WO2022202539A1 - キャリア付銅箔、銅張積層板及びプリント配線板 - Google Patents

キャリア付銅箔、銅張積層板及びプリント配線板 Download PDF

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WO2022202539A1
WO2022202539A1 PCT/JP2022/011923 JP2022011923W WO2022202539A1 WO 2022202539 A1 WO2022202539 A1 WO 2022202539A1 JP 2022011923 W JP2022011923 W JP 2022011923W WO 2022202539 A1 WO2022202539 A1 WO 2022202539A1
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Prior art keywords
copper foil
carrier
ultra
layer
thin copper
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PCT/JP2022/011923
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English (en)
French (fr)
Japanese (ja)
Inventor
眞 細川
慎哉 平岡
美智 溝口
哲也 金子
大輔 中島
光由 松田
Original Assignee
三井金属鉱業株式会社
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Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to JP2023509067A priority Critical patent/JPWO2022202539A1/ja
Priority to CN202280018893.5A priority patent/CN116964252A/zh
Priority to KR1020237030062A priority patent/KR20230159393A/ko
Publication of WO2022202539A1 publication Critical patent/WO2022202539A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/12—Electroforming by electrophoresis
    • C25D1/14—Electroforming by electrophoresis of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • 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
    • C25D5/10—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
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D5/16—Electroplating with layers of varying thickness
    • 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
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • 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
    • 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

Definitions

  • the present invention relates to a carrier-attached copper foil, a copper-clad laminate, and a printed wiring board.
  • via holes are formed by laser processing in a laminate in which an inner layer circuit board and an outer layer copper foil are laminated via an insulating layer, and the layers are connected by performing filling plating. method is widely used.
  • direct laser drilling is frequently used in which via holes are formed by directly irradiating an ultrathin copper foil (outer layer copper foil) with a laser (for example, Patent Document 1 (Japanese Patent Laid-Open No. 11-346060 Gazette)).
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2017-133105
  • Patent Document 3 Patent No.
  • the thickness accuracy of the ultra-thin copper layer measured by the weight thickness method is 3.0% or less
  • the A copper foil with a carrier is disclosed in which the average crystal grain size is controlled to 0.5 ⁇ m or less when a cross-sectional image of the thin copper layer is observed by FIB-SIM.
  • JP-A-11-346060 Japanese Patent Application Laid-Open No. 2017-133105 Japanese Patent No. 6158573
  • ultra-thin copper foils are required to have further improved laser processability (via processability).
  • the laser processability of ultra-thin copper foils in conventional carrier-attached copper foils is not necessarily sufficient, and there is still room for improvement.
  • the present inventors have recently found that in a carrier-attached copper foil comprising a carrier, a release layer, and an ultra-thin copper foil in this order, the planar size of the copper crystal grains present on the release layer side surface of the ultra-thin copper foil is specified. It has been found that excellent laser processability can be achieved by controlling it within the range of .
  • an object of the present invention is to provide a carrier-attached copper foil capable of realizing excellent laser processability.
  • a carrier-attached copper foil comprising a carrier, a release layer, and an ultra-thin copper foil in this order,
  • EBSD electron beam backscatter diffraction method
  • a carrier-attached copper foil comprising a carrier, a release layer, and an ultra-thin copper foil in this order, and a resin layer provided on the surface of the ultra-thin copper foil of the carrier-attached copper foil.
  • a copper clad laminate comprising A copper-clad laminate in which the plane size S1 of the copper crystal grains present on the release layer side surface of the ultrathin copper foil is 50 nm or more and 600 nm or less, as measured by an electron beam backscatter diffraction method (EBSD). provided.
  • EBSD electron beam backscatter diffraction method
  • a printed wiring board comprising the copper foil with carrier.
  • a method for manufacturing a printed wiring board characterized by manufacturing a printed wiring board using the copper foil with a carrier.
  • FIG. 1 is a schematic cross-sectional view of a laminate produced using a copper foil with a carrier according to the present invention
  • FIG. It is a cross-sectional schematic diagram for demonstrating the thickness of the ultra-thin copper foil in the copper foil with a carrier by this invention.
  • Carrier-attached copper foil comprises a carrier, a release layer, and an ultra-thin copper foil in this order.
  • the planar size S1 of the copper crystal grains present on the release layer side surface of the ultrathin copper foil measured by electron beam backscatter diffraction (EBSD) is 50 nm or more and 600 nm or less.
