JP2014172184A - Carrier-fitted copper foil, printed wiring board, printed circuit board, copper-clad laminate sheet, and method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carrier-fitted copper foil having a favorable peel strength and suited for forming fine pitches and a method for manufacturing a printed wiring board.SOLUTION: The provided carrier-fitted copper foil is a carrier-fitted copper foil furnished with a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrafine copper layer laminated on the intermediate layer wherein the intermediate layer includes, as an oxide having a spinel-type crystal structure, an oxide including an electroconductive oxide; a method for manufacturing a printed wiring board wherein a copper-clad laminate sheet is formed past a step of preparing the carrier-fitted copper foil and an insulating substrate, a step of laminating the carrier-fitted copper foil and insulating substrate, and a step of peeling, following the lamination of the carrier-fitted copper foil and insulating substrate, the carrier of the carrier-fitted copper foil and wherein a circuit is formed based on any method selected from among the semi-additive method, subtractive method, partly additive method, and modified semi-additive method is also provided.

Description

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

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. 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.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After forming a circuit pattern with a resist on the exposed ultrathin copper layer, the ultrathin copper layer is etched away with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.

  Here, for the surface of the ultra-thin copper layer of the copper foil with carrier, which becomes the adhesive surface with the resin, the peel strength between the ultra-thin copper layer and the resin substrate is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like. As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.

  However, if a very thin copper layer with such a large profile (irregularity, roughness) is used on a semiconductor package substrate that needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles during circuit etching Will remain, causing problems such as poor insulation between circuit patterns.

  For this reason, in WO2004 / 005588 (Patent Document 1), a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. Therefore, the further improvement is calculated | required about copper foil with a carrier.

  Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-006071 (Patent Document 3), the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been. By providing these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultrathin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.

WO2004 / 005588 JP 2007-007937 A JP 2010-006071 A

  In the development of a copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the resin substrate. For this reason, sufficient studies have not yet been made on fine pitch formation, and there is still room for improvement with respect to a technique that achieves both improved peel strength and fine pitch. Then, this invention makes it a subject to provide the copper foil with a carrier which has favorable peeling strength and is suitable for fine pitch formation.

  The present inventors paid attention to the function of the intermediate layer of the carrier-attached copper foil for the above problems. When the intermediate layer has an oxide having a spinel crystal structure, the peel strength when peeling between the intermediate layer and the ultrathin copper layer is increased. Further, the present inventors have found that the peel strength of the ultrathin copper layer before and after the pressing of the copper foil with carrier is stabilized and the etching property of the ultrathin copper layer is improved.

  The present invention has been completed on the basis of the above knowledge, and in one aspect, includes a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the intermediate layer. A copper foil with a carrier, wherein the intermediate layer has an oxide having a spinel crystal structure.

  In another embodiment of the copper foil with a carrier of the present invention, the intermediate layer has Mo, Ca, V, Pb, Ge, Cd, Hg, Sr, Al, W, Be, Co, Li, Cu, Ni, One or more selected from the element group consisting of Mg, Fe, Sn, Ti, Zn and Mn, and Mg, Zn, V, Ga, Rh, Ni, In, Co, Mn, Al, Fe and Cr 1 type or 2 types or more selected from the B element group which consists of, and oxygen.

  In another embodiment of the copper foil with a carrier of the present invention, the intermediate layer contains an electrically conductive oxide.

  In still another embodiment, the carrier-attached copper foil of the present invention has a depth direction (x: unit) obtained by analyzing the depth direction from the surface by XPS when peeled between the intermediate layer / ultra-thin copper layer. nm) 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, in the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x dx + xh (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 10% or more.

  In still another embodiment, the carrier-attached copper foil of the present invention has a depth direction (x: unit) obtained by analyzing the depth direction from the surface by XPS when peeled between the intermediate layer / ultra-thin copper layer. nm) 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, in the section [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x dx + xh (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 15% or more.

  In still another embodiment, the carrier-attached copper foil of the present invention has a depth direction (x: unit) obtained by analyzing the depth direction from the surface by XPS when peeled between the intermediate layer / ultra-thin copper layer. nm) 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, C = 区間 i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g) in the interval [0, 1.0] of the depth direction analysis from the intermediate layer surface. (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) and D = (と し e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫k (x) dx) / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx), and E = C−0.3 × D, E Satisfies 0% or more.

