WO2014157728A1 - キャリア付銅箔、プリント配線板、銅張積層板、電子機器及びプリント配線板の製造方法 - Google Patents

キャリア付銅箔、プリント配線板、銅張積層板、電子機器及びプリント配線板の製造方法 Download PDF

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Publication number
WO2014157728A1
WO2014157728A1 PCT/JP2014/059570 JP2014059570W WO2014157728A1 WO 2014157728 A1 WO2014157728 A1 WO 2014157728A1 JP 2014059570 W JP2014059570 W JP 2014059570W WO 2014157728 A1 WO2014157728 A1 WO 2014157728A1
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Prior art keywords
layer
carrier
copper foil
copper
ultrathin
Prior art date
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PCT/JP2014/059570
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English (en)
French (fr)
Japanese (ja)
Inventor
倫也 古曳
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Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020157031096A priority Critical patent/KR101803165B1/ko
Priority to CN201480019381.6A priority patent/CN105142897B/zh
Publication of WO2014157728A1 publication Critical patent/WO2014157728A1/ja

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    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
    • H05K3/205—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern using a pattern electroplated or electroformed on a metallic carrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • the present invention relates to a copper foil with a carrier, a printed wiring board, a copper clad laminate, an electronic device, and a method for manufacturing a printed wiring board.
  • a printed wiring board is generally manufactured through a process of forming a copper-clad laminate by bonding an insulating substrate to copper foil and then forming a conductor pattern on the copper foil surface by etching.
  • 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.
  • the peel strength between the ultrathin copper layer and the resin base material 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.
  • 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.
  • 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
  • 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.
  • the adhesion strength between the polyimide resin substrate and the ultra-thin 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.
  • the fine circuit formation method that accompanies the narrowing of the pitch is a method in which a wiring circuit is formed on an ultrathin copper layer, and then the ultrathin copper layer is removed by etching with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi). -Additive-Process) is used, the laser holeability of the ultra-thin copper layer is an important item in fabricating high-density integrated circuit boards.
  • MSAP sulfuric acid-hydrogen peroxide etchant
  • Patent Document 4 describes a copper-clad laminate with good laser drillability, but according to the study of the present inventors, there is still room for improvement in terms of etching properties. is there.
  • an object of the present invention is to provide a copper foil with a carrier, which is excellent in laser holeability of an ultrathin copper layer and is suitable for manufacturing a high-density integrated circuit board.
  • the present inventor conducted extensive research and found that a laser microscope on the peeling side of the ultrathin copper layer when the ultrathin copper layer was peeled off from the copper foil with a carrier that had been subjected to a predetermined heat treatment. It was found that controlling the surface roughness measured by the method is extremely effective in improving the laser holeability of the ultrathin copper layer.
  • the present invention is a copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order. After heating the copper foil with a carrier at 220 ° C. for 2 hours, JIS C 6471 When the ultrathin copper layer is peeled off according to the above, the copper foil with a carrier whose surface roughness Sz on the intermediate layer side of the ultrathin copper layer measured with a laser microscope is 1.40 ⁇ m or more and 4.05 ⁇ m or less It is.
  • the copper foil with a carrier of the present invention is measured with a laser microscope when the ultra thin copper layer is peeled off according to JIS C 6471 after the copper foil with a carrier is heated at 220 ° C. for 2 hours.
  • the standard deviation of the surface roughness Sz on the intermediate layer side of the ultrathin copper layer is 1.30 ⁇ m or less.
  • the copper foil with a carrier in another embodiment, when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the standard deviation of the surface roughness Sz on the intermediate layer side of the ultrathin copper layer to be measured is 0.01 ⁇ m or more and 1.20 ⁇ m or less.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off according to JIS C 6471, a laser microscope
  • the surface roughness Sz of the ultrathin copper layer measured on the intermediate layer side is 1.60 ⁇ m or more and 3.70 ⁇ m or less.
  • Another aspect of the present invention is a copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order, and after heating the copper foil with a carrier at 220 ° C. for 2 hours, JIS
  • the surface roughness Ra on the intermediate layer side of the ultrathin copper layer measured with a laser microscope is 0.14 ⁇ m or more and 0.35 ⁇ m or less. Copper foil.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the standard deviation of the surface roughness Ra on the intermediate layer side of the ultrathin copper layer to be measured is 0.11 ⁇ m or less.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the standard deviation of the surface roughness Ra on the intermediate layer side of the ultrathin copper layer to be measured is 0.001 ⁇ m or more and 0.10 ⁇ m or less.