  • FIG. 1 shows a schematic cross-sectional view of a laminate produced using the copper foil with a carrier according to the present invention.
  • a laminate 18 shown in FIG. 1 includes an ultra-thin copper foil 12 derived from the carrier-attached copper foil of the present invention, and a resin layer 16 . Roughening particles 14 are attached to the resin layer 16 side of the ultra-thin copper foil 12 as desired.
  • the surface of the laminate 18 on the ultra-thin copper foil 12 side (that is, the surface opposite to the resin layer 16) is a surface irradiated with a laser L (for example, a carbon dioxide gas laser) during laser processing, and is the surface of the carrier-attached copper foil. It corresponds to the peeling layer side surface of the thin copper foil 12 .
  • a laser L for example, a carbon dioxide gas laser
  • the surface of the ultra-thin copper foil 12 in the laminate 18 on the resin layer 16 side is the surface opposite to the release layer of the ultra-thin copper foil 12 in the carrier-attached copper foil. (If present, the surface on the roughening particle 14 side).
  • the mechanism by which the copper foil with carrier of the present invention can realize excellent laser processability is not necessarily clear, the following is an example. That is, in order to easily form vias in an ultra-thin copper foil by laser processing, it is necessary to suppress heat diffusion and raise the temperature of the ultra-thin copper foil in a short period of time. In this regard, by reducing the crystal size of the copper crystal grains that make up the ultra-thin copper foil, the number of crystal grain boundaries per unit area increases, hindering heat transfer, so the temperature of the ultra-thin copper foil tends to rise. It is considered to be. In particular, as a result of studies by the present inventors, as shown in FIG. It has been found that this is effective in performing finer via processing.
  • the carrier - attached copper foil by setting the planar size S1 of the copper crystal grains G1 present on the release layer side surface of the ultra - thin copper foil 12 within the predetermined range, excellent laser processability is realized. found that it can be done.
  • conventional carrier-attached copper foils control only the crystal size in the cross-sectional direction (z-axis direction) of the ultra-thin copper foil. It was nothing.
  • the planar size S1 of the copper crystal grains G1 existing on the release layer side surface of the ultra-thin copper foil 12 measured by EBSD is 50 nm or more and 600 nm or less, preferably 70 nm or more. It is 600 nm or less, more preferably 80 nm or more and 400 nm or less, still more preferably 80 nm or more and 300 nm or less.
  • the copper crystal grains forming the ultra-thin copper foil 12 may change in crystal size due to recrystallization caused by hot pressing during bonding to the resin.
  • the planar size S1 means the planar crystal size ( average crystal grain size) after bonding the carrier-attached copper foil to the resin.
  • the plane size S 1 is obtained by pressing a resin sheet (for example, prepreg) on the surface of the carrier-attached copper foil on the ultra-thin copper foil 12 side at 220° C. and a pressure of 4.0 MPa for 90 minutes to form the resin layer 16. After forming and removing the carrier together with the release layer to form a laminate 18 having the ultra-thin copper foil 12 and the resin layer 16 as shown in FIG. The value is obtained when the surface (that is, the surface of the ultra-thin copper foil 12 on the release layer side of the carrier-attached copper foil) is analyzed by EBSD.
  • the plane size S1 can be preferably calculated according to the procedure shown in the evaluation (8b) of Examples described later. Regarding the measurement conditions of the scanning electron microscope shown in the examples, the observation magnification, measurement area, current value and step size may be appropriately changed according to the size of the crystal grains.
  • the cross-sectional size S2 of the copper crystal grains constituting the ultra-thin copper foil 12 measured by EBSD is preferably 200 nm or more and 600 nm or less, more preferably 300 nm or more and 400 nm or less, further preferably It is 350 nm or more and 400 nm or less. That is, in order to efficiently form vias by laser processing, heat transfer in the cross-sectional direction (z-axis direction) of the ultra-thin copper foil 12 is required to some extent. On the other hand, in order not to diffuse heat more than necessary, it is preferable that the crystal size in the cross-sectional direction (z-axis direction) of the copper crystal grains is small.
  • the cross-sectional size S2 means the cross - sectional crystal size (average crystal grain size) after bonding the carrier-attached copper foil to the resin.
  • the cross - sectional size S2 is obtained by preparing the laminate 18 under the same conditions as in the calculation of the plane size S1, and then scanning the cross section in the thickness direction of the ultra - thin copper foil 12 in the laminate 18 behind the electron beam. It is a value when analyzed by the scattering diffraction method (EBSD).