  In yet 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, the carrier-attached copper foil of the present invention has a roughened 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 treatment layer is any one element selected from the group consisting of copper, nickel, cobalt, and zinc, or an alloy containing at least one kind. It is the layer which consists of.

  In yet another embodiment, the carrier-attached copper foil of the present invention is one type 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. It has the above layers.

  In yet another embodiment, the carrier-attached copper foil of the present invention is one type 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. It has the above layers.

  In another aspect, the present invention is a printed wiring board produced 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, it is possible to provide a copper foil with a carrier that has good peel strength and is suitable for fine pitch formation.

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

<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. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys 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 increases, so it is generally preferable that the thickness is 70 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

<Intermediate layer>
An intermediate layer is provided on the carrier. The intermediate layer preferably contains an electrically conductive oxide. In the present invention, an electrically conductive oxide refers to an oxide having an electrical conductivity higher than that of an insulator. The electrical conductivity of the electrically conductive oxide is, for example, 10 ⁻⁸ Scm ⁻¹ or more. Examples of the electrically conductive oxide include semiconductors and solid electrolytes. When the intermediate layer contains an electrically conductive oxide, the electrically conductive oxide has a function of preventing the diffusion of metal atoms. In the copper foil with a carrier, the electrode of the metal atoms from the copper foil carrier Diffusion to the thin copper layer can be satisfactorily prevented. For this reason, the peel strength of the ultrathin copper layer is stabilized before and after the carrier-attached copper foil is pressure-bonded to the substrate, and the etching property of the ultrathin copper layer is improved. Moreover, since the said oxide is an electroconductive oxide, formation of an ultra-thin copper layer becomes easy.
Here, as the electrically conductive oxide, for example, M ₂ O oxide (M is a metal, for example, Na ₂ O, K ₂ O, Li ₂ O), MO oxide (M is a metal, for example, MnO, NiO, CoO). , ZnO), M ₂ O ₃ oxide (M is a metal such as Cr ₂ O ₃ , Fe ₂ O ₃ , Y ₂ O ₃ , Yb ₂ O ₃ , V ₂ O ₃ , Ti ₂ O ₃ , Mn ₂ O _3. , In2O3, Al2O3), MO ₂ oxide _{(e.g., TiO 2, ThO 2, CrO} 2, V 2 O 4, SnO2), M 3 O 4 oxide _{(e.g., Co 3 O 4, Mn 3} O 4, Fe ₃ O ₄ ), MO ₃ oxide (for example, CrO ₃ , UO ₃ ), M ₂ O ₅ oxide (V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ ), M ₄ O ₆ oxide, M ₂ O ₇ oxide (e.g., Mn ₂ O _7), a composite oxide XYO ₂ (X, Y are different metals, for example, LiNiO _2), XYO ₃ oxide (e.g., LiMn _{3, FeTiO 3, MnTiO 3,} CoTiO 3, NiTiO 3, LiNbO 3, LiTaO 3, NaWO 3), XYO 4 oxides _{(e.g., MgWO 4, CdWO 4, NiWO} 4), XY 2 O 6 oxide (e.g., CaNb ₂ O ₆ ), X ₂ Y ₂ O ₆ oxide (eg Na ₂ Nb ₂ O ₆ ), XY ₂ O ₄ oxide (eg MoNa ₂ O ₄ , MoAg ₂ O ₄ , MoCu ₂ O ₄ , MoLi ₂ O ₄ , WLi ₂ O ₄ , TiSr ₂ O ₄ , MnCa ₂ O ₄ , FeCr ₂ O ₄ , TiZn ₂ O ₄ , SnMg ₂ O ₄ SnZn ₂ O ₄ , MgAl ₂ O ₄ , MoAl ₂ O ₄ , CuAl ₂ O ₄ , ZnAl ₂ O ₄ , ZnV ₂ O ₄ , TiMn ₂ O ₄ , ZnMn ₂ O ₄ , NiAl ₂ O ₄ , MgGa ₂ O ₄ , ZnGa ₂ O ₄ , CaGa ₂ O ₄ , TiMg ₂ O ₄ , VMg ₂ O ₄ , MgV ₂ O _{4 , FeV 2 O 4, ZnV 2} O 4, MgCr 2 O 4, MnCr 2 O 4, FeCr 2 O 4, CoCr 2 O 4, NiCr 2 O 4, CuCr 2 O 4, ZnCr 2 O 4, CdCr 2 O 4 , TiMn ₂ O ₄ , ZnMn ₂ O ₄ , MgFe ₂ O ₄ , TiFe ₂ O ₄ , MnFe ₂ O ₄ , CoFe ₂ O ₄ , NiFe ₂ O ₄ , CuFe ₂ O ₄ , ZnFe ₂ O ₄ , CdFe ₂ O ₄ , AlFe ₂ O ₄ , PbFe ₂ O ₄ , MgCo ₂ O ₄ , TiCo ₂ O ₄ , ZnCo ₂ O ₄ , SnCo ₂ O ₄ , FeNi ₂ O ₄ , GeNi ₂ O ₄ , MgRh ₂ O ₄ , ZnRh ₂ O _{4 , TiZn 2 O 4, SrAl 2} O 4, CrAl 2 O 4, MoAl 2 O 4, FeAl 2 O 4, CoAl 2 O 4, MgGa 2 O 4, ZnGa 2 O 4, MgIn 2 O 4, CaIn 2 O 4 , FeIn ₂ O ₄ , CoIn ₂ O ₄ , NiIn ₂ O ₄ , CdIn ₂ O ₄ , HgIn ₂ O ₄ ), X ₂ YO ₅ oxide (for example, Fe ₂ TiO ₅ , Al ₂ TiO ₅ ) and the like. Moreover, a well-known electroconductive oxide can be used as an electroconductive oxide. Note that a composite oxide in which a plurality of the above-described oxides are mixed can also be used. (For example, In ₂ O ₃ .SnO ₂ , Na ₂ O.Al ₂ O ₃ etc.)