  • a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, After heating the copper foil with a carrier at 220 ° C. for 2 hours and then peeling off the ultrathin copper layer in accordance with JIS C 6471, the surface on the intermediate layer side of the ultrathin copper layer measured with a laser microscope
  • This is a copper foil with a carrier having a roughness Rz of 0.62 ⁇ m or more and 1.59 ⁇ m or less and a standard deviation of the surface roughness Rz of 0.51 ⁇ m or less.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the standard deviation of the surface roughness Rz on the intermediate layer side of the ultrathin copper layer to be measured is 0.01 ⁇ m or more and 0.48 ⁇ m or less.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the sharpness Sku of the surface height distribution on the intermediate layer side of the ultrathin copper layer to be measured is 0.50 or more and 3.70 or less.
  • the copper foil with a carrier when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471, a laser microscope is used.
  • the sharpness Sku of the surface height distribution on the intermediate layer side of the ultrathin copper layer to be measured is 1.00 or more and 3.60 or less.
  • the thickness of the carrier is 5 to 70 ⁇ m.
  • the copper foil with a carrier of the present invention has a roughening treatment layer on the surface of the ultrathin copper layer in yet another aspect.
  • the roughening layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is a layer made of any simple substance or an alloy containing any one or more kinds.
  • the copper foil with a carrier of the present invention is one or more selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. It has a layer of.
  • a resin layer is provided on the ultrathin copper layer.
  • a resin layer is provided on the roughening treatment layer.
  • a resin layer is formed on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.
  • the present invention is a printed wiring board manufactured using the copper foil with a carrier of the present invention.
  • the present invention is a copper-clad laminate manufactured using the carrier-attached copper foil of the present invention.
  • the present invention is an electronic device manufactured using the printed wiring board 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, and the copper foil with carrier and the insulating substrate And then forming a copper-clad laminate through a step of peeling the carrier of the copper foil with carrier, and then by any one of the semi-additive method, subtractive method, partly additive method or modified semi-additive method A method of manufacturing a printed wiring board including a step of forming a circuit.
  • the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier of the present invention, the ultrathin copper layer of the copper foil with carrier so that the circuit is buried A step of forming a resin layer on a side surface, a step of forming a circuit on the resin layer, a step of peeling the carrier after forming a circuit on the resin layer, and after peeling the carrier, It is a manufacturing method of a printed wiring board including the process of exposing the circuit buried in the resin layer formed in the ultra-thin copper layer side surface by removing the ultra-thin copper layer.
  • a copper foil with a carrier that is excellent in laser holeability of an ultrathin copper layer and is suitable for manufacturing a high-density integrated circuit board.
  • FIGS. 8A to 8C are schematic views of a cross section of a wiring board in a process up to circuit plating and resist removal according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.
  • D to F are schematic views of the cross section of the wiring board in the process from the lamination of the resin and the second-layer copper foil with a carrier to the laser drilling according to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention. It is.
  • GI are schematic views of the cross section of the wiring board in the steps from via fill formation to first layer carrier peeling, according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention.
  • J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.
  • the copper foil with a carrier of the present invention includes a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer.
  • the method of using the copper foil with carrier itself is well known to those skilled in the art.
  • the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc.
  • the copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.
  • the copper foil with a carrier of the present invention is an electrode measured with a laser microscope when the ultra thin copper layer is peeled off in accordance with JIS C 6471 after heating the copper foil with a carrier at 220 ° C. for 2 hours.
  • the surface roughness Sz (10-point height on the surface) on the intermediate layer side of the thin copper layer is controlled to be 1.40 ⁇ m or more and 4.05 ⁇ m or less.
  • a carrier-attached copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and an ultrathin copper layer bonded to the insulating substrate is etched into a target conductor pattern to form a circuit. In this way, a printed wiring board is produced with a multi-layered substrate.
  • the laser holeability of the ultrathin copper layer is an important characteristic that greatly affects the design and productivity of the integrated circuit because it relates to various conditions such as hole diameter accuracy and laser output.
  • the laser piercing property of this ultra-thin copper layer is measured with a laser microscope when the copper foil with carrier is heated at 220 ° C.
  • the surface roughness Sz on the intermediate layer side of the ultrathin copper layer to be measured is improved by controlling it to 1.40 ⁇ m or more and 4.05 ⁇ m or less.
  • the surface roughness Sz on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope is less than 1.40 ⁇ m, the surface roughness of the ultra-thin copper layer is insufficient, so Absorbability deteriorates, making it difficult to make a hole, and even if it is made a problem, it becomes a small hole.
  • the surface roughness Sz on the intermediate layer side of the ultrathin copper layer measured by the laser microscope is more preferably 1.60 ⁇ m or more and 3.70 ⁇ m or less, preferably 1.80 ⁇ m or more and 3.50 ⁇ m or less, and 2.40 ⁇ m or more and 3 or less. More preferably, it is 70 ⁇ m or less.
  • the “heating at 220 ° C. for 2 hours” indicates a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.
  • the copper foil with a carrier of the present invention is the ultrathin film measured by a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off according to JIS C 6471.
