JP2014177657A - Copper foil with carrier, production method of copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and production method of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a carrier in which before a lamination process to an insulation substrate, an adhesion force between a carrier and an extra thin copper layer is high, after the lamination process to the insulation substrate, adhesion between the carrier and the extra thin copper layer is lowered, peeling can be easily performed at an interface between the carrier and the extra thin copper layer, and generation of a pinhole on an extra thin copper layer side surface is favorably suppressed.SOLUTION: A copper foil with a carrier is that satisfies a specific condition in an interval [0, 1.0] of a depth direction analysis from an intermediate surface when peeling is performed between an intermediate layer and an extra thin copper layer, and when a chrome atomic concentration (%) in the depth direction (x: unit nm) obtained by the depth direction analysis from a surface by XPS is assumed e(x), a zinc atomic concentration (%) is assumed f(x), a nickel atomic concentration (%) is assumed g(x), a copper atomic concentration (%) is assumed h(x), an oxygen sum atomic concentration (%) is assumed i(x), a carbon atomic concentration (%) is assumed j(x), and the other atomic concentration (%) is assumed k(x).

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. More specifically, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board for fine pattern use, a method for producing the copper foil with a carrier, a printed wiring board, a printed circuit board, a copper-clad laminate, and a printed board. The present invention relates to a method for manufacturing a 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 demand for miniaturization and high 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 printed circuit boards. There is a demand for high frequency response, and in particular, when an IC chip is mounted on a printed wiring board, a fine pitch of L / S = 20/20 or less is required.

  A printed wiring board is first manufactured as a copper clad laminate in which an insulating substrate mainly composed of a copper foil and a glass epoxy substrate, a BT resin, a 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 9 μm, and further, the thickness is becoming 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 general method of using a copper foil with a carrier is to peel the carrier through a release layer after the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded.

  As a technique related to a copper foil with a carrier, for example, in Patent Document 1, a diffusion prevention layer, a release layer, and an electrolytic copper plating are formed in this order on the surface of a carrier, and a Cr or Cr hydrated oxide layer is formed as a release layer A method for maintaining good peelability after hot pressing by using a simple substance or an alloy of Ni, Co, Fe, Cr, Mo, Ta, Cu, Al, P as a diffusion preventing layer is disclosed.

  Further, it is known that the release layer is formed of Cr, Ni, Co, Fe, Mo, Ti, W, P, alloys thereof, or hydrates thereof. Furthermore, Patent Documents 2 and 3 describe that it is effective to provide Ni, Fe or an alloy layer thereof as a 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 a carrier, it is necessary to avoid the peeling of the ultrathin copper layer from the carrier before the lamination process on the insulating substrate, while the ultrathin copper layer from the carrier is removed after the lamination process to the insulating substrate. Must be peelable. In addition, in the copper foil with a carrier, the presence of pinholes on the surface of the ultrathin copper layer is not preferable because it leads to poor performance of the printed wiring board.

  With respect to these points, the prior art has not been sufficiently studied, and there is still room for improvement. Therefore, an object of the present invention is to provide a copper foil with a carrier that can be peeled off after a lamination process on an insulating substrate, while the ultrathin copper layer does not peel off from the carrier before the lamination process on the insulating substrate. . Another object of the present invention is to provide a carrier-attached copper foil in which the generation of pinholes on the ultrathin copper layer side surface is suppressed.

  In order to achieve the above object, the present inventor conducted extensive research and used copper foil as a carrier, formed an intermediate layer between the ultrathin copper layer and the carrier, and formed this intermediate layer on the copper foil carrier. It is composed of a layer containing nickel and a layer containing chromium such as chromate in order, controlling the adhesion amount of nickel, chromium and zinc, and the intermediate layer surface when peeled between the intermediate layer / ultra thin copper layer It has been found that controlling chromium and zinc and nickel atom concentrations in the part is extremely effective. It is also extremely effective to control the chromium, zinc, and nickel atom concentration on the surface of the intermediate layer when the insulating substrate is thermocompression bonded to the ultrathin copper layer and the carrier is peeled off from the ultrathin copper layer. I found out.

