WO2014073696A1 - Feuille de cuivre traitée en surface et stratifié l'utilisant - Google Patents

Feuille de cuivre traitée en surface et stratifié l'utilisant Download PDF

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Publication number
WO2014073696A1
WO2014073696A1 PCT/JP2013/080481 JP2013080481W WO2014073696A1 WO 2014073696 A1 WO2014073696 A1 WO 2014073696A1 JP 2013080481 W JP2013080481 W JP 2013080481W WO 2014073696 A1 WO2014073696 A1 WO 2014073696A1
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WIPO (PCT)
Prior art keywords
copper foil
printed wiring
wiring board
treated copper
treated
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PCT/JP2013/080481
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English (en)
Japanese (ja)
Inventor
新井　英太
敦史 三木
康修 新井
嘉一郎 中室
Original Assignee
Jx日鉱日石金属株式会社
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Priority claimed from JP2012270786A external-priority patent/JP5362899B1/ja
Priority claimed from JP2013000676A external-priority patent/JP5362921B1/ja
Priority claimed from JP2013013698A external-priority patent/JP5362922B1/ja
Priority claimed from JP2013013702A external-priority patent/JP5362923B1/ja
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 KR1020157011076A priority Critical patent/KR101631423B1/ko
Priority to CN201380058656.2A priority patent/CN104781451A/zh
Publication of WO2014073696A1 publication Critical patent/WO2014073696A1/fr

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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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • 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
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present invention relates to a surface-treated copper foil and a laminate using the surface-treated copper foil, and in particular, a surface-treated copper foil suitable for a field where transparency of the remaining resin after etching the copper foil is required, and a laminate using the same. Regarding the board.
  • FPCs flexible printed wiring boards
  • the signal transmission speed has been increased, and impedance matching has become an important factor in FPC.
  • a resin insulation layer for example, polyimide
  • the demand for higher wiring density has further increased the number of FPC layers.
  • processing such as bonding to a liquid crystal substrate and mounting of an IC chip is performed on the FPC, but the alignment at this time is the resin insulation remaining after etching the copper foil in the laminate of the copper foil and the resin insulating layer
  • the visibility of the resin insulation layer is important because it is performed through a positioning pattern that is visible through the layer.
  • a copper clad laminate that is a laminate of a copper foil and a resin insulating layer can be manufactured using a rolled copper foil having a roughened plating surface.
  • This rolled copper foil usually uses tough pitch copper (oxygen content of 100 to 500 ppm by weight) or oxygen free copper (oxygen content of 10 ppm by weight or less) as a raw material, and after hot rolling these ingots, It is manufactured by repeating cold rolling and annealing to a thickness.
  • Patent Document 1 a polyimide film and a low-roughness copper foil are laminated, and a light transmittance at a wavelength of 600 nm of the film after copper foil etching is 40% or more, a haze value.
  • An invention relating to a copper clad laminate having (HAZE) of 30% or less and an adhesive strength of 500 N / m or more is disclosed.
  • Patent Document 2 has an insulating layer in which a conductive layer made of electrolytic copper foil is laminated, and the light transmittance of the insulating layer in the etching region when the circuit is formed by etching the conductive layer is 50% or more.
  • the electrolytic copper foil includes a rust-proofing layer made of a nickel-zinc alloy on an adhesive surface bonded to an insulating layer, and the surface roughness (Rz) of the adhesive surface ) Is 0.05 to 1.5 ⁇ m, and the specular gloss at an incident angle of 60 ° is 250 or more.
  • Patent Document 3 discloses a method for treating a copper foil for a printed circuit, in which a cobalt-nickel alloy plating layer is formed on the surface of the copper foil after a roughening treatment by copper-cobalt-nickel alloy plating, and further zinc-nickel.
  • An invention relating to a method for treating a copper foil for printed circuit, characterized by forming an alloy plating layer is disclosed.
  • JP 2004-98659 A WO2003 / 096776 Japanese Patent No. 2849059
  • Patent Document 1 a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency. Moreover, in patent document 2, the roughening process is not made and the adhesive strength of copper foil and resin is low and inadequate in uses other than the flexible printed wiring board for COF. Further, in the treatment method described in Patent Document 3, it was possible to finely process the copper foil with Cu—Co—Ni, but the resin after bonding the copper foil to the resin and removing it by etching was excellent. Transparency is not realized.
  • the present invention provides a surface-treated copper foil having excellent resin transparency after removing the copper foil by etching, and a laminate using the same.
  • the inventors have put down a printed matter with a mark on the surface of the treated copper foil that has been subjected to a predetermined surface treatment, on the polyimide substrate that has been bonded and removed from the treated surface side, Pay attention to the slope of the brightness curve near the edge of the mark drawn in the observation point-brightness graph obtained from the image of the mark portion taken by the CCD camera over the polyimide substrate and control the slope of the brightness curve
  • the resin transparency after the copper foil is removed by etching is affected without being affected by the type of the substrate resin film and the thickness of the substrate resin film.
  • the present invention completed on the basis of the above knowledge is, in one aspect, a surface-treated copper foil in which surface treatment is performed on at least one surface, and the copper foil is polyimide from the surface side on which the surface treatment is performed.
  • the copper foils on both sides are removed by etching, and a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate, and the printed matter is passed over the polyimide substrate.
  • Observation point-brightness produced by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends for the image obtained by the shooting when taken with a CCD camera.
  • ⁇ B is 50 or more in an observation point-brightness graph produced from the image obtained by the photographing.
  • Sv defined by the formula (1) in the brightness curve is 3.9 or more.
  • Sv defined by the formula (1) in the brightness curve is 5.0 or more.
  • the surface treatment is a roughening treatment, and the TD average roughness Rz of the roughened surface is 0.20 to 0.80 ⁇ m.
  • the 60 degree gloss of MD on the surface of the chemical treatment is 76 to 350%,
  • the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is 1.90 to 2.40.
  • the MD has a 60 degree gloss of 90 to 250%.
  • the average roughness Rz of the TD is 0.30 to 0.60 ⁇ m.
  • the A / B is 2.00 to 2.20.
  • the root mean square height Rq of the surface on which the surface treatment is performed is 0.14 to 0.63 ⁇ m.
  • the surface-treated copper foil of the present invention has a root mean square height Rq of 0.25 to 0.60 ⁇ m.
  • the skewness Rsk based on JIS B0601-2001 of the surface on which the surface treatment is performed is -0.35 to 0.53.
  • the surface skewness Rsk is -0.30 to 0.39.
  • the surface area G obtained when the surface on which the surface treatment is performed is viewed in plan, and the convex volume of the surface on which the surface treatment is performed.
  • the ratio E / G to E is 2.11 to 23.91.
  • the ratio E / G is 2.95 to 21.42.
  • the TD ten-point average roughness Rz of the surface is 0.20 to 0.64 ⁇ m.
  • the 10-point average roughness Rz of the surface TD is 0.40 to 0.62 ⁇ m.
  • the ratio D / C between the three-dimensional surface area D of the surface and the two-dimensional surface area (surface area obtained when the surface is viewed in plan) C is 1. 0 to 1.7.
  • the present invention is a laminated plate configured by laminating the surface-treated copper foil of the present invention and a resin substrate.