  • the standard deviation of the surface roughness Sz on the intermediate layer side of the copper layer is controlled to be 1.30 ⁇ m or less.
  • the variation of the laser hole diameter increases (that is, the standard deviation increases) or etching. There is a possibility that the problem that the variation of the factor becomes large (that is, the standard deviation becomes large) occurs.
  • the standard deviation of the surface roughness Sz on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is more preferably 0.01 ⁇ m or more and 1.20 ⁇ m or less, and 0.05 ⁇ m or more and 1.10 ⁇ m or less. It is still more preferable that it is 0.10 ⁇ m or more and 1.00 ⁇ m or less.
  • the copper foil with a carrier of the present invention is measured with a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off in accordance with JIS C 6471.
  • the surface roughness Ra (arithmetic average roughness) on the intermediate layer side of the ultrathin copper layer is controlled to be 0.14 ⁇ m or more and 0.35 ⁇ m or less.
  • a carrier-attached copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and an ultrathin copper layer bonded to the insulating substrate is etched into a target conductor pattern to form a circuit. In this way, a printed wiring board is produced with a multi-layered substrate.
  • the surface roughness Ra on the intermediate layer side of the ultrathin copper layer to be measured is improved by controlling it to 0.14 ⁇ m or more and 0.35 ⁇ m or less. If the surface roughness Ra on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope is less than 0.14 ⁇ m, the surface roughness of the ultra-thin copper layer is insufficient and Absorbability deteriorates, making it difficult to make a hole, and even if it is made a problem, it becomes a small hole.
  • the surface roughness Ra on the intermediate layer side of the ultrathin copper layer measured by the laser microscope is preferably 0.16 ⁇ m or more and 0.32 ⁇ m or less, more preferably 0.18 ⁇ m or more and 0.32 ⁇ m or less, and 0.20 ⁇ m or more and 0 or less. More preferably, it is not more than 32 ⁇ m.
  • the surface roughness Ra on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is preferably 0.14 ⁇ m or more and 0.30 ⁇ m or less.
  • the “heating at 220 ° C. for 2 hours” indicates a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.
  • the copper foil with a carrier of the present invention is measured by a laser microscope when the ultra thin copper layer is peeled off in accordance with JIS C 6471 after heating the copper foil with a carrier at 220 ° C. for 2 hours. It is preferable that the standard deviation of the surface roughness Ra on the intermediate layer side of the ultrathin copper layer is controlled to be 0.11 ⁇ m or less. When the standard deviation of the surface roughness Ra on the intermediate layer side of the ultrathin copper layer measured by the laser microscope exceeds 0.11 ⁇ m, the variation in the laser hole diameter becomes large (that is, the standard deviation becomes large). There is a possibility that the problem that the variation of the etching factor becomes large (that is, the standard deviation becomes large) occurs.
  • the standard deviation of the surface roughness Ra on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is preferably 0.001 ⁇ m or more and 0.10 ⁇ m or less, and 0.003 ⁇ m or more and 0.09 ⁇ m. Is more preferably 0.005 ⁇ m or more and 0.08 ⁇ m or less, and further preferably 0.005 ⁇ m or more and 0.06 ⁇ m or less.
  • the carrier-attached copper foil of the present invention in yet another aspect, measured with a laser microscope when the ultra-thin copper layer was peeled off in accordance with JIS C 6471 after the carrier-attached copper foil was heated at 220 ° C. for 2 hours.
  • the surface roughness Rz (ten-point average roughness) on the intermediate layer side of the ultrathin copper layer is controlled to be 0.62 ⁇ m or more and 1.59 ⁇ m or less.
  • a carrier-attached copper foil is bonded to an insulating substrate, the carrier is peeled off after thermocompression bonding, and an ultrathin copper layer bonded to the insulating substrate is etched into a target conductor pattern to form a circuit.
  • a printed wiring board is produced with a multi-layered substrate.
  • a laser hole is formed, and the inner layer and the outer layer are connected through the hole.
  • it is of course a problem that it is difficult to make a laser hole in an ultra-thin copper layer, and it is necessary to form the laser hole to an appropriate size to cause various problems even if it is too large or too small.
  • the laser holeability of the ultrathin copper layer is an important characteristic that greatly affects the design and productivity of the integrated circuit because it relates to various conditions such as hole diameter accuracy and laser output.
  • the laser piercing property of this ultra-thin copper layer is measured with a laser microscope when the copper foil with carrier is heated at 220 ° C. for 2 hours and then peeled off according to JIS C 6471. It has been found that the surface roughness Rz on the intermediate layer side of the ultrathin copper layer to be measured is improved by controlling it to 0.62 ⁇ m or more and 1.59 ⁇ m or less.