The present invention has been completed based on the above findings, and in one aspect,
A copper foil with a carrier comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer,
In the intermediate layer, the amount of adhered 100~40000μg / dm ² of nickel, adhesion amount 5~100μg / dm ² chromium deposition ^amount of zinc is 1~70μg / dm ^2,
When peeling between the intermediate layer / ultra-thin copper layer, e (x) is the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS. 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 (% ) Is i (x), carbon atomic concentration (%) is j (x), and other atomic concentration (%) is k (x).
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫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 1 to 30%, ∫f (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 0.1 to 5%, ∫g ( x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x ) dx) is 1 to 50% and [1.0, 4.0], ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + H (x) dx + + i (x) dx + ∫j (x) dx + ∫k (x) dx) is a copper foil with a carrier satisfying 40% or more.

  In one embodiment of the carrier-attached copper foil according to the present invention, when peeling between the intermediate layer / ultra-thin copper layer, a section [0, 1.0] of depth direction analysis from the intermediate layer surface by XPS ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 2 to 25%.

  In another embodiment of the copper foil with a carrier according to the present invention, when peeling between the intermediate layer / ultra-thin copper layer, the section [1.0, 4.0], ∫h (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫ j (x) dx + ∫k (x) dx) satisfies 1 to 30%.

  In still 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 carrier-attached copper foil according to the present invention, the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, When peeling between the intermediate layer / ultra-thin copper layer, e (x) is the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS. 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 (% ) Is i (x), carbon atomic concentration (%) is j (x), and other atomic concentration (%) is k (x).
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫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%, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 1 to 50% and [1 ., 4.0] in ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + + g (x) dx + + h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 40% or more.

In yet another embodiment of the carrier-attached copper foil according to the present invention, the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, When delamination is performed between the intermediate layer and the ultrathin copper layer, 区間 e (x) dx / (∫e (x) in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 1 to 25% .

In yet another embodiment of the carrier-attached copper foil according to the present invention, the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours, When peeling between the intermediate layer / ultra thin copper layer, in the section [1.0, 4.0] of the depth direction analysis from the intermediate layer surface by XPS, ∫h (x) dx / (∫e ( x) dx + ∫ f (x) dx + ∫ g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) is 2 to 40% Meet.

  In yet another embodiment of the carrier-attached copper foil according to the present invention, the intermediate layer is made of any one layer of nickel or an alloy containing nickel on a copper foil carrier, and chromium, a chromium alloy, or chromium. A layer containing one or more oxides is stacked in this order.

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

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

  In another embodiment of the copper foil with a carrier according to the present invention, the intermediate layer is formed by laminating nickel or a nickel-zinc alloy, and a zinc chromate treatment layer or a pure chromate treatment layer in this order on the copper foil carrier. Has been configured.

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

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

  In still another embodiment of the carrier-attached copper foil according to the present invention, the roughening layer is any selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc. It is the layer which consists of an alloy containing these 1 type or any 1 type or more.

  In still another embodiment of the copper foil with a carrier according to the present invention, one or more types selected from the group consisting of a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the roughening treatment layer. It has a layer of.

  In still another embodiment of the copper foil with a carrier according to the present invention, one or more selected from the group consisting of a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the ultrathin copper layer. It has a layer of.

  According to another aspect of the present invention, after forming any one layer of nickel or a nickel-containing alloy on a copper foil carrier, the present invention includes any one or more of chromium, a chromium alloy, or a chromium oxide. A step of forming a layer and a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating, and the intermediate layer is made of any one layer of nickel or an alloy containing nickel, or chromium, chromium It is a manufacturing method of the copper foil with a carrier in which zinc is contained in either of the layers containing any one or more of an alloy or chromium oxide.

  In yet another aspect of the present invention, after forming a plating layer containing nickel and zinc on a copper foil carrier, a step of forming an intermediate layer by forming a plating layer containing chromium or a chromate treatment layer; And forming a very thin copper layer by electrolytic plating on the intermediate layer.

  In another aspect of the present invention, after forming a plating layer containing nickel on a copper foil carrier, a step of forming an intermediate layer by forming a plating layer containing chromium and zinc or a zinc chromate treatment layer; And a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating.

  In another aspect of the present invention, an intermediate layer is formed by forming a plating layer containing nickel and zinc on a copper foil carrier, and then forming a plating layer containing zinc and zinc or a zinc chromate treatment layer. It is a manufacturing method of the copper foil with a carrier including a process and the process of forming an ultra-thin copper layer by electrolytic plating on the said intermediate | middle layer.

