WO2021193470A1 - Ligne de câblage de cuivre composite et corps multicouche ayant une couche de réserve - Google Patents

Ligne de câblage de cuivre composite et corps multicouche ayant une couche de réserve Download PDF

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WO2021193470A1
WO2021193470A1 PCT/JP2021/011514 JP2021011514W WO2021193470A1 WO 2021193470 A1 WO2021193470 A1 WO 2021193470A1 JP 2021011514 W JP2021011514 W JP 2021011514W WO 2021193470 A1 WO2021193470 A1 WO 2021193470A1
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copper
layer
plating layer
resist
layer containing
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PCT/JP2021/011514
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English (en)
Japanese (ja)
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牧子 佐藤
慎 寺木
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ナミックス株式会社
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Priority to KR1020227025550A priority Critical patent/KR20220158220A/ko
Priority to JP2022510450A priority patent/JPWO2021193470A1/ja
Priority to CN202180010197.5A priority patent/CN114982389A/zh
Publication of WO2021193470A1 publication Critical patent/WO2021193470A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to a laminate having composite copper wiring and a resist layer.
  • a resist material containing a photosensitive material is laminated on a printed circuit board produced by hot-bonding copper or the like, which is a conductor, to a resin, and 2) light or the like is selectively used.
  • a mask pattern also called a resist pattern
  • the conductor is etched using this pattern as a mask to form a circuit.
  • the resist material is classified into a positive type resist material in which the light-irradiated portion is removed by the development treatment and a negative type resist material in which the light-irradiated portion remains by the development treatment.
  • a laminate having a new resist layer and a method for manufacturing the same and a printed circuit board including a composite copper wiring manufactured by using the laminate having a resist layer and a method for manufacturing the same.
  • the inventors of the present application succeeded in suppressing the brightness while intentionally laminating a metal other than copper on a layer containing a copper oxide that was blackened by oxidation treatment, and were suitable for circuit formation.
  • a laminate can be produced.
  • the present invention has the following embodiments: [A1] The first surface and the second surface have a structure that is a surface made of copper. A layer containing a first copper oxide is provided on a part or all of the first surface of the structure. A first plating layer containing a metal other than copper is formed on a part or all of the surface of the layer containing the first copper oxide. Further, a laminate having a resist layer on a part or all of the surface of the first plating layer. [A2] The laminate according to A1, wherein the value of the brightness L * of the surface on which the first plating layer is formed is less than 50. [A3] The laminate according to A1 or A2, wherein when the heat treatment is performed at 225 ° C.
  • the color change of the surface on which the first plating layer is formed is 10 or less as compared before and after the heat treatment.
  • A4 The laminate according to any one of A1 to A3, wherein a part or all of the Rz having the resist layer on the surface on which the first plating layer is formed is 0.2 ⁇ m or more and 1.0 ⁇ m or less. ..
  • A5 The laminate according to any one of A1 to A4, wherein the RSm of a part or all of the surface having the resist layer on the surface on which the first plating layer is formed is 600 nm or less.
  • A6 The laminate according to any one of A1 to A5, wherein the first plating layer contains Ni.
  • the laminate according to A10 which has a resin base material on a part or all of the surface of the second plating layer.
  • A12 The laminate according to A11, wherein the peel strength between the resin base material and the second plating layer is 0.5 kgf / cm or more.
  • the resin base material is polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), or triphenylfosite (TPPI).
  • A11 or A12 which contains at least one insulating resin selected from the group consisting of fluororesins, polyetherimides, polyetheretherketones, polycycloolefins, bismaleimide resins, low dielectric constant polyimides and cyanate resins.
  • insulating resin selected from the group consisting of fluororesins, polyetherimides, polyetheretherketones, polycycloolefins, bismaleimide resins, low dielectric constant polyimides and cyanate resins.
  • [B1] It has a first surface and a second surface, which are surfaces made of copper.
  • a layer containing a first copper oxide is provided on a part or all of the first surface.
  • a step of forming a resist layer on a part or all of the surface of the first plating layer A method for manufacturing a laminate, including.
  • [B2] The production method according to B1, wherein the value of the brightness L * of the surface on which the first plating layer is formed is less than 50.
  • [B3] The production method according to B1 or B2, wherein when the heat treatment is performed at 225 ° C.
  • the color change of the surface on which the first plating layer is formed is 10 or less as compared before and after the heat treatment.
  • the production method according to B1 to B4, wherein the average thickness of the first plating layer is 30 nm or more and 70 nm or less.
  • the soft etching treatment is not performed on the surface on which the first plating layer is formed.
  • a manufacturing method in which the soft etching treatment is baflor polishing, scrub polishing and chemical polishing.
  • a layer containing a second copper oxide is provided on a part or all of the second surface of the structure.
  • the production method according to B9 which comprises a step of laminating a resin base material on a part or all of the surface on which the second plating layer is formed.
  • the production method according to B10 wherein the peel strength between the resin base material and the second plating layer is 0.5 kgf / cm or more.
  • the resin substrate is polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), or triphenylfosite (TPPI).
