JP6140481B2 - Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with a carrier, a method for producing a copper foil with a carrier, a printed wiring board, a printed circuit board, a copper clad laminate, and a method for producing a printed wiring board.

  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. Response 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.

  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 carrier-attached copper foil that does not deteriorate and can be easily peeled off at the carrier / ultra thin copper foil interface.

  In order to achieve the above-mentioned object, the present inventor conducted extensive research and found that the Ni adhesion amount of the intermediate layer was controlled within a predetermined range, and after removing the ultrathin copper layer from the carrier-attached copper foil, By controlling the variation in the in-plane distribution of the Ni adhesion amount on the peel surface, the in-plane distribution of the peel strength is controlled within a certain range, thereby improving the peelability at the carrier / ultra-thin copper foil interface. It was found to be extremely effective.

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 in the range of 5 to 40,000 μg / dm ² , and when peeled between the carrier / ultra-thin copper layer, the Ni adhesion amount on the peeled surface of the carrier is 20 mm in the width direction and the longitudinal direction. when the average value of the coating weight of Ni release surface of the carrier as measured by 10 points is a, the standard deviation of the coating weight of Ni release surface of the carrier was sigma intervals, X = σ × 100 / a Then, it is a copper foil with a carrier that satisfies X of 15.0% or less.

In one embodiment of the copper foil with a carrier according to the present invention, the intermediate layer contains Ni in a range of 100 to 20000 μg / dm ² .

In another embodiment the copper foil with carrier according to the present invention, when peeled in the carrier / ultra-thin copper layers, the X = σ × 100 / A satisfies 1.0 to 10.0%.

In yet another embodiment the copper foil with carrier according to the present invention, the air insulation substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, JIS When the ultrathin copper layer is peeled in accordance with C 6471, the amount of Ni deposited on the carrier peeling surface is measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction. the average value 'and the standard deviation of the coating weight of Ni release surface of the carrier sigma' a when the 'when, X' X '= σ' × 100 / a satisfies the following 20.0% .

In yet another embodiment the copper foil with carrier according to the present invention, the air insulation substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, JIS when in compliance with C 6471 peeling the ultra-thin copper layer, said X '= σ' × 100 / a ' satisfies 1.0 to 15.0%.

  In still another embodiment, the copper foil with a carrier according to the present invention has a peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with JIS C 6471 at 10 mm intervals in the width direction and the longitudinal direction. Coefficient of variation obtained from average value and standard deviation of peel strength measured point by point: K = (standard deviation × 100) / average value is 50% or less.

In yet another embodiment the copper foil with carrier according to the present invention, the air insulation substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, JIS Regarding the peel strength obtained by peeling the carrier from the ultrathin copper layer according to C 6471, the coefficient of variation obtained from the average value and standard deviation of the peel strength measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction: K ′ = (standard deviation × 100) / average value is 90% or less.

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

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

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

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

In yet another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is formed by laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer in this order on the carrier. Or a nickel-zinc alloy layer and a pure chromate treatment layer or a zinc chromate treatment layer are laminated in this order, and the nickel adhesion amount in the intermediate layer is 5 to 40,000 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 5 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 layer containing at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on the carrier, and nickel. A layer or an alloy layer containing nickel is laminated in this order, and the adhesion amount of nickel in the intermediate layer is 5 to 40000 μg / dm ² .

  In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer contains an organic substance in a thickness of 25 nm 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 the nickel in the intermediate layer is 5~40000μg / dm ^2, the amount of deposition of cobalt in case the amount of deposition of molybdenum 10~1000μg / dm ^2, which contains cobalt if it contains a molybdenum 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 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 or an alloy plating layer containing nickel on the carrier, at least a nitrogen-containing organic compound, a sulfur-containing organic compound, and After forming an organic material layer having a thickness of 25 nm to 80 nm containing any of carboxylic acids, or forming an organic material layer of thickness 25 nm to 80 nm containing at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, The method includes a step of forming an intermediate layer by forming a nickel plating layer or an alloy plating layer containing nickel, and a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer.

  In yet another embodiment of the method for producing a copper foil with a carrier according to the present invention, a nickel plating layer or an alloy plating layer containing nickel is formed on the carrier, and then any one of molybdenum, cobalt, and a molybdenum cobalt alloy. The method includes a step of forming an intermediate layer by forming a layer containing seeds or more, and a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the step of forming the intermediate layer, the carrier conveyance speed is 30 m / min or less.