  • the present invention is a printed wiring board using the surface-treated copper foil of the present invention.
  • the present invention is an electronic device using the printed wiring board of the present invention.
  • the present invention is a method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards of the present invention.
  • the present invention includes a step of connecting at least one printed wiring board of the present invention and another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, This is a method for manufacturing a printed wiring board in which two or more printed wiring boards are connected.
  • the present invention is an electronic device using one or more printed wiring boards in which at least two printed wiring boards of the present invention are connected.
  • the present invention is a method for manufacturing a printed wiring board, including at least a step of connecting the printed wiring board of the present invention and a component.
  • the step of connecting at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention and A method of manufacturing a printed wiring board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board of the present invention or a printed wiring board having two or more printed wiring boards of the present invention connected thereto and a component. It is.
  • the present invention provides a printed wiring board having an insulating resin substrate and a copper circuit provided on the insulating substrate, wherein the copper circuit is photographed with a CCD camera through the insulating resin substrate.
  • the edge of the copper circuit was prepared by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed copper circuit was stretched.
  • Bt is the top average value of the brightness curve generated from the portion to the portion without the copper circuit
  • Bb is the bottom average value
  • the value indicating the position of the intersection closest to the copper circuit among the intersections of the lightness curve and Bt is defined as t1, and 0 from the intersection of the lightness curve and Bt with reference to Bt.
  • .Sv defined by the following equation (1) when the value indicating the position of the intersection closest to the copper circuit in the depth range up to 1 ⁇ B is t2 Is a printed wiring board having a value of 3.5 or more.
  • Sv ( ⁇ B ⁇ 0.1) / (t1-t2) (1)
  • the present invention provides a copper-clad laminate having an insulating resin substrate and a copper foil provided on the insulating substrate, wherein the copper foil of the copper-clad laminate is formed into a line shape by etching.
  • the observation point is along the direction perpendicular to the direction in which the observed line-shaped copper foil extends.
  • the value indicating the position of the intersection closest to the surface-treated copper foil is t1, and in the depth range from the intersection of the lightness curve and Bt to 0.1 ⁇ B with reference to Bt, the value of the intersection of the lightness curve and 0.1 ⁇ B
  • Sv ( ⁇ B ⁇ 0.1) / (t1-t2) (1)
  • the copper foil used in the present invention is useful for a copper foil used by making a laminate by bonding to a resin substrate and removing it by etching.
  • the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.
  • the surface of the copper foil that adheres to the resin substrate that is, the surface on the surface treatment side, has the shape of the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after lamination.
  • a roughening treatment for performing electrodeposition may be performed.
  • the electrolytic copper foil has irregularities at the time of manufacture, the irregularities can be further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment.
  • this roughening treatment is performed by alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or nickel-zinc alloy plating.
  • alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or nickel-zinc alloy plating.
  • copper alloy plating bath for example, a plating bath containing one or more elements other than copper and copper, more preferably any selected from the group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum It is preferable to use a plating bath containing at least one kind.
  • the said roughening process makes a current density higher than the conventional roughening process, and shortens roughening processing time.
  • Ordinary copper plating or the like may be performed as a pretreatment before roughening, and ordinary copper plating or the like may be performed as a finishing treatment after roughening in order to prevent electrodeposits from dropping off.
  • the rolled copper foil according to the present invention includes a copper alloy foil containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. It is. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease.
  • the conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more.
  • the copper alloy foil may contain a total of elements other than copper of 0 mass% or more and 50 mass% or less, may contain 0.0001 mass% or more and 40 mass% or less, may contain 0.0005 mass% or more and 30 mass% or less, and 0.001 mass%. More than 20 mass% may be included.
  • the copper foil used in the present invention is subjected to the roughening treatment or the roughening treatment is omitted, and the heat-resistant plating layer (heat-resistant layer), the rust-proof plating layer (rust-proof layer) and the weather-resistant layer are on the surface. It may be given to.
  • a plating treatment using the Ni plating bath (1) or Ni—Zn plating bath (2) under the following conditions can be used.
  • Ni plating bath (1) ⁇ Liquid composition: Ni20-30g / L ⁇ PH: 2-3 ⁇ Current density: 6-7A / dm 2 ⁇ Bath temperature: 35-45 ° C ⁇ Coulomb amount: 1.2 to 8.4 As / dm 2 ⁇ Plating time: 0.2 to 1.2 seconds
  • Liquid composition Nickel 20-30 g / L, Zinc 0.5-2.5 g / L ⁇ PH: 2-3 ⁇ Current density: 6-7A / dm 2 ⁇ Bath temperature: 35-45 ° C ⁇ Coulomb amount: 1.2 to 8.4 As / dm 2 ⁇ Plating time: 0.2 to 1.2 seconds
  • a roughening treatment is omitted and a heat-resistant layer or a rust-preventing layer is provided on the copper foil by plating (plating that is normal plating or non-roughening plating), it is conventional.
  • the thickness of the copper foil used in the present invention is not particularly limited, but is, for example, 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, for example, 3000 ⁇ m or less, 1500 ⁇ m or less, 800 ⁇ m or less, 300 ⁇ m or less, 150 ⁇ m or less. 100 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, or 40 ⁇ m or less.
  • Electrolytic copper foil used for this invention Moreover, the manufacturing conditions of the electrolytic copper foil used for this invention are shown below.
  • Leveling agent 1 bis (3-sulfopropyl) disulfide
  • Leveling agent 2 amine compound: 10 to 30 ppm
  • As the amine compound an amine compound having the following chemical formula can be used.
  • 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.
  • Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be a 15 ⁇ 40mg / dm 2 of copper -100 ⁇ 3000 ⁇ g / dm 2 of cobalt -50 ⁇ 1500 ⁇ g / dm 2 of nickel
  • a ternary alloy layer can be formed, and the adhesion amount is 15 to 40 mg / dm 2 of copper—100 to 3000 ⁇ g / dm 2 of cobalt—100 to 1500 ⁇ g / dm 2 of nickel. It is preferable to carry out so as to form a ternary alloy layer.
  • the heat resistance may deteriorate and the etching property may deteriorate.
  • 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 Ni adhesion amount is less than 50 ⁇ g / dm 2 , the heat resistance may deteriorate.
  • the Ni adhesion amount exceeds 1500 ⁇ g / dm 2 , the etching residue may increase.
  • a preferable Co adhesion amount is 1000 to 2500 ⁇ g / dm 2
  • a preferable nickel adhesion amount is 500 to 1200 ⁇ g / dm 2
  • 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.
  • the plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating are as follows: 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 : 25 to 50 A / dm 2 Plating time: 0.2 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased.
  • the plating time By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.
  • the plating current density is set higher than the above range, the plating time needs to be set lower than the above range.
  • the copper-nickel-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
  • Plating bath composition Cu 10-50 g / L, Ni 3-20 g / L, P1-10 g / L pH: 1 to 4 Temperature: 30-40 ° C
  • Current density D k 30 to 50
  • Plating time 0.2 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased.
  • the plating time By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.
  • the plating current density is set higher than the above range, the plating time needs to be set lower than the above range.
  • the copper-nickel-cobalt-tungsten alloy plating conditions as the roughening treatment of the present invention are shown below.
