WO2020031721A1 - Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, stratifié plaqué de cuivre et carte de circuit imprimé - Google Patents

Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, stratifié plaqué de cuivre et carte de circuit imprimé Download PDF

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Publication number
WO2020031721A1
WO2020031721A1 PCT/JP2019/029224 JP2019029224W WO2020031721A1 WO 2020031721 A1 WO2020031721 A1 WO 2020031721A1 JP 2019029224 W JP2019029224 W JP 2019029224W WO 2020031721 A1 WO2020031721 A1 WO 2020031721A1
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Prior art keywords
copper foil
roughened
carrier
copper
roughened copper
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PCT/JP2019/029224
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English (en)
Japanese (ja)
Inventor
眞 細川
哲聡 ▲高▼梨
美智 溝口
慎哉 平岡
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 CN201980047289.3A priority Critical patent/CN112424399B/zh
Priority to MYPI2021000356A priority patent/MY186454A/en
Priority to KR1020217000738A priority patent/KR102480377B1/ko
Priority to JP2020536455A priority patent/JP6905157B2/ja
Publication of WO2020031721A1 publication Critical patent/WO2020031721A1/fr

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    • 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
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • 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
    • C25D5/48—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
    • 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 roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
  • the MSAP method is a method suitable for forming an extremely fine circuit, and is performed using a copper foil with a carrier in order to take advantage of its features. For example, as shown in FIGS. 1 and 2, an ultra-thin copper foil 10 is pressed and adhered on an insulating resin substrate 11 provided with a lower circuit 11 b on a base material 11 a using a prepreg 12 and a primer layer 13. After the carrier (not shown) is peeled off (step (a)), a via hole 14 is formed by laser drilling as needed (step (b)).
  • step (c) After performing chemical copper plating 15 (step (c)), masking is performed in a predetermined pattern by exposure and development using a dry film 16 (step (d)), and electrolytic copper plating 17 is performed (step (e)). )).
  • step (f) After removing the dry film 16 to form the wiring portion 17a (step (f)), unnecessary ultra-thin copper foil and the like between the wiring portions 17a and 17a adjacent to each other are removed by etching over their entire thickness ( Step (g)), a wiring 18 formed in a predetermined pattern is obtained.
  • the surface of the ultra-thin copper foil 10 is generally subjected to a roughening treatment.
  • Patent Document 1 International Publication No. WO 2016/117587
  • the average distance between the surface peaks on the surface on the release layer side is 20 ⁇ m or less
  • the maximum height difference of the undulation on the surface on the side opposite to the release layer is described.
  • a copper foil with a carrier provided with an ultra-thin copper foil having a thickness of 1.0 ⁇ m or less is disclosed, and according to such an embodiment, it is said that both fine circuit formability and laser workability can be achieved.
  • Patent Document 2 Japanese Patent Application Laid-Open No.
  • a shear strength is one of physical indices of physical contact between a circuit and a substrate, and in order to effectively avoid the above-described circuit peeling, it is required to maintain the shear strength at or above a certain level.
  • the roughened particles of the copper foil must be enlarged, and there is a problem that it is difficult to achieve compatibility with the etching property.
  • the present inventors have recently provided a surface profile in which the maximum height Sz, the interface development area ratio Sdr, and the peak vertex density Spd specified in ISO25178 are controlled to predetermined ranges in the roughened copper foil. As a result, it has been found that in etching a copper-clad laminate or manufacturing a printed wiring board, it is possible to achieve both excellent etching properties and high shear strength.
  • an object of the present invention is to provide a roughened copper foil capable of achieving both excellent etching properties and high shear strength in processing a copper-clad laminate or manufacturing a printed wiring board.
  • a roughened copper foil having a roughened surface on at least one side,
  • the roughened surface has a maximum height Sz measured according to ISO25178 of 0.65 to 1.00 ⁇ m, and a developed area ratio Sdr of the interface measured according to ISO25178 of 1.50 to 4. .20, and a roughened copper foil having a peak vertex density Spd of 6.50 ⁇ 10 6 to 8.50 ⁇ 10 6 pieces / mm 2 measured according to ISO25178.