  • PPE polyphenylene ether
  • PPO polyphenylene oxide
  • PBO polybenzoxazole
  • PTFE polytetrafluoroethylene
  • LCP liquid crystal polymer
  • TPPI triphenylfosite
  • [B13] The method for producing a laminate according to any one of B1 to B7, wherein the structure is a copper-clad laminate (CCL).
  • a step of peeling the resist layer after the etching process from the laminate The production method according to any one of B10 to B13, which comprises.
  • [B15] The production method according to B14, wherein the Rz of the surface on which the first plating layer is formed after the resist layer is peeled off is 0.2 ⁇ m or more and 1.0 ⁇ m or less.
  • the production method according to B14 or B15, wherein the RSm of the surface on which the first plating layer is formed after the resist layer is peeled off is 600 nm or less.
  • [C1] A step of irradiating a part of the resist layer of the laminate according to any one of A11 to A14 with light, developing the resist layer, and then etching the first surface to form a wiring pattern on the structure.
  • a step of peeling the resist layer after the etching process from the laminate A method of manufacturing a printed circuit board, including.
  • [C2] The production method according to C1, wherein the Rz of the surface on which the first plating layer is formed after the resist layer is peeled off is 0.2 ⁇ m or more and 1.0 ⁇ m or less.
  • [C3] The production method according to C1 or C2, wherein the RSm of the surface on which the first plating layer is formed after the resist layer is peeled off is 600 nm or less.
  • the composite copper wiring according to D1 which is conductive between the wiring made of copper and the first plating layer.
  • a layer containing a second copper oxide is provided on the second surface, and a second plating layer containing a metal other than copper is formed on the surface of the layer containing the second copper oxide, D1.
  • the composite copper wiring according to D3 which is conducting between the wiring made of copper and the second plating layer.
  • FIG. 1 shows a step of manufacturing a printed circuit board including composite copper wiring in one embodiment of the present invention and a process of manufacturing a general printed circuit board.
  • FIG. 2 is a schematic cross-sectional view of a composite copper wiring in one embodiment of the present invention, a printed circuit board in which composite copper wiring is laminated on one side of a resin base material, and a printed circuit board in which composite copper wiring is laminated on both sides of a resin base material. The figure is shown.
  • the composite copper wiring has a plating layer containing a metal other than copper and a layer containing a copper oxide on the first surface (1) of the wiring made of copper.
  • the second surface (2) which is a thermocompression bonding surface with the resin base material, may or may not have a plating layer containing a metal other than copper and a layer containing a copper oxide.
  • the second surface (2) may be roughened with copper particles or the like.
  • the third surface (3) may be the wiring made of copper as it is, or may have a copper wiring protective layer such as a copper oxide layer or a rust preventive layer.
  • FIG. 3 shows the time course of the contact angle between water and the surface on which the plating layer on which the resist layer is laminated is formed in the structure according to the embodiment of the present invention.
  • FIG. 3 shows the time course of the contact angle between water and the surface on which the plating layer on which the resist layer is laminated is formed in the structure according to the embodiment of the present invention.
  • FIG. 4 is a cross-sectional image of the composite copper wiring before peeling of the resist layer produced from Example 2 of the present invention by a scanning electron microscope (SEM) (top: 3000 times, bottom: 30,000 times).
  • SEM scanning electron microscope
  • One embodiment of the present invention is a structure in which the first surface and the second surface are surfaces made of copper.
  • Copper is preferably pure copper having a Cu purity of 99.9% by mass or more, more preferably formed of tough pitch copper, deoxidized copper, or oxygen-free copper, and has an oxygen content of 0.001% by mass to 0. It is more preferably formed of 0005% by mass oxygen-free copper.
  • the structure may be a single copper foil such as an electrolytic copper foil or a rolled copper foil, or a single copper plate. Further, a plurality of copper foils and copper plates may be laminated.
  • the thickness thereof is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
  • a copper plate a copper plate having a thickness of more than 100 ⁇ m is preferable.
  • 1 mm or more, 2 mm or more or 10 mm or more is more preferable, and 10 cm or less, 5 cm or less or 2.5 cm or less is further preferable.
  • the structure may be a copper-clad laminate (CCL).
  • An insulating plate obtained by laminating a sheet (called a resin base material or prepreg) impregnated with resin on a base material such as paper or glass and thermocompression bonding is called a laminated board, and copper foil is applied to both sides thereof. It is a copper-clad laminate.
  • TAB tape-automated bonding
  • COF chip on film
  • the insulating plate may be a resin sheet containing no paper or glass, and an adhesive sheet or an adhesive layer may be present at the interface between the copper and the insulating layer.
  • the resin contained in the resin base material is not particularly limited, but may be a thermoplastic resin or a thermosetting resin, and may be a polyphenylene ether (PPE), an epoxy, a polyphenylene oxide (PPO), or a polybenzoxazole (PBO).
  • the resin base material may further contain an inorganic filler or glass fiber.
  • the thickness of the resin base material is not particularly limited, but is preferably 1 ⁇ m or more and 100 mm or less.