The intermediate layer has a spinel crystal structure. When the intermediate layer has a spinel crystal structure, the peel strength when peeling between the intermediate layer and the ultrathin copper layer tends to be high, and the ultrathin copper layer is formed from the carrier during the manufacture of the copper foil with a carrier. There is an advantage that it is difficult to peel off.
The oxide having a spinel crystal structure is, for example, an XY ₂ O ₄ oxide (for example, MoNa ₂ O ₄ , MoAg ₂ O ₄ , MoCu ₂ O ₄ , MoLi ₂ O ₄ , WLi ₂ O ₄ , TiSr ₂ O ₄ , MnCa ₂ O ₄ , FeCr ₂ O ₄ , TiZn ₂ O ₄ , SnMg ₂ O ₄ , SnZn ₂ O ₄ , MgAl ₂ O ₄ , MoAl ₂ O ₄ , CuAl ₂ O ₄ , ZnAl ₂ O ₄ , ZnV ₂ O ₄ , TiMn ₂ O ₄ , ZnMn ₂ O ₄ , NiAl ₂ O ₄ , MgGa ₂ O ₄ , ZnGa ₂ O ₄ , CaGa ₂ O ₄ , TiMg ₂ O ₄ , VMg ₂ O ₄ , MgV ₂ O ₄ , FeV ₂ O ₄ , _{ZnV 2 O 4, MgCr 2 O} 4, MnCr 2 O 4, FeCr 2 O 4, CoCr 2 O 4, NiCr 2 O 4, CuCr 2 O 4, ZnCr 2 O 4, CdCr 2 O 4, TiMn 2 O 4, _{ZnMn 2 O 4, MgFe 2 O} 4, T _{Fe 2 O 4, MnFe 2 O} 4, CoFe 2 O 4, NiFe 2 O 4, CuFe 2 O 4, ZnFe 2 O 4, CdFe 2 O 4, AlFe 2 O 4, PbFe 2 O 4, MgCo 2 O 4, TiCo ₂ O ₄ , ZnCo ₂ O ₄ , SnCo ₂ O ₄ , FeNi ₂ O ₄ , GeNi ₂ O ₄ , MgRh ₂ O ₄ , ZnRh ₂ O ₄ , TiZn ₂ O ₄ , SrAl ₂ O ₄ , CrAl ₂ O ₄ , MoAl ₂ O ₄ , FeAl ₂ O ₄ , CoAl ₂ O ₄ , MgGa ₂ O ₄ , ZnGa ₂ O ₄ , MgIn ₂ O ₄ , CaIn ₂ O ₄ , FeIn ₂ O ₄ , CoIn ₂ O ₄ , NiIn ₂ O ₄ , CdIn ₂ O ₄ , HgIn ₂ O ₄ ). Note that the intermediate layer containing the above-described electrically conductive oxide and oxide having a spinel crystal structure can be formed by combining dry plating such as sputtering, metal plating, and chromate treatment.

