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WO2014084385A1 - Feuille de cuivre avec support - Google Patents

Feuille de cuivre avec support Download PDF

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Publication number
WO2014084385A1
WO2014084385A1 PCT/JP2013/082283 JP2013082283W WO2014084385A1 WO 2014084385 A1 WO2014084385 A1 WO 2014084385A1 JP 2013082283 W JP2013082283 W JP 2013082283W WO 2014084385 A1 WO2014084385 A1 WO 2014084385A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
copper
carrier
circuit
copper foil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/082283
Other languages
English (en)
Japanese (ja)
Inventor
友太 永浦
倫也 古曳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to CN201380062754.3A priority Critical patent/CN104822525B/zh
Priority to KR1020157015151A priority patent/KR101797333B1/ko
Publication of WO2014084385A1 publication Critical patent/WO2014084385A1/fr
Priority to PH12015501163A priority patent/PH12015501163A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0364—Conductor shape
    • H05K2201/0367—Metallic bump or raised conductor not used as solder bump

Definitions

  • the present invention relates to a copper foil with a carrier.
  • this invention relates to the copper foil with a carrier used as a material of 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 micro-thin copper layer is etched with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.
  • MSAP sulfuric acid-hydrogen peroxide etchant
  • 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 present inventor conducted extensive research and found that the Ni on the peel-side surface of the ultrathin copper layer when the ultrathin copper layer was peeled off from the copper foil with carrier that had been subjected to the predetermined heat treatment. It has been found that controlling the amount of adhesion is extremely effective for fine pitch formation on an ultrathin copper layer.
  • the present invention has been completed based on the above knowledge, and in one aspect, a copper foil with a carrier having a copper foil carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the intermediate layer includes Ni, 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 adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is 5 ⁇ g. / Dm 2 or more and 300 ⁇ g / dm 2 or less of the copper foil with carrier.
  • the carrier-attached copper foil of the present invention is a surface on the intermediate layer side of the ultrathin copper layer when the ultrathin copper layer is peeled off after heating the copper foil with carrier at 220 ° C. for 2 hours.
  • the adhesion amount of Ni is 5 ⁇ g / dm 2 or more and 250 ⁇ g / dm 2 or less.
  • the intermediate layer side of the ultrathin copper layer is 5 ⁇ g / dm 2 or more and 200 ⁇ g / dm 2 or less.
  • the intermediate layer side of the ultrathin copper layer adhesion amount of Ni on the surface of the is 5 [mu] g / dm 2 or more 156 ⁇ g / dm 2 or less.
  • the intermediate layer side of the ultrathin copper layer adhesion amount of Ni on the surface of the is 5 [mu] g / dm 2 or more 108 ⁇ g / dm 2 or less.
  • Ni content of the intermediate layer is 100 [mu] g / dm 2 or more 5000 [mu] g / dm 2 or less.
  • the intermediate layer has Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, an alloy thereof, and a water thereof. 1 type or 2 types or more selected from the group which consists of a Japanese thing, these oxides, and organic substance are included.
  • the intermediate layer when the intermediate layer contains Cr, it contains 5 to 100 ⁇ g / dm 2 of Cr, and when it contains Mo, 50 ⁇ g / dm 2 of Mo is contained.
  • it when it contains 1000 ⁇ g / dm 2 or less and contains Zn, it contains 1 ⁇ g / dm 2 or more and 120 ⁇ g / dm 2 or less of Zn.
  • the intermediate layer contains an organic substance in a thickness of 25 nm or more and 80 nm or less.
  • the carrier-attached copper foil of the present invention is an organic substance composed of one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.
  • the carrier-attached copper foil of the present invention has a roughened layer on the surface of the ultrathin copper layer.
  • the roughening treatment layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. It is a layer made of a single substance or an alloy containing one or more of them.
  • the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. It has the above layers.
  • the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. It has the above layers.
  • the copper foil with a carrier of the present invention comprises a resin layer on the ultrathin copper layer.
  • the copper foil with a carrier of the present invention includes a resin layer on the roughening treatment layer.
  • the carrier-attached copper foil of the present invention is a resin layer 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. Is provided.
  • the resin layer includes a dielectric.
  • 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 printed circuit 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 includes an insulating resin plate and a copper circuit provided on the insulating resin plate.
  • the copper circuit includes a copper layer and a copper layer in order from the insulating resin plate side.
  • a printed wiring board having a width of less than 20 ⁇ m and a width of a space between adjacent copper circuits of less than 20 ⁇ m.
  • the circuit width of the copper circuit is 17 ⁇ m or less, and the width of the space between adjacent copper circuits is 17 ⁇ m or less.
  • the present invention includes an insulating resin plate and a copper circuit provided on the insulating resin plate, and the copper circuit is sequentially formed on the copper layer and the copper layer from the insulating resin plate side.
  • the printed wiring board includes a provided copper plating layer, the circuit width of the copper circuit is less than 20 ⁇ m, and the width of the space between the copper circuit and the copper circuit is less than 20 ⁇ m.
  • the circuit width of the copper circuit is 17 ⁇ m or less, and the width of the space between adjacent copper circuits is 17 ⁇ m or less.
  • the present invention includes an insulating resin plate and a copper circuit provided on the insulating resin plate.
  • the copper circuit includes a copper layer and a copper layer in order from the insulating resin plate side.
  • the printed wiring board has a space width of less than 20 ⁇ m.
  • the circuit width of the copper circuit is 17 ⁇ m or less, and the width of the space between adjacent copper circuits is 17 ⁇ m or less.
  • the copper circuit has a circuit width of 10 ⁇ m or less, and a space between adjacent copper circuits has a width of 10 ⁇ m or less.
  • the circuit width of the copper circuit is 5 ⁇ m or less, and the width of the space between adjacent copper circuits is 5 ⁇ m or less.
  • the present invention includes an insulating resin plate and a copper circuit provided on the insulating resin plate, the circuit width of the copper circuit is less than 20 ⁇ m, the copper circuit and the copper circuit, Is a printed wiring board having a space width of less than 20 ⁇ m.
  • the circuit width of the copper circuit is 17 ⁇ m or less, and the width of the space between adjacent copper circuits is 17 ⁇ m or less.
  • the copper circuit has a circuit width of 10 ⁇ m or less, and a space between adjacent copper circuits has a width of 10 ⁇ m or less.
  • the circuit width of the copper circuit is 5 ⁇ m or less, and the width of the space between adjacent copper circuits is 5 ⁇ m or less.
  • a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried; Forming a circuit on the resin layer; Forming the circuit on the resin layer, and then peeling the carrier; and After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.
  • the step of forming a circuit on the resin layer is performed by laminating another copper foil with a carrier on the resin layer from the ultrathin copper layer side.
  • the circuit is formed using a copper foil with a carrier bonded to a layer.
  • another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier of the present invention.
  • the step of forming a circuit on the resin layer is any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Done by the method.