  • a layer containing a copper oxide comprises copper oxide (CuO) and / or cuprous oxide (Cu 2 O).
  • the layer containing the copper oxide can be formed by oxidizing the surface of the structure. The surface of the structure is roughened by this oxidation treatment.
  • the shape of the convex portion on the surface of the oxidized structure may be adjusted with respect to the layer containing the copper oxide by using a dissolving agent. Further, the surface of the layer containing the copper oxide may be reduced with a reducing agent. Since the specific resistance value of pure copper is 1.7 ⁇ 10-8 ( ⁇ m), copper oxide is 1 to 10 ( ⁇ m) and cuprous oxide is 1 ⁇ 10 6 to 1 ⁇ 10 7 ( ⁇ m). The conductivity of the layer containing copper oxide formed by the oxidation treatment is lower than that of pure copper.
  • the structure may contain a metal other than copper on a part or all of the surface of the layer containing the copper oxide.
  • metals other than copper are present on both sides of the structure.
  • the metal contained is not particularly limited, but at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au and Pt is contained. May be good.
  • metals having higher acid resistance and heat resistance than copper such as Ni, Pd, Au and Pt, are contained.
  • the metal other than copper may be present as a layer on the surface of the layer containing the copper oxide.
  • the layer containing a metal other than copper can be formed as a plating layer by, for example, plating the surface of the layer containing a copper oxide with a metal other than copper.
  • the plating method is not particularly limited, and electroplating, electroless plating, vacuum vapor deposition, chemical conversion treatment, and the like can be exemplified, but electrolytic plating is preferable because a uniform and thin plating layer is preferably formed.
  • the copper oxide on the surface is first reduced and the charge is used to become cuprous oxide or pure copper, which causes a time lag before plating. After that, the metal forming the metal layer begins to precipitate.
  • the amount of charge varies depending on the type of plating solution and the amount of copper oxide. For example, when Ni plating is applied to a copper member, in order to keep the thickness within a preferable range, 15 C per area dm 2 of the copper member to be electroplated. It is preferable to give a charge of 75 C or more, and more preferably a charge of 25 C or more and 65 C or less.
  • the copper oxide formed by the oxidation treatment is partially reduced to copper, and the conductivity of the layer containing the copper oxide is increased, which is the same conductor as copper, which is a conductor forming a structure. Conduction is possible with layers containing metals other than copper.
  • the method for confirming continuity is not particularly limited, but for example, copper, which is a conductor forming a structure, and copper other than copper, which is also a conductor, are used for a plane viewing area of 4 ⁇ m 2 of a plating layer containing a metal other than copper.
  • AFM interatomic force microscope
  • the region where the current value is -60 nA or less is the plating layer containing a metal other than copper.
  • conduction is established between copper, which is a conductor forming a structure, and a layer containing a metal other than copper. It may be.
  • the average vertical thickness of the layer containing a metal other than copper formed on the surface of the structure by plating is not particularly limited, but is preferably 10 nm or more, 20 nm or more, 30 nm or more, or 40 nm or more. However, it is preferably 80 nm or less, and more preferably 70 nm or less and 65 nm or less.
  • the average thickness of the metal other than copper contained in the layer containing copper oxide in the vertical direction is determined by dissolving the layer containing copper oxide in an acidic solution and measuring the amount of metal by ICP analysis. It can be calculated by dividing by the plane viewing area.
  • L * a * b * brightness L * in the surface on which the plating layer is formed are less than 60, less than 55, less than 50, less than 45, less than 40, less than 35, less than 30, less than 25 or less than 20. The smaller this value is, the more the reflection of the exposure light is suppressed.
  • a fragile layer due to surface oxidation or alteration does not occur on the surface on which the plating layer is formed.
  • the heat resistance (proneness of forming a fragile layer) can be evaluated by the color change of the surface on which the plating layer is formed during the heat treatment. When the color change is small, a fragile layer is unlikely to occur, and good adhesion to the resist layer can be obtained.
  • the color change ( ⁇ E * ab) of the surface on which the plating layer is formed is 10 or less, 5 or less, 3 or less, 2 or less, or 1 as compared before and after the heat treatment. The following is preferable.
  • the maximum height roughness (Rz) of the surface on which the plating layer is formed is preferably 1.0 ⁇ m or less, 0.9 ⁇ m or less, or 0.8 ⁇ m or less, preferably 0.1 ⁇ m or more. , 0.2 ⁇ m or more, or 0.3 ⁇ m or more is preferable.
  • Rz can be calculated by the method specified in JIS B 0601: 2001 (based on international standard ISO13565-1).
  • the average length (RSm) of the surface roughness curve element on which the plating layer is formed is 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less. Is preferable, and 100 nm or more, 200 nm or more, or 300 nm or more is preferable.
  • RSm represents the average of the lengths (that is, the lengths of contour curve elements: Xs1 to Xsm) in which unevenness is generated for one cycle included in the roughness curve at a certain reference length (lr), and is represented by the following equation. It is calculated by.
  • arithmetic mean roughness is defined as the minimum height of the unevenness
  • 1% of the reference length (lr) is defined as the minimum length
  • the unevenness for one cycle is defined.