  In yet another aspect of the present invention, after a nickel plating layer is formed on a copper foil carrier, a zinc chromate treatment layer is formed by electrolytic chromate, or after a nickel-zinc alloy plating layer is formed, electrolysis is performed. A method for producing a copper foil with a carrier comprising a step of forming an intermediate layer by forming a pure chromate treatment layer or a zinc chromate treatment layer by chromate, and a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer It is.

  In yet another aspect of the present invention, after a nickel plating layer is formed on a copper foil carrier, a zinc chromate treatment layer is formed by electrolytic chromate, or after a nickel-zinc alloy plating layer is formed, electrolysis is performed. Forming an intermediate layer by forming a pure chromate treatment layer or a zinc chromate treatment layer by chromate; forming an ultrathin copper layer by electrolytic plating on the intermediate layer; and roughening the ultrathin copper layer on the ultrathin copper layer. And a step of forming a chemical treatment 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 And then, a copper clad laminate is formed through a step of peeling the copper foil carrier of the copper foil with carrier, and then selected from a semi-additive method, a subtractive method, a partially additive method, and a modified semi-additive method A method of manufacturing a printed wiring board including a step of forming a circuit by any one of the methods.

  The copper foil with a carrier according to the present invention has high adhesion between the carrier and the ultrathin copper layer before the lamination process to the insulating substrate, while the carrier and the ultrathin copper layer after the lamination process to the insulation substrate. Adhesiveness is lowered, it can be easily peeled off at the carrier / ultra-thin copper layer interface, and the occurrence of pinholes on the surface of the ultra-thin copper layer can be satisfactorily suppressed.

It is a XPS depth profile of the depth direction of the intermediate | middle layer surface before board | substrate bonding of Example 3. FIG. It is a XPS depth profile of the depth direction of the intermediate | middle layer surface before board | substrate bonding of Example 7. FIG. It is an XPS depth profile of the depth direction of the intermediate | middle layer surface before the board | substrate bonding of the comparative example 3. FIG. It is an XPS depth profile of the depth direction of the ultra-thin copper layer surface after board | substrate bonding of Example 7. FIG.

<1. Career>
A copper foil is used as a carrier that can be used in the present invention. The carrier is 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.

<2. Intermediate layer>
An intermediate layer is provided on the copper foil carrier. The intermediate layer is configured by laminating any one layer of nickel or an alloy containing nickel on a copper foil carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. In addition, it is preferable that zinc is contained in any one layer of nickel or an alloy containing nickel and / or a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel may be an alloy composed of three or more elements. The chromium alloy is an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy may be an alloy composed of three or more elements. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may contain elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium. Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. Here, the pure chromate treatment layer refers to a chromate treatment layer treated with an aqueous solution of chromic anhydride, dichromic acid or potassium dichromate. The zinc chromate treatment layer refers to a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc.
The intermediate layer may be any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy on the copper foil carrier, and any of zinc chromate treatment layer, pure chromate treatment layer, and chromium plating. Preferably, the intermediate layer is formed by laminating nickel or a nickel-zinc alloy and a zinc chromate treatment layer or a pure chromate treatment layer in this order on the copper foil carrier. More preferably, they are laminated. 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 the chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of normal chromate, and the generation of pinholes can be further suppressed. it can.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

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

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

The intermediate nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. can do. Electroplating is preferable from the viewpoint of cost.
In addition, the chromate treatment layer can be formed by, for example, an electrolytic chromate treatment layer or an immersion chromate treatment layer, but the chromium concentration can be increased and the peel strength of the ultrathin copper layer from the copper foil carrier is good. Therefore, it is preferable to form with an electrolytic chromate treatment layer.

In the intermediate layer, the adhesion amount of nickel is 100~40000μg / dm ^2, the adhesion amount of chromium is 5~100μg / dm ^2, the adhesion amount of the zinc is 1~70μg / dm ^2. Although the amount of pinholes tends to increase as the amount of nickel increases, the number of pinholes is also suppressed within this range. Further, when the amount of zinc increases, the peel strength tends to be too high. However, if the amount of zinc adhered is within this range, the generation of pinholes is further suppressed. From the viewpoint of uniformly peeling the ultrathin copper layer uniformly and from the viewpoint of suppressing pinholes, the nickel adhesion amount is preferably 300 to 10000 μg / dm ^2, and preferably 500 to 3000 μg / dm ^2. more preferably, the chromium coating weight is preferably set to 10-50 / dm ^2, more preferably to 12~30μg / dm ^2, the zinc coating weight is preferably set to 5~30μg / dm ^2.