  • the cross - sectional size S2 can be preferably calculated according to the procedure shown in Evaluation (8d) of Examples described later.
  • S 2 /S 1 which is the ratio of the cross-sectional size S 2 to the plane size S 1 , is preferably 0.7 or more and 6.0 or less, more preferably 1.0 or more and 5.0. 0 or less, more preferably 1.7 or more and 3.0 or less.
  • the carrier-attached copper foil is measured by EBSD , and the plane size of the copper crystal grains G3 present on the surface opposite to the peeling layer of the ultra-thin copper foil 12 (the surface on the roughening particle 14 side if present) S3 is preferably 100 nm or more and 600 nm or less, more preferably 100 nm or more and 500 nm or less, still more preferably 100 nm or more and 400 nm or less, even more preferably 100 nm or more and 300 nm or less, particularly preferably 100 nm or more and 200 nm or less, most preferably 100 nm. 150 nm or less.
  • the crystal grains of the ultra-thin copper foil 12 tend to increase as the thickness increases, it is desired that the crystal grains do not become coarser than necessary.
  • the surface of the ultra-thin copper foil 12 on the resin layer 16 side (that is, the surface opposite to the laser L irradiation surface) is the peeling layer of the ultra-thin copper foil 12 in the carrier-attached copper foil. It is desirable that the plane size S3 of the copper crystal grains G3 constituting the surface opposite to the surface of the crystal grain G3 is also small.
  • the planar size S3 means the planar crystal size (average crystal grain size) after bonding the carrier-attached copper foil to the resin.
  • the plane size S3 is a value obtained by analyzing the back surface of the ultra-thin copper foil 12 in the laminate 18 by EBSD after producing the laminate 18 under the same conditions as the calculation of the plane size S1.
  • the back surface of the ultra-thin copper foil 12 is the surface at a position 0.1 ⁇ m shallower than the thickness of the ultra-thin copper foil 12 described later in the depth direction from the surface of the laminate 18 on the ultra-thin copper foil 12 side.
  • point to The plane size S3 can be preferably calculated according to the procedure shown in the evaluation (8c) of the example described later.
  • the thickness of the ultra-thin copper foil 12 is preferably 2.0 ⁇ m or less, more preferably 0.3 ⁇ m or more and 1.2 ⁇ m or less, still more preferably 0.3 ⁇ m or more and 1.0 ⁇ m or less, and particularly preferably 0.3 ⁇ m. It is more than 0.8 ⁇ m or less. By doing so, it becomes easier to control the plane size S 1 , the cross-sectional size S 2 , and the plane size S 3 within the predetermined ranges, and as a result, the laser processability can be improved more effectively.
  • the carrier-attached copper foil further includes a roughened layer composed of a plurality of roughened particles 14, the thickness of the ultra-thin copper foil 12 does not include the thickness of this roughened layer.
  • Measurement of the thickness of the ultra-thin copper foil 12 for example, after producing the laminate 18 under the same conditions as the calculation of the plane size S 1 , preferably using any of the following methods (i) and (ii) It can be carried out.
  • (i) Observe the cross section of the laminate 18 using a focused ion beam-scanning electron microscope (FIB-SEM). In the analysis of this cross section, as shown in FIG. 2, a line A is drawn through the most recessed portion 14a of the roughening particles and parallel to the average plane of the ultra-thin copper foil surface 12a. Then, a line segment B perpendicular to the line A is drawn from the most recessed portion 14a of the roughening particles toward the ultra-thin copper foil surface 12a.
  • FIB-SEM focused ion beam-scanning electron microscope
  • the thickness of the ultra-thin copper foil 12 is calculated by calculating the distance until this line segment B touches the ultra-thin copper foil surface 12a.
  • a plane milling process is performed from the ultra-thin copper foil 12 side of the laminate 18 by a cross-section polisher (CP). The plane milling process is continued, and the milling depth when the resin layer 16 starts to be exposed in a part of the laminate 18 is calculated from the milling rate measured in advance, and is taken as the thickness of the ultra-thin copper foil 12 . Whether or not the resin layer 16 is exposed can be determined by observing the processed surface of the laminate 18 at a low magnification (for example, about 1000 times) using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the surface of the ultra-thin copper foil 12 may be roughened to form a roughened layer.