  • Rsm can be measured according to "Method for measuring surface roughness of fine ceramic thin film by atomic force microscope (JIS R 1683: 2007)".
  • One embodiment of the present invention is a method for producing a structure having a layer containing copper oxide and a plating layer, wherein a first step of forming a layer containing copper oxide with an oxidizing agent and a layer containing copper oxide are used.
  • This is a manufacturing method including a second step of plating the surface of the formed structure.
  • it has a first surface and a second surface, which are surfaces made of copper, and a layer containing a first copper oxide is provided on a part or all of the first surface, and the first surface is formed.
  • a structure having a first plating layer containing a metal other than copper on a part or all of the surface of the layer containing a copper oxide can be produced.
  • the surface of the structure is oxidized with an oxidizing agent to form a layer of copper oxide and fine irregularities are formed on the surface.
  • the oxidation treatment may be a single-sided treatment or a double-sided treatment.
  • a roughening treatment step such as soft etching or etching is not necessary, but it may be performed.
  • degreasing treatment acid cleaning for homogenizing the surface by removing the natural oxide film, or alkali treatment for preventing the introduction of acid into the oxidation step after the acid cleaning may be performed.
  • the method of alkaline treatment is not particularly limited, but is preferably 0.1 to 10 g / L, more preferably 1 to 2 g / L in an alkaline aqueous solution, for example, a sodium hydroxide aqueous solution at 30 to 50 ° C. for 0.5 to 2 minutes. It should be processed to some extent.
  • the oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate or the like can be used.
  • Various additives for example, phosphates such as trisodium phosphate dodecahydrate
  • surface active molecules include porphyrin, porphyrin-membered ring, expanded porphyrin, ring-reduced porphyrin, linear porphyrin polymer, porphyrin sandwich coordination complex, porphyrin sequence, silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane.
  • (3-Aminopropyl) trimethoxysilane (1- [3- (trimethoxysilyl) propyl] urea) ((l- [3- (Trimethoxysilyl) propyl] urea)), (3-aminopropyl) triethoxy Silane, ((3-glycidyloxypropyl) trimethoxysilane), (3-chloropropyl) trimethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, dimethyldichlorosilane, 3- (trimethoxysilyl) propylmethacrylate, Ethyltriacetoxysilane, triethoxy (isobutyl) silane, triethoxy (octyl) silane, tris (2-methoxyethoxy) (vinyl) silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride,
  • the oxidation reaction conditions are not particularly limited, but the temperature of the chemical solution for oxidation is preferably 40 to 95 ° C, more preferably 45 to 80 ° C.
  • the reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.
  • the layer containing the copper oxide may be partially dissolved with a dissolving agent.
  • the solubilizer used in this step is not particularly limited, but is preferably a chelating agent, particularly a biodegradable chelating agent, such as ethylenediamine tetraacetic acid, diethanolglycine, L-glutamate diacetic acid / tetrasodium, ethylenediamine-N, N'-.
  • a biodegradable chelating agent such as ethylenediamine tetraacetic acid, diethanolglycine, L-glutamate diacetic acid / tetrasodium, ethylenediamine-N, N'-.
  • examples thereof include disuccinic acid, 3-hydroxy-2, 2'-sodium iminodysuccinate, methylglycine diacetate 3 sodium, aspartate diacetate 4 sodium, N- (2-hydroxyethyl) imino diacetate disodium, sodium gluconate and the like. can.
  • the pH of the chemical solution for dissolution is not particularly limited, but it is preferably alkaline, more preferably 8 to 10.5, further preferably 9.0 to 10.5, and pH 9.8 to 10. It is more preferably 2.
  • the copper oxide contained in the formed layer containing the copper oxide may be partially reduced by using a chemical solution containing a reducing agent (reducing chemical solution).
  • reducing agent dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine and the like can be used.
  • the chemical solution for reduction is a liquid containing a reducing agent, an alkaline compound (sodium hydroxide, potassium hydroxide, etc.), and a solvent (pure water, etc.).
  • the surface of the structure on which the layer containing copper oxide is formed is plated with a metal other than copper to produce a structure having a layer containing copper oxide and a plating layer. do.
  • the structures produced in these steps are subjected to a coupling treatment using a silane coupling agent or the like, a molecular bonding treatment, or a rust prevention treatment using benzotriazoles or the like. May be good.
  • One embodiment of the present invention is a laminate having a resist layer on the surface of a part of the structure.
  • the resist layer is preferably laminated on the surface of a part or all of the plating layer.
  • the resist layer is a layer containing a material that is cured or dissolved by photosensitivity, and is not particularly limited, but is preferably formed of a dry film resist (DFR), a positive liquid resist, or a negative liquid resist.
  • the DFR includes a binder polymer (including an alkali-developed type and a solvent-developed type) that contributes to film formability, and a monomer that causes a photopolymerization reaction by UV irradiation (for example, an acrylic ester-based or methacrylic ester-based monomer) and photopolymerization is started. It is preferable to include an agent.