The intermediate layer is an A element group composed of Mo, Ca, V, Pb, Ge, Cd, Hg, Sr, Al, W, Be, Co, Li, Cu, Ni, Mg, Fe, Sn, Ti, Zn, and Mn. And one or more selected from the B element group consisting of Mg, Zn, V, Ga, Rh, Ni, In, Co, Mn, Al, Fe and Cr, and It preferably contains oxygen. According to such a configuration, an oxide having a spinel crystal structure is included in the intermediate layer, and manufacturing stability is increased. Such a configuration includes, for example, those containing Zn and Sn among the above-mentioned XY ₂ O ₄ oxides, and these are particularly preferable because they tend to have high conductivity.

  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, ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + (I) (x) dx + (j) (x) dx + (k) (x) dx) is preferably controlled so as to satisfy 10% or more. According to such a configuration, oxygen is sufficiently present on the surface of the intermediate layer side of the ultrathin copper layer, the electroconductive oxide is sufficiently formed, and before and after thermocompression bonding such as when the peel strength is bonded to the substrate It becomes difficult to change. ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫ in the depth direction analysis interval [0, 1.0] from the surface of the intermediate layer h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is more preferably controlled to satisfy 15% or more, so as to satisfy 15% or more. Is more preferably controlled to satisfy 18% or more, and more preferably controlled to satisfy 20% or more. Note that ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx in the section [0, 1.0] in the depth direction analysis from the surface of the intermediate layer + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is not particularly limited, but for example, 70% or less, for example 60% or less, For example, it is 50% or less.

  The copper foil with a carrier of the present invention has C = ∫i (x) dx / (∫e (x) dx + ∫f (x) in the section [0, 1.0] in the depth direction analysis from the intermediate layer surface. ) dx + ∫g (x) dx + ∫h (x) dx + xi (x) dx + ∫j (x) dx + ∫k (x) dx) and D = (∫e (x) dx + ∫ f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫k (x) dx) / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) and E = C−0.3 × D, so that E satisfies 0% or more Preferably it is controlled. If the E = C−0.3 × D is 0% or more, the proportion of oxygen present on the surface on the intermediate layer side of the ultrathin copper layer is 30% or more of the metal. It is easy to form, and the peel strength is less likely to change before and after thermocompression bonding such as when it is bonded to a substrate. The E = C−0.3 × D is more preferably controlled to satisfy 10% or more, more preferably controlled to satisfy 15% or more, and so as to satisfy 20% or more. More preferably, it is controlled.

  The intermediate layer can be obtained by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost.

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

<Roughening treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve adhesion to the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is a 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 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.).

<Copper foil with carrier>
Thus, the copper foil with a carrier provided with the copper foil carrier, the intermediate layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the intermediate 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. Base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The printed wiring board can be finally manufactured by etching the ultrathin copper layer adhered to the substrate into a desired conductor pattern. Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  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, and with the carrier After laminating the 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, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a 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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

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

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

1. Manufacture of copper foil with carrier As a carrier, long electrolytic copper foil (JTC made by JX Nippon Mining & Metals Co., Ltd.) and rolled copper foil (Tough pitch copper foil JIS H3100 alloy number C1100 made by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 35 μm And an intermediate layer was formed on the surface. The formation of the intermediate layer was performed according to the processing order described in the item “Method for forming intermediate layer” in Table 1. That is, for example, what is described as “Ni / zinc chromate” indicates that “Ni” was first processed and then “Zinc chromate” was processed. In the “intermediate layer” item, “Ni” means that pure nickel plating was performed, and “Ni—Zn” means that nickel zinc alloy plating was performed. , “Ti sputtering” means that Ti plating was formed by sputtering, “heating” means that heat treatment was performed, “ “BTA treatment” means that a surface treatment using benzotriazole was performed. Each processing condition is shown below. In addition, when increasing the adhesion amount of each metal, set the current density higher and / or set the plating time longer and / or increase the concentration of each element in the plating solution. I did that. Also, when reducing the amount of each metal attached, set the current density low and / or set the plating time short and / or reduce the concentration of each element in the plating solution. I did that. The balance of the liquid composition such as a plating solution is water.