  • the copper foil with carrier for forming a circuit on the surface has a substrate or a resin layer on the surface of the carrier of the copper foil with carrier.
  • 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.
  • 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. It is the schematic of the cross section of the width direction of the circuit pattern in an Example, and the outline of the calculation method of the etching factor (EF) using this schematic diagram. It is a schematic diagram which shows the measurement location of the sample sheet which concerns on an Example.
  • the copper foil with a carrier of this invention has a copper foil carrier, an intermediate
  • 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. Bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. After thermocompression bonding, the copper foil carrier was peeled off and adhered to the insulating substrate An ultra-thin copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.
  • the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer is It is 5 ⁇ g / dm 2 or more and 300 ⁇ g / dm 2 or less.
  • a copper foil with a carrier is bonded to an insulating substrate, the copper foil carrier is peeled off after thermocompression bonding, and the ultrathin copper layer adhered to the insulating substrate is etched into the intended conductor pattern.
  • the surface of the ultrathin copper layer ( If the amount of Ni adhering to the surface on the side opposite to the side bonded to the insulating substrate is large, the ultrathin copper layer is difficult to be etched and it is difficult to form a fine pitch circuit. For this reason, the copper foil with a carrier of the present invention is controlled so that the Ni adhesion amount on the surface of the ultrathin copper layer after peeling as described above becomes 300 ⁇ g / dm 2 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 adhesion amount of Ni is controlled to be 5 ⁇ g / dm 2 or more.
  • the Ni deposition amount is preferably 5 [mu] g / dm 2 or more 250 [mu] g / dm 2 or less, more preferably 5 [mu] g / dm 2 or more 200 [mu] g / dm 2 or less, more preferably 5 [mu] g / dm 2 or more 156 ⁇ g / dm 2 or less , more preferably 5 [mu] g / dm 2 or more 108 ⁇ g / dm 2 or less.
  • the copper foil carrier that can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil.
  • 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.
  • the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys can also be used.
  • a copper alloy foil is also included.
  • the thickness of the copper foil carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 ⁇ 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 copper foil carrier is typically 12-300 ⁇ m, more typically 12-150 ⁇ m, even more typically 12-100 ⁇ m, and even more typically 12-70 ⁇ m. And more typically 18-35 ⁇ m.
  • An intermediate layer containing Ni is provided on one side or both sides of the copper foil carrier. Another layer may be provided between the copper foil carrier and the intermediate layer.
  • the intermediate layer contains Ni, Cr, Mo, Zn, organic matter, and the like.
  • the adhesion amount of Ni on the surface on the intermediate layer side of the ultrathin copper layer was 300 ⁇ g / the dm 2 below, in order to control the Ni deposition amount of the thus ultrathin copper layer surface after delamination, as well as reducing the Ni content in the intermediate layer, Ni is diffused into the ultra-thin copper layer-side It is necessary for the intermediate layer to contain a metal species (Cr, Mo, Zn, etc.) or an organic substance that suppresses this.
  • a metal species Cr, Mo, Zn, etc.
  • Ni content of the intermediate layer is preferably at 100 [mu] g / dm 2 or more 5000 [mu] g / dm 2 or less, more preferably at 200 [mu] g / dm 2 or more 4000 ⁇ g / dm 2 or less, 300 [mu] g / dm more preferably at 2 or more 3000 ⁇ g / dm 2 or less, and even more preferably 400 [mu] g / dm 2 or more 2000 [mu] g / dm 2 or less.
  • middle layer contains 1 type, or 2 or more types selected from the group which consists of Cr, Mo, and Zn is preferable.
  • Cr it is preferable to contain 5 to 100 ⁇ g / dm 2 of Cr, and more preferably 5 ⁇ g / dm 2 to 50 ⁇ g / dm 2 .
  • Mo is preferably contained 50 [mu] g / dm 2 or more 1000 [mu] g / dm 2 or less of Mo, and more preferably contains 70 [mu] g / dm 2 or more 650 ⁇ g / dm 2 or less.
  • containing Zn is preferably contained 1 [mu] g / dm 2 or more 120 [mu] g / dm 2 or less of Zn, more preferably containing 2 [mu] g / dm 2 or more 70 [mu] g / dm 2 or less, 5 [mu] g / dm 2 or more 50 [mu] g / dm 2 It is more preferable to contain the following.
  • the organic substance contained in the intermediate layer it is preferable to use one or two or more kinds selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids.
  • the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent.
  • Specific examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
  • the sulfur-containing organic compound it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
  • the carboxylic acid it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
  • the organic material is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm.
  • the intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
  • the method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil.
  • the intermediate layer is formed on the copper foil carrier by dissolving the above-mentioned organic substances in a solvent and immersing the copper foil carrier in the solvent, or showering, spraying method, dropping method on the surface on which the intermediate layer is to be formed.
  • the concentration of the organic agent in the solvent at this time is preferably in the range of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. for all the organic substances described above.
  • the concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low.
  • the intermediate layer of the carrier-attached copper foil of the present invention is made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, and organic substances. One or two or more selected from the group may be included.
  • the intermediate layer may be a plurality of layers.
  • the intermediate layer is a single metal layer made 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 made of one or more elements selected from the group consisting of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn; Forms 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, Zn It can be configured by doing.
  • a rust prevention layer such as a Ni plating layer on the opposite side of the copper foil carrier.
  • an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.
  • 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.
  • 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 0.5 to 12 ⁇ m, more typically 2 to 5 ⁇ m. In addition, you may provide an ultra-thin copper layer on both surfaces of a copper foil 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, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. Also good.
  • 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.).
  • the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate.
  • Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included).
  • the chromate treatment layer examples include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .
  • the heat-resistant layer and the rust-proof layer known heat-resistant layers and rust-proof layers can be used.
  • the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum
  • it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like.
  • the heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum.
  • An oxide, nitride, or silicide containing one or more elements selected from the above may be included.
  • the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy.
  • the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer.
  • the nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities.
  • the total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m 2 , preferably 10 to 500 mg / m 2 , preferably 20 to 100 mg / m 2 .
  • the amount of nickel deposited on the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2 , and 1 mg / m 2 to 50 mg / m 2 . More preferably.
  • the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall of a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.
  • the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer with an adhesion amount of 1 mg / m 2 to 100 mg / m 2 , preferably 5 mg / m 2 to 50 mg / m 2 , and an adhesion amount of 1 mg / m 2.
  • a tin layer of ⁇ 80 mg / m 2 , preferably 5 mg / m 2 ⁇ 40 mg / m 2 may be sequentially laminated.
  • the nickel alloy layer may be nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. You may be comprised by any one of these.
  • the heat-resistant layer and / or rust-preventing layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m 2 to 150 mg / m 2 and 10 mg / m 2 to 70 mg / m 2 . It is more preferable.
  • silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent.
  • Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and ⁇ -aminopropyl.