  • DFR it is preferable to use a dry film having a three-layer structure of cover form / photoresist / carrier film.
  • the photoresist While peeling off the cover film, the photoresist is thermocompression-bonded to the structure and laminated, and after the lamination, the carrier film is peeled off to form a DFR which is a resist layer on the structure.
  • the positive type liquid resist and the negative type liquid resist include novolak resin solubilized in an organic solvent.
  • a resist layer can be formed by applying it to the surface of a structure and then drying it.
  • the thickness of the resist layer is not particularly limited, but is preferably 5 ⁇ m to 200 ⁇ m.
  • the Rz of the surface on which the resist layer is formed and the plating layer is formed is preferably 1.0 ⁇ m or less, 0.9 ⁇ m or less, or 0.8 ⁇ m or less, and is 0.1 ⁇ m or more, 0.2 ⁇ m or more, or It is preferably 0.3 ⁇ m or more.
  • the RSm of the surface on which the plating layer is formed, on which the resist layer is formed is preferably 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, preferably 100 nm or more, 200 nm or more, or 300 nm. The above is preferable.
  • Such surface roughness is related to the adhesion and peelability of the resist layer. If Rz is too small, the adhesion to the resist layer is insufficient, and if it is too large, it becomes difficult to peel off the resist layer after the etching treatment. On the other hand, if RSm is too large, the adhesion to the resist layer is insufficient, and if it is too small, it becomes difficult to peel off the resist layer after the etching treatment.
  • the laminate may have a resin base material on the surface opposite to the surface on which the resist layer of the structure is formed.
  • the resin base material is preferably laminated on the structure by thermocompression bonding. It is preferable that the resin base material and the structure have high adhesion. Adhesion shall be measured as peel strength based on the 90 ° peel test (Japanese Industrial Standards (JIS) C5016 "Flexible Printed Wiring Board Test Method"; Corresponding International Standards IEC249-1: 1982, IEC326-2: 1990). Can be done.
  • the peel strength between the resin base material and the structure is preferably 0.40 kgf / cm or more, 0.50 kgf / cm or more, or 0.60 kgf / cm or more.
  • One embodiment of the present invention is a method for producing a laminate containing a structure and a resist layer, which comprises a step of forming a resist layer on the structure according to the present invention.
  • Examples of the step of forming the resist layer include attaching a photoresist while heating using a dry film; applying a positive liquid resist or a negative liquid resist at room temperature and drying the resist layer.
  • soft etching is performed before forming the resist layer in order to increase the adhesion.
  • the structure adheres to the resist. Since the properties can be obtained, it is not necessary to perform the soft etching treatment before the step of forming the resist layer.
  • the soft etching treatment include baflor polishing, scrub polishing, jet scrub polishing, chemical polishing, and a combination thereof.
  • Examples of the chemical polishing include impregnation with an aqueous solution containing sulfuric acid and hydrogen peroxide; an aqueous solution containing copper chloride; an aqueous solution containing persulfate; an organic solvent containing azimidbenzene; and an aqueous solution containing permanganic acid.
  • thermocompression bonding thermocompression bonding
  • the recommended conditions for example, temperature, pressure, time
  • the following conditions can be considered as recommended conditions for each base material manufacturer.
  • a composite copper member is formed on the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 300 ° C. for 1 minute to 5 hours. It is preferably thermocompression bonded. for example, 1-1)
  • the resin base material is R-1551 (manufactured by Panasonic) Heat under a pressure of 1 MPa, reach 100 ° C., and hold at that temperature for 5-10 minutes. Then, it is further heated under a pressure of 3.3 MPa, reaches 170 to 180 ° C., and then thermocompression bonded by holding at that temperature for 50 minutes.
  • a composite copper member is applied to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 350 ° C. for 1 minute to 5 hours. Is preferably thermocompression bonded. for example, 2-1)
  • the resin base material is R5620 (manufactured by Panasonic Corporation) Thermocompression bonding is performed while heating to 100 ° C. under a pressure of 0.5 MPa, then the temperature and pressure are raised, and the temperature and pressure are held at 2.0 to 3.0 MPa and 200 to 210 ° C. for 120 minutes for further thermocompression bonding. ..
  • Thermocompression bonding is performed by heating under a pressure of 1.6 to 2.3 MPa, holding at 177 ° C. for 30 minutes, further heating, and holding at 216 ° C. for 60 minutes.
  • the resin base material contains PTFE resin or is made of PTFE resin. It is preferable that the composite copper member is thermocompression bonded to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 400 ° C. for 1 minute to 5 hours. for example, 3-1)
  • the resin base material is NX9255 (manufactured by Park Electrochemical) Heat to 260 ° C. under a pressure of 0.69 MPa, increase the pressure to 1.03 to 1.72 MPa, heat to 385 ° C., and hold at 385 ° C. for 10 minutes for thermocompression bonding.
  • a wiring made of copper has a layer containing a copper oxide on a part of the surface thereof, and has a plating layer containing a metal other than copper on the surface of the layer containing the copper oxide. It is a composite copper wiring.