  • the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope is less than 0.62 ⁇ m, the surface roughness of the ultra-thin copper layer is insufficient and the laser in the drilling process Absorbability deteriorates, making it difficult to make a hole, and even if it is made a problem, it becomes a small hole.
  • the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured by the laser microscope exceeds 1.59 ⁇ m, the surface roughness of the ultrathin copper layer is too large, and the laser during the drilling process As a result, there is a problem that the absorbability of water becomes excessive and the hole becomes too large.
  • the surface roughness Rz of the ultrathin copper layer measured by the laser microscope is preferably 0.70 ⁇ m or more and 1.52 ⁇ m or less, more preferably 0.80 ⁇ m or more and 1.50 ⁇ m or less, and 0.90 ⁇ m or more and 1 More preferably, it is 40 ⁇ m or less.
  • the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is more preferably 1.10 ⁇ m or more and 1.50 ⁇ m or less.
  • the “heating at 220 ° C. for 2 hours” indicates a typical heating condition in the case where a copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded.
  • the copper foil with a carrier of the present invention is the ultrathin film measured by a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off according to JIS C 6471.
  • the standard deviation of the surface roughness Rz on the intermediate layer side of the copper layer is controlled to be 0.51 ⁇ m or less.
  • the standard deviation of the surface roughness Rz on the intermediate layer side of the ultra-thin copper layer measured with the laser microscope exceeds 0.51 ⁇ m, the variation of the laser hole diameter becomes large (that is, the standard deviation becomes large) or etching. There arises a problem that the variation of the factor becomes large (that is, the standard deviation becomes large).
  • the standard deviation of the surface roughness Rz on the intermediate layer side of the ultrathin copper layer measured with the laser microscope is preferably 0.01 ⁇ m or more and 0.48 ⁇ m or less, and 0.04 ⁇ m or more and 0.40 ⁇ m or less. More preferably, it is 0.04 ⁇ m or more and 0.35 ⁇ m or less, and more preferably 0.05 ⁇ m or more and 0.20 ⁇ m or less.
  • the copper foil with a carrier of the present invention is an ultrathin copper measured by a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then the ultrathin copper layer is peeled off according to JIS C 6471.
  • the degree of sharpness Sku (Cultosis) of the surface height distribution on the intermediate layer side of the layer is controlled to 0.50 or more and 3.70 or less. If the Sku is less than 0.50, the shape of the convex part on the surface of the ultra-thin copper layer will be flat, so that the laser absorbability during drilling will be poor and it will be difficult to drill holes. There is a possibility that the problem of becoming a small hole may occur.
  • the copper foil with a carrier of the present invention is an ultrathin copper layer measured with a laser microscope when the copper foil with a carrier is heated at 220 ° C. for 2 hours and then peeled off in accordance with JIS C 6471.
  • the sharpness Sku of the surface height distribution on the intermediate layer side is more preferably controlled to 1.00 or more and 3.60 or less, and even more preferably controlled to 1.50 or more and 3.30 or less, More preferably, it is controlled to 1.50 or more and 3.20 or less, more preferably 1.50 or more and 3.10 or less, and more preferably 1.50 or more and 3.00 or less. Even more preferably.
  • Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, LCD film. Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll.
  • copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
  • high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011)
  • Sn-containing copper Ag-containing copper
  • Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
  • copper 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, 5 ⁇ m or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 ⁇ m or less. Accordingly, the thickness of the carrier is typically 8 to 70 ⁇ m, more typically 12 to 70 ⁇ m, and more typically 18 to 35 ⁇ m. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost.
  • the thickness of the carrier is typically 5 ⁇ m or more and 35 ⁇ m or less, preferably 5 ⁇ m or more and 18 ⁇ m or less, preferably 5 ⁇ m or more and 12 ⁇ m or less, preferably 5 ⁇ m or more and 11 ⁇ m or less, preferably 5 ⁇ m or more and 10 ⁇ m or less. It is as follows.
  • the thickness of a carrier is small, it is easy to generate
  • R 1 and R 2 are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.
  • the surface roughness Sz, Ra, Rz on the intermediate layer side of the ultrathin copper layer, their standard deviation, and Sku are controlled by adjusting the surface form of the carrier on the ultrathin copper layer side.
  • Examples of the adjustment of the surface form of the carrier on the ultrathin copper layer side include the following adjustment methods (1) to (3).
  • the form of the ultrathin copper layer side surface of the carrier is close to the form of the carrier side ultrathin copper layer surface. Therefore, by adjusting the form of the surface of the carrier on the side of the ultrathin copper layer, an ultrathin copper foil with a carrier having the form of the surface of the desired carrier side ultrathin copper layer can be obtained.
  • a soft etching process or a reverse electrolysis process is performed on a carrier having low roughness and high gloss.