  • Triethoxysilane N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, ⁇ -mercaptopropyltrimethoxysilane or the like may be used.
  • the silane coupling treatment layer may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like.
  • a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like.
  • you may use 2 or more types of such silane coupling agents in mixture.
  • it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.
  • the amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl
  • the silane coupling treatment layer is 0.05 mg / m 2 to 200 mg / m 2 , preferably 0.15 mg / m 2 to 20 mg / m 2 , preferably 0.3 mg / m 2 to 2.0 mg in terms of silicon atoms. / M 2 is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.
  • Resin layer on ultrathin copper layer of copper foil with carrier of the present invention (surface treatment layer formed on ultrathin copper layer by surface treatment when ultrathin copper layer is surface-treated) May be provided.
  • the resin layer may be an insulating resin layer.
  • the resin layer may be an adhesive resin, that is, an adhesive, or may be a semi-cured (B-stage) insulating resin layer for adhesion.
  • 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 resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, 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. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No.
  • Japanese Patent Laid-Open No. 2002-179772 Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, and Japanese Patent Application Laid-Open No. 4570070. No. 5-53218, Japanese Patent No. 3949676, 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.
  • the type of the resin layer is not particularly limited.
  • epoxy resin polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine Resins, thermosetting polyphenylene oxide resins, cyanate ester resins, carboxylic acid anhydrides, polyvalent carboxylic acid anhydrides, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-
  • the epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials.
  • the epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidylamine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resin , Biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a mixture of two or more types, or a hydrogenated product
  • the phosphorus-containing epoxy resin a known epoxy resin containing phosphorus can be used.
  • the phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.
  • the epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • a compound represented by the following chemical formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ) an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.
  • the phosphorus-containing epoxy resin which is the component E obtained using the above-mentioned compound as a raw material, is a mixture of one or two compounds having the structural formula shown in any one of the following chemical formulas 3 to 5. Is preferred. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.
  • the brominated (brominated) epoxy resin a known brominated (brominated) epoxy resin can be used.
  • the brominated (brominated) epoxy resin is a brominated epoxy resin having the structural formula shown in Chemical formula 6 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule. It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.
  • maleimide resin aromatic maleimide resin, maleimide compound or polymaleimide compound
  • known maleimide resins aromatic maleimide resins, maleimide compounds or polymaleimide compounds
  • maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1, It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and a polymer obtained
  • the maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine. Polymerization adducts obtained by polymerizing and may be used. As the polyamine or aromatic polyamine, known polyamines or aromatic polyamines can be used.
  • polyamine or aromatic polyamine m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4 '
  • 1 type, or 2 or more types of well-known polyamine and / or aromatic polyamine or the above-mentioned polyamine or aromatic polyamine can be used.
  • a known phenoxy resin can be used as the phenoxy resin.
  • combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin.
  • an epoxy resin a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
  • the bisphenol known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- Bisphenol obtained as an adduct of 10-phosphophenanthrene-10-oxide) and quinones such as hydroquinone and naphthoquinone can be used.
  • the linear polymer having a crosslinkable functional group a known linear polymer having a crosslinkable functional group can be used.
  • the linear polymer having a crosslinkable functional group preferably has a functional group that contributes to the curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group.
  • the linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C. to 200 ° C.
  • Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like.
  • the resin layer may contain a crosslinking agent.
  • a known crosslinking agent can be used as the crosslinking agent.
  • a urethane-based resin can be used as the crosslinking agent.
  • a known rubber resin can be used as the rubber resin.
  • the rubbery resin is described as a concept including natural rubber and synthetic rubber.
  • the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( Acrylic ester copolymer), polybutadiene rubber, isoprene rubber and the like. Furthermore, when ensuring the heat resistance of the resin layer to be formed, it is also useful to select and use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like. Regarding these rubber resins, it is desirable to have various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin.
  • CTBN carboxy group-terminated butadiene nitrile
  • C-NBR carboxy-modified nitrile butadiene rubber
  • a known polyimide amide resin can be used as the polyamide imide resin.
  • polyimide amide resin for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride and vitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide.
  • trimellitic anhydride, diphenylmethane diisocyanate and carboxyl group-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. What is obtained can be used.
  • a known rubber-modified polyamideimide resin can be used as the rubber-modified polyamideimide resin.
  • the rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin.
  • the reaction of the polyamide-imide resin and the rubber resin is performed for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component.
  • a known polyamideimide resin can be used as the polyamideimide resin.
  • As the rubber resin a known rubber resin or the aforementioned rubber resin can be used.
  • Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, ⁇ -butyrolactone and the like are preferably used alone or in combination.
  • a known phosphazene resin can be used as the phosphazene resin.
  • the phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements.
  • the phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule.
  • a known fluororesin can be used as the fluororesin.
  • fluororesin examples include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6).
  • PTFE polytetrafluoroethylene (tetrafluoroethylene)
  • PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer (4.6).
  • a fluororesin composed of at least one thermoplastic resin selected from polysulfide and aromatic polyether and a fluororesin may be used.
  • the resin layer may contain a resin curing agent.
  • a known resin curing agent can be used as the resin curing agent.
  • resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride.
  • amines such as dicyandiamide, imidazoles and aromatic amines
  • phenols such as bisphenol A and brominated bisphenol A
  • novolaks such as phenol novolac resins and cresol novolac resins
  • acid anhydrides such as phthalic anhydride.
  • the resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
  • a specific example of the biphenyl type phenol resin is shown in Chemical Formula 8.
  • imidazoles can be used, such as 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole etc. are mentioned, These can be used individually or in mixture. Of these, imidazoles having the structural formula shown in Chemical Formula 10 below are preferably used.
  • the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles function as a catalyst during curing of the epoxy resin and contribute as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.
  • amine resin curing agent known amines can be used.
  • the amine resin curing agent for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides, and these are obtained by polymerizing or condensing with epoxy resins or polyvalent carboxylic acids.
  • One or more selected from the group of amine adducts to be used may be used.
  • the resin curing agent for the amines examples include 4,4′-diaminodiphenylene sulfone, 3,3′-diaminodiphenylene sulfone, 4,4-diaminodiphenylel, 2,2-bis [4 It is preferable to use at least one of-(4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenoxy) phenyl] sulfone.
  • the resin layer may contain a curing accelerator.
  • a known curing accelerator can be used as the curing accelerator.
  • tertiary amine, imidazole, urea curing accelerator and the like can be used.
  • the resin layer may include a reaction catalyst.
  • a known reaction catalyst can be used as the reaction catalyst. For example, finely pulverized silica or antimony trioxide can be used as a reaction catalyst.
  • the anhydride of the polyvalent carboxylic acid is preferably a component that contributes as a curing agent for the epoxy resin.
  • the anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.
  • the thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.
  • the polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group.
  • the polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.
  • the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin.
  • the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid.
  • aromatic diamine As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used.