  • FIG. 2 shows a schematic diagram of an example of composite copper wiring. Wiring is a conductor through which electricity is transmitted, and an electronic circuit is formed by mounting electronic components (resistors, capacitors, diodes, transistors, etc.) on it. It is preferable that the layer containing the copper oxide is conductive. The conductivity of the copper oxide-containing layer allows conduction between the copper wiring and the plating layer containing a metal other than copper.
  • the composite copper wiring may be manufactured from the structure or laminate according to the present invention.
  • One embodiment of the present invention is a printed circuit board including the composite copper wiring according to the present invention.
  • the printed circuit board now operates as an electronic circuit by soldering the printed wiring board (PWB) with only the conductor wiring and no electronic components attached, and the electronic components.
  • the printed circuit board (PCB) of the state is included.
  • a part of the resist layer contained in the laminate according to the present invention is irradiated with light, developed, and then the surface on which the resist layer is formed is etched to remove unnecessary portions. It is a method of manufacturing a composite copper wiring and a printed circuit board including the composite copper wiring, which includes a step of forming a circuit by removing and forming a predetermined wiring pattern in the structure.
  • the light to be irradiated may be light that cures or dissolves the resin contained in the resist layer.
  • light having a wavelength of 100 nm to 500 nm is preferable.
  • light having a wavelength of 10 nm to 900 nm is preferable.
  • the amount of light and the irradiation time depend on the thickness of the resist layer. Although not particularly limited, an irradiation amount of 1, 10 or 100 to 1000 mJ / cm 2 is preferable.
  • the resist layer unnecessary for the mask pattern is removed by development.
  • the binder polymer contained in the photoresist is an alkali-developed type, it is preferable to carry out an alkali treatment.
  • the alkaline treatment it is preferable to immerse the product in a 0.5% to 1.5% aqueous solution of NaCO 3 at 25 ° C. to 35 ° C. for 1.5 to 2.5 times the minimum development time, and then wash with water.
  • Etching dissolves and removes metals other than copper, copper oxides and copper that are not protected by the resist layer.
  • the conditions for this removal are not particularly limited, but at 20 ° C. to 60 ° C., hydrogen peroxide / hydrochloric acid mixed solution, hydrogen peroxide / sulfuric acid mixed solution, 20% to 50% cupric chloride, ferric chloride aqueous solution, etc. It is preferable to wash it with water after immersing it in water.
  • a layer containing a metal other than copper, a layer containing a copper oxide, and copper protected by a resist layer form a composite copper wiring.
  • a process of forming a copper oxide layer on a side surface of the composite copper wiring made of copper formed by etching (for example, illustrated in the third surface of FIG. 2), a blackening process, After performing rust preventive treatment, coupling treatment, etc., copper oxide layer, blackening treatment layer (black chromate layer), rust preventive agent layer (including benzotriazoles, etc.), coupling treatment layer (silane coupling agent, etc.)
  • a copper wiring protective layer such as (including) may be formed.
  • a treatment for roughening the side surface made of copper may be performed.
  • a step of peeling off the resist layer after the etching treatment may be included.
  • the peeling method is not particularly limited, but when the binder polymer contained in the photoresist is an alkali-developed type, it is placed in a 1 to 5% NaOH aqueous solution at 40 ° C to 60 ° C within 180 seconds, 120 seconds or 90 seconds. It is preferable to remove the resist layer by impregnating it within and then wash it with water.
  • the Rz of the surface on which the plating layer is formed after the resist layer is peeled off is preferably 1.0 ⁇ m or less, 0.9 ⁇ m or less, or 0.8 ⁇ m or less, and 0.1 ⁇ m or more and 0.2 ⁇ m or more. Alternatively, it is preferably 0.3 ⁇ m or more.
  • the Rsm of the surface on which the plating layer is formed after the resist layer is peeled off is preferably 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, preferably 100 nm or more and 200 nm or more. Alternatively, 300 nm or more is preferable.
  • a copper wiring protective layer such as (including an agent) may be formed.
  • a treatment for roughening the side surface made of copper may be performed. It is preferable that these treatments do not affect the roughness of the plating layer containing a metal other than copper and the surface thereof of the composite copper wiring, and the continuity between the wiring made of copper and the plating layer containing a metal other than copper. ..
  • solder resist which is an ink serving as an insulating film
  • the solder resist is applied except for the portion where the electronic component is mounted.
  • the solder resist 1) an alkali-developed solder resist capable of forming a fine pattern by exposing the uncured portion with a dilute alkaline phenomenon liquid; 2) pattern printing by a screen printing method and UV Examples thereof include a heat-curable solder resist, which is a type of UV-curable solder resist that is cured by irradiating light (ultraviolet rays); and 3) a type of solder resist that is pattern-printed by a screen printing method and cured by heating.
  • It may include a step of soldering the surface on which the plating layer is formed in the portion not subjected to the solder resist treatment. By this step, it is possible to suppress the natural oxidation of the metal forming the circuit and improve the efficiency of soldering when mounting the electronic component.
  • a step of soldering electronic components may be further included.