  • This roughening layer is provided with a plurality of roughening particles 14 (nobs), and each of these roughening particles 14 preferably consists of copper particles.
  • the copper particles may consist of metallic copper, or may consist of a copper alloy.
  • the roughening treatment for forming the roughened surface can be preferably carried out by forming roughening particles 14 of copper or copper alloy on the ultrathin copper foil 12 .
  • a plating method that undergoes at least two types of plating processes including a baking plating process for depositing fine copper grains on the ultra-thin copper foil 12 and a covering plating process for preventing the fine copper grains from falling off.
  • a roughening treatment is preferably carried out.
  • the surface of the ultra-thin copper foil 12 may be subjected to antirust treatment to form an antirust treatment layer.
  • the antirust treatment preferably includes plating with zinc.
  • the plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment.
  • the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr and Co.
  • the Ni/Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in mass ratio.
  • the rust prevention treatment preferably further includes chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc.
  • a particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
  • the surface of the ultrathin copper foil 12 may be treated with a silane coupling agent to form a silane coupling agent layer.
  • a silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating it, and drying it.
  • silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.
  • epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)but
  • amino-functional silane coupling agents or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or 3-methacrylic Acrylic functional silane coupling agents such as roxypropyltrimethoxysilane, or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, and the like.
  • the carrier-attached copper foil is at least one selected from the group consisting of a roughening layer composed of a plurality of roughening particles 14 on the ultrathin copper foil 12, an antirust treatment layer, and a silane coupling agent layer. It is preferred to further comprise a layer of
  • the carrier-attached copper foil further comprises a roughened layer, an antirust treatment layer, and a silane coupling agent layer
  • the order in which these layers are arranged is not particularly limited. It is preferable that the roughened layer, the antirust layer and the silane coupling agent layer are laminated in this order.
  • the carrier-attached copper foil has a carrier.
  • a carrier is a support for supporting the ultra-thin copper foil to improve its handling properties, and a typical carrier includes a metal layer. Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, resin film or glass whose surface is metal-coated with copper or the like, and copper foil is preferred.
  • the copper foil may be a rolled copper foil or an electrolytic copper foil, preferably an electrolytic copper foil.
  • the thickness of the carrier is typically 250 ⁇ m or less, preferably 7 ⁇ m or more and 200 ⁇ m or less.
  • the carrier-attached copper foil has a release layer on the carrier.
  • the release layer is a layer that has the function of weakening the peeling strength of the carrier, ensuring the stability of the strength, and suppressing interdiffusion that may occur between the carrier and the copper foil during press molding at high temperatures.
  • the release layer is generally formed on one side of the carrier, but may be formed on both sides.
  • the release layer may be either an organic release layer or an inorganic release layer. Examples of organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like. Examples of the nitrogen-containing organic compound include triazole compounds, imidazole compounds, etc. Among them, triazole compounds are preferable in terms of easily stabilizing peelability.
  • Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino- 1H-1,2,4-triazole and the like.
  • Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
  • Examples of carboxylic acids include monocarboxylic acids, dicarboxylic acids, and the like.
  • examples of inorganic components used for the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment films, and the like.
  • the thickness of the release layer is typically 1 nm or more and 1 ⁇ m or less, preferably 5 nm or more and 500 nm or less.
  • Another functional layer may be provided between the release layer and the carrier and/or the ultrathin copper foil 12.
  • auxiliary metal layers include auxiliary metal layers.
  • the auxiliary metal layer preferably consists of nickel and/or cobalt. By forming such an auxiliary metal layer on the surface side of the carrier and/or on the surface side of the ultra-thin copper foil 12, it is possible to reduce mutual interaction that may occur between the carrier and the ultra-thin copper foil 12 during hot press molding at high temperature or for a long period of time. Diffusion can be further suppressed, and the stability of carrier peeling strength can be ensured.
  • the thickness of the auxiliary metal layer is preferably 0.001 ⁇ m or more and 3 ⁇ m or less.
  • the carrier-attached copper foil of the present invention is produced by (1) preparing a carrier, (2) forming a release layer on the carrier, and (3) forming an ultra-thin copper foil on the release layer. It can be manufactured by An example of a preferred method for manufacturing the carrier-attached copper foil according to the present invention will be described below.
  • a carrier is prepared as a support.
  • a typical carrier contains a metal layer.