· "In ₂ O ₃ · SnO ₂ sputtering": In ₂ O ₃ · SnO ₂ coating by sputtering In ₂ O ₃ · SnO _2: forming a In ₂ O ₃ · SnO ₂ layer by using a sputtering target of 99Mass% composition did.
Target: In ₂ O ₃ · SnO ₂ : 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

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

“Heating”: Heat treatment Heat treatment was performed at 200 ° C. for 1 hour at an oxygen concentration of 100 volppm in a nitrogen atmosphere.

"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": nickel zinc alloy plating In the above nickel plating formation conditions, zinc in the form of zinc sulfate (ZnSO4) is added to the nickel plating solution, and the zinc concentration is in the range of 0.05 to 5 g / L. Adjusted to form a nickel zinc alloy plating.

· "Sn": tinned (liquid composition) stannous sulfate (SnSO ₄₎ 40~60g / L, sulfuric acid 90~110g / L, cresol sulfonic acid 990~110g / L, gelatin 1.5～2.5G / L, β-naphthol 1.5-2.5 g / L
(Liquid temperature) 20-35 ° C
(Current density) 2-3 A / dm ²
(Energization time) 1 to 20 seconds

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

· "Fe": iron plating (liquid composition) ferrous chloride _{(FeCl 2 · 4H 2 O)} 280~330g / L
Calcium chloride (CaCl ₂ · 2H ₂ O) 150-200 g / L
(PH) 2.5-3.0
(Liquid temperature) 60-70 ° C
(Current density) 1-10 A / dm ²
(Energization time) 1 to 10 seconds

"Co": Cobalt plating (Liquid composition) Cobalt sulfate: 10-200 g / L, Sodium citrate: 2-240 g / L
(PH) 2-5
(Liquid temperature) 20-35 ° C
(Current density) 2-3 A / dm ²
(Energization time) 1 to 20 seconds

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

"Anodizing": Anodizing treatment NaOH: 10 to 20 g / L
Electrolyte temperature: 20-50 ° C
Current density: 1-10 A / dm ²
Energizing time: 1 to 20 seconds

-"Pure chromate": Electrolytic 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.

"Mg chromate": Mg chromate treatment Under the above-mentioned electrolytic pure chromate treatment conditions, magnesium in the form of magnesium sulfate (MgSO ₄ ) is added to the solution, and the magnesium concentration is adjusted in the range of 0.05 to 5 g / L. Magnesium chromate treatment was performed.
"Co chromate": Co chromate treatment Under the above-mentioned electrolytic pure chromate treatment conditions, cobalt in the form of cobalt sulfate (CoSO ₄ ) is added to the solution, and the cobalt concentration is adjusted in the range of 0.05 to ₅ g / L. Cobalt chromate treatment was performed.

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

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

· "SiO ₂ sputter": sputtering with SiO ₂ Plating SiO _2: tin oxide target 99Mass% of the composition SiO ₂ layer was formed by using.
Target: SiO ₂ : 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

- "Na ₂ O · Al ₂ O ₃ sputtering": Na by sputtering ₂ O · Al ₂ O ₃ plating _{Na 2 O · Al 2 O 3} : using the sputtering target of 99Mass% of the composition Na ₂ O · Al ₂ O _Three layers were formed.
Target: Na ₂ O · Al ₂ O ₃ : 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

“Bi ₄ Ti ₃ O ₁₂ sputtering”: Bi ₄ Ti ₃ O ₁₂ plating by sputtering Bi ₄ Ti ₃ O ₁₂ : A Bi ₄ Ti ₃ O ₁₂ layer was formed using a sputtering target having a composition of 99 mass%.
Target: Bi ₄ Ti ₃ O ₁₂ : 99 mass%
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

"Mo-Co": Molybdenum cobalt alloy plating (Liquid composition) Cobalt sulfate: 10-200 g / L, Sodium molybdate: 5-200 g / L, Sodium citrate: 2-240 g / L
(PH) 2-5
(Liquid temperature) 10-70 ° C
(Current density) 0.5 to 10 A / dm ²
(Energization time) 1 to 20 seconds