  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 a measurement result of the Ni adhesion amount of the intermediate | middle layer in the width direction which concerns on Example 2 and 5. FIG.

<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. How to use 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.

  When the amount of Ni adhesion on the intermediate layer is controlled within a predetermined range and the ultrathin copper layer is peeled off from the carrier-attached copper foil, if the variation in the in-plane distribution of the Ni adhesion amount on the carrier peeling surface is large, the peel strength The variation in the in-plane distribution also increases, and the peelability at the carrier / ultra-thin copper foil interface becomes poor. For this reason, when the copper foil with a carrier of the present invention peels between the carrier / ultra-thin copper layers, the average amount when the Ni adhesion amount on the peeled surface of the carrier is measured 10 points at intervals of 20 mm in the width direction and the longitudinal direction. Ni film thickness accuracy when the value is A and the standard deviation is σ: X = σ × 100 / A is used as an index of variation in the in-plane distribution of the Ni adhesion amount on the peeling surface of the carrier, and this is controlled. Thus, the in-plane distribution of the peel strength is controlled within a certain range, thereby improving the peelability at the carrier / ultra-thin copper foil interface. In the present invention, the Ni film thickness accuracy: X is controlled to satisfy 15.0% or less, and X is preferably controlled to satisfy 1.0 to 10.0%. It is more preferably controlled to satisfy 0 to 9.5%, more preferably controlled to satisfy 1.0 to 9.0%, and 1.5 to 8.5% is satisfied. It is more preferable to be controlled so that 1.5 to 8.0% is satisfied. Ni film thickness precision: X can be controlled by keeping the current density of Ni plating at the time of forming the intermediate layer low and controlling the amount of adhesion at the conveyance speed. It is also effective to keep the parallelism between the carrier and the anode when forming the intermediate layer uniform.

Also, control the dispersion of the in-plane distribution of Ni on the peeled surface of the carrier when the ultrathin copper layer is peeled off from the copper foil with a carrier by thermocompression bonding the insulating substrate to the ultrathin copper layer under specified conditions. It is also preferable to improve the peelability at the carrier / ultra thin copper foil interface. From this point of view, a copper foil with a carrier of the present invention, the air insulation substrate in ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, the JIS C 6471 When the ultrathin copper layer was peeled off in accordance with the above, the average value when the adhesion amount of Ni on the peeling surface of the carrier was measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction was defined as A ′, and the standard deviation was σ. When X ′ = σ ′ × 100 / A ′, it is preferable that X ′ is controlled to satisfy 20.0% or less, and X ′ is 1.0 to 15.0%. More preferably, it is controlled to satisfy 1.0 to 14%, more preferably 1.0 to 13%, and more preferably 1.0 to 13%. More preferably, it is controlled to satisfy 1.5 to 12%. And more preferable to be controlled so as to satisfy the 10%. 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.

  It is also preferable to improve the peelability at the interface between the carrier and the ultrathin copper foil by controlling the variation in the peel strength when the ultrathin copper layer is peeled off from the copper foil with the carrier without thermocompression bonding with the insulating substrate. . From such a viewpoint, the copper foil with a carrier according to the present invention is 10 points at intervals of 20 mm in the width direction and the longitudinal direction with respect to the peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with JIS C 6471. The coefficient of variation obtained from the average value and the standard deviation of the measured peel strength is preferably controlled so that K = (standard deviation × 100) / average value is 50% or less, and K = 1.0 to 45 % Is more preferably controlled to satisfy 1.0 to 40%, more preferably controlled to satisfy 1.0 to 40%, and more preferably controlled to satisfy 1.5 to 35%. Preferably, it is controlled to satisfy 2.0 to 30%.

In addition, controlling the variation in peel strength when peeling an ultrathin copper layer from a carrier-attached copper foil after thermocompression bonding with an insulating substrate also improves the peelability at the interface between the carrier and the ultrathin copper foil. preferable. From this point of view, a copper foil with a carrier of the present invention, the air insulation substrate in ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, the JIS C 6471 Regarding the peel strength obtained by peeling the carrier from the ultrathin copper layer in conformity, the coefficient of variation obtained from the average value and standard deviation of the peel strength measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction: K ′ = (Standard deviation × 100) / average value is preferably controlled to 90% or less, more preferably K ′ = 1.0 to 85%, and more preferably 1.0 to 80%. Is more preferably controlled to satisfy 1.5 to 75%, and more preferably controlled to satisfy 2.0 to 70%. .