  • Plating bath composition Cu 5-20 g / L, Ni 5-20 g / L, Co 5-20 g / L, W 1-10 g / L pH: 1-5
  • Temperature 30-50 ° C
  • Current density D k 30 to 50
  • Plating time 0.2 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased.
  • the plating time By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.
  • the plating current density is set higher than the above range, the plating time needs to be set lower than the above range.
  • the copper-nickel-molybdenum-phosphorus alloy plating conditions as the roughening treatment of the present invention are shown below.
  • Plating bath composition Cu 5-20 g / L, Ni 5-20 g / L, Mo 1-10 g / L, P 1-10 g / L pH: 1-5
  • Temperature 30-50 ° C
  • Current density D k 30 to 50
  • Plating time 0.2 to 3 seconds Note that the surface-treated copper foil according to one embodiment of the present invention is subjected to a roughening treatment under conditions where the plating time is shorter than before and the current density is increased.
  • the plating time By performing the roughening treatment under a condition in which the plating time is shortened and the current density is increased as compared with the conventional case, finer roughened particles are formed on the copper foil surface than in the conventional case.
  • the plating current density is set higher than the above range, the plating time needs to be set lower than the above range.
  • cobalt nickel cobalt -100 ⁇ 700 ⁇ g / dm 2 weight deposited on the roughened surface is 200 ⁇ 3000 ⁇ g / dm 2 - can form a nickel alloy plating layer.
  • This treatment can be regarded as a kind of rust prevention treatment in a broad sense.
  • This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered. If the amount of cobalt adhesion is less than 200 ⁇ g / dm 2 , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated.
  • the treated surface becomes reddish, which is not preferable.
  • the amount of cobalt deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into account, and etching spots may occur, and acid resistance and chemical resistance may deteriorate.
  • a preferable cobalt adhesion amount is 500 to 2500 ⁇ g / dm 2 .
  • the nickel adhesion amount is less than 100 ⁇ g / dm 2 , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated.
  • nickel exceeds 1300 microgram / dm ⁇ 2 > alkali etching property will worsen.
  • a preferable nickel adhesion amount is 200 to 1200 ⁇ g / dm 2 .
  • Plating bath composition Co 1-20 g / L, Ni 1-20 g / L pH: 1.5 to 3.5 Temperature: 30-80 ° C Current density D k : 1.0 to 20.0 A / dm 2 Plating time: 0.5-4 seconds
  • a zinc plating layer having an adhesion amount of 30 to 250 ⁇ g / dm 2 is further formed on the cobalt-nickel alloy plating. If the zinc adhesion amount is less than 30 ⁇ g / dm 2 , the heat deterioration rate improving effect may be lost. On the other hand, when the zinc adhesion amount exceeds 250 ⁇ g / dm 2 , the hydrochloric acid deterioration rate may be extremely deteriorated.
  • the zinc coating weight is 30 ⁇ 240 ⁇ g / dm 2, more preferably 80 ⁇ 220 ⁇ g / dm 2.
  • the galvanizing conditions are as follows: Plating bath composition: Zn 100 to 300 g / L pH: 3-4 Temperature: 50-60 ° C Current density Dk: 0.1 to 0.5 A / dm 2 Plating time: 1 to 3 seconds
  • a zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer may be formed on the outermost surface by chromate treatment or application of a silane coupling agent. Good.
  • the surface treatment is a roughening treatment
  • the TD average roughness Rz of the roughened surface is 0.30 to 0.80 ⁇ m
  • the MD of the roughened surface is 60 ° gloss
  • the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is 1.90 to 2.40. It is good also as a certain structure.
  • the surface roughness Rz (1), glossiness (2), and particle surface area ratio (3) in the copper foil having such a configuration will be described below.
  • the average roughness Rz of TD is more than 0.80 ⁇ m, the unevenness of the resin surface after the copper foil is removed by etching may increase, resulting in a problem that the transparency of the resin becomes poor. There is a fear.
  • the TD average roughness Rz of the roughened surface is more preferably 0.30 to 0.70 ⁇ m, still more preferably 0.35 to 0.60 ⁇ m, still more preferably 0.35 to 0.55 ⁇ m, and Even more preferred is 35 to 0.50 ⁇ m.
  • the average roughness Rz of TD of the roughening surface of the surface-treated copper foil of this invention is 0.20.
  • the term “roughened surface” means that when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, It means the surface of the surface-treated copper foil after the treatment.
  • the surface-treated copper foil having the above-described configuration preferably has a surface-treated surface having a glossiness of 76 to 350%, preferably 80 to 350%, and 90 to 300%. Is more preferable, 90 to 250% is still more preferable, and 100 to 250% is still more preferable.
  • Sv and (DELTA) B concerning this invention can be controlled by controlling the glossiness of MD of the copper foil before surface treatment, and the surface roughness Rz of TD.
  • Sv, Rsk, Rq and ratio E / G according to the present invention can be controlled by controlling the TD glossiness and the TD surface roughness Rz of the copper foil before the surface treatment.
  • the TD surface roughness (Rz) of the copper foil before the surface treatment is 0.30 to 0.80 ⁇ m, preferably 0.30 to 0.50 ⁇ m, and the incident angle 60 in the rolling direction (MD) is 60.
  • the glossiness at 350 degrees is 350 to 800%, preferably 500 to 800%, the current density is higher than the conventional roughening treatment and the roughening treatment time is shortened.
  • the glossiness of the surface-treated copper foil is 90 to 350% at an incident angle of 60 degrees in the rolling direction (MD).
  • Sv and ⁇ B can be controlled to predetermined values.
  • Such a copper foil can be produced by adjusting the oil film equivalent of rolling oil (high gloss rolling), or by chemical polishing such as chemical etching or electrolytic polishing in a phosphoric acid solution.
  • the surface roughness (Rz) and surface area of the copper foil after processing, Sv, ⁇ B can be controlled easily.
  • the TD roughness (Rz) of the treated side surface of the copper foil before the surface treatment is set.
  • the glossiness at an incident angle of 60 degrees in the rolling direction (MD) is 350 to 800%, preferably 500 to 800%.
  • the current density is made higher than that of the conventional roughening treatment, and the roughening treatment time is shortened.
  • the copper foil before the roughening treatment preferably has a 60 degree gloss of MD of 500 to 800%, more preferably 501 to 800%, and still more preferably 510 to 750%. . If the 60 degree glossiness of MD of the copper foil before the roughening treatment is less than 500%, the transparency of the resin may be poorer than the case of 500% or more. The problem that it becomes difficult may arise.
  • the high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000 or less.
  • the oil film equivalent defined by the following formula is set to 12000 to 24000 for high gloss rolling.
  • 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 a low-viscosity rolling oil or slowing the sheet passing speed may be used.
  • Chemical polishing is performed with an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a lower concentration than usual and for a long time.
  • the above control method is the same even when the roughening treatment is omitted and a heat-resistant layer or a rust-preventing layer is provided on the copper foil by plating (plating that is not normal plating or roughening plating).
  • the surface-treated copper foil in the above configuration preferably has a ratio A / B of 1.90 to 2.40, and more preferably 2.00 to 2.20.
  • the form and formation density of the particles are determined, and the surface roughness Rz, glossiness, and particle area ratio A / B can be controlled.
  • the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan view from the copper foil surface side is controlled to 1.90 to 2.40.