  • the surface roughness Rz is 0.2 ⁇ m to 0.6 ⁇ m, or the surface roughness Ra is 0.2 ⁇ m to 0.6 ⁇ m, or the surface roughness Sz is 0.2 ⁇ m to 0.6 ⁇ m, and 60 degrees.
  • Soft etching treatment for example, an aqueous solution of 5-15 vol% sulfuric acid and 0.5-5.0 wt% hydrogen peroxide, 0.5-10% at 10-30 ° C for carriers having a specular gloss of 500% or more.
  • An etching process for 10 minutes) or a reverse electrolytic process (a process for forming irregularities by electropolishing the glossy surface).
  • the “reverse electropolishing” is electropolishing.
  • electropolishing since electropolishing is intended for smoothing, if electropolishing is applied to an electrolytic copper foil, the normal idea is that the surface opposite to the glossy surface (rough surface) is the target. However, since the uneven surface is formed by electropolishing on the glossy surface here, the electropolishing process is the opposite of the normal one, that is, the reverse electropolishing process.
  • the amount of copper dissolved by reverse electrolysis is 2 to 20 g / m 2 .
  • the current density in the reverse electropolishing process is 0.5 to 50 A / dm 2 .
  • the oil film equivalent is expressed by the following equation.
  • Oil film equivalent ⁇ (rolling oil viscosity [cSt]) ⁇ (sheet feeding speed [mpm] + roll peripheral speed [mpm]) ⁇ / ⁇ (roll biting angle [rad]) ⁇ (yield stress of material [kg / mm 2 ]) ⁇
  • the rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
  • a known method such as using highly viscous rolling oil or increasing the sheet passing speed may be used.
  • a carrier is manufactured under predetermined electrolytic conditions. Specifically, using a copper sulfate electrolyte (copper concentration: 80 to 120 g / L, sulfuric acid concentration 70 to 90 g / L), high concentration glue (Nika concentration: 3 to 10 ppm by mass) as an additive, An electrolytic copper foil carrier is produced under the conditions of a high current density (75 to 110 A / dm 2 ) and a high linear flow rate (3.7 to 5.0 m / sec).
  • a copper sulfate electrolyte copper concentration: 80 to 120 g / L, sulfuric acid concentration 70 to 90 g / L
  • high concentration glue Nika concentration: 3 to 10 ppm by mass
  • An intermediate layer is provided on one or both sides of the carrier. Another layer may be provided between the carrier and the intermediate layer.
  • the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate.
  • the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included.
  • the intermediate layer may be a plurality of layers. Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
  • the intermediate layer When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.
  • a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.
  • the intermediate layer When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
  • the intermediate layer can be constituted by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium.
  • the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer.
  • Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm 2 or more 40000 ⁇ g / dm 2 or less, more preferably 100 [mu] g / dm 2 or more 4000 ⁇ g / dm 2 or less, more preferably 100 [mu] g / dm 2 or more 2500 g / dm 2 or less, more Preferably, it is 100 ⁇ g / dm 2 or more and less than 1000 ⁇ g / dm 2 , and the amount of chromium deposited on the intermediate layer is preferably 5 ⁇ g / dm 2 or more and 100 ⁇ g / dm 2 or less.
  • a rust preventive layer such as a Ni plating layer on the opposite side of the carrier
  • An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper 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 ⁇ m or less. Typically, it is 0.5 to 12 ⁇ m, more typically 1 to 5 ⁇ m, more typically 1.5 to 5 ⁇ m, and more typically 2 to 5 ⁇ m. In addition, you may provide an ultra-thin copper layer on both surfaces of a carrier.
  • a roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate.
  • the roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy.
  • the roughening process may be fine.
  • the roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing at least one of them. It may be.
  • 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.
  • 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.
  • 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.
  • one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer.
  • One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface.
  • 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 as a roughening treatment - cobalt - nickel alloy plating by electrolytic plating, deposition amount in the 15 ⁇ 40 mg / dm cobalt -100 copper -100 ⁇ 3000 ⁇ g / dm 2 of 2 ⁇ 1500 ⁇ g / dm 2 of nickel
  • Such a ternary alloy layer can be formed. If the amount of deposited Co is less than 100 ⁇ g / dm 2 , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate.
  • the etching stain means that Co remains without being dissolved when etched with copper chloride
  • the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.
  • Plating bath composition Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L pH: 1 to 4 Temperature: 30-50 ° C Current density D k : 20 to 30 A / dm 2 Plating time: 1-5 seconds
  • a carrier-attached copper foil including a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated 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.
  • 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.
  • the printed wiring board can be finally manufactured by etching the ultrathin copper layer adhered to the substrate into a desired conductor pattern.
  • the carrier-attached copper foil comprising a carrier and an ultra-thin copper layer laminated on the intermediate layer on the carrier comprises a roughening treatment layer on the ultra-thin copper layer.