<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>
Wherein the range of the intermediate layer is 5~40000μg / dm ² of Ni, preferably contains in the range of 100~10000μg / dm ^2, more preferably comprises in the range of 500~5000μg / dm ^2, 700~3000μg / dm ^It is preferable to include in the range of ² . If the amount of nickel is too small, peeling between the ultrathin copper layer / carrier becomes impossible, while the amount of pinholes tends to increase as the amount of nickel increases. If it is said range, the number of pinholes will be suppressed.
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 includes 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 is an alloy made 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. It is preferable that 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 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, It is preferable for obtaining the property that the ultrathin copper layer can be peeled from the carrier. If a chromate treatment layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the peelability is hardly improved and the chromate treatment layer If the nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) and the ultrathin copper layer are directly laminated, the nickel amount in the nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) Accordingly, the peel strength is too strong or too weak to obtain an appropriate peel strength.

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

Intermediate nickel layer or nickel-containing alloy layer (eg nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV can do. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.
In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed.
Moreover, it is preferable that the adhesion amount of nickel in the intermediate layer is 5 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 . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultra-thin copper layer, the intermediate layer is made of a metal species (Cr, Zn) that suppresses the diffusion of Ni to the ultra-thin copper layer side while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this point of view, Ni content of the intermediate layer is preferably from 5~40000μg / dm ^2, more preferably not less 100 [mu] g / dm ² or more 10000 / dm ² or less, 500 [mu] g / dm ² or more 5000 [mu] g / more preferably at dm ² or less, and even more preferably 700 [mu] g / dm ² or more 3000Myug / 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 or chromium alloy The density of the layer containing one or more chromium oxides 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 the layer to diffuse, and it is possible to control the variation in the in-plane distribution of the Ni adhesion amount on the peeled surface of the carrier after peeling the ultrathin copper layer from the carrier-attached copper foil.

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 5 to 40000 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. The intermediate layer of the copper foil with a carrier according to the present invention includes an organic layer containing at least 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. The adhesion amount of nickel in the intermediate layer may be 5 to 40000 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 that suppresses the diffusion of Ni to the ultrathin copper layer side while reducing the Ni adhesion amount of the intermediate layer and It is preferable that the intermediate layer includes an organic material layer containing any of carboxylic acids. From this point of view, Ni content of the intermediate layer is preferably from 5~40000μg / dm ^2, more preferably not less 100 [mu] g / dm ² or more 10000 / dm ² or less, 300 [mu] g / dm ² or more 5000 [mu] g / more preferably at dm ² or less, and even more preferably 500 [mu] g / dm ² or more 3000Myug / dm ² or less. Moreover, BTA (benzotriazole), MBT (mercaptobenzothiazole), etc. are mentioned as an organic substance containing either the said nitrogen containing organic compound, sulfur containing organic compound, and carboxylic acid.

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

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

The method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil. The intermediate layer is formed on the carrier by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or showering, spraying method, dropping method and electrodeposition method on the surface on which the intermediate layer is to be formed. Etc., and there is no need to adopt a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of a concentration of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. in all the organic substances described above. The concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low. In addition, the organic substance thickness of an intermediate | middle layer tends to become large, so that the density | concentration of organic substance is high, and the contact time of the carrier to the solvent which dissolved the organic substance mentioned above is long. And when the organic substance thickness of an intermediate | middle layer is thick, it exists in the tendency for the effect of organic substance to suppress the spreading | diffusion to the ultra-thin copper layer side of Ni to become large.
In addition, if the carrier transport speed (line speed) during the formation of 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. is there. 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 carrier after the ultrathin copper layer is peeled off from the copper foil with carrier Variations in the in-plane distribution of the Ni adhesion amount on the peeled surface can be controlled.
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 5~40000μg / dm ^2, the adhesion amount of molybdenum is 10~1000μg / dm ^2, the adhesion amount of the cobalt is 10~1000μg / 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 5~40000μg / dm ^2, preferably to 100~30000μg / 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-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

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

<Method for manufacturing printed wiring board>
In one embodiment of a method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, the carrier After laminating the attached copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, The method includes a step of forming a circuit by any one of the modified semi-additive method, the partly additive method, and the subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

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

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

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

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

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

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

  In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.