  • the roughness of the roughened surface is controlled to 0.30 to 0.80 ⁇ m to eliminate extremely rough portions, while the glossiness of the roughened surface is increased. It can be as high as 80 to 350%.
  • the particle size of the roughened particles on the roughened surface can be reduced.
  • the particle size of the roughened particles affects the resin transparency after the copper foil is removed by etching, but such control means that the particle size of the roughened particles is reduced within an appropriate range. Therefore, the resin transparency after removing the copper foil by etching becomes better, and the peel strength becomes better.
  • the ratio A / B between the surface area A of the roughened particles and the area B obtained when the roughened particles are viewed in plan view from the copper foil surface side is controlled to 1.90 to 2.40.
  • the roughness of the roughened surface is controlled to 0.30 to 0.80 ⁇ m to eliminate extremely rough portions, while the glossiness of the roughened surface is increased. It can be as high as 80 to 350%.
  • the particle size of the roughened particles on the roughened surface can be reduced.
  • the particle size of the roughened particles affects the resin transparency after the copper foil is removed by etching, but such control means that the particle size of the roughened particles is reduced within an appropriate range. Therefore, the resin transparency after removing the copper foil by etching becomes better, and the peel strength becomes better.
  • the root mean square height Rq of at least one surface is preferably controlled to 0.14 to 0.63 ⁇ m.
  • the peel strength is increased and the resin is satisfactorily bonded to the resin, and the transparency of the resin after the copper foil is removed by etching is increased.
  • the root mean square height Rq is less than 0.14 ⁇ m, the roughening treatment on the surface of the copper foil becomes insufficient, causing a problem that the resin cannot be sufficiently bonded.
  • the root mean square height Rq is more than 0.63 ⁇ m, the unevenness of the resin surface after the copper foil is removed by etching becomes large, resulting in a problem that the transparency of the resin becomes poor.
  • the root mean square height Rq of the roughened surface is more preferably 0.25 to 0.60 ⁇ m, still more preferably 0.32 to 0.56 ⁇ m.
  • the root mean square height Rq of the surface is an index indicating the degree of unevenness in the surface roughness measurement with a non-contact type roughness meter in accordance with JIS B 0601 (2001), and is represented by the following formula:
  • the surface roughness is the height of irregularities (peaks) in the Z-axis direction, and is the root mean square of the height Z (x) of the peaks at the reference length lr.
  • the root mean square height Rq of the height of the mountain at the reference length lr ⁇ ⁇ (1 / lr) ⁇ ⁇ Z 2 (x) dx (where integral is an integrated value from 0 to lr) ⁇
  • the treatment is performed at a low current density so that the plating film is not uneven as described above, and when the roughening treatment is performed, a high current density is obtained.
  • the skewness Rsk represents the Z (x) cube average at the reference length made dimensionless by the cube of the root mean square height Rq.
  • the root mean square height Rq is an index indicating the degree of unevenness in surface roughness measurement with a non-contact type roughness meter in accordance with JIS B 0601 (2001), and is expressed by the following equation (A).
  • the height of the unevenness (mountain) in the Z-axis direction is the root mean square of the height Z (x) of the mountain at the reference length lr.
  • the skewness Rsk is expressed by the following equation (B) using the root mean square height Rq.
  • the skewness Rsk on the surface of the copper foil is an index indicating the objectivity of the unevenness on the surface of the copper foil when centered on the average surface of the uneven surface on the surface of the copper foil.
  • Rsk ⁇ 0
  • the height distribution is biased upward with respect to the average plane
  • Rsk>0 the height distribution is biased downward with respect to the average plane. I can say that.
  • the upward bias is large, when the copper foil is attached to polyimide (PI) and then removed by etching, the PI surface has a concave shape, and when light is irradiated from the light source, irregular reflection within the PI increases.
  • the PI surface has a convex shape, and when light is irradiated from the light source, irregular reflection on the PI surface increases. .
  • the skewness Rsk of at least one surface is controlled to ⁇ 0.35 to 0.53.
  • the skewness Rsk of the surface of the copper foil that has been surface-treated is preferably ⁇ 0.30 or more, more preferably ⁇ 0.20 or more, and preferably ⁇ 0.10 or less.
  • the skewness Rsk of the surface-treated copper foil is preferably 0.15 or more, preferably 0.20 or more, preferably 0.50 or less, preferably 0.45 or less, preferably 0.40 or less, Even more preferably 0.39 or less.
  • the skewness Rsk of the surface of the copper foil subjected to the surface treatment is preferably ⁇ 0.30 or more, preferably 0.50 or less, and more preferably 0.39 or less.
  • the treatment is performed at a low current density so that the plating film is not uneven as described above, and when the roughening treatment is performed, a high current density is obtained. By reducing the size of the roughened particles and plating in a short time, it is possible to perform surface treatment with low roughness, thereby controlling the skewness Rsk of the surface.
  • At least one surface has a ratio E / G of the surface area G obtained when the surface is viewed in plan and the convex volume E of the surface is 2.11 to 23.91. It is preferable to be controlled. With such a configuration, the peel strength is increased and the resin is satisfactorily bonded to the resin, and the transparency of the resin after the copper foil is removed by etching is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin are facilitated.
  • the ratio E / G is less than 2.11 ⁇ m, the roughening treatment on the surface of the copper foil becomes insufficient, resulting in a problem that the resin cannot be sufficiently bonded.
  • the ratio E / G is more than 23.91 ⁇ m, the unevenness of the resin surface after removing the copper foil by etching becomes large, resulting in a problem that the transparency of the resin becomes poor.
  • the ratio E / G is more preferably 2.95 to 21.42 ⁇ m, still more preferably 10.54 to 13.30 ⁇ m.
  • the “surface area G obtained when the surface is viewed in plan” is the sum of the surface areas of the portions that become peaks or the valleys based on a certain height (threshold).
  • the “surface convex volume E” is the total volume of a portion that becomes a peak or a portion that becomes a valley based on a certain height (threshold). Control of the ratio E / G between the surface area G of the surface and the convex volume E is performed by adjusting the current density of the roughened particles and the plating time as described above. When the plating process is performed at a high current density, small rough particles are obtained, and when the plating process is performed at a low current density, large rough particles are obtained. Since the number of particles formed under these conditions is determined by the plating time, the convex volume E is determined by a combination of the current density and the plating time.
  • the surface-treated copper foil of the present invention may be a non-roughened copper foil or a roughened copper foil on which roughened particles are formed, and the average roughness Rz of the TD on the roughened surface is 0.20-0. It is preferably 64 ⁇ m. With such a configuration, the peel strength becomes higher, the resin adheres well to the resin, and the transparency of the resin after the copper foil is removed by etching becomes higher. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin can be made easier.
  • the average roughness Rz of TD When the average roughness Rz of TD is less than 0.20 ⁇ m, the roughening treatment on the surface of the copper foil may be insufficient, and there may be a problem that the resin cannot be sufficiently adhered. On the other hand, if the average roughness Rz of TD exceeds 0.64 ⁇ m, the unevenness of the resin surface after the copper foil is removed by etching may be increased, resulting in a problem that the transparency of the resin becomes poor. There is a fear.
  • the average TD roughness Rz of the treated surface is more preferably 0.40 to 0.62 ⁇ m, and still more preferably 0.46 to 0.55 ⁇ m.