  • a carrier a release layer provided on the carrier, and the roughened copper foil provided on the release layer with the roughened surface facing outward.
  • a copper foil with a carrier.
  • a copper-clad laminate including the roughened copper foil.
  • a printed wiring board provided with the roughened copper foil.
  • FIG. 3 is a process flow chart for explaining the MSAP method, showing the first half of the process (steps (a) to (d)).
  • FIG. 3 is a process flow chart for explaining the MSAP method, showing the latter half of the process (steps (e) to (g)). It is a schematic diagram for explaining the measuring method of the shear strength.
  • the “maximum height Sz” is a parameter that is measured according to ISO25178 and that represents the distance from the highest point to the lowest point on the surface.
  • the maximum height Sz can be calculated by measuring the surface profile of a predetermined measurement area (for example, a 6812 ⁇ m 2 two-dimensional area) on the roughened surface with a commercially available laser microscope.
  • the “interface development area ratio Sdr” indicates how much the development area (surface area) of the defined area, measured in accordance with ISO25178, is increased with respect to the area of the defined area. Parameter. The smaller this value is, the more nearly flat the surface shape is, and the Sdr of the completely flat surface is 0. On the other hand, a larger value indicates a surface shape with more irregularities. For example, a surface having an Sdr of 0.4 indicates that the surface has increased by 40% surface area from a perfectly flat surface.
  • the interface development area ratio Sdr can be calculated by measuring the surface profile of a predetermined measurement area (for example, a two-dimensional area of 6812 ⁇ m 2 ) on the roughened surface with a commercially available laser microscope.
  • the “peak vertex density Spd” is a parameter that is measured according to ISO25178 and represents the number of peaks per unit area. A large value indicates that the number of contact points with other objects is large.
  • the peak vertex density Spd can be calculated by measuring the surface profile of a predetermined measurement area (for example, a 6812 ⁇ m 2 two-dimensional area) on the roughened surface with a commercially available laser microscope.
  • the “electrode surface” of the carrier refers to the surface that was in contact with the cathode when the carrier was manufactured.
  • the “deposited surface” of the carrier refers to a surface on which electrolytic copper is deposited during the production of the carrier, that is, a surface not in contact with the cathode.
  • the copper foil according to the present invention is a roughened copper foil.
  • This roughened copper foil has a roughened surface on at least one side.
  • the roughened surface has a maximum height Sz of 0.65 to 1.00 ⁇ m, an interface development area ratio Sdr of 1.50 to 4.20, and a peak vertex density Spd of 6.50 ⁇ 10 5. 6 to 8.50 ⁇ 10 6 pieces / mm 2 .
  • the maximum height Sz, the developed area ratio Sdr of the interface, and the peak density Spd of the peaks are given a surface profile controlled to a predetermined range, thereby processing the copper-clad laminate.
  • Excellent etching properties and high shear strength are inherently incompatible. This is because, as described above, in order to improve the etching property of the copper foil, it is generally required to reduce the size of the roughened particles. Is required to be large.
  • unexpectedly excellent etching properties and high shear strength can both be achieved. That is, the shear strength is not simply proportional to the specific surface area, the roughened height, etc., which have been conventionally used for evaluation, and it has been difficult to control the shear strength.
  • the present inventors evaluated the evaluation by combining the development area ratio Sdr of the interface and the peak vertex density Spd in addition to the maximum height Sz in order to correlate with the physical properties such as the etching property and the shear strength. It was found that it was effective to do so.
  • the edge height and the edge density, and the specific surface area which are favorable for securing a high shear strength, while having a fine surface excellent in etching property, are provided.
  • the roughened copper foil has a maximum height Sz of the roughened surface of 0.65 to 1.00 ⁇ m, preferably 0.65 to 0 ⁇ m. .90 ⁇ m, more preferably 0.65 to 0.80 ⁇ m.