<3. 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.

<4. Ultra-thin 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.

<5. Roughening>
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 layer is a layer made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or an alloy containing any one or more of them. Also good. In addition, after forming coarse particles with copper or a copper alloy, a roughening treatment is performed in which secondary particles or tertiary particles are further made of nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc alone or an alloy. You can also. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc alone or an alloy, and further, chromate treatment, silane coupling treatment, etc. Processing may be performed. Alternatively, a heat-resistant or rust-proof layer is formed with nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc alone or with an alloy without roughening, and chromate treatment or silane coupling is performed on the surface. Processing such as processing may be performed. 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.).

<6. Copper foil with carrier>
Embodiments of the method for producing a copper foil with a carrier of the present invention are described below.
In the method for producing a copper foil with a carrier according to the present invention, after forming any one layer of nickel or an alloy containing nickel on a copper foil carrier, any one of chromium, a chromium alloy, or an oxide of chromium is formed. Including a step of forming a layer including the above and a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating, and the intermediate layer is any one layer of nickel or an alloy containing nickel, or Zinc may be contained in any of the layers containing one or more of chromium, a chromium alloy, and an oxide of chromium.
Moreover, the manufacturing method of the copper foil with a carrier of this invention forms an intermediate | middle layer by forming the plating layer containing chromium and a chromate treatment layer after forming the plating layer containing nickel and zinc on a copper foil carrier And a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating.
In the method for producing a copper foil with a carrier according to the present invention, an intermediate layer is formed by forming a plating layer containing nickel and then a plating layer containing zinc and chromium or a zinc chromate treatment layer on the copper foil carrier. A step of forming and a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating may be included.
Moreover, the method for producing a copper foil with a carrier according to the present invention comprises forming a plating layer containing nickel and zinc on a copper foil carrier, and then forming a plating layer containing zinc and chromium or a zinc chromate treatment layer. A step of forming a layer and a step of forming an ultrathin copper layer on the intermediate layer by electrolytic plating may be included.
Moreover, the manufacturing method of the copper foil with a carrier of this invention is forming a nickel chromate treatment layer by electrolytic chromate after forming a nickel plating layer on a copper foil carrier, or forming a nickel-zinc alloy plating layer. Then, a step of forming an intermediate layer by forming a pure chromate treatment layer or a zinc chromate treatment layer by electrolytic chromate and a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer may be included.
Furthermore, the manufacturing method of the copper foil with a carrier of this invention is that a nickel plating layer is formed on a copper foil carrier, and then a zinc chromate treatment layer is formed by electrolytic chromate, or a nickel-zinc alloy plating layer is formed. Then, a step of forming an intermediate layer by forming a pure chromate treatment layer or a zinc chromate treatment layer by electrolytic chromate, a step of forming an ultrathin copper layer by electrolytic plating on the intermediate layer, and the ultrathin copper Forming a roughening treatment layer on the layer.
Thus, the copper foil with a carrier provided with the copper foil carrier, the intermediate | middle layer formed on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the intermediate | middle layer is manufactured. 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. A copper-clad laminate can be obtained by bonding to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc., and peeling the carrier after thermocompression bonding. Further, an ultrathin copper layer bonded to the insulating substrate of the copper-clad laminate can be etched into a target conductor pattern, and finally a printed wiring board or a printed circuit board can be manufactured. In the case of the copper foil with a carrier according to the present invention, the peeled portion is mainly the interface between the intermediate layer and the ultrathin copper layer.