  • the roughness (Rz) and the glossiness of the TD on the treated side surface of the copper foil before the surface treatment are controlled.
  • TD of the copper foil before the surface treatment direction perpendicular to the rolling direction (width direction of the copper foil), and in the case of electrolytic copper foil, perpendicular to the foil passing direction of the copper foil in the electrolytic copper foil manufacturing apparatus Direction
  • surface roughness (Rz) is 0.20 to 0.55 ⁇ m, preferably 0.20 to 0.42 ⁇ m.
  • the rolling is performed by adjusting the oil film equivalent of the rolling oil (high gloss rolling), rolling is performed by adjusting the surface roughness of the rolling roll, or chemical polishing such as chemical etching or It is prepared by electropolishing in a phosphoric acid solution.
  • surface roughness (Rz) of copper foil before processing is made into the above-mentioned range
  • glossiness of TD of copper foil before processing is made into the following range
  • surface roughness of copper foil after processing (Rz) surface area, Sv, Rq, Rsk, the ratio E / G of the surface area G of the copper foil surface and the convex volume E can be controlled.
  • the copper foil before the surface treatment has a TD 60 degree gloss of 400 to 710%, and preferably 500 to 710%.
  • the high gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13000 to 24000 or less.
  • 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 a low-viscosity rolling oil or slowing the sheet passing speed may be used.
  • the surface roughness of the rolling roll can be, for example, 0.01 to 0.25 ⁇ m in terms of arithmetic average roughness Ra (JIS B0601).
  • the surface-treated copper foil of the present invention is bonded to both sides of the polyimide base resin, then the copper foil on both sides is removed by etching, and a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate. Then, when the printed matter is photographed with a CCD camera through the polyimide substrate, the brightness at each observation point is measured along the direction perpendicular to the direction in which the observed line-shaped mark extends about the image obtained by photographing.
  • the intersection closest to the line-shaped mark among the intersections of the lightness curve and Bt is t1
  • Bt is determined from the intersection of the lightness curve and Bt.
  • Sv defined by the equation (1) is 3 .5 or more.
  • FIGS. 1A and 1B are schematic views for defining Bt and Bb when the mark width is about 0.3 mm. When the mark width is about 0.3 mm, a V-shaped brightness curve may be obtained as shown in FIG. 1A, or a brightness curve having a bottom as shown in FIG. 1B. .
  • the “top average value Bt of the lightness curve” indicates the average value of lightness when measured at 5 locations (a total of 10 locations on both sides) at 30 ⁇ m intervals from the positions 50 ⁇ m away from the end positions on both sides of the mark.
  • the “bottom average value Bb of the lightness curve” indicates the minimum value of lightness at the tip of the V-shaped valley when the lightness curve is V-shaped as shown in FIG. When it has the bottom of (b), the value of the center part of about 0.3 mm is shown.
  • the mark width may be about 0.2 mm, 0.16 mm, or 0.1 mm.
  • top average value Bt of the lightness curve is 5 points at 30 ⁇ m intervals from a position 100 ⁇ m apart, a position 300 ⁇ m apart, or a position 500 ⁇ m apart from the end positions on both sides of the mark (total 10 on both sides). Location) It may be the average value of brightness when measured.
  • FIG. 2 is a schematic diagram that defines t1, t2, and Sv. “T1 (pixel ⁇ 0.1)” is a value indicating an intersection point closest to the line-shaped mark among intersection points of the lightness curve and Bt and a position of the intersection point (value on the horizontal axis of the observation point-lightness graph) ).
  • T2 (pixel ⁇ 0.1) is the line-shaped mark among the intersections of the lightness curve and 0.1 ⁇ B in the depth range from the intersection of the lightness curve and Bt to 0.1 ⁇ B with reference to Bt. And the value (the value on the horizontal axis of the observation point-lightness graph) indicating the closest intersection and the position of the intersection.
  • Sv grade / pixel ⁇ 0.1
  • One pixel on the horizontal axis corresponds to a length of 10 ⁇ m.
  • Sv is measured on both sides of the mark, and a small value is adopted. Further, when the shape of the lightness curve is unstable and there are a plurality of the “intersections between the lightness curve and Bt”, the intersection closest to the mark is adopted. In the image taken by the CCD camera, the brightness is high at the portion where the mark is not attached, but the brightness decreases as soon as the end of the mark is reached. If the visibility of the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the visibility of the polyimide substrate is poor, the lightness does not suddenly drop from “high” to “low” in the vicinity of the mark end, but the state of decline is slow and the state of lightness decline is unclear. End up.
  • the present invention is based on such a polyimide substrate from which the surface-treated copper foil of the present invention is bonded and removed, and a mark printed matter is placed under the polyimide substrate and photographed with a CCD camera over the polyimide substrate.
  • Sv is preferably 3.9 or more, more preferably 4.5 or more, even more preferably 5.0 or more, and even more preferably 5.5 or more.
  • the upper limit of Sv is not particularly limited, but is, for example, 70 or less, 30 or less, 15 or less, and 10 or less. According to such a configuration, the boundary between the mark and the non-mark portion becomes clearer, the positioning accuracy is improved, the error due to the mark image recognition is reduced, and the alignment can be performed more accurately.
  • the ratio D / C between the three-dimensional surface area D and the two-dimensional surface area C of the surface of the copper foil on the surface treatment side greatly affects the transparency of the resin. That is, if the surface roughness Rz is the same, the smaller the ratio D / C, the better the transparency of the resin described above. Therefore, in the surface-treated copper foil of the present invention, the ratio D / C is preferably 1.0 to 1.7, more preferably 1.0 to 1.6.
  • the ratio D / C between the three-dimensional surface area D and the two-dimensional surface area C of the surface on the surface treatment side is, for example, when the surface is roughened, and the surface area D of the roughened particles and the copper foil are copper. It can also be referred to as the ratio D / C with the area C obtained when viewed from the foil surface.
  • the surface state of the copper foil after the surface treatment and the form and formation density of the roughened particles are determined.
  • Rz, glossiness, and copper foil surface area ratio D / C, Sv, ⁇ B, Rq, Rsk, and copper foil surface area G to convex volume E ratio E / G can be controlled.
  • the etching factor is preferably 1.8 or more, preferably 2.0 or more, preferably 2.2 or more, and 2.3 or more. Preferably, it is 2.4 or more.
  • the area ratio (A / B) of the particles, glossiness, surface roughness Rz, Sv, ⁇ B, Rq, Rsk, the ratio E / G of the surface area G of the copper foil surface and the convex volume E can be measured.
  • Transmission loss When the transmission loss is small, attenuation of the signal when performing signal transmission at a high frequency is suppressed, so that a stable signal transmission can be performed in a circuit that transmits the signal at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency.
  • the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB / 10 cm, more preferably less than 4.1 dB / 10 cm. Even more preferred is less than 0.7 dB / 10 cm.
  • the laminate can be produced by bonding the surface-treated copper foil of the present invention to the resin substrate from the surface-treated surface side.
  • the resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like.
  • a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film, Teflon for FPC (Registered trademark) film or the like can be used.
  • a prepreg is prepared by impregnating a base material such as a glass cloth with a resin and curing the resin to a semi-cured state. It can be carried out by superposing a copper foil on the prepreg from the opposite surface of the coating layer and heating and pressing.