  • the roughened copper foil has a development area ratio Sdr of an interface of the roughened surface of 1.50 to 4.20, preferably 1.80 to 3.50, more preferably 2.00 to 3.20. 00.
  • the roughened copper foil has a peak vertex density Spd of the roughened surface of 6.50 ⁇ 10 6 to 8.50 ⁇ 10 6 / mm 2 , and preferably 7.65 ⁇ 10 6 to 8 It is 0.50 ⁇ 10 6 pieces / mm 2 , more preferably 7.80 ⁇ 10 6 to 8.30 ⁇ 10 6 pieces / mm 2 .
  • the roughened copper foil has Sz ⁇ Sdr ⁇ Spd, which is a product of the maximum height Sz on the roughened surface, the developed area ratio Sdr of the interface, and the peak vertex density Spd, of 7.50 ⁇ 10 6 to 2.70 ⁇ . It is preferably 10 7 ( ⁇ m ⁇ piece / mm 2 ), more preferably 9.00 ⁇ 10 6 to 2.60 ⁇ 10 7 ( ⁇ m ⁇ piece / mm 2 ), and still more preferably 1.00 ⁇ 10 7. 2.00 ⁇ 10 7 ( ⁇ m ⁇ piece / mm 2 ). Within such a range, it becomes easier to achieve both excellent etching properties and high shear strength.
  • the thickness of the roughened copper foil is not particularly limited, but is preferably 0.1 to 35 ⁇ m, more preferably 0.5 to 5.0 ⁇ m, and further preferably 1.0 to 3.0 ⁇ m.
  • the roughened copper foil is not limited to a copper foil having a surface roughened, but may be a copper foil with a carrier that has been roughened.
  • the roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have a roughened surface on both sides, or may have a roughened surface only on one side.
  • the roughened surface typically includes a plurality of roughened particles (cob), and each of the plurality of roughened particles is preferably made of copper particles.
  • the copper particles may be made of metallic copper or may be made of a copper alloy.
  • the roughening treatment for forming the roughened surface can be preferably performed by forming roughened particles of copper or a copper alloy on a copper foil.
  • a roughening treatment is performed according to a plating method that includes at least two types of plating steps including a baking plating step of depositing and depositing fine copper particles on a copper foil and a cover plating step of preventing falling of the fine copper particles. Is preferably performed.
  • the baking plating step 30 to 50 ppm (more preferably 35 to 50 ppm) of carboxybenzotriazole (CBTA) is added to a copper sulfate solution containing a copper concentration of 5 to 20 g / L and a sulfuric acid concentration of 180 to 240 g / L,
  • the electrodeposition is preferably performed at a temperature of 15 to 35 ° C. and 12 to 24 A / dm 2 (more preferably 12 to 18 A / dm 2 ).
  • the overplating step is performed in a copper sulfate solution containing a copper concentration of 50 to 100 g / L and a sulfuric acid concentration of 200 to 250 g / L at a temperature of 40 to 60 ° C.
  • the baking plating step by adding carboxybenzotriazole within the above concentration range to the plating solution, while maintaining the etching properties close to pure copper, a bump that is favorable to satisfy the above-described surface parameters on the treated surface. It is easy to form. Furthermore, in the baking plating step and the cover plating step, by performing electrodeposition at a lower current density than in the conventional method, it becomes easier to form a favorable bump on the treated surface to satisfy the above-mentioned surface parameters.
  • the roughened copper foil may be subjected to a rust-proof treatment to form a rust-proof treatment layer.
  • the rust prevention treatment preferably includes a plating treatment using zinc.
  • the plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment.
  • the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further include other elements such as Sn, Cr, and Co.
  • the adhesion ratio of Ni / Zn in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and further preferably 2.7 to 4 by mass ratio.
  • the rust prevention treatment preferably further includes a chromate treatment, and this chromate treatment is more preferably performed on the surface of the zinc-containing plating after the plating treatment using zinc. By doing so, rust prevention can be further improved.
  • a particularly preferred rust preventive treatment is a combination of a zinc-nickel alloy plating treatment and a subsequent chromate treatment.