  • examples of such carriers include aluminum foil, copper foil, stainless steel (SUS) foil, and resin films or glasses whose surfaces are metal-coated with copper or the like. Copper foil is preferred.
  • the copper foil may be a rolled copper foil or an electrolytic copper foil, preferably an electrolytic copper foil.
  • the thickness of the carrier is typically 250 ⁇ m or less, preferably 7 ⁇ m or more and 200 ⁇ m or less.
  • the surface of the carrier on the release layer side is preferably smooth. That is, in the manufacturing process of the carrier-attached copper foil, the ultra-thin copper foil 12 is formed on the release layer side of the carrier. Therefore, by smoothing the surface of the carrier on the release layer side, the outer surface of the ultra-thin copper foil 12 can also be smoothed, making it easier to make the crystal growth surface of the ultra-thin copper foil 12 uniform. As a result, it becomes easier to obtain an ultra-thin copper foil composed of copper crystal grains having a desired crystal size.
  • the surface of the carrier on the release layer side can be smoothed, for example, by polishing the surface of the cathode used in electrolytic foil production of the carrier with a buff of a predetermined number to adjust the surface roughness.
  • the surface profile of the cathode adjusted in this way is transferred to the electrode surface of the carrier, and an ultra-thin copper foil is formed on the electrode surface of the carrier via a peeling layer to obtain copper crystal grains having the predetermined crystal size. It becomes easy to form an ultra-thin copper foil composed of.
  • the buff number is preferably #1,000 or more and #3,500 or less, more preferably #1,000 or more and #2,500 or less.
  • the carrier is peeled off from the deposition surface side of the carrier electrolytically manufactured using an electrolytic solution containing additives. It may be the surface on the layer side.
  • the release layer may be either an organic release layer or an inorganic release layer. Preferred examples of the organic peeling layer and the inorganic peeling layer are as described above.
  • the release layer may be formed by contacting at least one surface of the carrier with a release layer component-containing solution to fix the release layer component on the surface of the carrier. When the carrier is brought into contact with the release layer component-containing solution, this contact may be performed by immersion in the release layer component-containing solution, spraying the release layer component-containing solution, or flowing the release layer component-containing solution.
  • a method of forming a coating of the peeling layer component by a vapor phase method such as vapor deposition or sputtering.
  • Fixing of the release layer component to the carrier surface may be carried out by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like.
  • the thickness of the release layer is typically 1 nm or more and 1 ⁇ m or less, preferably 5 nm or more and 500 nm or less.
  • the ultra-thin copper foil 12 is formed on the release layer.
  • the ultra-thin copper foil 12 may be formed by wet film forming methods such as electroless copper plating and electrolytic copper plating, dry film forming methods such as sputtering and chemical vapor deposition, or a combination thereof.
  • the ultra-thin copper foil 12 is formed by electrolytic copper plating.
  • the copper concentration is 40 g / L or more and 80 g / L or less (more preferably 50 g / L or more and 70 g / L or less)
  • the sulfuric acid concentration is 180 g / L or more and 260 g / L or less (more preferably 200 g / L or more and 250 g / L or less) )
  • CBTA carboxybenzotriazole
  • the CBTA concentration in the electrolytic solution is more preferably 0.1 ppm or more and 100 ppm or less, more preferably 0.1 ppm or more and 50 ppm or less, particularly preferably 0.1 ppm or more and 30 ppm or less, and most preferably 0.1 ppm or more and 10 ppm or less. be.
  • CBTA carboxybenzotriazole
  • the surface of the ultrathin copper foil is subjected to roughening treatment, antirust treatment and/or silane coupling agent treatment to form a roughened layer composed of a plurality of roughening particles, an antirust treatment layer and/or silane coupling An agent layer may be formed.
  • the carrier-attached copper foil of the present invention is preferably used for producing a copper-clad laminate for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate comprising the copper foil with carrier.
  • a copper-clad laminate consists of a carrier-attached copper foil comprising a carrier, a release layer, and an ultra-thin copper foil in this order, and a surface of the carrier-attached copper foil (the opposite side to the release layer of the ultra-thin copper foil). and a resin layer provided on the surface).
  • the plane size S of copper crystal grains present on the surface of the ultra-thin copper foil on the release layer side (the surface opposite to the resin layer) measured by electron beam backscatter diffraction (EBSD) 1 is 50 nm or more and 600 nm or less.