  • a step of forming a multilayer circuit board by thermocompression bonding a resin base material to the surface on which the plating layer is formed after peeling the resist layer may be included.
  • a copper foil (DR-WS, thickness: 18 ⁇ m) manufactured by Furukawa Electric Co., Ltd. was used as the structure.
  • Example 2 has a non-glossy surface (coarse when compared with the opposite surface).
  • Surface: Rz 0.8 ⁇ m)
  • a glossy surface was used for Comparative Examples 1 to 3 and 5
  • a non-glossy surface was used for Comparative Examples 6 and 7.
  • Example 3 and Comparative Example 4 as a structure, CCL (manufactured by Panasonic Corporation, model number R5775, thickness: 0) in which H-VLP copper foil having a thickness of 18 ⁇ m was laminated on both sides of prepreg R5670KJ (thickness 100 ⁇ m). .1 mm) was used.
  • CCL manufactured by Panasonic Corporation, model number R5775, thickness: 0
  • H-VLP copper foil having a thickness of 18 ⁇ m was laminated on both sides of prepreg R5670KJ (thickness 100 ⁇ m). .1 mm
  • Example 1 was energized for 35 seconds
  • Example 2 was energized for 50 seconds
  • Example 3 was energized for 40 seconds
  • Comparative Example 6 was energized for 35 seconds
  • Comparative Example 7 was energized for 70 seconds.
  • the structure was electroplated, washed with water, and then dried.
  • test pieces (results are shown in Table 1)
  • the test pieces of Comparative Examples 2, 3, 4, and 6 were soft-etched by applying an aqueous solution of 1.8% hydrogen peroxide; 5% sulfuric acid to the evaluation surface and treating at 25 ° C. for 43 seconds.
  • the test piece of Comparative Example 5 was etched using MEC Etchbond CZ-8101 (manufactured by MEC Co., Ltd.), which is an organic acid-based microetching agent, at a spray pressure of 0.2 MPa and a time of 30 seconds. evaluated.
  • Rz Contour curves were created from the observation results using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.) for the surfaces to which the dry films of the test pieces of Examples and Comparative Examples were attached, and were defined in JIS B 0601: 2001.
  • Rz was calculated by the above method.
  • the scan width was 100 ⁇ m
  • the scan type was an area
  • the Light source was Blue
  • the cutoff value was 1/5.
  • the object lens was set to x100
  • the contact lens was set to x14
  • the digital zoom was set to x1
  • the Z pitch was set to 10 nm
  • data was acquired at three locations
  • Rz was the average value of the three locations.
  • the method for measuring the average thickness of the plating on the surface to which the dry film of the test pieces of Examples and Comparative Examples was attached in the vertical direction was obtained by dissolving the test piece in 12% nitrate.
  • the liquid is analyzed using an ICP emission spectrometer 5100 SVDV ICP-OES (manufactured by Azilent Technology Co., Ltd.) to measure the metal concentration, and the metal density and the surface area of the metal layer are taken into consideration to form a layered metal layer. The thickness was calculated.
  • Peel strength with resin base material (Prepreg R5670KJ (manufactured by Panasonic Corporation, thickness 100 ⁇ m) is laminated on the surface of the test pieces of Examples and Comparative Examples to which the dry film is not attached, and a vacuum high pressure press machine is used.
  • a vacuum high pressure press machine was used.
  • the test piece after thermocompression bonding was used as a measurement sample after a heat resistance test (after the heat resistance test) in which one was left as it was (normal state) and the other was allowed to stand in an oven at 180 ° C. for 48 hours.
  • the peel strength (kgf / cm) was measured for these measurement samples by a 90 ° peeling test (Japanese Industrial Standards (JIS) C5016).
  • (7) Stability of wettability The wettability of the surface to which the dry film of the test pieces of Examples and Comparative Examples was attached was verified by the contact angle with water.
  • the contact angle of the test piece was measured at the time of preparing the test piece (day 0) and after leaving it at 25 ° C. for 10 days. Specifically, it was carried out at room temperature using a contact angle meter (DropMaster500), and the contact angle with water after 60 seconds was measured with a liquid volume of 1 ⁇ mL.
  • the wettability of the surface to which the dry film is attached was maintained even 10 days after the test piece was prepared. This indicates that the surface roughness of the surface to which the dry film is attached does not change even after 10 days have passed.
  • Laminated body > 1.
  • Thermocompression bonding of resin base material Prepreg R5670KJ manufactured by Panasonic Corporation
  • Thickness 100 ⁇ m was laminated and thermocompression bonded using a vacuum high pressure press machine under the conditions of a press pressure of 2.9 MPa, a temperature of 210 ° C., and a press time of 120 minutes.
  • the laminated body was exposed and developed so as to form a plurality of ⁇ 50 ⁇ m dot-shaped DFRs. After development, an etching treatment was carried out using an aqueous solution of hydrochloric acid 1.3 mol / L; H 2 O 2 31.6 mol / L at a speed of 1.82 m / min at 45 ° C. After the etching process, the number of Dots remaining without being etched by the CCD camera was measured.