  • FPC it is laminated on a copper foil under high temperature and high pressure without using an adhesive on a substrate such as a polyimide film, or a polyimide precursor is applied, dried, cured, etc.
  • a laminated board can be manufactured by performing.
  • the thickness of the polyimide base resin is not particularly limited, but generally 25 ⁇ m or 50 ⁇ m can be mentioned.
  • the laminate of the present invention can be used for various printed wiring boards (PWB) and is not particularly limited.
  • PWB printed wiring boards
  • the single-sided PWB, the double-sided PWB, and the multilayer PWB 3
  • rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material.
  • a laminate of a surface-treated copper foil and a resin substrate is prepared.
  • a specific example of the laminate of the surface-treated copper foil and the resin substrate according to the present invention at least one of a main substrate, an attached circuit substrate, and a resin substrate such as polyimide used for electrically connecting them.
  • a laminated board manufactured by accurately positioning the flexible printed circuit board and crimping it to the wiring ends of the main circuit board and the attached circuit board Is mentioned.
  • the laminate is a laminate in which the wiring end portions of the flexible printed circuit board and the main body substrate are bonded together by pressure bonding, or the wiring edge portions of the flexible printed circuit board and the circuit board are bonded together by pressure bonding.
  • the laminated board has a mark formed of a part of the copper wiring and a separate material. The position of the mark is not particularly limited as long as it can be photographed by photographing means such as a CCD camera through the resin constituting the laminated plate.
  • the position of the mark when the above-mentioned mark is photographed by the photographing means through the resin, the position of the mark can be detected well. And the position of the said mark can be detected in this way, and based on the position of the said detected mark, the positioning of the laminated board of surface-treated copper foil and a resin substrate can be performed favorably.
  • the photographing means can detect the position of the mark well by such a positioning method, and the printed wiring board can be positioned more accurately.
  • the connection failure is reduced and the yield is improved.
  • a method for connecting one printed wiring board and another printed wiring board soldering, connection through an anisotropic conductive film (Anisotropic Conductive Film, ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used.
  • the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted.
  • a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention.
  • One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board.
  • “copper circuit” includes copper wiring.
  • the printed wiring board of the present invention may be connected to a component to produce a printed wiring board.
  • at least one printed wiring board of the present invention is connected to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention.
  • a printed wiring board in which two or more printed wiring boards are connected may be manufactured by connecting two or more printed wiring boards and components.
  • components electronic components such as connectors, LCDs (Liquid Crystal Displays), glass substrates used in LCDs, ICs (Integrated Circuits), LSIs (Large scale integrated circuits), VLSIs (Very Large Scaler). ), ULSI (Ultra-Large Scale Integrated circuit) and other electronic components including semiconductor integrated circuits (eg, IC chips, LSI chips, VLSI chips, ULSI chips), components for shielding electronic circuits, and covers on printed wiring boards, etc. Examples of the parts necessary to fix the are included.
  • the positioning method according to the embodiment of the present invention may include a step of moving a laminated board (including a laminated board of copper foil and a resin substrate and a printed wiring board).
  • a laminated board including a laminated board of copper foil and a resin substrate and a printed wiring board.
  • it may be moved by a conveyor such as a belt conveyor or a chain conveyor, may be moved by a moving device provided with an arm mechanism, or may be moved by floating a laminated plate using gas.
  • a moving means a moving device or moving means (including a roller or a bearing) that moves a laminated plate by rotating an object such as a substantially cylindrical shape, a moving device or moving means that uses hydraulic pressure as a power source, Moving devices and moving means powered by air pressure, moving devices and moving means powered by motors, gantry moving linear guide stages, gantry moving air guide stages, stacked linear guide stages, linear motor drive stages, etc. It may be moved by a moving device or moving means having a stage. Moreover, you may perform the movement process by a well-known moving means.
  • the positioning method according to the embodiment of the present invention may be used for a surface mounter or a chip mounter.
  • the printed wiring board which has the circuit provided on the resin board and the said resin board may be sufficient as the laminated board of the surface treatment copper foil and the resin board which are positioned in this invention. In that case, the mark may be the circuit.
  • positioning includes “detecting the position of a mark or an object”.
  • alignment includes “after detecting the position of a mark or object, moving the mark or object to a predetermined position based on the detected position”.
  • the circuit on the printed wiring board is used as a mark instead of the mark on the printed material, and the Sv value can be measured by photographing the circuit through a resin with a CCD camera.
  • the lined copper was used as a mark instead of a printed mark, and the lined copper was photographed with a CCD camera through the resin.
  • the value of Sv can be measured.
  • the copper clad laminate of the present invention is, in one embodiment, a copper clad laminate having an insulating resin substrate and a copper foil, and the copper foil of the copper clad laminate is line-shaped by etching. For each observation point along the direction perpendicular to the direction in which the observed line-shaped copper foil extends for the image obtained by the photographing when the copper foil is photographed with a CCD camera through the insulating resin substrate.
  • the top average value of the lightness curve generated from the end of the line-shaped copper foil to the portion without the line-shaped copper foil is Bt
  • the bottom average value is Bb
  • the copper clad laminate of the present invention is, in one embodiment, a copper clad laminate composed of an insulating resin substrate and a surface-treated copper foil laminated on the insulating substrate from the surface side where the surface treatment is performed.
  • the sheet After the surface-treated copper foil of the copper-clad laminate is formed into a line-shaped surface-treated copper foil by etching, the sheet is passed through the insulating resin substrate laminated from the surface side where the surface treatment is performed. Observations made by measuring the brightness at each observation point along the direction perpendicular to the direction in which the observed surface-treated copper foil was stretched, with respect to the image obtained by the photographing when photographed with a CCD camera.
  • the top average value of the lightness curve generated from the end of the line-shaped surface-treated copper foil to the portion without the line-shaped surface-treated copper foil is Bt
  • the bottom average value is Bb
  • the value indicating the position of the close intersection is t1
  • the line-shaped surface among the intersections of the lightness curve and 0.1 ⁇ B When the value indicating the position of the intersection closest to the treated copper foil is t2, Sv defined by the equation (1) is 3.5 or more.
  • Liquid composition Nickel 5-20 g / L, Cobalt 1-8 g / L pH: 2-3 Liquid temperature: 40-60 ° C Current density: 5 to 20 A / dm 2 Coulomb amount: 10-20 As / dm 2 The plating time was 0.5 to 2.0 seconds.
  • a heat-resistant layer 2 was formed on the copper foil provided with the heat-resistant layer 1. The conditions for forming the heat-resistant layer 2 are shown below.
  • Liquid composition Nickel 2-30 g / L, Zinc 2-30 g / L pH: 3-4 Liquid temperature: 30-50 ° C Current density: 1 to 2 A / dm 2 Coulomb amount: 1 to 2 As / dm 2
  • the roughening plating process was not performed, and the heat-resistant layer 3 was directly formed on the prepared copper foil.
  • the conditions for forming the heat-resistant layer 3 are shown below.