When the copper foil with a carrier of the present invention is peeled between the intermediate layer / ultra thin copper layer, 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), zinc atomic concentration (%) is f (x), nickel atomic concentration (%) is g (x), and copper atomic concentration (%) is h (x). If the total atomic concentration (%) of oxygen is i (x), the atomic concentration (%) of carbon is j (x), and the other atomic concentration (%) is k (x), In the interval [0, 1.0] of the depth direction analysis, ∫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 1-30%, ∫f (x) dx / (∫e (x) dx + ∫f (x) dx + ∫ g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 0.1 to 5%, ∫g (x) dx / (∫ e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 1 50% and [1.0, .0], ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 40% or more.
In addition, the copper foil with a carrier according to the present invention, when peeled between the intermediate layer / ultra-thin copper layer, in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS, ∫e (x ) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) preferably satisfies 2 to 25%.
Further, the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours. When exfoliated with, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from XPS depth direction analysis is defined as e (x), and the atomic concentration of zinc (%) Is f (x), nickel atomic concentration (%) is g (x), copper atomic concentration (%) is h (x), oxygen total atomic concentration (%) is i (x), When the atomic concentration (%) of carbon is j (x) and the other atomic concentration (%) is k (x), in the interval [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫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%, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) Is 1 to 50% and [1.0, 4.0], ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h ( x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) preferably satisfies 40% or more.
Further, the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours. ∫e (x) dx / (∫e (x) dx + ∫f (x) dx in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) preferably satisfies 1 to 25%.
Thus, in the copper foil with a carrier of the present invention, chromium and zinc are present in a certain amount or more on the outermost surface of the intermediate layer when peeled between the intermediate layer / ultra thin copper layer, and nickel is more than the outermost surface. The concentration is also high inside. For this reason, generation | occurrence | production of the pinhole in an ultra-thin copper layer side surface is suppressed favorably. Also, in the copper foil with carrier after thermocompression bonding, chromium and zinc are present in a certain amount or more on the outermost surface of the intermediate layer when the copper foil carrier is peeled from the ultrathin copper layer, and nickel is the outermost surface. The concentration is higher than inside. For this reason, generation | occurrence | production of the pinhole in an ultra-thin copper layer side surface is suppressed favorably.

When the carrier-attached copper foil of the present invention is peeled between the intermediate layer / ultra-thin copper layer, in the section [1.0, 4.0] in the depth direction analysis from the surface of the intermediate layer by XPS, h ( x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x ) dx) preferably satisfies 1 to 30%.
Further, the copper foil with a carrier of the present invention is obtained by thermocompression bonding an insulating substrate to an ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² and 220 ° C. × 2 hours. In the section [1.0, 4.0] of the depth direction analysis from the intermediate layer surface by XPS, ∫h (x) dx / (∫e (x) dx + ∫f (x ) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) preferably satisfies 2 to 40%.
Thus, in the copper foil with a carrier of the present invention, copper is present in a certain amount or more inside the intermediate layer when peeled between the intermediate layer / ultra thin copper layer. As the copper concentration in the intermediate layer increases, the adhesion between the intermediate layer and the ultrathin copper layer increases. Therefore, the peel strength can be controlled by controlling the copper concentration in nickel. Moreover, also in the copper foil with a carrier after thermocompression bonding, copper exists in a certain amount or more inside the intermediate layer when the copper foil carrier is peeled from the ultrathin copper layer. For this reason, there exists an effect that the fall of the extreme peeling strength after thermocompression-bonding can be prevented.
The higher the nickel current density is set to increase the electrodeposition rate per unit time, and the higher the transport speed of the carrier copper foil, the lower the density of the nickel layer. When the density of the nickel layer is reduced, the copper of the carrier copper foil is easily diffused into the nickel layer, and the concentration of copper in the nickel can be controlled. Further, when the current density in the chromate treatment is increased and the conveying speed of the carrier copper foil is decreased, the chromium concentration increases and the chromium concentration can be controlled.

  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.

<7. Manufacturing method of printed wiring board using copper foil with carrier>
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 forming a circuit by any one method selected from a subtractive method, a partly additive method, and a modified semi-additive method. It is also possible for the insulating substrate to contain an inner layer circuit.

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

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

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

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

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

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

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

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

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

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

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

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

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

1. Manufacture of copper foil with carrier As a copper foil carrier, a long electrolytic copper foil (JTC made by JX Nippon Mining & Metals) having a thickness of 35 μm and a rolled copper foil having a thickness of 33 μm (tough pitch copper foil made by JX Nippon Mining & Metals) JIS H3100 alloy number C1100) was prepared. With respect to the shiny surface of this copper foil, the intermediate layer forming treatment described in Tables 1 to 3 is performed under the following conditions in order on the carrier surface and the ultrathin copper layer side in a roll-to-roll type continuous line under the following conditions. went. Washing and pickling were performed between the processing steps on the carrier surface side and the ultrathin copper layer side.