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

2. Evaluation of copper foil with carrier The copper foil with carrier obtained as described above was evaluated by the following methods.
<Determination of oxide composition and presence of oxide having spinel structure in intermediate layer>
About the copper foil with a carrier, the ultra-thin copper layer was peeled off from the carrier based on JISC6471 (method A). Subsequently, the concentration of each metal element, oxygen, and carbon in the depth direction (x: unit nm) was measured on the surface on the intermediate layer side of the carrier by the depth direction analysis from the surface by XPS under the following conditions. When the same element and oxygen as the constituent elements of the oxide having the spinel structure were present at the same depth, it was determined that the oxide having the spinel structure was present in the intermediate layer. In addition, it means that the measurement position of various atomic concentration is deep (far) from the surface, so that the value of x is large. Note that the measurement interval of various atomic concentrations in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
(XPS 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 )
When it was determined that the oxide having the spinel structure exists in the intermediate layer, the presence / absence determination of the oxide having the spinel structure by XPS in Table 1 was “present”. When it was determined that the oxide having the spinel structure was not present in the intermediate layer, the presence / absence determination of the oxide having the spinel structure by XPS in Table 1 was “None”.
Note that the crystal structure of the oxide was also identified by X-ray diffraction (XRD). When specifying the oxide crystal structure by X-ray diffraction (XRD), the thickness of the intermediate layer is adjusted so that the thickness of the intermediate layer is sufficient for X-ray diffraction (XRD) measurement (ie, the thickness is insufficient). In this example, the thickness was measured after the thickness was increased).

<Determination of oxide composition and presence of electrically conductive oxide in intermediate layer>
About the copper foil with a carrier, the ultra-thin copper layer was peeled off from the carrier based on JISC6471 (method A). Subsequently, the concentration of each metal element, oxygen, and carbon in the depth direction (x: unit nm) was measured on the surface on the intermediate layer side of the carrier by the depth direction analysis from the surface by XPS under the following conditions. When the same element and oxygen as the constituent elements of the above-described electrically conductive oxide exist at the same depth, it was determined that the electrically conductive oxide was present in the intermediate layer. In addition, it means that the measurement position of various atomic concentration is deep (far) from the surface, so that the value of x is large. Note that the measurement interval of various atomic concentrations in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
(XPS 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 )
When it was determined that the electrically conductive oxide was present in the intermediate layer, the presence / absence determination of the electrically conductive oxide by XPS in Table 1 was “present”. In addition, when it was determined that the electrically conductive oxide was not present in the intermediate layer, the presence / absence determination of the electrically conductive oxide by XPS in Table 1 was “None”.

<Electrical conductivity of oxide>
If it is determined that the above-mentioned electrically conductive oxide is present in the intermediate layer, the presence of the element detected in the XPS measurement for the determination is determined as “present”. The past reported value (document value) of the electrical conductivity of the object was adopted.

<Oxide structure>
If it is determined that the above-mentioned electrically conductive oxide is present in the intermediate layer, the presence of the element detected in the XPS measurement for the determination is determined as “present”. The structure reported in the past was adopted as the structure of the object.

<A element concentration, B element concentration and oxygen concentration of the intermediate layer>
About the copper foil with a carrier, the ultra-thin copper layer was peeled off from the carrier based on JISC6471 (method A). Subsequently, with respect to the surface on the intermediate layer side of the carrier, the depth from the intermediate layer where the conductive oxide in the depth direction (x: unit nm) is present by the depth analysis from the surface by XPS under the following conditions. K (nm) was measured. Furthermore, element A (Co, Li, Cu, Ni, Mg, Fe, Sn, Ti, Zn, Mn, Mo, Ca, V, Pb, Ge, Cd, Hg at a depth K (nm) from the intermediate layer. , Sr, Al, W, Be) concentration a, B element (Mg, Zn, V, Ga, Rh, Ni, In, Co, Mn, Al, Fe, Cr) concentration b, and oxygen concentration c. It was measured. In addition, it means that the measurement position of various atomic concentration is deep (far) from the surface, so that the value of x is large. Note that the measurement interval of various atomic concentrations in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
(XPS 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 )
When all of the A element, B element, and oxygen were detected, “present” was written in the presence / absence determination column for the A element, B element, and oxygen by XPS in the table. Further, when at least one of A element, B element, and oxygen was not detected, “None” was described in the presence / absence determination column of A element, B element, and oxygen by XPS in the table.
<E = C-0.3 × D>
About the copper foil with a carrier, the ultra-thin copper layer was peeled off from the carrier based on JISC6471 (method A). Subsequently, for the surface on the intermediate layer side of the carrier, in the section [0, 1.0] of the depth direction analysis from the surface of the intermediate layer by the depth direction analysis from the surface by XPS under the following conditions, C = ∫ i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) and D = (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫k (x) dx) / (∫e ( x) dx + ∫ f (x) dx + ∫ g (x) dx + ∫ h (x) dx + ∫ i (x) dx + ∫ j (x) dx + ∫ k (x) dx), E = C The value of E was calculated as −0.3 × D.
In addition, it means that the measurement position of various atomic concentration is deep (far) from the surface, so that the value of x is large. Note that the measurement interval of various atomic concentrations in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In the present invention, the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (SiO ₂ conversion) (measured every 0.1 minutes by sputtering time).
(XPS 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 )