  • dicarboxylic acid phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
  • rubber resin to be reacted with the aromatic polyamide resin a known rubber resin or the aforementioned rubber resin can be used. This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.
  • the resin layer is a cured resin layer (the “cured resin layer” means a cured resin layer) and a half in order from the copper foil side (that is, the ultrathin copper layer side of the copper foil with carrier).
  • the resin layer which formed the cured resin layer sequentially may be sufficient.
  • the cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.
  • a semi-cured resin layer having a coefficient of thermal expansion after curing of 0 ppm / ° C. to 50 ppm / ° C. may be provided on the cured resin layer.
  • the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less.
  • the cured resin layer may have a glass transition temperature of 300 ° C. or higher.
  • the semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin.
  • the resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group.
  • epoxy resin a known epoxy resin or an epoxy resin described in this specification can be used.
  • maleimide resins aromatic maleimide resins, linear polymers having crosslinkable functional groups, known maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, or the aforementioned maleimide resins.
  • An aromatic maleimide resin or a linear polymer having a crosslinkable functional group can be used.
  • the said cured resin layer is a polymeric polymer layer which has hardened
  • the polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process.
  • the polymer polymer layer is preferably made of one or a mixture of two or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin.
  • the thickness of the polymer layer is preferably 3 ⁇ m to 10 ⁇ m.
  • the said high molecular polymer layer contains any 1 type, or 2 or more types of an epoxy resin, a maleimide-type resin, a phenol resin, and a urethane resin.
  • the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 ⁇ m to 50 ⁇ m.
  • the epoxy resin composition preferably contains the following components A to E.
  • Component A An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
  • B component High heat-resistant epoxy resin.
  • Component C Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a mixture of these.
  • Component D A rubber-modified polyamideimide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
  • E component Resin curing agent.
  • the B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg.
  • the “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
  • the phosphorus-containing epoxy resin of component C the aforementioned phosphorus-containing epoxy resin can be used.
  • the phosphazene resin described above can be used as the C component phosphazene resin.
  • the rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D.
  • the resin curing agent described above can be used as the E component resin curing agent.
  • a solvent is added to the resin composition shown above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board.
  • the resin varnish is prepared by adding a solvent to the resin composition described above so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard.
  • a semi-cured resin film in the range of 5% to 35% can be formed.
  • the solvent a known solvent or the aforementioned solvent can be used.
  • the resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side
  • the curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed.
  • the first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide.
  • the second thermosetting resin layer may be formed using an epoxy resin component.
  • the thickness t1 ( ⁇ m) of the first thermosetting resin layer is Rz ( ⁇ m) of the roughened surface roughness of the copper foil with carrier, and the thickness of the second thermosetting resin layer is t2 ( ⁇ m). Then, t1 is preferably a thickness that satisfies the condition of Rz ⁇ t1 ⁇ t2.
  • the resin layer may be a prepreg in which a skeleton material is impregnated with a resin.
  • the resin impregnated in the skeleton material is preferably a thermosetting resin.
  • the prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.
  • the skeleton material may include aramid fibers, glass fibers, or wholly aromatic polyester fibers.
  • the skeleton material is preferably an aramid fiber, a glass fiber, or a nonwoven fabric or woven fabric of wholly aromatic polyester fibers.
  • the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher.
  • the wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer includes 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid.
  • the main component is an acid polymer.
  • this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.
  • the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric.
  • a known amino-based or epoxy-based silane coupling agent or the aforementioned silane coupling agent can be used depending on the purpose of use.
  • the prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 ⁇ m or less, or a skeleton material made of glass cloth having a nominal thickness of 30 ⁇ m or less. Also good.
  • the resin layer may include a dielectric (dielectric filler).
  • a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit.
  • the dielectric (dielectric filler) include BaTiO 3 , SrTiO 3 , Pb (Zr—Ti) O 3 (common name PZT), PbLaTiO 3 ⁇ PbLaZrO (common name PLZT), SrBi 2 Ta 2 O 9 (common name SBT), and the like.
  • a composite oxide dielectric powder having a perovskite structure is used.
  • the dielectric (dielectric filler) may be powdery.
  • the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 ⁇ m to 3.0 ⁇ m, preferably 0.02 ⁇ m to 2.0 ⁇ m. Must be in range.
  • the particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state.
  • the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA.
  • the image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using an IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.
  • the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric.
  • the copper foil with a carrier which has can be provided.
  • Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish).
  • MEK methyl ethyl ketone
  • cyclopentanone dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene
  • methanol ethanol
  • propylene glycol monomethyl ether Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve
  • the ultrathin copper layer or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling agent layer, for example, it is applied by a roll coater method or the like, and then heat-dried as necessary. Removing the solvent Te and to B-stage.
  • 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 resin layer composition is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%.
  • the resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard. In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples were sampled from a resin-coated copper foil with a resin thickness of 55 ⁇ m.
  • 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 120 ⁇ 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 greater than 120 ⁇ m, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
  • the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, More preferably, the thickness is 1 ⁇ m to 5 ⁇ m in order to reduce the thickness of the multilayer printed wiring board.
  • the thickness of the resin layer is preferably 0.1 to 50 ⁇ m, more preferably 0.5 ⁇ m to 25 ⁇ m, and more preferably 1.0 ⁇ m to 15 ⁇ m. preferable.
  • the total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 ⁇ m to 120 ⁇ m, preferably 5 ⁇ m to 120 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, and 10 ⁇ m to 60 ⁇ m. Are more preferred.
  • the thickness of the cured resin layer is preferably 2 ⁇ m to 30 ⁇ m, preferably 3 ⁇ m to 30 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the thickness of the semi-cured resin layer is preferably 3 ⁇ m to 55 ⁇ m, more preferably 7 ⁇ m to 55 ⁇ m, and even more preferably 15 to 115 ⁇ m. If the total resin layer thickness exceeds 120 ⁇ m, it may be difficult to produce a thin multilayer printed wiring board.
  • the total resin layer thickness is less than 5 ⁇ m, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 ⁇ m, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 ⁇ m, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.
  • the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, in order to improve the adhesion between the resin layer and the copper foil with carrier, a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
  • a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
  • the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points
  • 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.
  • the carrier-attached copper foil of the present invention is produced.
  • 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.
  • a carrier is peeled off after being bonded to an insulating substrate such as a base epoxy resin, a glass cloth / glass nonwoven fabric composite base epoxy resin and a glass cloth base epoxy resin, a polyester film, a polyimide film, etc.
  • the peeled portion is mainly the interface between the intermediate layer and the ultrathin copper layer.
  • the ultrathin copper layer bonded to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board, a printed circuit board, and a printed wiring board can be manufactured.
  • a printed wiring board, a printed circuit board, and a printed wiring board are manufactured according to a conventional method (for example, a subtractive method or a modified semi-additive method (MSAP)). Can do.