・ Ni plating Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²
・ Ni-Zn plating Nickel sulfate: 250-300 g / L
Zinc sulfate 50-400g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. pH: 3-6
Bath temperature: 50-70 ° C
Current density: 3-15A / dm
・ Ni-Co plating Cobalt sulfate: 50-200 g / L
Nickel sulfate: 50-200 g / L
Trisodium citrate: 15-30 g / L
Bath temperature: 25-60 ° C
pH: 3-6
Current density: 1-15 A / dm ²
・ Ni-P plating Nickel sulfate: 200-300 g / L
Nickel chloride: 35-50 g / L
Boric acid: 30-50 g / L
Phosphorous acid: 1-30 g / L
pH: 1-3
Bath temperature: 40-70 ° C
Current density: 3-15 A / dm ²

-Cr plating solution composition: chromic anhydride 200-400 g / L, sulfuric acid 1.5-4 g / L
pH: 1-4
Liquid temperature: 45-60 degreeC
Current density: 10 to 40 A / dm ²

・ Immersion chromate treatment Zinc chromate: Potassium dichromate 1-10 g / L, Zinc sulfate 0.1-5 g / L
Pure chromate: chromic anhydride (or potassium dichromate) 1-10 g / L
pH: 2-4
Liquid temperature: 50-60 degreeC
Immersion time: 1 to 20 seconds

Electrolytic chromate treatment Zinc chromate: Potassium dichromate 1-10 g / L, Zinc sulfate 0.1-5 g / L
Pure chromate: chromic anhydride (or potassium dichromate) 1-10 g / L
pH: 2-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²

Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 3 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier. In addition, about Examples 1-3, 5, 7, 11, 13-15, the copper foil with a carrier whose thickness of an ultra-thin copper layer is 1, 2, 5, 12 micrometers was also produced, respectively.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

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

2. Various evaluations of copper foil with carrier Various evaluations were carried out by the following methods for the copper foil with carrier obtained as described above. The results are shown in Tables 1-3.

<Measurement of adhesion amount>
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 chromium deposited and zinc deposited was determined by atomic absorption spectrometry after dissolving the sample in 7% by mass of hydrochloric acid. It was measured by performing an analysis.

<XPS analysis>
After bonding the ultrathin copper layer side of the copper foil with a carrier on an insulating substrate and performing pressure bonding under the conditions of 20 kgf / cm ² and 220 ° C. × 2 hours, the copper foil carrier is peeled off from the ultrathin copper layer. It was. Subsequently, the exposed intermediate layer surface was subjected to XPS measurement to create a depth profile. XPS operating conditions are shown below. The XPS measurement on the exposed intermediate layer surface was performed by measuring the metal atomic concentration in the depth direction (x: unit nm) by analyzing the depth direction from the intermediate layer surface by XPS. In addition, the larger the value of x, the deeper (farther) the measurement position of the metal atomic concentration is from the surface.
・ 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 1.8 nm / min (SiO ₂ conversion)
Moreover, also about the copper foil with a carrier before the said thermocompression bonding, the copper foil carrier was peeled off from the ultra-thin copper layer, the XPS measurement was performed for the exposed copper foil carrier surface, and the depth profile was created.
In addition, whether it peeled between the intermediate | middle layer and the ultra-thin copper layer can be confirmed by producing the depth profile of the ultra-thin copper layer side like the intermediate | middle layer side. As shown in FIG. 4, nickel and chromium, which are constituent elements on the intermediate layer side, are hardly detected on the ultrathin copper foil side. When the atomic concentration of nickel on the surface of the ultrathin copper layer side was 20 at% or less and the atomic concentration of chromium was 5 at% or less, it was determined that peeling occurred between the intermediate layer and the ultrathin copper layer.
Further, the binding energy of the 2P3 / 2 orbit of chromium in the intermediate layer was detected by XPS.

<Pinhole>
The number of pinholes was visually measured using a consumer photographic backlight as a light source.

<Peel strength>
After bonding the ultra-thin copper layer side of the copper foil with carrier on the insulating substrate and performing pressure bonding under the conditions of 20 kgf / cm ² and 220 ° C. × 2 hours in the atmosphere, the peel strength is measured with a load cell. The foil carrier side was pulled and measured according to the 90 ° peeling method (JIS C 6471 8.1). Further, the peel strength of the carrier-attached copper foil before being bonded onto the insulating substrate was also measured.

