JP5997080B2 - 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 object, the present inventor conducted extensive research and found that after peeling the ultra-thin copper layer from the carrier-attached copper foil, the variation of the chromium concentration on the separation surface of the carrier and the in-plane distribution of the chromium concentration was By controlling, the in-plane distribution of the peel strength was controlled within a certain range, and it was found that this is extremely effective in improving the peelability at the carrier / ultra-thin copper foil interface.

The present invention has been completed based on the above knowledge, and in one aspect, a carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer The intermediate layer contains nickel and chromium, and when the intermediate layer / extra thin copper layer is peeled in accordance with JIS C 6471, the depth obtained from the depth direction analysis from the surface by XPS The atomic concentration (%) of chromium in the direction (x: unit nm) is e (x), the atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), The atomic concentration (%) of copper is h (x), the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and other atomic concentrations (%) Is k (x), and E (x) = ∫e (x) dx / (∫e (x) in the section [0, 1.0] of the depth direction analysis from the surface of the intermediate layer of the carrier dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) and E (x) Is the standard deviation of E (x) when measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction, and σ _E is the standard deviation of the chromium concentration, and X _E = σ _E × 100 / (E When the arithmetic mean value of 20 points (x)), X _E satisfies less 40.0%, the arithmetic average value of 20 points of the E (x) is a copper foil with carrier satisfying 1% to 30% .

In one embodiment, the carrier-attached copper foil according to the present invention is analyzed in the depth direction from the intermediate layer surface of the carrier by XPS when peeled in accordance with JIS C 6471 between the intermediate layer / ultra-thin copper layer. In the interval [0, 1.0], the arithmetic average value of 20 points of E (x) satisfies 2 to 25%, and the variation coefficient of the chromium concentration: X _E = σ _E × 100 / (E (x) The arithmetic average value of 20 points) satisfies 1.0 to 30.0%.

  In another embodiment of the copper foil with a carrier according to the present invention, the binding energy of 2P3 / 2 orbit of chromium detected by XPS of the intermediate layer is in the range of 576 to 580 eV.

In yet another embodiment of the copper foil with a carrier according to the present invention, an insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in JIS. Chromium atomic concentration (%) in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS when peeled between the intermediate layer / ultra thin copper layer according to C 6471 E (x), zinc atomic concentration (%) as f (x), nickel atomic concentration (%) as g (x), copper atomic concentration (%) as h (x), oxygen I (x) is the total atomic concentration (%) of carbon, j (x) is the atomic concentration (%) of carbon, and k (x) is the other atomic concentration (%). In the interval [0, 1.0] of the depth direction analysis, E ′ (x) = ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) The standard deviation of the 'E when measured 10 points at 20mm intervals (x) 10 and longitudinally at 20mm intervals in the width direction' (x) the E and sigma _E ', the coefficient of variation of the chromium concentration: X _E Assuming that “= σ _E ” × 100 / (the arithmetic average value of 20 points of E ′ (x)), X _E ′ satisfies 60.0% or less, and the arithmetic average value of 20 points of the above E ′ (x) Satisfies 0.5-30%.

In yet another embodiment of the copper foil with a carrier according to the present invention, an insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in JIS. In the section [0, 1.0] of the depth direction analysis from the surface of the intermediate layer of the carrier by XPS when peeling is performed between the intermediate layer / ultra thin copper layer in accordance with C 6471, the E ′ (x ) Satisfying 1 to 25% of the arithmetic average value of 20 points, and the coefficient of variation of the chromium concentration: X _E '= σ _E ' × 100 / (the arithmetic average value of 20 points of E ′ (x)) is 1. Satisfies 0-50.0%.

  In yet another embodiment, the copper foil with a carrier according to the present invention is 10 points long and 20 mm long in the width direction with respect to the peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with JIS C 6471. Coefficient of variation obtained from the average value and standard deviation of peel strength measured at 10 points at intervals of 20 mm in the direction: K = (standard deviation × 100) / average value is 50% or less.