  • the preferred aspects of the carrier-attached copper foil described above also apply to the carrier-attached copper foil included in the copper-clad laminate.
  • the carrier-attached copper foil may be provided on one side of the resin layer, or may be provided on both sides.
  • the resin layer comprises resin, preferably insulating resin.
  • the resin layer is preferably prepreg and/or resin sheet.
  • Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper.
  • insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins.
  • the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
  • the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation.
  • the thickness of the resin layer is not particularly limited, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 2 ⁇ m or more and 400 ⁇ m or less, and still more preferably 3 ⁇ m or more and 200 ⁇ m or less.
  • the resin layer may be composed of multiple layers.
  • a resin layer such as a prepreg and/or a resin sheet may be provided in advance on the carrier-attached copper foil via a primer resin layer applied on the surface of the ultra-thin copper foil.
  • the carrier-attached copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board provided with the above copper foil with carrier, or a method for producing the printed wiring board.
  • the printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated in this order. Also, the resin layer is as described above for the copper-clad laminate. In any case, a known layer structure can be adopted for the printed wiring board.
  • printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the ultrathin copper foil of the present invention to one side or both sides of a prepreg to form a cured laminate, and then forming a circuit, or a multi-layered multilayer of these.
  • a printed wiring board etc. are mentioned.
  • Other specific examples include a flexible printed wiring board, a COF, a TAB tape, etc., in which the ultra-thin copper foil of the present invention is formed on a resin film to form a circuit.
  • a resin-coated copper foil is formed by applying the above-described resin layer to the ultrathin copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above-described printed wiring board.
  • the ultra-thin copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive method (MSAP), the subtractive method, etc., and the ultra-thin copper foil is removed.
  • MSAP modified semi-additive method
  • SAP semi-additive method
  • the carrier-attached copper foil of the present invention can also be preferably used in a manufacturing method using a coreless build-up method in which insulating resin layers and conductor layers are alternately laminated without using a so-called core substrate.
  • Examples 1-4 and 6-11 A copper foil with a carrier provided with a roughened copper foil was produced and evaluated as follows.
  • Example 2 a sulfuric acid copper sulfate solution having the composition shown below was used as the copper electrolyte. Then, using an electrode with a surface roughness Ra of 0.20 ⁇ m as the cathode and a DSA (dimensionally stable anode) as the anode, electrolysis was performed at a solution temperature of 45 ° C. and a current density of 55 A / dm 2 to obtain a thickness of 18 ⁇ m. An electrolytic copper foil was obtained as a carrier.
  • the electrode surface of the pickled carrier was treated with a carboxybenzotriazole (CBTA) concentration of 1 g/L, a sulfuric acid concentration of 150 g/L, and a copper concentration of 10 g. /L at a liquid temperature of 30° C. for 30 seconds to adsorb the CBTA component onto the electrode surface of the carrier.
  • CBTA carboxybenzotriazole
  • a CBTA layer was formed as an organic release layer on the electrode surface of the carrier.
  • the organic peeling layer was formed in the same manner as in Examples 1, 3, 4, and 6 to 11, except that the CBTA layer was formed by adsorbing the CBTA component on the deposition surface instead of the electrode surface of the carrier. was formed.
  • the carrier on which the organic release layer was formed was immersed in a solution containing nickel concentration of 20 g/L prepared using nickel sulfate, and the liquid temperature was 45° C., pH 3, current density 5 A/L. Under conditions of dm 2 , a deposition amount of nickel equivalent to a thickness of 0.001 ⁇ m was deposited onto the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
  • the surface of the ultra-thin copper foil thus formed was subjected to a roughening treatment to form a roughened copper foil, thereby obtaining a carrier-attached copper foil.
  • This roughening treatment consists of a baking plating process for depositing fine copper grains on an ultrathin copper foil and a covering plating process for preventing the fine copper grains from falling off.
  • 9-phenylacridine (9PA) and chlorine are added to an acidic copper sulfate solution containing a copper concentration of 10 g / L and a sulfuric acid concentration of 200 g / L at a liquid temperature of 25 ° C. so that the 9PA concentration is 60 ppm and the chlorine concentration is 50 ppm.
  • electrodeposition was performed using an acidic copper sulfate solution containing a copper concentration of 70 g/L and a sulfuric acid concentration of 240 g/L under smooth plating conditions of a liquid temperature of 52° C. and a current density of 15 A/dm 2 .