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

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

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

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

1. Manufacture of copper foil with carrier As a 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.) 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-Mo" means that nickel-molybdenum alloy plating was performed, and "Ni-W" means that nickel-tungsten alloy plating was performed. "Ni-Sn" means that nickel-tin alloy plating was performed, and "Mo-Co" means that molybdenum-cobalt alloy plating was performed. "i" means that Ni plating was formed by sputtering, and "sputtered Cr" means that Cr plating was formed by sputtering, and "pure chromate". This means that pure chromate treatment has been carried out. “Zinc chromate” means that zinc chromate treatment has been carried out. “BTA treatment” means that benzoate has been treated. This means that the surface treatment was performed using triazole, and “MBT treatment” 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) 1-25 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 was added to the nickel plating solution, and the cobalt concentration was 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: Surface treatment using benzotriazole (Liquid composition) Benzotriazole: 0.1 to 20 g / L
(PH) 2-5
(Liquid temperature) 20-40 ° C
(Immersion time) 5-30s

MBT treatment: surface 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

  During the formation of the intermediate layer, Ni film thickness accuracy: control of X and X ′, variation coefficient of peel strength: K and K ′ keep the current density of Ni plating low, and control the adhesion amount with the conveyance speed. The parallelism between the carrier and the anode was kept uniform.

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 film thickness accuracy of intermediate 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 average value when the adhesion amount of Ni on the peeling surface of the carrier was measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction using a fluorescent X-ray measurement device (Minipal, manufactured by PANalytical) was A ′. And the standard deviation was σ ′, and Ni film thickness accuracy: X ′ = σ ′ × 100 / A ′ was determined. Moreover, Ni film thickness precision: X was measured similarly also about the ultra-thin copper layer of the copper foil with a carrier before bonding to a resin substrate.

<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 average value and standard deviation of the peel strength measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction in accordance with the 90 ° peeling method (JIS C 6471 8.1). The coefficient of variation obtained from ((standard deviation × 100) / average value) was determined. Moreover, the peel strength was similarly measured for each sample before thermocompression bonding with the resin, and the coefficient of variation was obtained.

<Thickness of organic material in the intermediate layer>
For each sample before thermocompression bonding with resin, after peeling the ultrathin copper layer of the carrier-attached copper foil from the carrier, the exposed surface of the intermediate layer side of the exposed ultrathin copper layer and the exposed surface of the intermediate layer side of the carrier Is measured by XPS, and a depth profile is created. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth was defined as B (nm), and the sum of A and B was defined as the thickness (nm) of the organic substance in the intermediate layer. The larger the value of x, the deeper (farther) the measurement position of the metal atomic concentration is from the surface. Note that the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )
As described above, as a result of measuring the organic material thickness of the intermediate layer, the organic material thickness of the intermediate layer of Example 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 18, since Ni film thickness accuracy before bonding to the substrate: X was 15.0% or less, good peelability was exhibited before and after thermocompression bonding. In Examples 19 and 20, since the conveyance speed at the time of forming the intermediate layer was high, the peelability was good, although not as much as in Examples 1-18.
Since Comparative Examples 1 and 2 did not form an intermediate layer, they could not be peeled before and after thermocompression bonding. Comparative Examples 3 and 4 could not be peeled before and after thermocompression bonding 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. In Comparative Examples 6 and 7, the amount of Cr deposited in the intermediate layer was small, so that peeling was not possible after thermocompression bonding. Since the comparative example 8 had too much adhesion amount of Zn of the intermediate | middle layer, it was not able to peel after thermocompression bonding. In Comparative Examples 9 to 12, the Ni film thickness accuracy before substrate bonding: X was poor, and a portion that could not be peeled after thermocompression bonding occurred.
In FIG. 1, the measurement result of the Ni adhesion amount of the intermediate | middle layer in the width direction which concerns on Example 2 and 5 is shown.

Claims (34)