  • a roughening treatment layer may be provided on the ultrathin copper layer
  • a heat resistant layer and a rust prevention layer may be provided on the roughening treatment layer
  • a chromate treatment is performed on the heat resistance layer and the rust prevention layer.
  • a layer may be provided, and a silane coupling treatment layer may be provided on the chromate treatment layer.
  • the carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be.
  • the resin layer may be an insulating resin layer.
  • the resin layer may be an adhesive, or may be a semi-cured (B stage) insulating resin layer for bonding.
  • the semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.
  • the resin layer may contain a thermosetting resin or a thermoplastic resin.
  • the resin layer may include a thermoplastic resin.
  • the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, or the like can be given as a preferable one. .
  • the resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like.
  • the resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No.
  • WO 2008/114858 International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.
  • a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin solution, which is used on the ultrathin copper layer, the heat-resistant layer, the rust-proof layer, the chromate film layer, or the silane cup.
  • MEK methyl ethyl ketone
  • On the ring agent layer for example, it is applied by a roll coater method or the like, and then heat-dried as necessary to remove the solvent to obtain a B-stage state.
  • a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C.
  • the copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off.
  • the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.
  • this resin-attached copper foil with a carrier can reduce the number of prepreg materials used when manufacturing a multilayer printed wiring board.
  • the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.
  • the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous.
  • the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 ⁇ m or less can be manufactured.
  • the thickness of this resin layer is preferably 0.1 to 80 ⁇ m.
  • the thickness of the resin layer is less than 0.1 ⁇ m, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.
  • the thickness of the resin layer is made thicker than 80 ⁇ m, it becomes difficult to form a resin layer having a desired thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.
  • this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer
  • the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.
  • a printed circuit board is completed by mounting electronic components on the printed wiring board.
  • the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
  • an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a printed circuit on which the electronic components are mounted.
  • An electronic device may be manufactured using a substrate. 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.
  • 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
  • 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
  • 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.
  • 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 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; Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate; Performing a desmear process on the region including the through hole or / and the blind via, 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 for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like; Providing a plating resist on the electroless plating layer; Expo
  • 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; Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin 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, Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like; Providing a plating resist on the electroless plating layer; Expo
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 pattern; Removing the ultrathin copper layer and the catalyst nucleus by a method such as etch
  • the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.
  • 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
  • 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
  • ⁇ Through holes and / or blind vias and subsequent desmear steps may not be performed.
  • the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.
  • the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example.
  • the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed.
  • the following method for producing a printed wiring board can be similarly performed using an attached copper foil.
  • a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
  • FIG. 2-A a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
  • a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
  • the resist is removed to form a circuit plating having a predetermined shape.
  • an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, and then another carrier is attached.
  • a copper foil (second layer) is bonded from the ultrathin copper layer side.
  • the carrier is peeled off from the second layer copper foil with carrier.
  • the other carrier-attached copper foil may be the carrier-attached copper foil of the present invention, a conventional carrier-attached copper foil, or a normal copper foil.
  • one or more circuits may be formed on the second layer circuit shown in FIG. 4-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.
  • the circuit plating is embedded in the resin layer.
  • the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating the formation of a fine circuit.
  • the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy.
  • FIGS. 5-J and 5-K when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.
  • a known resin or prepreg can be used as the embedding resin (resin).
  • a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used.
  • the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).
  • the carrier-attached copper foil used in the first layer may have a substrate or a resin layer on the surface of the carrier-attached copper foil.
  • substrate or resin layer By having the said board
  • any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer.
  • Examples 1 to 9, 11, 12 and Comparative Examples 1 to 5 In the electrolytic cell, a titanium rotating drum and electrodes were arranged around the drum with a distance between the electrodes. Next, electrolysis is performed in the electrolytic cell under the carrier foil production conditions shown in Table 1, copper is deposited on the surface of the rotating drum, the copper deposited on the surface of the rotating drum is peeled off, and electrolysis with a thickness of 18 ⁇ m is continuously performed. A copper foil was produced and used as a copper foil carrier. In Examples 1, 2, 6, 8, 9, and 12, the thickness of the copper foil carrier after the surface treatment was 12 ⁇ m, 5 ⁇ m, 70 ⁇ m, 12 ⁇ m, 35 ⁇ m, and 35 ⁇ m, respectively.
  • Comparative Example 3 was a copper foil carrier having a thickness of 12 ⁇ m.
  • the copper foil carrier was surface treated under the conditions described in Table 1.
  • the electrolysis time was 0.5 to 2 minutes, and the electrolyte temperature was 40 to 60 ° C.
  • the surface treatment of Examples 2 and 8 will be described.
  • a cathode is arranged on the deposition surface (also referred to as mat surface or M surface) side of the formed electrolytic copper foil, and the copper foil mat is subjected to electrolytic treatment by direct current using the copper foil as an anode.
