier was made into the metal adhesion amount of an intermediate | middle layer.

<Ni adhesion amount of ultrathin copper layer>
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 ultrathin copper layer was dissolved in nitric acid having a concentration of 20% by mass, and the amount of nickel deposited was measured by ICP emission analysis. Similarly, for the ultrathin copper layer of the carrier-attached copper foil before being bonded to the resin substrate, the ultrathin copper layer is peeled off from the carrier in accordance with JIS C 6471 (Method A), and the ultrathin copper layer is concentrated. After dissolving with 20% by mass of nitric acid, the amount of nickel deposited was measured by ICP emission analysis.
Further, as another test, a copper foil with a carrier was placed on a substrate of a BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on the ultrathin copper layer side, in the atmosphere, pressure: 20 kgf / cm ² , 220 After bonding by thermocompression bonding under the condition of ° C x 2 hours, the ultrathin copper layer is peeled off from the carrier in accordance with JIS C 6471 (Method A), and then etched under the following etching conditions. The thin copper layer was removed from the surface on the intermediate layer side to a depth of 0.1 μm.
(Etching conditions)
・ Etching solution: 20 vol% of SE-07 manufactured by Mitsubishi Gas Chemical (diluted stock solution 5 times with water, copper concentration 50 g / L)
・ Temperature: 35 ± 2 ℃
Spray pressure: 0.1 MPa (spraying is performed so that the etching solution hits the copper layer to be etched perpendicularly)

The above-described etching “from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm” was determined as follows. First, etching is performed under the following conditions using JTC foil (thickness: 35 μm) manufactured by JX Nippon Mining & Metals.
(Etching conditions)
・ Etching solution: 20 vol% of SE-07 manufactured by Mitsubishi Gas Chemical (diluted stock solution 5 times with water, copper concentration 50 g / L)
・ Temperature: 35 ± 2 ℃
Spray pressure: 0.1 MPa (spraying is performed so that the etching solution hits the copper layer to be etched perpendicularly)
The relationship between the etching time and the thickness reduced by etching when the ultrathin copper layer is removed under such etching conditions is obtained. The thickness decreased by etching is estimated by weight difference before and after etching / density / etching area.
The relationship between the etching time thus obtained and the thickness t (μm) of the ultrathin copper layer removed by etching was t = 0.0336 × etching time (s).
Therefore, in order to perform etching to a depth of 0.1 μm under the above conditions, a process of 2.98 seconds≈3 seconds is required. Therefore, the etching “from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm” was actually performed for 2.98 seconds≈3 seconds.
Subsequently, the ultrathin copper layer was dissolved in nitric acid having a concentration of 20% by mass, and the amount of nickel deposited was measured by ICP emission analysis. Etching was performed under the following conditions.

<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>
A copper foil with a carrier was attached to a polyimide substrate and heat-pressed at 220 ° C. for 2 hours, and then the ultrathin copper layer was peeled off from the carrier. Subsequently, after applying a photosensitive resist to the surface of the ultra-thin copper layer on the polyimide substrate, 50 L / S = 5 μm / 5 μm wide circuits are printed by an exposure process to remove unnecessary portions of the copper layer. The etching process was performed under the following spray etching conditions.
(Spray etching conditions)
Etching solution: Ferric chloride aqueous solution (Baume degree: 40 degrees)
Liquid temperature: 60 ° C
Spray pressure: 2.0 MPa
Etching was continued, the time until the circuit top width reached 4 μm was measured, and the circuit bottom width (the length of the base X) and the etching factor at that time were evaluated. The etching factor is the distance of the length of sagging from the intersection of the vertical line from the upper surface of the copper foil and the resin substrate, assuming that the circuit is etched vertically when sagging at the end (when sagging occurs) Is a ratio of a to the thickness b of the copper foil: b / a, and the larger the value, the larger the inclination angle, and the etching residue does not remain and the sagging is small. It means to become. FIG. 1 shows a schematic diagram of a cross section in the width direction of a circuit pattern and an outline of a method for calculating an etching factor using the schematic diagram. This X was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. In addition, it calculated by a = (X (μm) −4 (μm)) / 2. The etching factor is obtained by measuring 12 points in the circuit and taking an average value. Thereby, the quality of etching property can be determined easily. Also, by calculating the standard deviation of the 12 etching factors, it is possible to determine whether the linearity of the circuit formed by etching is good or bad. The etching property was also evaluated for an ultrathin copper layer before being attached to the substrate.
In the present invention, an etching factor of 5 or more is etching property: ◯, 2.5 or more and less than 5 is etching property: Δ, less than 2.5 or calculation is impossible or circuit formation is impossible. -Evaluated. Moreover, it can be said that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. When the standard deviation of the etching factor was less than 0.5, the linearity was evaluated as ◯, when 0.5 to less than 1.0 was determined as the linearity: Δ, and 1.0 or more was determined as the linearity: x.
Moreover, the etching property about the ultra-thin copper layer etched to the depth of 0.1 μm under the same conditions was also evaluated.

<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 application, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (in terms of SiO ₂ ) (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 6 is 39 nm, the organic material thickness of the intermediate layer of Example 7 is 40 nm, the organic material thickness of the intermediate layer of Example 14 is 30 nm, The organic layer thickness of the intermediate layer of Example 17 was 35 nm, the organic layer thickness of the intermediate layer of Comparative Example 11 was 16 nm, and the organic layer thickness of the intermediate layer of Comparative Example 12 was 11 nm.
The results are shown in Tables 1 and 2.