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

In yet another embodiment the copper foil with carrier according to the present invention, in the intermediate layer, the amount of adhered 100~40000μg / dm ² of nickel, adhesion amount 5~100μg / dm ² chromium coating weight of zinc Satisfies 1 to 70 μg / dm ² .

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

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

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

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

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

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

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

  In still another embodiment of the copper foil with a carrier according to the present invention, the roughening layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. Or a layer made of an alloy containing one or more of them.

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

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

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

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

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

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

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

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

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

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

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

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

  According to the present invention, the adhesion between the carrier and the ultrathin copper foil is high before the laminating process to the insulating substrate, while the adhesion between the carrier and the ultrathin copper foil due to the laminating process to the insulating substrate is extremely increased. It is possible to provide a copper foil with a carrier that does not deteriorate and can be easily peeled off at the carrier / ultra thin copper foil interface.

It is a XPS depth profile of the depth direction before the board | substrate bonding of the intermediate | middle layer surface of Example 5. FIG. It is a XPS depth profile of the depth direction after the board | substrate bonding of the intermediate | middle layer surface of Example 5. FIG. It is a XPS depth profile of the depth direction before the board | substrate bonding of the intermediate | middle layer surface of the comparative example 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. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. A copper layer is etched into the intended conductor pattern, and finally a printed wiring board, a printed circuit board, a copper clad laminate, or the like can be produced.

  When the copper foil with a carrier of the present invention is peeled in accordance with JIS C 6471 between the intermediate layer / ultra thin copper layer, the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS ) Chromium atomic concentration (%) is e (x), zinc atomic concentration (%) is f (x), nickel atomic concentration (%) is g (x), copper atomic concentration (%) ) Is h (x), oxygen total atomic concentration (%) is i (x), carbon atomic concentration (%) is j (x), and other atomic concentration (%) is k (x). Then, E (x) = 、 e (x) dx / (∫e (x) dx + ∫f (x) dx) in the interval [0, 1.0] of the depth direction analysis from the intermediate layer surface of the carrier + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is controlled appropriately so as to satisfy 1 to 30% The peel strength can be maintained and is preferably controlled to satisfy 2 to 25%. It is more preferably controlled to satisfy 0%, more preferably controlled to satisfy 4 to 18%, and more preferably controlled to satisfy 5 to 16%. It is more preferable to control to satisfy ˜15%.

Further, when the insulating substrate is thermocompression bonded to the ultrathin copper layer under a predetermined condition, and the ultrathin copper layer is peeled off from the carrier-attached copper foil, the interval [0, 1 .0] is also preferable in that the appropriate peel strength can be maintained after pressing. From such a point of view, the copper foil with a carrier of the present invention is obtained by thermally bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in JIS C 6471. In accordance with the separation between the intermediate layer and the ultrathin copper layer in conformity, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS is expressed as e (x ), The atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), and the total atomic concentration of oxygen Depth direction analysis from the surface of the intermediate layer of carriers, where (%) is i (x), carbon atomic concentration (%) is j (x), and other atomic concentration (%) is k (x) In the interval [0, 1.0], E ′ (x) = ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 0.5-30% Is preferably controlled to satisfy 1 to 25%, more preferably 1.5 to 22%, and more preferably 2.0 to 20 % Is more preferably controlled to satisfy 2.0%, more preferably controlled to satisfy 2.0 to 15%, and more preferably controlled to satisfy 2.0 to 10%. preferable. “Thermo-compression 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.