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 in a range of 5 to 40,000 μg / dm ² ,
When peeled between the carrier / ultra-thin copper layer, the average amount of Ni deposited on the carrier peeled surface when the amount of Ni deposited on the carrier peeled surface was measured 10 points at intervals of 20 mm in the width and longitudinal directions. the is a, when the standard deviation of the coating weight of Ni release surface of the carrier was sigma, when X = sigma × 100 / a, a copper foil with a carrier which X satisfies the following 15.0%. The said intermediate | middle layer is copper foil with a carrier of Claim 1 containing Ni in the range of 100-20000 microgram / dm < ² >. 3. The copper foil with a carrier according to claim 1 , wherein when peeling between the carrier / ultra-thin copper layer, the X = σ × 100 / A satisfies 1.0 to 10.0%. In air insulating substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, when peeling off the said ultra-thin copper layer in conformity with JIS C 6471, the carrier When the adhesion amount of Ni on the peeling surface of the substrate was measured 10 points at intervals of 20 mm in the width direction and the longitudinal direction, the average value of the adhesion amount of Ni on the peeling surface of the carrier was A ′, and the adhesion amount of Ni on the peeling surface of the carrier The carrier-attached copper foil according to claim 1, wherein X ′ satisfies 20.0% or less when X ′ = σ ′ × 100 / A ′. In air insulating substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, when peeling off the said ultra-thin copper layer in conformity with JIS C 6471, the The copper foil with a carrier according to claim 4, wherein X ′ = σ ′ × 100 / A ′ satisfies 1.0 to 15.0%.   Regarding the peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with JIS C 6471, the coefficient of variation obtained from the average value and standard deviation of the peel strength measured at 10 points at intervals of 20 mm in the width direction and the longitudinal direction: The copper foil with a carrier according to claim 1, wherein K = (standard deviation × 100) / average value is 50% or less. In air insulating substrate to the ultra-thin copper layer, pressure: 20 kgf / cm ^2, and thermally bonding under the conditions of a 220 ° C. × 2 hours, resulting in peeling the carrier from ultrathin copper layer in conformity with JIS C 6471 Coefficient of variation obtained from average value and standard deviation of peel strength measured 10 points at intervals of 20 mm in the width direction and the longitudinal direction for the peel strength to be obtained: K ′ = (standard deviation × 100) / average value is 90% or less The copper foil with a carrier according to any one of claims 1 to 6.   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 1-7.   The copper foil with a carrier according to claim 8, wherein the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide includes a chromate treatment layer.   The said intermediate | middle layer is copper foil with a carrier in any one of Claims 1-9 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 in any one of Claims 1-10 comprised by laminating | stacking 1 type of layer 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 adhesion amount of nickel in the intermediate layer is 5 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. 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,
11. The copper foil with a carrier according to claim 1, wherein an adhesion amount of nickel in the intermediate layer is 5 to 40000 μg / dm ² . The intermediate layer is formed by laminating an organic layer containing at least one 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. ,
11. The copper foil with a carrier according to claim 1, wherein an adhesion amount of nickel in the intermediate layer is 5 to 40000 μg / dm ² .   The copper foil with a carrier according to claim 13 or 14, 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 the nickel in the intermediate layer is 5~40000μg / dm ^2, the amount of deposition of cobalt in case the amount of deposition of molybdenum 10~1000μg / dm ^2, which contains cobalt if it contains a molybdenum 10 It is -1000 microgram / dm < ² >, The copper foil with a carrier in any one of Claims 1-10.   The copper foil with a carrier according to any one of claims 1 to 16, 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 1-17 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 18.   The copper with a carrier according to claim 18 or 19, wherein the surface of the roughened layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. Foil.   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. 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 1-21 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 1-21 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 1-21 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 1-21 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 1-21 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.   On the carrier, after forming a nickel plating layer or an alloy plating layer containing nickel, an organic material layer having a thickness of 25 nm to 80 nm containing at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid is formed, or After forming an organic substance layer having a thickness of 25 nm to 80 nm containing at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, an intermediate layer is formed by forming a nickel plating layer or an alloy plating layer containing nickel. The manufacturing method of the copper foil with a carrier in any one of Claims 1-21 including the process and the process of forming an ultra-thin copper layer on the said intermediate | middle layer by electrolytic plating.   Forming an intermediate layer by forming a layer containing any one or more of molybdenum, cobalt, and a molybdenum cobalt alloy after forming a nickel plating layer or an alloy plating layer containing nickel on the carrier; The manufacturing method of the copper foil with a carrier in any one of Claims 1-21 including the process of forming an ultra-thin copper layer by electrolytic plating on a layer.   The method for producing a carrier-attached copper foil according to any one of claims 22 to 28, wherein in the step of forming the intermediate layer, the carrier conveyance speed is 30 m / min or less.   The manufacturing method of the copper foil with a carrier in any one of Claims 22-29 further including 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 1-21.   The printed circuit board manufactured using the copper foil with a carrier in any one of Claims 1-21.   The copper clad laminated board manufactured using the copper foil with a carrier in any one of Claims 1-21. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 21 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

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