  • the roughened copper foil may be one in which the surface is subjected to a silane coupling agent treatment to form a silane coupling agent layer.
  • a silane coupling agent treatment to form a silane coupling agent layer.
  • the silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, applying the diluted silane coupling agent, and then drying.
  • silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-2 (amino Amino functions such as ethyl) 3-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Functional silane coupling agent, or mercapto-functional silane coupling agent such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agent such as vinyltrimethoxysilane or vinylphenyltrimethoxysilane, or 3-methacryloxypropyl Trimming Acrylic-functional silane coupling agent such as Kishishiran, or imi
  • the roughened copper foil preferably further includes a rust-proofing layer and / or a silane coupling agent layer on the roughened surface, and more preferably a rust-proofing layer and a silane coupling agent layer. It has both.
  • the rust preventive layer and the silane coupling agent layer may be formed not only on the roughened surface of the roughened copper foil but also on the side where the roughened surface is not formed.
  • the roughened copper foil of the present invention may be provided in the form of a copper foil with a carrier. That is, according to a preferred embodiment of the present invention, a carrier, a release layer provided on the carrier, comprising the roughened copper foil provided on the release layer with a roughened surface outside, A copper foil with a carrier is provided.
  • a known layer configuration can be adopted for the copper foil with a carrier, except that the roughened copper foil of the present invention is used.
  • the carrier is a support for supporting the roughened copper foil to improve its handleability
  • a typical carrier includes a metal layer.
  • a carrier include an aluminum foil, a copper foil, a stainless steel (SUS) foil, a resin film whose surface is metal-coated with copper or the like, a glass, and the like, and preferably a copper foil.
  • the copper foil may be a rolled copper foil or an electrolytic copper foil, but is preferably an electrolytic copper foil.
  • the thickness of the carrier is typically less than 250 ⁇ m, preferably 9-200 ⁇ m.
  • the surface of the carrier on the release layer side is preferably smooth. That is, in the manufacturing process of the copper foil with a carrier, an extremely thin copper foil (before performing the roughening treatment) is formed on the surface of the carrier on the release layer side. Therefore, by keeping the surface on the release layer side of the carrier smooth, the outer surface of the ultra-thin copper foil can also be smooth, and by performing a roughening treatment on the smooth surface of this ultra-thin copper foil, A roughened surface having the maximum height Sz within the predetermined range, the developed area ratio Sdr of the interface, and the peak vertex density Spd can be easily realized.
  • the surface of the carrier on the release layer side can be smoothed, for example, by adjusting the surface roughness by polishing the surface of the cathode used for electrolytically forming the carrier with a buff of a predetermined count. That is, the surface profile of the cathode adjusted in this way is transferred to the electrode surface of the carrier, and the ultra-thin copper foil is formed on the electrode surface of the carrier via a release layer, so that the outer surface of the ultra-thin copper foil is formed.
  • a smooth surface state that can easily realize the above-described roughened surface can be provided.
  • Preferred buff counts are # 2000 to # 3000, more preferably # 2000 to # 2500.
  • the release layer is a layer having a function of reducing the peeling strength of the carrier, ensuring the stability of the strength, and further suppressing a possible interdiffusion between the carrier and the copper foil during press molding at a high temperature.
  • the release layer is generally formed on one surface of the carrier, but may be formed on both surfaces.
  • the release layer may be either an organic release layer or an inorganic release layer.
  • the organic component used in the organic release layer include a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.
  • the nitrogen-containing organic compound include a triazole compound, an imidazole compound, and the like. Among them, a triazole compound is preferable because the releasability is easily stabilized.
  • triazole compounds examples 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.
  • sulfur-containing organic compound examples include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazole thiol, and the like.
  • carboxylic acids include monocarboxylic acids, dicarboxylic acids, and the like.
  • examples of the inorganic component used for the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and a chromate-treated film.
  • the release layer may be formed by, for example, bringing a solution containing a release layer component into contact with at least one surface of the carrier and fixing the release layer component to 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 dipping in the release layer component-containing solution, spraying the release layer component-containing solution, flowing down the release layer component-containing solution, or the like.