After peeling the ultra-thin copper layer from the carrier-attached copper foil, if the variation in the in-plane distribution of the chromium concentration on the peeling surface of the carrier is large, the variation in the in-plane distribution of the peeling strength also increases, and the carrier / ultra-thin copper foil interface The peelability at is poor. Therefore, when the carrier-attached copper foil of the present invention is peeled between the carrier / ultra-thin copper layer, the E (x) is measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction. The standard deviation is σ _E , and the coefficient of variation of chromium concentration: X _E is used as an indicator of variation in the in-plane distribution of chromium concentration on the peeling surface of the carrier, and by controlling this, the in-plane distribution of peeling strength is kept constant. By controlling within the range, the peelability at the carrier / ultra-thin copper foil interface is improved. In the present invention, the coefficient of variation of the chromium concentration: X _E is controlled to satisfy 40.0% or less, and X _E is preferably controlled to satisfy 1.0 to 30.0%. , More preferably 1.0 to 28%, more preferably 1.5 to 25%, and more preferably 1.5 to 22%. More preferably, it is more preferably controlled so as to satisfy 2.0 to 20%. Variation coefficient of chromium concentration: control of X _E keeps the current density of the Cr plating at the intermediate layer formed lower, it can be performed by controlling the deposition amount at the conveying 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 chromium concentration on the peeled surface of the carrier when the insulating substrate is thermocompression bonded to the ultrathin copper layer under specified conditions and the ultrathin copper layer is peeled off from the copper foil with carrier. Is preferable for improving the peelability at the carrier / ultra-thin copper foil interface. From this point of view, the copper foil with a carrier of the present invention is obtained by thermally bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in JIS C 6471. When the ultra-thin copper layer was peeled off in accordance with the standard deviation of E ′ (x) when the E ′ (x) was measured at 10 points at 20 mm intervals in the width direction and 10 points at 20 mm intervals in the longitudinal direction. Assuming that σ _E ′ and the coefficient of variation of chromium concentration: X _E ′ = σ _E ′ × 100 / (20 points arithmetic average of E ′ (x)), X _E ′ satisfies 60.0% or less. Is preferably controlled so that X _E ′ satisfies 1.0 to 50.0%, and is controlled so as to satisfy 1.0 to 45%. More preferably, it is controlled to satisfy 1.5 to 40%, more preferably 1.5 to 35% More preferably it is controlled so, and more preferable to be controlled so as to satisfy the 2.0 to 30%.

  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 point of view, the copper foil with a carrier of the present invention has a peeling strength obtained by peeling the carrier from an 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: K = (standard deviation × 100) / preferably controlled so that the average value is 50% or less. It is more preferably controlled to satisfy 1.0 to 45%, more preferably controlled to satisfy 1.0 to 40%, and controlled to satisfy 1.5 to 35%. More 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, the copper foil with a carrier of the present invention is obtained by thermally bonding an insulating substrate to an ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in JIS C 6471. Regarding the peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with the standard, the variation obtained from the average value and standard deviation of the peel strength measured at 10 points at 20 mm intervals in the width direction and 10 points at 20 mm intervals in the longitudinal direction. Coefficient: K ′ = (standard deviation × 100) / average value is preferably controlled to 90% or less, more preferably K ′ = 1.0 to 85%, more preferably 1 More preferably, it is controlled to satisfy 0.0 to 80%, more preferably, it is controlled to satisfy 1.5 to 75%, and it is controlled to satisfy 2.0 to 70%. It is more preferable

<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 titanium or stainless steel drum, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

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

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

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

The intermediate nickel layer or nickel alloy layer (eg nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. can do. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.
In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed.
Further, the amount of adhered 100~40000μg / dm ² of nickel in the intermediate layer, the adhesion amount of chromium 5~100μg / dm ^2, the amount of deposition of zinc is preferably 1~70μg / dm ^2. As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after the ultrathin copper layer is peeled from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultra-thin copper layer, the intermediate layer is made of a metal species (Cr, Zn) that suppresses the diffusion of Ni to the ultra-thin copper layer side while reducing the amount of Ni deposited on the intermediate layer. Is preferably included. From this point of view, Ni content of the intermediate layer is preferably from 100~40000μg / dm ^2, more preferably not less 200 [mu] g / dm ² or more 20000μg / dm ² or less, 500 [mu] g / dm ² or more 10000 / further preferably at dm ² or less, more preferably at 700 [mu] g / dm ² or more 5000 [mu] g / 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.