  • Liquid composition Nickel 25 g / L, zinc 2 g / L pH: 2.5 Liquid temperature: 40 ° C Current density: 6 A / dm 2 Coulomb amount: 4.8 As / dm 2 Plating time: 0.8 seconds Further, in Experimental Example B1-15, the roughening plating treatment was not performed, and the heat-resistant layer 4 was directly formed on the prepared copper foil. The conditions for forming the heat-resistant layer 4 are shown below. Liquid composition: Nickel 0.3 g / L, zinc 2.5 g / L, pyrophosphate bath Liquid temperature: 40 ° C.
  • a rust preventive layer was further formed on the copper foil to which the heat resistant layers 1 and 2 or the heat resistant layer 3 or the heat resistant layer 4 were applied. The conditions for forming the rust preventive layer are shown below.
  • Liquid composition potassium dichromate 1-10 g / L, zinc 0-5 g / L pH: 3-4 Liquid temperature: 50-60 ° C Current density: 0-2A / dm 2 (for immersion chromate treatment) Coulomb amount: 0 to 2 As / dm 2 (for immersion chromate treatment)
  • the weathering layer was further formed. The formation conditions are shown below.
  • N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Experimental Examples A1-17, A1-24 to A1-27), N-2- (aminoethyl) -3-Aminopropyltriethoxysilane (Experimental Examples A1-1 to A1-16), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (Experimental Examples A1-18, A1-28, A1-29) , A1-30), 3-aminopropyltrimethoxysilane (Experimental Example A1-19), 3-aminopropyltriethoxysilane (Experimental Examples A1-20, A1-21), 3-triethoxysilyl-N- (1 , 3-Dimethyl-butylidene) propylamine (Experimental Example 22), N-phenyl-3-aminopropyltrimethoxysilane
  • silane coupling agents can be used in combination of two or more.
  • coating and drying were performed with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane to form a weather resistant layer.
  • the rolled copper foil was manufactured as follows. After producing copper ingots having the compositions shown in Tables 2 and 3 and performing hot rolling, annealing and cold rolling of a continuous annealing line at 300 to 800 ° C. were repeated to obtain a rolled sheet having a thickness of 1 to 2 mm. . This rolled sheet was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thickness shown in Table 2 to obtain a copper foil. “Tough pitch copper” in the “Type” column of Tables 2 and 3 indicates tough pitch copper specified in JIS H3100 C1100, and “Oxygen-free copper” indicates oxygen-free copper specified in JIS H3100 C1020.
  • “Tough pitch copper + Ag: 100 ppm” means that 100 mass ppm of Ag is added to tough pitch copper.
  • the electrolytic copper foil used was an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metals. When electrolytic polishing or chemical polishing was performed, the plate thickness after electrolytic polishing or chemical polishing was described. Tables 2 and 3 list the points of the copper foil preparation process before the surface treatment. “High gloss rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the value of the oil film equivalent. “Normal rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the oil film equivalent value described.
  • “Chemical polishing” and “electropolishing” mean the following conditions. “Chemical polishing” was performed using an etching solution of 1 to 3% by mass of H 2 SO 4 , 0.05 to 0.15% by mass of H 2 O 2 , and the remaining water, and the polishing time was 1 hour. “Electropolishing” is a condition of 67% phosphoric acid + 10% sulfuric acid + 23% water, a voltage of 10 V / cm 2 , and a time shown in Table 2 (the amount of polishing is 1 to 2 ⁇ m when electrolytic polishing is performed for 10 seconds) ).
  • a rolled copper foil (“Tough pitch copper” in the "Type” column of the table indicates that it is a rolled copper foil) was produced as follows. A predetermined copper ingot was manufactured and hot-rolled, and then annealing and cold rolling of a continuous annealing line at 300 to 800 ° C. were repeated to obtain a rolled sheet having a thickness of 1 to 2 mm. This rolled sheet was annealed in a continuous annealing line at 300 to 800 ° C. and recrystallized, and finally cold-rolled to the thickness shown in Table 1 to obtain a copper foil. “Tough pitch copper” in the table indicates tough pitch copper standardized in JIS H3100 C1100.
  • the surface roughness (Rz) was calculated
  • the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc.
  • the surface-treated copper foil was an ultrathin copper layer of a copper foil with a carrier, the above measurement was performed on the roughened surface of the ultrathin copper layer.
  • the root mean square height Rq of the surface was measured with the Olympus laser microscope OLS4000.
  • the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction, or the electrolytic copper foil is electrolytic copper foil
  • the value was calculated
  • the measurement environment temperature of the root mean square height Rq of the surface with a laser microscope was 23 to 25 ° C.
  • the skewness Rsk of the surface-treated surface of the copper foil was measured with a laser microscope OLS4000 manufactured by Olympus Corporation for the surface-treated surface of the copper foil after the surface treatment of each example and comparative example.
  • the rolled copper foil is measured in the direction (TD) perpendicular to the rolling direction, or the electrolytic copper foil is electrolytic copper foil
  • the value was calculated
  • the measurement environment temperature of the surface skewness Rsk with a laser microscope was set to 23 to 25 ° C.
  • a -Particle area ratio (A / B);
  • the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc.
  • the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc.
  • the glossiness was calculated
  • the heat-resistant layer, rust-proof when surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the surface of the copper foil or without performing the roughening treatment, the heat-resistant layer, rust-proof
  • the surface-treated copper foil after the surface treatment of the layer, weather resistant layer, etc. is bonded to both surfaces of the polyimide film from the surface-treated surface side, and the surface-treated copper foil is etched (ferric chloride aqueous solution)
  • a sample film was prepared by removing. Subsequently, a printed material on which a line-shaped black mark is printed is laid under the sample film, and the printed material is photographed with a CCD camera (line CCD camera of 8192 pixels) through the sample film.
  • FIG. 3 is a schematic diagram showing the configuration of the photographing apparatus used at this time and the method of measuring the inclination of the brightness curve. Further, ⁇ B, t1, t2, and Sv were measured by the following photographing apparatus as shown in FIG. One pixel on the horizontal axis corresponds to a length of 10 ⁇ m.
  • the glossiness of the glossy paper 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.
  • the photographing device has a CCD camera, a stage (white) on which a polyimide substrate is placed with a marked paper underneath, an illumination power source that irradiates light onto the photographing portion of the polyimide substrate, and a paper with a mark to be photographed.
  • a transporter (not shown) for transporting the evaluation polyimide substrate placed below onto the stage is provided.
  • the main specifications of the camera are as follows: ⁇ Photographing device: Sheet inspection device Mujken manufactured by Nireco Corporation Line CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits) ⁇ Power supply for lighting: High frequency lighting power supply (power supply unit x 2) ⁇ Illumination: fluorescent lamp (30W, model name: FPL27EX-D, twin fluorescent lamp) As a line for Sv measurement, a line indicated by an arrow drawn on the contaminant of FIG. 6 of 0.7 mm 2 was used. The width of the line is 0.3 mm. Further, the line CCD camera field of view is arranged in a dotted line in FIG.
  • the signal is confirmed at 256 gradations on the full scale, and the place where the black mark of the printed matter does not exist (on the white glossy paper above) without placing the polyimide film (polyimide substrate) to be measured.
  • the lens aperture was adjusted so that the peak gradation signal of 230 ⁇ 5 falls within the range (when a portion outside the mark printed on the contaminants is measured with a CCD camera from the transparent film side).