  • a method of forming a film of the release layer component by a vapor phase method such as vapor deposition or sputtering can also be adopted.
  • the fixation of the release layer component to the carrier surface may be performed by adsorption and 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 from 1 nm to 1 ⁇ m, preferably from 5 nm to 500 nm.
  • another functional layer may be provided between the release layer and the carrier and / or the roughened copper foil.
  • auxiliary metal layers include nickel and / or cobalt.
  • the auxiliary metal layer comprises nickel and / or cobalt.
  • the roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate provided with the roughened copper foil.
  • This copper-clad laminate comprises the roughened copper foil of the present invention and a resin layer provided in close contact with the roughened surface of the roughened copper foil.
  • the roughened copper foil may be provided on one side of the resin layer, or may be provided on both sides.
  • the resin layer contains a resin, preferably an insulating resin.
  • the resin layer is preferably a prepreg and / or a resin sheet.
  • the prepreg is a general term for a composite material in which a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, and paper is impregnated with a synthetic resin.
  • Preferred examples of the insulating resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, and a phenol resin.
  • the insulating resin forming the resin sheet include an insulating resin such as an epoxy resin, a polyimide resin, and a polyester resin.
  • the resin layer may contain filler particles composed 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, but is preferably 1 to 1000 ⁇ m, more preferably 2 to 400 ⁇ m, and further preferably 3 to 200 ⁇ m.
  • the resin layer may be composed of a plurality of layers.
  • a resin layer such as a prepreg and / or a resin sheet may be provided on the roughened copper foil via a primer resin layer previously applied to the copper foil surface.
  • the roughened copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred embodiment of the present invention, there is provided a printed wiring board provided with the roughened copper foil.
  • the printed wiring board according to this aspect has a layer configuration in which a resin layer and a copper layer are stacked.
  • the copper layer is a layer derived from the roughened copper foil of the present invention.
  • the resin layer is as described above for the copper clad laminate.
  • the printed wiring board can adopt a known layer configuration except that the roughened copper foil of the present invention is used.
  • the printed wiring board a single-sided or double-sided printed wiring board formed with a circuit after forming a cured laminate by bonding the roughened copper foil of the present invention to one or both sides of the prepreg, or a multilayer of these.
  • Examples include a multilayer printed wiring board.
  • Other specific examples include a flexible printed wiring board, a COF, a TAB tape, and the like, which form a circuit by forming the roughened copper foil of the present invention on a resin film.
  • a resin-coated copper foil (RCC) in which the above-described resin layer is applied to the roughened copper foil of the present invention is formed, and the resin layer is laminated on the above-described printed board as an insulating adhesive layer.
  • the roughened copper foil is removed by using the roughened copper foil as a whole or a part of the wiring layer to form a circuit by a modified semi-additive (MSAP) method, a subtractive method, or the like, or the roughened copper foil.
  • MSAP modified semi-additive
  • An electronic material for glass, an electromagnetic shielding film obtained by applying a conductive adhesive to the roughened copper foil of the present invention, and the like are also included.
  • the roughened copper foil of the present invention is suitable for the MSAP method. For example, when a circuit is formed by the MSAP method, a configuration as shown in FIG. 2 can be adopted.
  • Examples 1 to 8 and 12 to 14 A copper foil with a carrier provided with a roughened copper foil was prepared and evaluated as follows.
  • auxiliary metal layer Formation of auxiliary metal layer
  • 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, at a liquid temperature of 45 ° C., pH 3, and a current density of 5 A / L. Under the condition of dm 2 , nickel having a thickness equivalent to 0.001 ⁇ m was deposited on the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
  • Roughening treatment The surface of the ultra-thin copper foil thus formed was subjected to a roughening treatment.
  • This roughening treatment includes a baking plating step of depositing and depositing fine copper particles on an ultra-thin copper foil, and a cover plating step for preventing the fine copper particles from falling off.
  • carboxybenzotriazole (CBTA) having a concentration shown in Table 1 was 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.