  • the printed wiring board of the present invention has an insulating resin plate and a copper circuit provided on the insulating resin plate, and the copper circuit is provided on the copper layer and the copper layer sequentially from the insulating resin plate side.
  • Ni layer including a copper plating layer provided on the Ni layer, the adhesion amount of Ni in the Ni layer is 5 ⁇ g / dm 2 or more and 300 ⁇ g / dm 2 or less, the circuit width of the copper circuit is less than 20 ⁇ m, and adjacent The width of the space between the copper circuits is less than 20 ⁇ m.
  • the circuit width of a copper circuit is 17 micrometers or less, and the width of the space between adjacent copper circuits is 17 micrometers or less.
  • the circuit width of a copper circuit is 15 micrometers or less, and the width of the space between adjacent copper circuits is 15 micrometers or less. Moreover, it is more preferable that the circuit width of the copper circuit is 10 ⁇ m or less, and the width of the space between adjacent copper circuits is 10 ⁇ m or less. It is even more preferable that the circuit width of the copper circuit is 5 ⁇ m or less and the width of the space between adjacent copper circuits is 5 ⁇ m or less. Although it is not necessary to provide a lower limit of the circuit width, for example, the circuit width of the copper circuit is 3 ⁇ m or more, and the width of the space between adjacent copper circuits is 3 ⁇ m or more.
  • the circuit width of the copper circuit is 5 ⁇ m or more.
  • the width of the space between adjacent copper circuits is 5 ⁇ m or more, for example, the circuit width of the copper circuit is 7 ⁇ m or more, and the width of the space between adjacent copper circuits is 7 ⁇ m or more, for example, the circuit width of the copper circuit Is 9 ⁇ m or more, and the width of the space between adjacent copper circuits is 9 ⁇ m or more.
  • the above-mentioned copper plating layer can be formed on well-known conditions, such as the conditions of the plating solution used in order to form an ultra-thin copper layer.
  • the printed wiring board of the present invention has an insulating resin plate and a copper circuit provided on the insulating resin plate, and the copper circuit is provided on the copper layer and the copper layer in this order from the insulating resin plate side.
  • the circuit width of the copper circuit may be less than 20 ⁇ m, and the width of the space between the copper circuit and the copper circuit may be less than 20 ⁇ m.
  • the circuit width of the copper circuit is preferably 17 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 17 ⁇ m or less.
  • the circuit width of the copper circuit is preferably 15 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 15 ⁇ m or less.
  • the circuit width of the copper circuit is 10 ⁇ m or less, and the width of the space between adjacent copper circuits is 10 ⁇ m or less. It is even more preferable that the circuit width of the copper circuit is 5 ⁇ m or less and the width of the space between adjacent copper circuits is 5 ⁇ m or less. Although it is not necessary to provide a lower limit of the circuit width, for example, the circuit width of the copper circuit is 3 ⁇ m or more, and the width of the space between adjacent copper circuits is 3 ⁇ m or more. For example, the circuit width of the copper circuit is 5 ⁇ m or more.
  • the width of the space between adjacent copper circuits is 5 ⁇ m or more, for example, the circuit width of the copper circuit is 7 ⁇ m or more, and the width of the space between adjacent copper circuits is 7 ⁇ m or more, for example, the circuit width of the copper circuit Is 9 ⁇ m or more, and the width of the space between adjacent copper circuits is 9 ⁇ m or more.
  • the printed wiring board of the present invention has an insulating resin plate and a copper circuit provided on the insulating resin plate, and the copper circuit is provided on the copper layer and the copper layer in this order from the insulating resin plate side.
  • the amount of Ni deposited on the Ni layer is 5 ⁇ g / dm 2 or more and 300 ⁇ g / dm 2 or less, the circuit width of the copper circuit is less than 20 ⁇ m, and the width of the space between adjacent copper circuits is 20 ⁇ m It may be less.
  • the circuit width of the copper circuit is preferably 17 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 17 ⁇ m or less.
  • the circuit width of the copper circuit is preferably 15 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 15 ⁇ m or less.
  • the circuit width of the copper circuit is preferably 10 ⁇ m or less, and the width of the space between adjacent copper circuits is more preferably 10 ⁇ m or less. It is even more preferable that the circuit width of the copper circuit is 5 ⁇ m or less and the width of the space between adjacent copper circuits is 5 ⁇ m or less. Although it is not necessary to provide a lower limit of the circuit width, for example, the circuit width of the copper circuit is 3 ⁇ m or more, and the width of the space between adjacent copper circuits is 3 ⁇ m or more. For example, the circuit width of the copper circuit is 5 ⁇ m or more.
  • the width of the space between adjacent copper circuits is 5 ⁇ m or more, for example, the circuit width of the copper circuit is 7 ⁇ m or more, and the width of the space between adjacent copper circuits is 7 ⁇ m or more, for example, the circuit width of the copper circuit Is 9 ⁇ m or more, and the width of the space between adjacent copper circuits is 9 ⁇ m or more.
  • the printed wiring board of this invention has an insulating resin board and the copper circuit provided on the insulating resin board, and the circuit width of a copper circuit is less than 20 micrometers, Between a copper circuit and a copper circuit The width of the space may be less than 20 ⁇ m.
  • the circuit width of the copper circuit is preferably 17 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 17 ⁇ m or less.
  • the circuit width of the copper circuit is preferably 15 ⁇ m or less, and the width of the space between adjacent copper circuits is preferably 15 ⁇ m or less.
  • the circuit width of the copper circuit is 3 ⁇ m or more, and the width of the space between adjacent copper circuits is 3 ⁇ m or more.
  • the circuit width of the copper circuit is 5 ⁇ m or more.
  • the width of the space between adjacent copper circuits is 5 ⁇ m or more, for example, the circuit width of the copper circuit is 7 ⁇ m or more, and the width of the space between adjacent copper circuits is 7 ⁇ m or more, for example, the circuit width of the copper circuit Is 9 ⁇ m or more, and the width of the space between adjacent copper circuits is 9 ⁇ m or more.
  • the printed circuit board of the present invention, the printed circuit board, and the copper circuit of the printed circuit board are attached to the insulating resin plate from the ultrathin copper layer side by thermocompression bonding, and peeled off the copper foil carrier. It can be formed by etching the thin copper layer portion.
  • the insulating resin board used here is not particularly limited as long as it has characteristics applicable to a printed wiring board.
  • a paper base phenolic resin, a paper base epoxy resin, a synthetic fiber cloth base for rigid PWB are used.
  • Material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin, glass cloth base material epoxy resin, etc. can be used, polyester film or polyimide film etc. can be used for FPC it can.
  • the printed wiring board and the printed board thus produced can be mounted on various electronic components that require high-density mounting of the mounted components.
  • 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; 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. 1A 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 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. 3H, and these circuits may be formed using 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 copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1).
  • the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled.
  • the color difference ⁇ E * ab based on JIS Z8730 on the surface of 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 is 45 or more.