  In the copper foil with a carrier of the present invention, it is preferable that the binding energy of the 2P3 / 2 orbit of chromium detected by XPS of the intermediate layer is in the range of 576 to 580 eV. According to such a configuration, chromium present in the intermediate layer becomes not chromium metal but chromium oxide, and the generation of pinholes on the surface of the ultrathin copper layer can be suppressed more favorably.

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

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

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

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

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

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

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

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

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

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

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

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier,
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as 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.) having a thickness of 35 μm And an intermediate layer was formed on the surface. The formation of the intermediate layer was performed according to the processing order described in the item “Method for forming intermediate layer” in Table 1. That is, for example, what is described as “Ni / zinc chromate” indicates that “Ni” was first processed and then “Zinc chromate” was processed. In the “intermediate layer” item, “Ni” means that pure nickel plating was performed, and “Cr” means that pure chromium plating was performed. Meaning "Ni-Zn" means that nickel-zinc alloy plating was performed, and "Ni-Co" means that nickel-cobalt alloy plating was performed. , "Ni-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 “sputtered Ni” means that Ni plating was formed by sputtering. “Cr” means that Cr plating was formed by sputtering, “Pure chromate” means pure chromate treatment, and “Zinc chromate”. This means that the zinc chromate treatment was performed. Each processing condition is shown below. In addition, when increasing the adhesion amount of Ni, Zn, Cr, Mo, Co, W, and Sn, setting the current density higher and / or setting the plating time longer, and / or The concentration of each element in the plating solution was increased. Moreover, when reducing the adhesion amount of Ni, Zn, Cr, Mo, Co, W, and Sn, setting the current density lower and / or setting the plating time short, and / or The concentration of each element in the plating solution was lowered. The balance of the liquid composition such as a plating solution is water.

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

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

"Ni-Co": nickel cobalt alloy plating In the above nickel plating formation conditions, cobalt in the form of cobalt sulfate 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-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-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-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) 2.0 to 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.

"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

When the intermediate layer is formed, the coefficient of variation of chromium concentration: control of X _E and X _E ′, the coefficient of variation of peel strength: K and K ′ keep the current density of Cr plating low, and control the adhesion amount by the conveyance speed And by maintaining the parallelism between the carrier and the anode 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 at a concentration of 20% by mass. The amount of zinc and chromium deposited was dissolved in hydrochloric acid at a concentration of 7% by mass and quantitative analysis was performed by atomic absorption spectrometry. Measured by doing. In addition, the measurement of the said nickel, zinc, and chromium adhesion amount was performed 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.

<XPS analysis>
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. Thereafter, the ultrathin copper layer was peeled off from the carrier in accordance with JIS C 6471 (Method A). Subsequently, for the surface on the intermediate layer side of the carrier, the Cr atom concentration in the depth direction section [0, 1.0] (x: unit nm) by the depth direction analysis from the surface by XPS under the following conditions: E ′ (x) is measured, and the chromium concentration: E ′ (x) is measured from the standard deviation σ _E ′ of E ′ (x) when measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction. Coefficient of variation of chromium concentration: X _E '= σ _E ' × 100 / (20 points of arithmetic average value of E ′ (x)) is obtained, and 10 points at intervals of 20 mm in the width direction and at intervals of 20 mm in the longitudinal direction. An arithmetic average value of 20 points of E ′ (x) when 10 points were measured was obtained. The larger the value of x, the deeper (farther) the measurement position of the metal atomic concentration is from the surface. The measurement interval of the atomic concentration 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 Cr concentration in the depth direction was measured at 0.28 nm (SiO ₂ equivalent) intervals (measured every 0.1 minutes by sputtering time).
In Tables 1 and 2, “Cr (%) average value” column of “XPS analysis intermediate layer side (after substrate bonding) surface depth x = 0 to 1.0 nm (in terms of SiO ₂ )”, “Cr ( %) Standard deviation ”column and“ Cr (%) coefficient of variation ”column, respectively, 20 of E ′ (x) when 10 points are measured at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction. The arithmetic mean value of the points, the standard deviation σ _E ′ of E ′ (x) when the chromium concentration E ′ (x) was measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction, The value of the coefficient of variation X _E 'is described.
(XPS analysis conditions)
・ 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 )
Similarly, for the copper foil with a carrier before being bonded to the resin substrate, the chromium concentration: E (x) is measured, the arithmetic average value of 20 points of E (x) is obtained, and the E (x) Using the standard deviation σ _E , the coefficient of variation of the chromium concentration: X _E = σ _E × 100 / (20 points arithmetic average value of E (x)) was obtained.
In Tables 1 and 2, the “Cr (%) average value” column of “XPS analysis intermediate layer side (before substrate bonding) surface depth x = 0 to 1.0 nm (in terms of SiO ₂ )”, “Cr ( %) Standard deviation ”column and“ Cr (%) coefficient of variation ”column, respectively, 10 points at 20 mm intervals in the width direction and 20 points of E (x) when measured at 20 mm intervals in the longitudinal direction, respectively. , The standard deviation σ _E of E (x) when the chromium concentration E (x) is measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction, and the coefficient of variation X _{E of the} chromium concentration The value of was described.
Further, the binding energy of the 2P3 / 2 orbit of chromium in the intermediate layer was detected by XPS.