  • Roughening treatment was performed at the current density.
  • 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 a smooth plating condition of a liquid temperature of 52 ° C. and a current density shown in Table 1. .
  • various samples having different characteristics of the roughened surface were produced by appropriately changing the CBTA concentration and the current density in the baking plating step, and the current density in the covering plating step as shown in Table 1.
  • the surface subjected to the zinc-nickel alloy plating treatment was subjected to chromate treatment under the conditions of pH 12 and current density of 1 A / dm 2 .
  • a laminate for evaluation was prepared using the obtained copper foil with a carrier. That is, a roughened copper foil with a carrier is laminated on the surface of the inner substrate via a prepreg (GHPL-830NSF, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 0.1 mm), and the pressure is set to 4.0 MPa and the temperature is increased. After thermocompression bonding at 220 ° C. for 90 minutes, the carrier was peeled off to obtain a copper-clad laminate as a laminate for evaluation.
  • GHPL-830NSF manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 0.1 mm
  • a plurality of the evaluation laminates were prepared, and each of the evaluation laminates was etched with a sulfuric acid-hydrogen peroxide-based etchant at different times, and an etching amount required for completely eliminating copper on the surface ( Depth) was measured. The measurement was performed by confirming with an optical microscope (500 times).
  • the control of the etching time was performed by changing the transport speed of the etching apparatus. More specifically, under the condition that the etching amount is 1.60 ⁇ m when the transport speed of the etching apparatus is 1.0 m / min, the transport speed is gradually reduced so that the etching amount is increased by 0.1 ⁇ m (that is, the etching speed is increased).
  • the evaluation laminate was etched with the time being gradually increased).
  • the etching amount calculated from the transport speed when the residual copper was no longer detected by the optical microscope was defined as the etching amount necessary for completely removing the copper.
  • etching amount required for completely removing the copper obtained by the above measurement was rated and evaluated based on the following criteria, and the evaluations A and B were judged to be acceptable. The results were as shown in Table 1. ⁇ Etching evaluation criteria> -Evaluation A: Required etching amount is 2.7 ⁇ m or less. -Evaluation B: Required etching amount is more than 2.7 ⁇ m and 3.0 ⁇ m or less. -Evaluation C: Required etching amount is more than 3.0 ⁇ m.
  • Adhesion of plating circuit (shear strength) A dry film was adhered to the above-described laminate for evaluation, and exposure and development were performed. After depositing a copper layer having a thickness of 13.5 ⁇ m by pattern plating on the layered product masked with the developed dry film, the dry film was peeled off. The exposed copper portion was etched with a sulfuric acid-hydrogen peroxide-based etchant to produce a shear strength measuring circuit sample having a height of 15 ⁇ m, a width of 10 ⁇ m, and a length of 150 ⁇ m. Using a bonding strength tester (4000 Plus Bondtester, manufactured by Nordson DAGE), the shear strength when the circuit sample for shear strength measurement was pushed down from the side was measured.
  • a bonding strength tester 4000 Plus Bondtester, manufactured by Nordson DAGE
  • the stacked body 134 on which the circuit 136 is formed is placed on the movable stage 132, and the stage 132 is moved together with the stage 132 in the direction of the arrow in FIG.
  • a lateral force was applied to the side surface of the circuit 136 to push it down, and the force (gf) at that time was measured by the detector 138, and the measured value was adopted as the shear strength.
  • the test type was a destruction test, and the measurement was performed under the conditions of a test height of 10 ⁇ m, a descent speed of 0.050 mm / s, a test speed of 100.0 ⁇ m / s, a tool moving amount of 0.05 mm, and a fracture recognition point of 10%. .
  • the obtained shear strength was rated and evaluated based on the following criteria, and the evaluations A and B were determined to be acceptable. The results were as shown in Table 1.
  • Example 9 (comparison) Except that the preparation of the carrier was performed according to the procedure shown below, and that the ultra-thin copper foil was roughened by the black plating step shown below instead of the baking plating step and the cover plating step, Preparation and evaluation of a copper foil with a carrier were performed in the same manner as in Example 1. The results were as shown in Table 1.