  • the surface was subjected to reverse electropolishing to dissolve 3 to 8 g / m 2 of copper in Example 2 and 8 to 15 g / m 2 in Example 8.
  • the reverse current density electrolytic polishing Example 2 in 5 ⁇ 15A / dm 2 was in Examples 8 16 ⁇ 25A / dm 2.
  • the 60 ° specular gloss in the copper foil width direction was 13 to 40, and the 60 ° specular gloss in the copper foil length direction was 20 to 94.
  • the 60-degree specular gloss was measured at an incident angle of 60 degrees using a gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741.
  • An intermediate layer was formed under the following conditions.
  • An Ni layer having an adhesion amount of 4000 ⁇ g / dm 2 was formed by electroplating on a roll-to-roll continuous plating line under the following conditions.
  • Nickel sulfate 250-300 g / L Nickel chloride: 35 to 45 g / L Nickel acetate: 10-20g / L Trisodium citrate: 15-30 g / L Brightener: Saccharin, butynediol, etc.
  • Sodium dodecyl sulfate 30 to 100 ppm pH: 4-6 Bath temperature: 50-70 ° C Current density: 3 to 15 A / dm 2
  • Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L pH: 3-4 Liquid temperature: 50-60 ° C Current density: 0.1 to 2.6 A / dm 2 Coulomb amount: 0.5-30 As / dm 2
  • an ultrathin copper layer having a thickness of 1 to 10 ⁇ m was formed on the intermediate layer by electroplating under the following conditions to obtain a copper foil with a carrier.
  • a roughening layer, a heat-resistant layer, a chromate layer, and a silane coupling layer were further provided on the ultrathin copper layer.
  • Example 10 A rolled copper foil (tough pitch copper, JIS H3100 C1100) was prepared, and cold rolling was performed on the rolled copper foil using a rolling roll whose surface was roughened by sandblasting. At this time, the rolling roll roughness Ra was set to 0.39 to 0.42 ⁇ m, and the oil film equivalent was set to 35000. This obtained the copper foil carrier. Then, the copper foil with a carrier was produced by forming an intermediate
  • ⁇ Thickness of ultrathin copper layer> The thickness of the ultrathin copper layer of the prepared copper foil with carrier was observed using FIB-SIM (magnification: 10000-30000 times). By observing the cross section of the ultrathin copper layer, five points were measured at intervals of 30 ⁇ m, and the average value was obtained.
  • Rz (laser) on the intermediate layer side of the ultrathin copper layer is measured according to Olympus laser microscope OLS4000 (LEXT) in accordance with JIS B0601-1994. (OLS 4000).
  • Rz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Rz (laser) was defined as the value of Rz (laser).
  • the standard deviation of the value of 10 places was calculated about Rz (laser).
  • the surface roughness Ra (laser) on the intermediate layer side of the ultrathin copper layer was measured with an Olympus laser microscope OLS4000 in accordance with JIS B0601-1994.
  • Ra (laser) was arbitrarily measured at 10 locations, and the average value of the 10 locations of Ra (laser) was defined as the value of Ra (laser).
  • the standard deviation of the value of 10 places was calculated about Ra (laser).
  • the surface roughness Sz (laser) on the intermediate layer side of the ultrathin copper layer was measured with an Olympus laser microscope OLS4000 in accordance with ISO25178.
  • Sz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Sz (laser) was taken as the value of Sz (laser). Moreover, the standard deviation of the value of 10 places was calculated about Sz (laser). Furthermore, in accordance with ISO25178, the Sku of the surface on the intermediate layer side of the ultrathin copper layer was measured with a laser microscope OLS4000 manufactured by Olympus.
  • Rz (laser) on the side on which the ultra-thin copper layer is formed in accordance with JIS B0601-1994, Olympus Corporation Measurement was performed with a laser microscope OLS4000 (LEXT OLS 4000).
  • Rz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Rz (laser) was defined as the value of Rz (laser).
  • the standard deviation of the value of 10 places was calculated about Rz (laser).
  • the surface roughness Ra (laser) of the carrier on the side on which the ultrathin copper layer is formed was measured with an Olympus laser microscope OLS4000 in accordance with JIS B0601-1994.
  • Ra (laser) was arbitrarily measured at 10 locations, and the average value of the 10 locations of Ra (laser) was defined as the value of Ra (laser).
  • the standard deviation of 10 Ra (laser) values was calculated.
  • the surface roughness Sz (laser) of the carrier on the side on which the ultrathin copper layer was formed was measured with an Olympus laser microscope OLS4000 in accordance with ISO25178.
  • Sz (laser) was arbitrarily measured at 10 locations, and the average value at 10 locations of the Sz (laser) was taken as the value of Sz (laser). Moreover, the standard deviation of the value of 10 places was calculated about Sz (laser). Furthermore, in accordance with ISO25178, Sku on the surface of the carrier on the side on which the ultrathin copper layer was formed was measured with an Olympus laser microscope OLS4000.