  • the color differences ⁇ L, ⁇ a, and ⁇ b are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ⁇ L: black and white, ⁇ a: reddish green, ⁇ b: yellow blue.
  • ⁇ E * ab is expressed by the following formula using these color differences.
  • the above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
  • the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer.
  • the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm 2 ) and the processing time can be shortened (for example, 0.1 to 1.3 seconds).
  • Ni alloy plating (for example, Ni—W alloy plating, Ni—Co—P alloy plating, Ni—Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm 2 ), and the processing time can be set long (20 to 40 seconds).
  • the color difference ⁇ E * ab based on JIS Z8730 on the ultrathin copper layer surface is 45 or more, for example, when forming a circuit on the ultrathin copper layer surface of the copper foil with carrier, the contrast between the ultrathin copper layer and the circuit As a result, visibility is improved and circuit alignment can be performed with high accuracy.
  • the color difference ⁇ E * ab based on JIS Z8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.
  • the contrast with the circuit plating becomes clear. , Visibility becomes good. Accordingly, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 1-C, the circuit plating can be accurately formed at a predetermined position. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. At this time, 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. Also, as shown in FIGS. 4-J and 4-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 for the first layer may have a substrate or a resin layer on the surface of the copper foil carrier of the carrier-attached copper foil.
  • substrate or resin layer since the copper foil with a carrier used for the first layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves.
  • the substrate or the resin layer is not particularly limited as long as it has an effect of supporting the carrier-attached copper foil used in the first layer.
  • the current density should be set low and / or the plating time should be set short, and / or each in the plating solution
  • the element concentration was lowered.
  • the concentration of the organic substance in the liquid used for the treatment of providing the organic layer on the carrier is increased and / or the organic layer
  • the processing time for providing the substrate on the carrier was lengthened.
  • the balance of the liquid composition such as a plating solution is water.
  • Nickel plating Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, luster Agents: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm (PH) 4-6 (Liquid temperature) 55-65 ° C (Current density) 1 to 11 A / dm 2 (Energization time) 1 to 20 seconds
  • Ni-Zn Nickel zinc alloy plating
  • zinc in the form of zinc sulfate (ZnSO 4 ) is added to the nickel plating solution, and the zinc concentration is in the range of 0.05 to 5 g / L. In this way, a nickel zinc alloy plating was formed.
  • Cr Chrome plating (Liquid composition) CrO 3 : 200 to 400 g / L, H 2 SO 4 : 1.5 to 4 g / L (PH) 1-4 (Liquid temperature) 45-60 ° C (Current density) 10 to 40 A / dm 2 (Energization time) 1 to 20 seconds
  • Chroxate Electrolytic chromate treatment (Liquid composition) Potassium dichromate: 1-10 g / L, Zinc: 0 g / L (PH) 7-10 (Liquid temperature) 40-60 ° C (Current density) 0.1 to 2.6 A / dm 2 (Coulomb amount) 0.5 to 90 As / dm 2 (Energization time) 1-30 seconds
  • Zn-chromate zinc chromate treatment
  • zinc in the form of zinc sulfate (ZnSO 4 ) is added to the solution, and the zinc concentration is adjusted in the range of 0.05 to 5 g / L.
  • the zinc chromate treatment was performed.
  • Ni—Mo nickel molybdenum alloy plating (Liquid composition) Ni sulfate hexahydrate: 50 g / dm 3 , sodium molybdate dihydrate: 60 g / dm 3 , sodium citrate: 90 g / dm 3 (Liquid temperature) 30 ° C (Current density) 1 ⁇ 4A / dm 2 (Energization time) 3 to 25 seconds
  • Organic substance layer formation treatment An aqueous solution containing carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L and having a liquid temperature of 40 ° C. and pH 5 was sprayed by spraying for 20 to 120 seconds.
  • CBTA carboxybenzotriazole
  • Ni oxide layer forming treatment Nickel oxide layer forming treatment
  • a Ni layer is formed by Ni plating under the following conditions, and then the Ni layer is subjected to an anodic treatment under the following conditions. Was oxidized to form a nickel oxide layer.
  • Nickel sulfate 240 g / L
  • Nickel chloride 45 g / L
  • Boric acid 30 g / L (PH) 5 (Liquid temperature) 40 ° C (Current density) 10 A / dm 2 (Electrolysis time) 20 seconds
  • -Anodic treatment conditions Sulfuric acid solution: 0.5 mol / L (Liquid temperature) 25 ° C (Current density) 10 A / dm 2 (Processing time) 30 seconds
  • Ni-Co Nickel cobalt alloy plating (Liquid composition) Co: 1 to 2 g / L, Ni: 30 to 70 g / L (PH) 1.5 to 3.5 (Liquid temperature) 30 ⁇ 80 °C (Current density) 1.0-20.0 A / dm 2 (Energization time) 0.5-4 seconds
  • Ni-P Nickel phosphorus alloy plating (Liquid composition) Ni: 30 to 70 g / L, P: 0.2 to 1.2 g / L (PH) 1.5 to 2.5 (Liquid temperature) 30-40 ° C (Current density) 1.0-10.0 A / dm 2 (Energization time) 0.5-30 seconds
  • Ni-Cu-Co Nickel copper cobalt alloy plating (Liquid composition) Ni: 30 to 70 g / L, Cu: 1 to 2 g / L, Co: 1 to 2 g / L (PH) 1-4 (Liquid temperature) 30-50 ° C (Current density) 1.0-10.0 A / dm 2 (Energization time) 0.5-30 seconds
  • Ni-Fe Nickel iron alloy dry plating by sputtering
  • a nickel iron alloy layer was formed using a sputtering target having a composition of Ni: 99 mass% and Fe: 1 mass%.
  • Ni—Ti Nickel-titanium alloy dry plating by sputtering
  • a nickel-titanium alloy layer was formed using a sputtering target having a composition of Ni: 99 mass% and Ti: 1 mass%.
  • Ni-Al Nickel aluminum alloy dry plating by sputtering
  • a nickel aluminum alloy layer was formed using a sputtering target having a composition of Ni: 99 mass% and Al: 1 mass%.
  • 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 produce a copper foil with a carrier.
  • a sample was dissolved in a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass), and was subjected to atomic absorption spectrometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. Measurement was performed by quantitative analysis.
  • the said nickel, zinc, chromium, molybdenum adhesion amount was measured as follows. First, after peeling an ultrathin copper layer from a copper foil with a carrier, only the vicinity of the surface on the intermediate layer side of the ultrathin copper layer is dissolved (only 0.5 ⁇ m thickness from the surface is dissolved. As shown in FIG.
  • Example 2 in Examples 1 to 8, 14 to 28 and Comparative Examples 1 to 4 and 9 to 13 in which the thickness of the ultrathin copper layer is 5 ⁇ m, 10% of the thickness of the ultrathin copper layer is dissolved.