  • ⁇ Sulfuric acid acidic copper sulfate solution composition > -Copper concentration: 80g / L -Free sulfuric acid concentration: 140g / L -Bis (3-sulfopropyl) disulfide concentration: 30 mg / L -Diallyldimethylammonium chloride polymer concentration: 50 mg / L -Chlorine concentration: 40mg / L
  • Electrolysis is performed on the deposition surface of the ultra-thin copper foil using the following black roughening copper electrolytic solution having the following composition at a solution temperature of 30 ° C., a current density of 50 A / dm 2 , and a time of 4 sec. Was performed.
  • Example 10 Comparison
  • Preparation and evaluation of a copper foil with a carrier were performed in the same manner as in Example 1, except that the surface of the ultrathin copper foil was not subjected to a roughening treatment.
  • the results were as shown in Table 1.
  • Example 11 Comparison
  • Preparation and evaluation of a copper foil with a carrier were performed in the same manner as in Example 1, except that the baking plating step and the cover plating step were performed as follows. The results were as shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

La présente invention concerne une feuille de cuivre rugosifiée qui permet d'obtenir un bon équilibre entre d'excellentes propriétés de gravure et une résistance au cisaillement élevée lors du traitement d'un stratifié plaqué de cuivre ou de la production d'une carte de circuit imprimé. Cette feuille de cuivre rugosifiée a une surface rugosifiée sur au moins un côté ; et la surface rugosifiée a une hauteur maximale Sz allant de 0,65 µm à 1,00 µm telle que mesurée conformément à la norme ISO 25178, un rapport de surface étendu Sdr de l'interface allant de 1,50 à 4,20 tel que mesuré conformément à la norme ISO 25178, et une densité de pics Spd allant de 6,50 × 106 pics/2 à 8,50 × 106 pics/mm2 telle que mesurée conformément à la norme ISO 25178.
PCT/JP2019/029224 2018-08-10 2019-07-25 Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, stratifié plaqué de cuivre et carte de circuit imprimé WO2020031721A1 (fr)

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CN201980047289.3A CN112424399B (zh) 2018-08-10 2019-07-25 粗糙化处理铜箔、带载体的铜箔、覆铜层叠板及印刷电路板
MYPI2021000356A MY186454A (en) 2018-08-10 2019-07-25 Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board
KR1020217000738A KR102480377B1 (ko) 2018-08-10 2019-07-25 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
JP2020536455A JP6905157B2 (ja) 2018-08-10 2019-07-25 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板

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JP7051988B1 (ja) 2020-11-27 2022-04-11 古河電気工業株式会社 粗化処理銅箔、銅張積層板、及びプリント配線板
WO2022215330A1 (fr) * 2021-04-09 2022-10-13 福田金属箔粉工業株式会社 Feuille de cuivre traitée en surface, et stratifié plaqué de cuivre et carte de circuit imprimé utilisant tous les deux ladite feuille de cuivre traitée en surface
US20230043755A1 (en) * 2019-12-24 2023-02-09 Nippon Denkai, Ltd. Surface-treated copper foil and method for manufacturing same
WO2023054398A1 (fr) * 2021-09-30 2023-04-06 三井金属鉱業株式会社 Feuille de cuivre rendue rugueuse, stratifié plaqué de cuivre et procédé de fabrication de carte de circuit imprimé
WO2023189839A1 (fr) * 2022-03-31 2023-10-05 三井金属鉱業株式会社 Feuille métallique avec support
KR20240009403A (ko) 2021-05-20 2024-01-22 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