(Evaluation results)
In all of Examples 1 to 19, pinholes were well suppressed, and even better peel strength was exhibited. In addition, the copper foil with a carrier with which the thickness of the ultra-thin copper layer produced about Examples 1-3, 5, 7, 11, 13-15 is 1, 2, 5, 12 micrometers also has the thickness of an ultra-thin copper layer. The same result as in the case of 3 μm was obtained.
In Comparative Examples 1 and 2, the intermediate layer was not formed, and the adhesion amount of nickel, chromium, and zinc was small, so that the carrier could not be peeled from the ultrathin copper layer even before thermocompression bonding.
In Comparative Examples 4, 5, 6, and 9, since the adhesion amount of nickel was small, the carrier could not be peeled from the ultrathin copper layer even before thermocompression bonding.
In Comparative Examples 3, 8, and 10, since the amount of chromium deposited was small, the carrier could not be peeled after bonding to the substrate.
In Comparative Example 7, since the amount of nickel deposited was too large, pinholes in the ultrathin copper layer increased and the peel strength was too low.
In Comparative Examples 11 and 12, since the chromium concentration on the intermediate layer surface was high, many pinholes were generated.
In Comparative Example 13, since the concentration of nickel on the surface of the intermediate layer formed on the carrier was high, the number of pinholes increased and the peel strength was too low.
In Comparative Example 14, since the amount of chromium deposited was large, pinholes in the ultrathin copper layer occurred frequently, and the peel strength was too low.
In Comparative Example 15, since the amount of zinc adhered was large, the peel strength was too high, and it was impossible to peel off after pressing.
In Reference Examples 1 and 2, since zinc-free chromate was used instead of zinc chromate, more pinholes were generated than in the examples.
FIG. 1 shows an XPS depth profile in the depth direction of the surface of the intermediate layer before bonding the substrates in Example 3. FIG. 2 shows an XPS depth profile in the depth direction of the surface of the intermediate layer before bonding the substrates in Example 7. FIG. 3 shows an XPS depth profile in the depth direction of the surface of the intermediate layer before bonding the substrates in Comparative Example 3. FIG. 4 shows an XPS depth profile in the depth direction of the surface of the ultrathin copper layer after bonding the substrates of Example 7.

Claims (26)