  • Example 10 in which the thickness of the ultrathin copper layer is 4 ⁇ m and Comparative Example 5, 12.5% of the thickness of the ultrathin copper layer is dissolved
  • Example 9 in which the thickness of the ultrathin copper layer is 3 ⁇ m.
  • 11 and Comparative Example 6 dissolve 16.7% of the thickness of the ultrathin copper layer, and for Example 12 and Comparative Example 7 where the thickness of the ultrathin copper layer is 2 ⁇ m
  • Example 13 and Comparative Example 8 in which the thickness of the ultrathin copper layer is 1 ⁇ m, the thickness is very thin.
  • the thickness of the ultrathin copper layer when the unevenness of the ultrathin copper layer is large and the thickness of the ultrathin copper layer is 1.5 ⁇ m or less, the thickness of 0.5 ⁇ m was dissolved from the surface on the intermediate layer side of the ultrathin copper layer. Sometimes, the roughening component on the surface of the ultrathin copper layer is also dissolved. Therefore, in such a case, 30% of the thickness of the ultrathin copper layer on the intermediate layer side is dissolved.
  • the adhesion amount of nickel, zinc, and chromium can be measured by the above-described method.
  • the “metal adhesion amount” refers to the metal adhesion amount (mass) per sample unit area (1 dm 2 ).
  • ⁇ Thickness of organic material in the intermediate layer> After peeling the ultrathin copper layer of the carrier-attached copper foil from the carrier, XPS measurement was performed on the surface of the exposed ultrathin copper layer on the intermediate layer side and the surface of the exposed carrier on the intermediate layer side to create a depth profile.
  • the depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier.
  • the resulting depth was defined as B (nm), and the sum of A and B was defined as the thickness (nm) of the organic substance in the intermediate layer.
  • the measurement interval of the atomic concentration of the metal in the depth direction is preferably 0.18 to 0.30 nm (in terms of SiO 2 ).
  • the atomic concentration of the metal in the depth direction was measured at intervals of 0.28 nm (in terms of SiO 2 ) (measured every 0.1 minutes by sputtering time).
  • the depth profile of the carbon concentration by the above XPS measurement is obtained from both ends in the long side direction of each sample sheet on the surface on the intermediate layer side of the exposed ultrathin copper layer and the surface on the intermediate layer side of the exposed carrier.
  • FIG. 6 shows three measurement points on the surface of the exposed ultrathin copper layer on the intermediate layer side and three points on the surface of the exposed carrier on the intermediate layer side.
  • the depth A (nm) at which the carbon concentration first became 3 at% or less from the surface and the depth B (nm) at which the carbon concentration first became 3 at% or less from the surface on the intermediate layer side of the carrier were calculated.
  • the sum of the arithmetic average value of A (nm) and the arithmetic average value of B (nm) was defined as the thickness (nm) of the organic substance in the intermediate layer.
  • XPS operating conditions are shown below.
  • ⁇ Device XPS measuring device (ULVAC-PHI, Model 5600MC) ⁇ Achieving vacuum: 3.8 ⁇ 10 ⁇ 7 Pa
  • X-ray Monochromatic AlK ⁇ or non-monochromatic MgK ⁇ , X-ray output 300 W, detection area 800 ⁇ m ⁇ , angle between sample and detector 45 °
  • Ion beam ion species Ar + , acceleration voltage 3 kV, sweep area 3 mm ⁇ 3 mm, sputtering rate 2.8 nm / min (in terms of SiO 2 )
  • XPS means X-ray photoelectron spectroscopy.
  • an XPS measuring device model 5600MC or an equivalent measuring device manufactured and sold by ULVAC-PHI
  • ULVAC-PHI an equivalent measuring device manufactured and sold by ULVAC-PHI
  • Other XPS measurements by setting the measurement interval for each element concentration in the depth direction to 0.10 to 0.30 nm (SiO 2 equivalent) and the sputtering rate to 1.0 to 3.0 nm / min (SiO 2 equivalent)
  • An apparatus may be used.
  • ⁇ Ni adhesion amount on ultrathin copper layer surface The copper foil with a carrier was bonded to a BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on the ultrathin copper layer side and heat-pressed at 220 ° C. for 2 hours. Thereafter, the ultrathin copper layer was peeled off from the copper foil carrier in accordance with JIS C 6471 (Method A). Subsequently, the adhesion amount of Ni on the surface of the intermediate layer side of the ultrathin copper layer was measured by dissolving the sample with nitric acid having a concentration of 20% by mass and using an ICP emission spectroscopic analyzer (model: SPS3100) manufactured by SII.
  • BT resin triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Example 9 and the comparative example 6 whose thickness of an ultra-thin copper layer is 3 micrometer, 16.7% of the thickness of an ultra-thin copper layer melt
  • Example 12 and Comparative Example 7 25% of the thickness of the ultrathin copper layer is dissolved, and the thickness of the ultrathin copper layer is 1 ⁇ m. That for Example 13 and Comparative Example 8, in.) To 50% dissolution of the thickness of the ultra-thin copper layer, it is possible to measure the deposition amount of the Ni middle layer side of the surface of the ultrathin copper layer.
  • the thickness of the ultrathin copper layer when the unevenness of the ultrathin copper layer is large and the thickness of the ultrathin copper layer is 1.5 ⁇ m or less, the thickness of 0.5 ⁇ m was dissolved from the surface on the intermediate layer side of the ultrathin copper layer. Sometimes, the roughening component on the surface of the ultrathin copper layer is also dissolved. Therefore, in such a case, 30% of the thickness of the ultrathin copper layer on the intermediate layer side is dissolved.
  • 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. 5 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.
  • ⁇ Pinhole> The surface of the copper foil with carrier on the ultrathin copper layer side was attached to BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and heat-pressed at 220 ° C. for 2 hours. Next, while holding the carrier-side copper foil sample with your hand up and taking care not to tear the ultrathin copper layer halfway without forcibly peeling it off, remove the carrier from the ultrathin copper layer. Was peeled off by hand. Subsequently, the number of pinholes was visually measured on the surface of an ultrathin copper layer on a BT resin (triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a consumer photographic backlight as a light source. did.
  • BT resin triazine-bismaleimide resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.

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  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Electroplating Methods And Accessories (AREA)
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Abstract

L'invention concerne une feuille de cuivre dotée d'un support. Ladite feuille de cuivre avec support rend possible la formation d'un câblage microscopique présentant une L/S inférieure à 20µm/20µm, par ex. 15µm/15µm. Cette feuille de cuivre avec support comprend, dans cet ordre: un support de feuille de cuivre, une couche intermédiaire et une couche de cuivre ultra-mince. La couche intermédiaire contient du nickel. Si cette feuille de cuivre avec support est chauffée pendant deux heures à 220°C et si la couche de cuivre ultra-mince est ensuite séparée selon JIS C 6471, la quantité de nickel sur la surface de la couche de cuivre ultra-mince côté couche intermédiaire est comprise entre 5 et 300 µg/dm2 inclus.