  • the measurement environmental temperature of Sz, Rz, Ra and Sku on the surface with a laser microscope was set to 23 to 25 ° C.
  • Sz, Ra, Rz, and Sku of the copper foil carrier after surface treatment were measured.
  • the untreated surface of the ultrathin copper layer (the surface on the intermediate layer side of the ultrathin copper layer) is irradiated with one shot of laser under the following conditions, and the shape of the hole after irradiation is observed with a microscope and measured. did.
  • the table shows how many (X) holes were actually drilled by trying to drill holes at 12 points as “real numbers” (X / 12). "Percentage” (%) is shown.
  • the table also shows the average diameter of the holes generated at this time, the standard deviation of the diameter of the generated holes, and the average diameter / beam diameter. The diameter of the hole was the diameter of the smallest circle surrounding the hole.
  • 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 ⁇ m 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 is etched (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.
  • 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.
  • an etching factor of 4 or more is etching property: ⁇ , 2.5 or more and less than 4 are etching property: ⁇ , less than 2.5 or calculation is impossible or circuit formation is impossible. It was evaluated as-.
  • the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer is 0.62 ⁇ m or more and 1.59 ⁇ m or less, and the standard for the surface roughness Rz (laser) Since the deviation was 0.51 ⁇ m or less, the laser drilling property and the etching property were good.
  • Comparative Examples 1 and 5 since the surface roughness Rz (laser) on the intermediate layer side of the ultrathin copper layer was less than 0.62 ⁇ m, the laser holeability was poor.

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PCT/JP2014/059570 2013-03-29 2014-03-31 キャリア付銅箔、プリント配線板、銅張積層板、電子機器及びプリント配線板の製造方法 WO2014157728A1 (ja)

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JP2014208910A (ja) * 2013-03-29 2014-11-06 Jx日鉱日石金属株式会社 キャリア付銅箔、プリント配線板、銅張積層板、電子機器及びプリント配線板の製造方法
CN105555012A (zh) * 2014-10-22 2016-05-04 Jx日矿日石金属株式会社 铜放热材、印刷配线板及其制造方法、以及使用有该铜放热材的产品
EP3048864A3 (en) * 2015-01-21 2017-04-12 JX Nippon Mining & Metals Corporation Copper foil provided with carrier, laminate, printed wiring board, and method for fabricating printed wiring board
TWI817166B (zh) * 2021-07-23 2023-10-01 先豐通訊股份有限公司 電路板及其製作方法

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KR20160093555A (ko) * 2015-01-29 2016-08-08 제이엑스금속주식회사 표면 처리 동박, 캐리어가 부착된 동박, 기재, 수지 기재, 적층체, 프린트 배선판, 전자 기기 및 프린트 배선판의 제조 방법
JP6782561B2 (ja) * 2015-07-16 2020-11-11 Ｊｘ金属株式会社 キャリア付銅箔、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
JP6058182B1 (ja) 2015-07-27 2017-01-11 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
JP6339636B2 (ja) 2015-08-06 2018-06-06 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
JP6200042B2 (ja) 2015-08-06 2017-09-20 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
JP6190500B2 (ja) 2015-08-06 2017-08-30 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
JP6578379B2 (ja) * 2015-12-25 2019-09-18 三井金属鉱業株式会社 キャリア付銅箔、樹脂付銅箔、及びプリント配線板の製造方法
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JP2014208910A (ja) * 2013-03-29 2014-11-06 Jx日鉱日石金属株式会社 キャリア付銅箔、プリント配線板、銅張積層板、電子機器及びプリント配線板の製造方法
CN105555012A (zh) * 2014-10-22 2016-05-04 Jx日矿日石金属株式会社 铜放热材、印刷配线板及其制造方法、以及使用有该铜放热材的产品
TWI670381B (zh) * 2014-10-22 2019-09-01 日商Ｊｘ日鑛日石金屬股份有限公司 銅放熱材、印刷配線板及其製造方法、以及使用有該銅放熱材之製品
CN105555012B (zh) * 2014-10-22 2020-03-03 Jx日矿日石金属株式会社 铜放热材、印刷配线板及其制造方法、以及使用有该铜放热材的产品
EP3048864A3 (en) * 2015-01-21 2017-04-12 JX Nippon Mining & Metals Corporation Copper foil provided with carrier, laminate, printed wiring board, and method for fabricating printed wiring board
US10178775B2 (en) 2015-01-21 2019-01-08 Jx Nippon Mining & Metals Corporation Copper foil provided with carrier, laminate, printed wiring board, and method for fabricating printed wiring board
TWI817166B (zh) * 2021-07-23 2023-10-01 先豐通訊股份有限公司 電路板及其製作方法

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