  • the roughened surface of the obtained copper foil with carrier was subjected to antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
  • antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
  • a zinc-nickel alloy plating treatment was applied to the surface.
  • the zinc-nickel alloy plated surface was subjected to chromate treatment using an aqueous solution containing 1 g/L of chromic acid under the conditions of pH 12 and current density 1 A/dm 2 .
  • Silane coupling agent treatment An aqueous solution containing a commercially available silane coupling agent is adsorbed on the surface of the roughened copper foil side of the carrier-attached copper foil, and the water is evaporated with an electric heater to perform the silane coupling agent treatment. did At this time, the carrier side was not treated with the silane coupling agent.
  • the laminate 18 shown in FIG. 1 was produced as follows. First, a 0.10 mm thick prepreg (GHPL-830NX-A manufactured by Mitsubishi Gas Chemical Co., Ltd.) was prepared. The obtained copper foil with carrier is laminated on this prepreg so that the roughened surface (surface on the roughened particle 14 side) is in contact with the prepreg, and pressed at a temperature of 220 ° C. and a pressure of 4.0 MPa for 90 minutes. The resin layer 16 was formed by carrying out. After that, the carrier was peeled off together with the peeling layer to obtain a laminate 18 including the ultra-thin copper foil 12 and the resin layer 16 .
  • GHPL-830NX-A manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • the ultra-thin copper foil 12 side surface of the laminate 18 after plane milling was performed for 5 minutes (equivalent to a thickness of 50 nm) was used as the outermost surface of the ultra-thin copper foil 12, and marking and FIB marker processing were performed.
  • the outermost surface of the ultra-thin copper foil 12 was observed using an FE gun type scanning electron microscope (Carl Zeiss, Crossbeam 540) equipped with an EBSD detector (Oxford Instruments, Symmetry). rice field. Then, EBSD data was obtained using EBSD measurement software (AZtec 5.0 HF1 manufactured by Oxford Instruments), and the obtained EBSD data was converted to OIM format.
  • the measurement conditions of the scanning electron microscope during observation were as follows. ⁇ Scanning electron microscope measurement conditions> - acceleration voltage: 15 kV - Step size: 22.9 nm - Region width: 5.86 ⁇ m - Area height: 4.4 ⁇ m -Scan Phase: Cu - sample angle: 70°
  • the crystal distribution is measured using crystal size calculation software (manufactured by AMETEK, OIM Analysis v7.3.1 x64), and the copper crystals present on the outermost surface of the ultra-thin copper foil 12.
  • Planar size S 1 of grain G 1 average grain size, item of “Grain Size-Average Area” on software was calculated. The results were as shown in Table 1.
  • a misorientation of 5° or more was regarded as a crystal grain boundary.
  • the crystal structure of copper is a cubic crystal structure, in consideration of the twin grain boundary, the case corresponding to the following (i) or (ii) was not regarded as a grain boundary.
  • ii) Twin grain boundaries with an orientation relationship of 38.9° rotation around the ⁇ 110> axis
  • the back surface of the ultra-thin copper foil 12 is the surface at a position 0.1 ⁇ m shallower than the thickness of the ultra-thin copper foil 12 measured in (8a) above in the depth direction from the outermost surface of the ultra-thin copper foil 12. did.
  • the planar size S 3 of the copper crystal grains G 3 existing on the back surface of the ultra-thin copper foil 12 was calculated. The results were as shown in Table 1.
  • the cross-sectional size S2 of the copper crystal grains forming the ultra - thin copper foil 12 was measured as follows. First, from the surface of the laminate 18 on the ultra-thin copper foil 12 side, a cross-section was processed in the thickness direction by a cross-section polisher (CP) under the condition of an acceleration voltage of 5 kV. Then, for the cross section of the ultra-thin copper foil 12, copper crystals constituting the ultra-thin copper foil 12 are performed in the same manner as in (8b) above, except that the measurement conditions of the scanning electron microscope are changed as follows.
  • Example 5 (Comparison) A commercially available copper foil with a carrier was used as it was. Various properties of the carrier-attached copper foil were evaluated (evaluations (8a) to (8e)) in the same manner as in Examples 1 to 4 and 6 to 11. The results were as shown in Table 1.

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PCT/JP2022/011923 2021-03-26 2022-03-16 キャリア付銅箔、銅張積層板及びプリント配線板 WO2022202539A1 (ja)

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