PCT/JP2013/082283 2012-11-30 2013-11-29 Feuille de cuivre avec support Ceased WO2014084385A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014200106A1 (fr) * 2013-06-13 2014-12-18 Jx日鉱日石金属株式会社 Feuille de cuivre avec support, stratifié plaqué de cuivre, carte imprimée, dispositif électronique et procédé de production de carte imprimée
JP2016050364A (ja) * 2014-08-29 2016-04-11 Ｊｘ金属株式会社 キャリア付銅箔、銅張積層板、プリント配線板、電子機器、積層体、キャリア付銅箔の製造方法、銅張積層板の製造方法及びプリント配線板の製造方法
JP2016190323A (ja) * 2015-03-30 2016-11-10 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板、電子機器及びプリント配線板の製造方法
JP7777987B2 (ja) 2020-02-04 2025-12-01 三井金属株式会社 キャリア付金属箔

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6854114B2 (ja) * 2016-01-04 2021-04-07 Ｊｘ金属株式会社 表面処理銅箔
US10383222B2 (en) 2016-01-04 2019-08-13 Jx Nippon Mining & Metals Corporation Surface-treated copper foil
CN113386417A (zh) * 2021-07-08 2021-09-14 江西柔顺科技有限公司 一种覆铜板及其制备方法
CN119013437A (zh) * 2022-11-28 2024-11-22 福田金属箔粉工业株式会社 表面处理铜箔及使用了该表面处理铜箔的覆铜层压板以及印刷配线板
WO2025070175A1 (fr) * 2023-09-28 2025-04-03 三井金属鉱業株式会社 Feuille de cuivre avec support, stratifié cuivré, et carte de circuit imprimé
JP7789269B2 (ja) * 2023-09-28 2025-12-19 三井金属株式会社 キャリア付銅箔、銅張積層板及びプリント配線板

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003094553A (ja) * 2001-09-20 2003-04-03 Nippon Denkai Kk 複合銅箔及びその製造方法
WO2006064965A1 (fr) * 2004-12-15 2006-06-22 Ibiden Co., Ltd. Carte a circuit imprime
JP2007007937A (ja) * 2005-06-29 2007-01-18 Furukawa Circuit Foil Kk キャリア付き極薄銅箔、ポリイミド系フレキシブル銅張積層板、及びポリイミド系フレキシブルプリント配線板
CN101080956A (zh) * 2004-12-15 2007-11-28 揖斐电株式会社 印刷电路板
JP2010006071A (ja) * 2009-08-21 2010-01-14 Furukawa Electric Co Ltd:The 表面処理銅箔、キャリア付き極薄銅箔、フレキシブル銅張積層板及びポリイミド系フレキシブルプリント配線板

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4672907B2 (ja) * 2001-06-04 2011-04-20 Ｊｘ日鉱日石金属株式会社 銅又は銅合金の支持体を備えた複合銅箔及び該複合銅箔を使用したプリント基板
JP3854207B2 (ja) * 2002-09-06 2006-12-06 日鉱金属株式会社 銅又は銅合金の支持体を備えた複合銅箔及び該複合銅箔を使用したプリント基板
JP4829647B2 (ja) * 2006-03-10 2011-12-07 三菱瓦斯化学株式会社 プリント配線板及びその製造方法
KR101318871B1 (ko) * 2008-07-22 2013-10-17 후루카와 덴키 고교 가부시키가이샤 표면 처리 동박 및 동장 적층판
JP5165773B2 (ja) * 2011-02-10 2013-03-21 フリージア・マクロス株式会社 キャリヤー付金属箔及びこれを用いた積層基板の製造方法
WO2012132578A1 (fr) * 2011-03-29 2012-10-04 Jx日鉱日石金属株式会社 Feuille de cuivre dotée d'un support de cuivre, procédé de production de cette dernière, feuille de cuivre pour un circuit électronique, procédé de production de cette dernière et procédé de formation d'un circuit électronique
WO2012132572A1 (fr) * 2011-03-30 2012-10-04 Jx日鉱日石金属株式会社 Feuille de cuivre avec support de cuivre, procédé pour produire ladite feuille de cuivre, feuille de cuivre pour circuit électronique, procédé pour produire ladite feuille de cuivre, et procédé pour former un circuit électronique

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003094553A (ja) * 2001-09-20 2003-04-03 Nippon Denkai Kk 複合銅箔及びその製造方法
WO2006064965A1 (fr) * 2004-12-15 2006-06-22 Ibiden Co., Ltd. Carte a circuit imprime
JP2007142348A (ja) * 2004-12-15 2007-06-07 Ibiden Co Ltd プリント配線板
KR20070086941A (ko) * 2004-12-15 2007-08-27 이비덴 가부시키가이샤 프린트 배선판
EP1835790A1 (fr) * 2004-12-15 2007-09-19 Ibiden Co., Ltd. Carte a circuit imprime
CN101080956A (zh) * 2004-12-15 2007-11-28 揖斐电株式会社 印刷电路板
US20070273047A1 (en) * 2004-12-15 2007-11-29 Ibiden Co., Ltd Printed wiring board and manufacturing method thereof
CN101646301A (zh) * 2004-12-15 2010-02-10 揖斐电株式会社 印刷电路板
US20100252308A1 (en) * 2004-12-15 2010-10-07 Ibiden Co., Ltd. Printed wiring board and manufacturing method thereof
CN102170752A (zh) * 2004-12-15 2011-08-31 揖斐电株式会社 印刷电路板
JP2007007937A (ja) * 2005-06-29 2007-01-18 Furukawa Circuit Foil Kk キャリア付き極薄銅箔、ポリイミド系フレキシブル銅張積層板、及びポリイミド系フレキシブルプリント配線板
JP2010006071A (ja) * 2009-08-21 2010-01-14 Furukawa Electric Co Ltd:The 表面処理銅箔、キャリア付き極薄銅箔、フレキシブル銅張積層板及びポリイミド系フレキシブルプリント配線板

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014200106A1 (fr) * 2013-06-13 2014-12-18 Jx日鉱日石金属株式会社 Feuille de cuivre avec support, stratifié plaqué de cuivre, carte imprimée, dispositif électronique et procédé de production de carte imprimée
JP5651811B1 (ja) * 2013-06-13 2015-01-14 Jx日鉱日石金属株式会社 キャリア付銅箔、銅張積層板、プリント配線板、電子機器、及び、プリント配線板の製造方法
JP2016050364A (ja) * 2014-08-29 2016-04-11 Ｊｘ金属株式会社 キャリア付銅箔、銅張積層板、プリント配線板、電子機器、積層体、キャリア付銅箔の製造方法、銅張積層板の製造方法及びプリント配線板の製造方法
JP2016190323A (ja) * 2015-03-30 2016-11-10 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板、電子機器及びプリント配線板の製造方法
JP7777987B2 (ja) 2020-02-04 2025-12-01 三井金属株式会社 キャリア付金属箔

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