<Peel strength>
Heat the copper foil with a carrier to the BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Crimped and pasted. Subsequently, the carrier side was pulled with a load cell, and the peel strength measured at 10 points at 20 mm intervals in the longitudinal direction and 10 points at 20 mm intervals in the width direction in accordance with the 90 ° peeling method (JIS C 6471 8.1). The coefficient of variation obtained from the average value (arithmetic average value) and standard deviation: ((standard deviation × 100) / average value (arithmetic 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.

In each of Examples 1 to 13, the chromium concentration in the section [0, 1.0] of the XPS depth direction analysis from the surface of the intermediate layer of the carrier before substrate bonding satisfies 1 to 30%, and Coefficient of variation of chromium concentration: X _E was 40.0% or less, and good peelability was exhibited before and after thermocompression bonding. In Examples 14 and 15, the intermediate layer did not contain zinc, and the conveyance speed at the time of forming the intermediate layer was high.
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.
FIG. 1 shows an XPS depth profile in the depth direction of the intermediate layer surface of Example 5 before substrate bonding. FIG. 2 shows an XPS depth profile in the depth direction after the substrates are bonded to the surface of the intermediate layer of Example 5. FIG. 3 shows an XPS depth profile in the depth direction before the substrates are bonded to the surface of the intermediate layer of Comparative Example 5.

Claims (28)

A carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer,
The intermediate layer includes nickel and chromium;
When peeling between the intermediate layer / ultra-thin copper layer according to JIS C 6471, the atomic concentration of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS (%) ) Is e (x), the atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), The total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), the other atomic concentration (%) is k (x),
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface of the carrier, E (x) =) e (x) dx / (∫e (x) dx + xf (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx)
When E (x) is measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction, the standard deviation of E (x) is σ _E, and the variation coefficient of chromium concentration is X _E = σ _E X100 / (20 (arithmetic average value of E (x))) X _E satisfies 40.0% or less, and 20 (20) arithmetic average value of E (x) satisfies 1 to 30% Copper foil. When peeling between the intermediate layer / ultra-thin copper layer in accordance with JIS C 6471, in the section [0, 1.0] of the depth direction analysis from the intermediate layer surface of the carrier by XPS, the E (x ) Satisfies the arithmetic average value of 20 points of 2 to 25%, and the coefficient of variation of the chromium concentration: X _E = σ _E × 100 / (the arithmetic average value of 20 points of E (x)) is 1.0 to 30 The copper foil with a carrier according to claim 1 satisfying 0.0%.   The copper foil with a carrier according to claim 1 or 2, wherein the binding energy of the 2P3 / 2 orbit of chromium detected by XPS of the intermediate layer is within a range of 576 to 580 eV. An insulating substrate is thermocompression-bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in the air, and peeled between the intermediate layer / ultrathin copper layer in accordance with JIS C 6471. When
E (x) is the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from analysis of the depth direction from the surface by XPS, and f (x) is the atomic concentration (%) of zinc. The atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), the total atomic concentration (%) of oxygen is i (x), and the atomic concentration of carbon (% ) Is j (x), other atomic concentration (%) is k (x),
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface of the carrier, E ′ (x) = ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx)
The standard deviation of E ′ (x) when E ′ (x) is measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction is σ _E ′, and the coefficient of variation in chromium concentration: X _E Assuming that “= σ _E ” × 100 / (the arithmetic average value of 20 points of E ′ (x)), X _E ′ satisfies 60.0% or less, and the arithmetic average value of 20 points of the above E ′ (x) The copper foil with a carrier according to any one of claims 1 to 3, which satisfies 0.5 to 30%. An insulating substrate is thermocompression-bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in the air, and peeled between the intermediate layer / ultrathin copper layer in accordance with JIS C 6471. When
In the interval [0, 1.0] of the depth direction analysis from the intermediate layer surface of the carrier by XPS, the arithmetic average value of 20 points of the E ′ (x) satisfies 1 to 25%, and the chromium concentration The coefficient of variation: X _E '= σ _E ' × 100 / (20 points arithmetic average value of E ′ (x)) satisfies 1.0 to 50.0%.   About peel strength obtained by peeling the carrier from the ultrathin copper layer in accordance with JIS C 6471, average value and standard deviation of peel strength measured at 10 points at 20 mm intervals in the width direction and 10 points at 20 mm intervals in the longitudinal direction. The coefficient of variation obtained from: K = (standard deviation × 100) / average value is 50% or less. The copper foil with a carrier according to claim 1. An insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours in the atmosphere, and the carrier is peeled off from the ultrathin copper layer in accordance with JIS C 6471. Coefficient of variation obtained from average value and standard deviation of peel strength measured at 10 points at intervals of 20 mm in the width direction and 10 points at intervals of 20 mm in the longitudinal direction: 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. In the intermediate layer, the amount of adhered 100~40000μg / dm ² of nickel, either deposition amount of chromium of claims 1 to 7 which 5~100μg / dm ^2, the adhesion amount of the zinc satisfies 1~70μg / dm ² The copper foil with a carrier as described in 2.   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 1-8.   The copper foil with a carrier according to claim 9, 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 1-10 containing zinc.   The intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy, zinc chromate treatment layer, pure chromate treatment layer, and chromium plating layer on the carrier. The copper foil with a carrier according to any one of claims 1 to 11, wherein one kind of layer is laminated in this order. The intermediate layer is on the carrier,
A nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer are laminated in this order, or
The nickel-zinc alloy layer and the pure chromate treatment layer or zinc chromate treatment layer are laminated in this order,
The amount of adhered 100~40000μg / dm ² of nickel in the intermediate layer, the amount of adhered 5~100μg / dm ² chromium deposition amount of zinc to any of claims 1 to 11 is 1~70μg / dm ² The copper foil with a carrier of description.   The copper foil with a carrier according to any one of claims 1 to 13, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil.   The copper foil with a carrier in any one of Claims 1-14 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 16. A copper foil with a carrier according to Item 15.   The copper with a carrier according to claim 15 or 16, comprising at least one layer selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. Foil.   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 1-18 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 1-18 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 1-18 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 1-18 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 1-18 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 the electrolytic plating on the said intermediate | middle layer. A method for producing copper foil.   The manufacturing method of the copper foil with a carrier in any one of Claims 19-23 which further includes the process of forming a roughening process layer on the said ultra-thin copper layer.   The printed wiring board manufactured using the copper foil with a carrier in any one of Claims 1-18.   The printed circuit board manufactured using the copper foil with a carrier in any one of Claims 1-18.   The copper clad laminated board manufactured using the copper foil with a carrier in any one of Claims 1-18. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 18 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate 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.