In each of Examples 1 to 17, the carrier-attached copper foil was thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in the atmosphere, and JIS C 6471. In accordance with the above, when the carrier is peeled off and removed by etching from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm, the adhesion amount of Ni remaining in the ultrathin copper layer is 200 μg / dm ² or less. Therefore, the peelability and etching property of the ultrathin copper layer were good.
Since Comparative Examples 1 and 2 did not form an intermediate layer, they could not be peeled after thermocompression bonding. In Comparative Examples 3 and 4, the ultrathin copper layer could not be peeled off because Ni was not present in the intermediate layer. In Comparative Example 5, since the intermediate layer was only Ni, it could not be peeled after thermocompression bonding. Comparative Examples 6 and 8 could not be peeled after thermocompression bonding because the amount of Cr deposited in the intermediate layer was small. Comparative Example 9 could not be peeled off after thermocompression bonding because the amount of Zn deposited on the intermediate layer was too large. In Comparative Examples 7 and 10-14, when the ultrathin copper layer was removed by etching from the surface on the intermediate layer side to a depth of 0.1 μm, the adhesion amount of Ni remaining in the ultrathin copper layer was high and etched after thermocompression bonding. As a result, the linearity of the circuit deteriorated.

Claims (29)

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 Ni;
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. A carrier-attached copper foil in which the adhesion amount of Ni remaining in the ultrathin copper layer is 200 μg / dm ² or less when removed by etching from the surface on the intermediate layer side to a depth of 0.1 μm. 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 ultrathin copper layer is peeled off in accordance with JIS C 6471, The amount of adhesion of Ni remaining in the ultrathin copper layer is 1 to 150 µg / dm ² when the ultrathin copper layer is removed by etching from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 µm. Copper foil with carrier. 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 ultrathin copper layer is peeled off in accordance with JIS C 6471, The amount of adhesion of Ni remaining in the ultrathin copper layer is 3 to 50 μg / dm ² when the ultrathin copper layer is removed by etching from the surface on the intermediate layer side of the ultrathin copper layer to a depth of 0.1 μm. The copper foil with a carrier of description. 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 copper foil with a carrier according to any one of claims 1 to 3, wherein an adhesion amount of Ni remaining in the layer is 5 to 400 µg / dm ² . 5. The adhesion amount of Ni remaining in the ultrathin copper layer is 1 to 400 μg / dm ² when the carrier is peeled from the ultrathin copper layer in accordance with JIS C 6471. 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 in any one of Claims 1-5.   The copper foil with a carrier according to claim 6, wherein the layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium includes a chromate treatment layer.   The said intermediate | middle layer is copper foil with a carrier in any one of Claims 1-7 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 8, wherein one kind of 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
The nickel-zinc alloy layer and the pure chromate treatment layer or zinc chromate treatment layer are laminated in this order,
The amount of adhered 100~40000μg / dm ² of nickel in the intermediate layer, the amount of adhered 5~100μg / dm ² chromium deposition amount of zinc to claim 1 which is 1~70μg / dm ² The copper foil with a carrier of description. The intermediate layer is formed by laminating a nickel layer or an alloy layer containing nickel 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 8, wherein an adhesion amount of nickel in the intermediate layer is 100 to 40000 µg / dm ² . The intermediate layer is formed by laminating an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer or an alloy layer containing nickel on the carrier,
The copper foil with a carrier according to any one of claims 1 to 8, wherein an adhesion amount of nickel in the intermediate layer is 100 to 40000 µg / dm ² .   The copper foil with a carrier according to any one of claims 1 to 8, 11 and 12, 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 It is -1000 microgram / dm < ² >, The copper foil with a carrier in any one of Claims 1-8.   The copper foil with a carrier according to claim 1, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil.   The copper foil with a carrier in any one of Claims 1-15 which has a roughening process layer in the said 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 19. A copper foil with a carrier according to Item 16.   The copper with a carrier according to claim 16 or 17 which has one or more sorts of layers chosen from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of said roughening treatment layer. Foil.   The surface of the said ultra-thin copper layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer, In any one of Claims 1-15 Copper foil with carrier.   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 The manufacturing method of the copper foil with a carrier in any one of Claims 1-19 including the process of forming an ultra-thin copper layer by electrolytic plating on a 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 The manufacturing method of the copper foil with a carrier in any one of Claims 1-19 including the process of forming.   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 The manufacturing method of the copper foil with a carrier in any one of Claims 1-19 including the process of forming a 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 The manufacturing method of the copper foil with a carrier in any one of Claims 1-19 including the process of 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 with the carrier in any one of Claims 1-19 including the process of forming an intermediate | middle layer by forming a zinc chromate process layer, and the process of forming an ultra-thin copper layer by electrolytic plating on the said intermediate | middle layer. A method for producing copper foil.   The manufacturing method of the copper foil with a carrier in any one of Claims 20-24 which further includes the process of forming a roughening process layer on the said ultra-thin copper layer.   The printed wiring board manufactured using the copper foil with a carrier in any one of Claims 1-19.   The printed circuit board manufactured using the copper foil with a carrier in any one of Claims 1-19.   The copper clad laminated board manufactured using the copper foil with a carrier in any one of Claims 1-19. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 19 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.