KR20240009404A (ko) 2021-05-20 2024-01-22 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
KR20240009937A (ko) 2021-05-20 2024-01-23 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
WO2024195538A1 (fr) * 2023-03-23 2024-09-26 三井金属鉱業株式会社 Procédé de fabrication de carte de circuit imprimé
WO2024195539A1 (fr) * 2023-03-23 2024-09-26 三井金属鉱業株式会社 Procédé de fabrication de carte de circuit imprimé

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WO2019163962A1 (fr) * 2018-02-23 2019-08-29 古河電気工業株式会社 Feuille de cuivre électrolytique, électrode négative d'élément secondaire au lithium-ion utilisant la feuille de cuivre électrolytique, élément secondaire au lithium-ion, stratifié à placage de cuivre et carte de circuit imprimé
WO2021157362A1 (fr) * 2020-02-04 2021-08-12 三井金属鉱業株式会社 Feuille de cuivre traitée par rugosification, feuille de cuivre avec support, carte stratifiée cuivrée, et carte de circuit imprimé

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WO2016117587A1 (fr) * 2015-01-22 2016-07-28 三井金属鉱業株式会社 Film de cuivre ultra-mince à support et son procédé de fabrication
JP2018026590A (ja) * 2015-08-06 2018-02-15 Ｊｘ金属株式会社 キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法

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US20230043755A1 (en) * 2019-12-24 2023-02-09 Nippon Denkai, Ltd. Surface-treated copper foil and method for manufacturing same
US11952675B2 (en) * 2019-12-24 2024-04-09 Nippon Denkai, Ltd. Surface-treated copper foil and method for manufacturing same
JP7051988B1 (ja) 2020-11-27 2022-04-11 古河電気工業株式会社 粗化処理銅箔、銅張積層板、及びプリント配線板
WO2022113806A1 (fr) * 2020-11-27 2022-06-02 古河電気工業株式会社 Feuille de cuivre rugosifiée, stratifié plaqué cuivre et carte de circuit imprimé
JP2022085378A (ja) * 2020-11-27 2022-06-08 古河電気工業株式会社 粗化処理銅箔、銅張積層板、及びプリント配線板
WO2022215330A1 (fr) * 2021-04-09 2022-10-13 福田金属箔粉工業株式会社 Feuille de cuivre traitée en surface, et stratifié plaqué de cuivre et carte de circuit imprimé utilisant tous les deux ladite feuille de cuivre traitée en surface
JP2022161636A (ja) * 2021-04-09 2022-10-21 福田金属箔粉工業株式会社 表面処理銅箔及び該表面処理銅箔を用いた銅張積層板並びにプリント配線板
US12063747B2 (en) 2021-04-09 2024-08-13 Fukuda Metal Foil & Powder Co., Ltd. Surface-treated copper foil, copper-clad laminate and printed wiring board using the surface-treated copper foil
JP7273883B2 (ja) 2021-04-09 2023-05-15 福田金属箔粉工業株式会社 表面処理銅箔及び該表面処理銅箔を用いた銅張積層板並びにプリント配線板
CN116917552A (zh) * 2021-04-09 2023-10-20 福田金属箔粉工业株式会社 表面处理铜箔及使用该表面处理铜箔的覆铜层压板以及印刷线路板
KR20240009937A (ko) 2021-05-20 2024-01-23 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
KR20240009404A (ko) 2021-05-20 2024-01-22 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
KR20240009403A (ko) 2021-05-20 2024-01-22 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어 구비 구리박, 동장 적층판 및 프린트 배선판
WO2023054398A1 (fr) * 2021-09-30 2023-04-06 三井金属鉱業株式会社 Feuille de cuivre rendue rugueuse, stratifié plaqué de cuivre et procédé de fabrication de carte de circuit imprimé
JP7427846B1 (ja) 2022-03-31 2024-02-05 三井金属鉱業株式会社 キャリア付金属箔
WO2023189839A1 (fr) * 2022-03-31 2023-10-05 三井金属鉱業株式会社 Feuille métallique avec support
WO2024195538A1 (fr) * 2023-03-23 2024-09-26 三井金属鉱業株式会社 Procédé de fabrication de carte de circuit imprimé
WO2024195539A1 (fr) * 2023-03-23 2024-09-26 三井金属鉱業株式会社 Procédé de fabrication de carte de circuit imprimé

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KR102480377B1 (ko) 2022-12-23
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