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

<Peel strength>
Heat the copper foil with a carrier to the BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere under pressure of 20 kgf / cm ² and 220 ° C. × 2 hours. Crimped and pasted. Subsequently, the carrier side was pulled with a load cell, and the peel strength was measured according to the 90 ° peel method (JIS C 6471 8.1). Moreover, except that only the temperature of thermocompression bonding was different at 300 ° C., a test similar to the above was performed to measure the peel strength. Further, the peel strength was measured in the same manner for each sample before thermocompression bonding with the resin. Further, the rate of change (%) in peel strength before and after thermocompression bonding was also calculated. The rate of change (%) in peel strength before and after thermocompression bonding was calculated by the following formula.
Change rate of peel strength before and after thermocompression bonding (%) = ((peel strength after thermocompression bonding (N / m)) − (peel strength before thermocompression bond (N / m))) / (peel strength before thermocompression bonding) (N / m))

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

Claims (15)

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,
The copper foil with a carrier in which the said intermediate | middle layer has the oxide which has a spinel type crystal structure.   A element in which the intermediate layer is made of Mo, Ca, V, Pb, Ge, Cd, Hg, Sr, Al, W, Be, Co, Li, Cu, Ni, Mg, Fe, Sn, Ti, Zn, and Mn One or more selected from the group, and one or more selected from the B element group consisting of Mg, Zn, V, Ga, Rh, Ni, In, Co, Mn, Al, Fe and Cr The copper foil with a carrier of Claim 1 containing oxygen and oxygen.   The copper foil with a carrier according to claim 1 or 2, wherein the intermediate layer contains an electrically conductive oxide. 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 interval [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + The copper foil with a carrier according to any one of claims 1 to 3, wherein ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfies 10% or more. 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 interval [0, 1.0] of the depth direction analysis from the intermediate layer surface, ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + The copper foil with a carrier according to claim 4, wherein ∫h (x) dx + ∫i (x) dx + + j (x) dx + ∫k (x) dx) satisfies 15% or more. 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 interval [0, 1.0] in the depth direction analysis from the intermediate layer surface, C = ∫i (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) and D = (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫k (x) dx) / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫ i (x) dx + ∫j (x) dx + ∫k (x) dx), where E = C−0.3 × D, E satisfies 0% or more. Copper foil with carrier.   The copper foil with a carrier according to any one of claims 1 to 6, 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 1-7 which have a roughening process layer in the said ultra-thin copper layer surface.   The copper foil with a carrier according to claim 8, wherein the roughening treatment layer is a single layer selected from the group consisting of copper, nickel, cobalt, and zinc, or a layer made of an alloy including at least one of them.   The copper with a carrier according to claim 8 or 9, wherein the surface of the roughened layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. Foil.   The surface of the said ultra-thin copper layer has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate process layer, and a silane coupling process layer, The claim in any one of Claims 1-10. Copper foil with carrier.   The printed wiring board manufactured using the copper foil with a carrier in any one of Claims 1-11.   The printed circuit board manufactured using the copper foil with a carrier in any one of Claims 1-11.   The copper clad laminated board manufactured using the copper foil with a carrier in any one of Claims 1-11. Preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 10,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.