  • the etching factor was calculated from the SEM cross-sectional image of the test piece using the following formula.
  • FIG. 4 shows an SEM cross-sectional image of Example 2. The larger the value of the etching factor, the better the etching accuracy, and generally, the value is about 2.5 to 3.5. From this index, 4.0 or more was evaluated as 0, and less than 4.0 was evaluated as ⁇ .
  • wiring was formed by etching with an aqueous solution of hydrochloric acid 1.3 mol / L; H 2 O 2 31.6 mol / L at a speed of 1.82 m / min at 45 ° C. .. Then, it was immersed in a solution of a 3% NaOH aqueous solution (water temperature 40 ° C.), and the remaining DFR on the wiring was peeled off.
  • a solder resist pattern was formed by applying a liquid solder resist: APB-300 (Tamura Corporation) on the wiring after peeling, and exposing and coating the wiring under the condition of 100 mJ / cm 2 with a DI exposure machine.
  • Flux ES1100 (made by Senju Metal) is applied to a 0.5 mm x 2 mm opening (also called a surface treatment part) on the wiring on which the solder resist pattern is not formed, nitrogen purged to 1500 ppm, and heat treatment is performed at 240 ° C. went. After the heat treatment, the presence or absence of swelling of the solder resist was confirmed by observing the appearance.
  • wiring was formed by etching with an aqueous solution of hydrochloric acid 1.3 mol / L; H 2 O 2 31.6 mol / L at a speed of 1.82 m / min at 45 ° C. .. Then, it was immersed in a solution of a 3% NaOH aqueous solution (water temperature 40 ° C.), and the remaining DFR on the wiring was peeled off. Comparative Examples 3 and 4 were then subjected to an etching treatment using a mech etch bond CZ-8101 (Mech Co., Ltd.), which is an organic acid-based microetching agent, with a stock solution, a spray pressure of 0.2 MPa, and a time of 30 seconds.
  • a mech etch bond CZ-8101 Mechanism Co., Ltd.
  • a solder resist pattern was formed by applying a liquid solder resist: APB-300 (Tamura Corporation) on the wiring and exposing and coating the wiring under the condition of 100 mJ / cm 2 with a DI exposure machine. After preflux treatment was performed on the 0.5 mm ⁇ 2 mm opening on the wiring on which the solder resist pattern was not formed, a solder paste (manufactured by Senju Metal Industry Co., Ltd., model number RGS800) was applied. Then, nitrogen was purged to 1500 ppm, and heat treatment was performed at 240 ° C. After the heat treatment, the presence or absence of swelling of the solder paste was confirmed by observing the appearance.
  • a solder paste manufactured by Senju Metal Industry Co., Ltd., model number RGS800
  • the surface on which the solder resist and the Ni plating layer are formed has high adhesion, and 2) the solder and Ni are formed.
  • the adhesion of the surface on which the plating layer was formed was also high. Furthermore, the continuity between the copper foil portion, which is the conductor, and the solder was confirmed.

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Abstract

Le but de la présente invention est de fournir : une nouvelle ligne de câblage de cuivre composite ; et un corps multicouche ayant une couche de réserve, ledit corps multicouche étant utilisé pour la production d'une ligne de câblage de cuivre composite. La présente invention concerne une ligne de câblage en cuivre composite dans laquelle une ligne de câblage en cuivre, qui présente une première surface, une deuxième surface et une troisième surface, comporte une couche contenant un premier oxyde de cuivre sur la première surface tout en étant pourvue d'une première couche de placage qui contient un métal autre que le cuivre sur la surface de la couche contenant le premier oxyde de cuivre.
PCT/JP2021/011514 2020-03-24 2021-03-19 Ligne de câblage de cuivre composite et corps multicouche ayant une couche de réserve WO2021193470A1 (fr)

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KR1020227025550A KR20220158220A (ko) 2020-03-24 2021-03-19 복합 구리 배선 및 레지스트층을 갖는 적층체
JP2022510450A JPWO2021193470A1 (fr) 2020-03-24 2021-03-19
CN202180010197.5A CN114982389A (zh) 2020-03-24 2021-03-19 复合铜布线以及具有抗蚀层的层压体

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11220255A (ja) * 1997-11-17 1999-08-10 Macdermid Inc 多層プリント回路板の製造方法
JP2018053327A (ja) * 2016-09-29 2018-04-05 Ｊｘ金属株式会社 キャリア付金属箔、積層体、積層体の製造方法、プリント配線板の製造方法及び電子機器の製造方法
WO2019093494A1 (fr) * 2017-11-10 2019-05-16 ナミックス株式会社 Feuil composite de cuivre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11220255A (ja) * 1997-11-17 1999-08-10 Macdermid Inc 多層プリント回路板の製造方法
JP2018053327A (ja) * 2016-09-29 2018-04-05 Ｊｘ金属株式会社 キャリア付金属箔、積層体、積層体の製造方法、プリント配線板の製造方法及び電子機器の製造方法
WO2019093494A1 (fr) * 2017-11-10 2019-05-16 ナミックス株式会社 Feuil composite de cuivre

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