  • the camera scan time (the time when the camera shutter is open and the time when light is captured) is fixed at 250 ⁇ s, and the lens aperture is adjusted so that it falls within the above gradation.
  • a white gloss with a glossiness of 43.0 ⁇ 2 is provided on the back surface of the line-shaped copper foil.
  • the above “line-shaped black mark” is used except that ⁇ B, t1, t2, and Sv are measured from the lightness curve generated from the end of the mark to the portion without the mark.
  • the surface of the surface-treated copper foil is treated with a polyimide film (experimental examples A1-1 to A1-30 and experimental examples B1-1 to B1-15 having a thickness of 25 ⁇ m or 50 ⁇ m by Kaneka or a thickness of 50 ⁇ m by Toray DuPont).
  • the surface-treated copper foil after the surface treatment of the layer, weather resistant layer, etc. is bonded to both surfaces of the polyimide film from the surface-treated surface side, and the surface-treated copper foil is etched (ferric chloride aqueous solution) Removed to create a sample film.
  • a printed material black circle with a diameter of 6 cm was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer.
  • ⁇ indicates that the outline of the black circle of the printed material is clear when the length is 90% or more of the circumference
  • “Clear” indicates that the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. “O” (passed above), a black circle with a clear outline of 0 to less than 80% of the circumference and a broken outline were evaluated as “x” (failed).
  • ⁇ Peel strength (adhesive strength);
  • the normal peel strength was measured with a tensile tester Autograph 100, and the normal peel strength of 0.7 N / mm or more could be used for laminated substrates.
  • a polyimide film of either Kaneka thickness 25 ⁇ m or 50 ⁇ m or Toray DuPont thickness 50 ⁇ m was used.
  • the test coupon based on JISC6471 was created.
  • the prepared test coupon was exposed to high temperature and high humidity of 85 ° C. and 85% RH for 48 hours, and then floated in a solder bath at 300 ° C. to evaluate solder heat resistance.
  • the area where the interface discolored due to blistering in an area of 5% or more of the copper foil area in the test coupon is x (failed), area
  • the color change was less than 5%, the case was evaluated as ⁇ , and the case where no color change occurred was evaluated as ⁇ .
  • the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc.
  • the copper foil was bonded to both surfaces of a polyimide film with a thermosetting adhesive for laminating (thickness 50 ⁇ m, Upilex manufactured by Ube Industries).
  • a thermosetting adhesive for laminating thinness 50 ⁇ m, Upilex manufactured by Ube Industries.
  • the circuit width was set such that the bottom width of the circuit cross section was 20 ⁇ m.
  • Equipment Spray type small etching equipment
  • Spray pressure 0.2 MPa
  • Etching solution Ferric chloride aqueous solution (specific gravity 40 Baume)
  • Liquid temperature 50 ° C
  • the photosensitive resist film was peeled off by dipping in a 45 ° C. NaOH aqueous solution for 1 minute.
  • the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc.
  • the surface treated side of the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 ⁇ m manufactured by Kuraray Co., Ltd.), and then the characteristic impedance was measured by etching.
  • a microstrip line was formed so as to be 50 ⁇ , and a transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained.
  • copper foil thickness was 18 micrometers.
  • the thickness of the copper foil was thicker than 18 ⁇ m, the thickness was reduced to 18 ⁇ m by electrolytic polishing. On the other hand, when the thickness was thinner than 18 ⁇ m, the thickness was increased to 18 ⁇ m by copper plating.
  • ⁇ ⁇ less than 3.7 dB / 10 cm, ⁇ 3.7 dB / 10 cm or more and less than 4.1 dB / 10 cm, ⁇ 4 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm, ⁇ , 5.0 dB / 10 cm or more was defined as x.
  • the above-described measurements can be performed on the surface of the copper circuit or the copper foil by dissolving and removing the resin.
  • the surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after roughening the copper foil surface or without the roughening treatment, the heat-resistant layer, rust-proof Said measurement was performed about the surface of the surface-treated copper foil after surface-treating a layer, a weather resistance layer, etc. The conditions and evaluation of each test are shown in Tables 1 to 11.
  • FIG. 4 shows (a) Experimental Example B3-1, (b) Experimental Example A3-1, (c) Experimental Example A3-2, (d) Experimental Example A3-3, (e) Experimental Example A3-4, (f) Experimental Example A3-5, (g) Experimental Example A3-6, (h) Experimental Example A3-7, (i) Experimental Example A3-8, (j) Experimental Example A3-9 (K) SEM observation photographs of the copper foil surface of Experimental Example B3-2 and (l) Experimental Example B3-3 are shown respectively.
  • the third mark from the closest to the description of the sheet of 0.5 area 0.5 mm 2 of 0.16 mm (contaminants width of the mark from 0.3 mm (the arrow in FIG. 7 refers The same Sv value and ⁇ B value were measured after changing to the mark (S), but in both cases, the Sv value and ⁇ B value were the same as when the mark width was 0.3 mm.
  • the position 50 ⁇ m away from the end positions on both sides of the mark is defined as the position 100 ⁇ m away, the position 300 ⁇ m away, and the position 500 ⁇ m away.
  • the Sv value and ⁇ B value were measured in the same manner by changing to the average value of the brightness when measured at 5 locations (total of 10 locations on both sides) at 30 ⁇ m intervals.
  • the Sv value when the average value of brightness when measuring 5 locations at 30 ⁇ m intervals from a position 50 ⁇ m away from the end positions on both sides of the mark (a total of 10 locations on both sides) is “top average value Bt of the brightness curve”
  • the value was the same as the ⁇ B value.

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Abstract

L'invention concerne une feuille de cuivre traitée en surface présentant une excellente transparence de la résine après l'élimination par gravure de la feuille de cuivre, et un stratifié utilisant celle-ci. La présente invention concerne une feuille de cuivre traitée en surface, dans laquelle, lorsqu'on fait adhérer la feuille de cuivre sur les deux surfaces d'un substrat en résine de polyimide à partir du côté de la surface traitée, qu'on élimine ensuite par gravure ladite feuille des deux surfaces et qu'on saisit une image de matière imprimée sur laquelle une marque linéaire est imprimée, étant admis que la différence entre la valeur moyenne supérieure (Bt) et la valeur moyenne inférieure (Bb) d'une courbe de luminosité produite à partir de l'extrémité de la marque jusqu'à une section sur laquelle la marque n'est pas dessinée est ΔB (ΔB = Bt-Bb) dans le graphique obtenu des points d'observation/luminosité, et lorsque la valeur exprimant la position de l'intersection la plus proche de la marque linéaire parmi les intersections entre la courbe de luminosité et Bt est t1 dans le graphique points d'observation/luminosité, et que la valeur exprimant la position de l'intersection la plus proche de la marque linéaire parmi les intersections entre la courbe de luminosité et 0,1ΔB est t2, dans une plage allant jusqu'à une profondeur de 0,1ΔB avec Bt à partir de l'intersection entre la courbe de luminosité et Bt en tant que référence, alors Sv défini dans cette formule (1) est égal à 3,5 ou plus. Sv=(ΔB×0,1)/(t1-t2) (1)
PCT/JP2013/080481 2012-11-09 2013-11-11 Feuille de cuivre traitée en surface et stratifié l'utilisant WO2014073696A1 (fr)

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