A copper foil with a carrier comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer,
In the intermediate layer, the amount of adhered 100~40000μg / dm ² of nickel, adhesion amount 5~100μg / dm ² chromium deposition ^amount of zinc is 1~70μg / dm ^2,
When peeling between the intermediate layer / ultra-thin copper layer, e (x) is the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS. 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 (% ) Is i (x), carbon atomic concentration (%) is j (x), and other atomic concentration (%) is k (x).
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫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 1 to 30%, ∫f (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 0.1 to 5%, ∫g ( x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x ) dx) is 1 to 50% and [1.0, 4.0], ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + Copper foil with carrier satisfying が h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 40% or more.   When delamination is performed between the intermediate layer and the ultrathin copper layer, 区間 e (x) dx / (∫e (x) in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface by XPS dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfy 2 to 25% The copper foil with a carrier according to claim 1.   When peeling between the intermediate layer / ultra thin copper layer, in the section [1.0, 4.0] of the depth direction analysis from the intermediate layer surface by XPS, ∫h (x) dx / (∫e ( x) dx + ∫ f (x) dx + (g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx) 1-30% The copper foil with a carrier of Claim 1 or 2 which satisfy | fills.   The copper foil with a carrier according to any one of claims 1 to 3, wherein a binding energy of 2P3 / 2 orbit of chromium detected by XPS of the intermediate layer is in a range of 576 to 580 eV. When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours, and peeled between the intermediate layer / ultrathin copper layer, the surface by XPS The atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis of e is x (e), the atomic concentration (%) of zinc is f (x), and nickel atoms The concentration (%) 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) and other atomic concentrations (%) as k (x),
In the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫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%, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 1 to 50% and [1 ., 4.0] in ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + + g (x) dx + + h (x) dx + ∫i (x) The copper foil with a carrier according to any one of claims 1 to 4, wherein dx + ∫j (x) dx + ∫k (x) dx) satisfies 40% or more. When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in the atmosphere and separated between the intermediate layer / ultrathin copper layer, the intermediate by XPS区間 e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h) in the interval [0, 1.0] of the depth direction analysis from the layer surface The copper foil with a carrier according to any one of claims 1 to 5, wherein (x) dx + + i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 1 to 25%. When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm ² , 220 ° C. × 2 hours in the atmosphere and separated between the intermediate layer / ultrathin copper layer, the intermediate by XPS In the section [1.0, 4.0] of the depth direction analysis from the layer surface, ∫h (x) dx / (∫e (x) dx + 区間 f (x) dx + ∫g (x) dx + The copper foil with a carrier according to any one of claims 1 to 6, wherein ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + xk (x) dx) satisfies 2 to 40%.   The intermediate layer is formed by laminating any one layer of nickel or an alloy containing nickel on a copper foil 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 comprised.   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 intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy on the copper foil carrier, and any of zinc chromate treatment layer, pure chromate treatment layer, and chromium plating. The copper foil with a carrier according to any one of claims 1 to 9, wherein one kind of layer is laminated in this order.   The said intermediate | middle layer is copper foil with a carrier of Claim 10 comprised by laminating | stacking nickel or a nickel-zinc alloy, a zinc chromate treatment layer, or a pure chromate treatment layer in this order on the copper foil carrier.   The copper foil with a carrier according to any one of claims 1 to 11, wherein the copper foil carrier is formed of an electrolytic copper foil or a rolled copper foil.   The copper foil with a carrier in any one of Claims 1-12 which have a roughening process layer in the said ultra-thin copper layer surface.   The roughening treatment layer is a single layer selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or a layer made of an alloy containing at least one of them. Item 14. A copper foil with a carrier according to Item 13.   The copper foil with a carrier of Claim 13 or 14 which has 1 or more types of layers selected from the group which consists of a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the said roughening process layer.   The copper with a carrier according to any one of claims 1 to 12, which has one or more layers selected from the group consisting of a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. Foil.   Forming any one layer of nickel or a nickel-containing alloy on a copper foil carrier, and then forming a layer containing any one or more of chromium, a chromium alloy or a chromium oxide; Forming an ultrathin copper layer on the layer by electrolytic plating, and any one layer of nickel or an alloy containing nickel as the intermediate layer, or one of chromium, a chromium alloy, and an oxide of chromium The manufacturing method of the copper foil with a carrier in which zinc is contained in either of the layers containing 1 or more types.   After forming a plating layer containing nickel and zinc on a copper foil carrier, a step of forming an intermediate layer by forming a plating layer containing chromium or a chromate treatment layer, and an extremely thin layer by electrolytic plating on the intermediate layer The manufacturing method of copper foil with a carrier including the process of forming a copper layer.   After forming a plating layer containing nickel on a copper foil carrier, forming an intermediate layer by forming a plating layer containing chromium and zinc or a zinc chromate-treated layer, and forming an electrode on the intermediate layer by electrolytic plating The manufacturing method of copper foil with a carrier including the process of forming a thin copper layer.   Forming a plating layer containing nickel and zinc on a copper foil carrier, and then forming an intermediate layer by forming a plating layer containing chromium and zinc or a zinc chromate treatment layer; and electroplating on the intermediate layer The process of forming an ultra-thin copper layer by the manufacturing method of copper foil with a carrier.   After forming a nickel plating layer on a copper foil carrier, by forming a zinc chromate treatment layer by electrolytic chromate, or after forming a nickel-zinc alloy plating layer, a pure chromate treatment layer or zinc chromate treatment by electrolytic chromate The manufacturing method of copper foil with a carrier including the process of forming an intermediate | middle layer by forming a layer, and the process of forming an ultra-thin copper layer on the said intermediate | middle layer by electrolytic plating.   After forming a nickel plating layer on a copper foil carrier, by forming a zinc chromate treatment layer by electrolytic chromate, or after forming a nickel-zinc alloy plating layer, a pure chromate treatment layer or zinc chromate treatment by electrolytic chromate Forming an intermediate layer by forming a layer, forming an ultrathin copper layer on the intermediate layer by electrolytic plating, and forming a roughened layer on the ultrathin copper layer. The manufacturing method of copper foil with a carrier.   The printed wiring board manufactured using the copper foil with a carrier in any one of Claims 1-16.   The printed circuit board manufactured using the copper foil with a carrier in any one of Claims 1-16.   The copper clad laminated board manufactured using the copper foil with a carrier in any one of Claims 1-16. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 16 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the copper foil carrier of the copper foil with carrier,
Thereafter, a step of forming a circuit by any one method selected from a semi-additive method, a subtractive method, a partly additive method, and a modified semi-additive method;
A method of manufacturing a printed wiring board including: