WO2011138876A1 - 印刷回路用銅箔 - Google Patents
印刷回路用銅箔 Download PDFInfo
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- WO2011138876A1 WO2011138876A1 PCT/JP2011/052276 JP2011052276W WO2011138876A1 WO 2011138876 A1 WO2011138876 A1 WO 2011138876A1 JP 2011052276 W JP2011052276 W JP 2011052276W WO 2011138876 A1 WO2011138876 A1 WO 2011138876A1
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- copper foil
- copper
- particle layer
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- layer
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- C25D5/10—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
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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
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- 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
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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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
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- 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
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
Definitions
- the present invention relates to a copper foil for printed circuit, and in particular, after forming a primary particle layer of copper on the surface of the copper foil, a secondary particle layer by copper-cobalt-nickel alloy plating is formed thereon.
- the present invention relates to a copper foil for a printed circuit that can reduce the occurrence of powder falling from the copper foil, increase the peel strength, and improve the heat resistance.
- the copper foil for printed circuits of the present invention is particularly suitable for fine pattern printed circuits and magnetic head FPCs (Flexible Printed Circuits), for example.
- Copper and copper alloy foils have greatly contributed to the development of electrical and electronic industries, and are indispensable particularly as printed circuit materials.
- Copper foil for printed circuit is generally used to produce a copper-clad laminate by laminating and bonding to a base material such as a synthetic resin board or film through an adhesive or under high temperature and high pressure without using an adhesive.
- a necessary circuit is printed through a resist coating and exposure process, and then an etching process for removing unnecessary portions is performed. Finally, the required elements are soldered to form various printed circuit boards for the electronic device.
- the copper foil for printed circuit boards differs in the surface (roughening surface) adhere
- the requirements for the roughened surface formed on the copper foil are as follows: 1) No oxidation discoloration during storage, 2) High peel strength with substrate, high temperature heating, wet processing, soldering, chemicals It is sufficient even after treatment or the like, and 3) that there is no so-called lamination stain that occurs after lamination with the substrate and etching.
- the roughening treatment of the copper foil plays a major role as determining the adhesiveness between the copper foil and the base material.
- a copper roughening treatment in which electrodeposition of copper was initially employed was adopted, but various techniques were proposed thereafter, and copper--for the purpose of improving the heat-resistant peel strength, hydrochloric acid resistance and oxidation resistance.
- Nickel roughening is established as one typical processing method.
- the present applicant has proposed a copper-nickel roughening treatment (see Patent Document 1) and has achieved results.
- the surface of the copper-nickel treatment is black, and particularly in the rolled foil for flexible substrates, this copper-nickel treatment black has been recognized as a symbol as a product.
- the copper-nickel roughening treatment is excellent in heat-resistant peel strength, oxidation resistance, and hydrochloric acid resistance, it is difficult to etch with an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 ⁇ m.
- an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 ⁇ m.
- the processing layer becomes an etching residue. Therefore, the applicant has previously developed a Cu—Co treatment (see Patent Documents 2 and 3) and a Cu—Co—Ni treatment (see Patent Document 4) as fine pattern treatments.
- the tendency of the circuit to be easily peeled off by the hydrochloric acid etching solution becomes stronger, and the prevention thereof is necessary.
- the circuit becomes thinner, the circuit is also easily peeled off due to a high temperature during processing such as soldering, and the prevention thereof is also necessary.
- As fine patterning progresses it is no longer an essential requirement to be able to etch a printed circuit having a pitch of 150 ⁇ m or less with a CuCl 2 etchant, for example, and alkali etching is becoming a necessary requirement with diversification of resists and the like.
- the black surface is also important from the viewpoint of copper foil fabrication and chip mounting in terms of increasing alignment accuracy and heat absorption.
- the present applicant formed a cobalt plating layer or a cobalt-nickel alloy plating layer on the surface of the copper foil and then formed a cobalt plating layer or a cobalt-nickel alloy plating layer.
- it has many of the above-mentioned general properties, especially the above-mentioned properties comparable to Cu-Ni treatment, and it does not reduce the heat-resistant peel strength when using an acrylic adhesive,
- rust prevention represented by chromium oxide single coating treatment or mixed coating treatment of chromium oxide and zinc and / or zinc oxide. Processing is performed.
- the present inventor is concerned with the treatment of a copper foil for printed circuits in which a cobalt-nickel alloy plating layer is formed on the surface of the copper foil after a roughening treatment by copper-cobalt-nickel alloy plating, and further a zinc-nickel alloy plating layer is formed.
- a cobalt-nickel alloy plating layer is formed on the surface of the copper foil after a roughening treatment by copper-cobalt-nickel alloy plating, and further a zinc-nickel alloy plating layer is formed.
- Patent Document 7 and Patent Document 8 disclose initial techniques of roughening treatment by copper-cobalt-nickel alloy plating.
- the shape of the roughened particles composed of the copper-cobalt-nickel alloy plating formed on the surface of the copper foil is dendritic, it peels off from the upper part or the root of the dendron, A problem commonly referred to as the powdering phenomenon occurred.
- This powder-off phenomenon is a troublesome problem, and the roughened layer of copper-cobalt-nickel alloy plating is characterized by excellent adhesion to the resin layer and excellent heat resistance.
- the particles easily fall off due to an external force, resulting in problems such as peeling due to “rubbing” during processing, contamination of the roll with peeling powder, and etching residue due to peeling powder.
- Copper - cobalt - (Example 1, Cu: 3.3mg / dm 2 , Co: 6.3mg / dm 2, Ni: 1.6mg / dm 2) blackening treatment by nickel alloy plating on the assumption be made is
- the copper foil is pre-plated with copper, and the outermost layer is a smooth layer of cobalt or cobalt-nickel.
- Patent Document 9 provides a smooth layer of cobalt or a cobalt-nickel layer as the outermost layer is the main requirement for preventing powder falling.
- the powder-off of the copper-cobalt-nickel alloy plating is rather the particle shape of the primary particle layer of copper applied to the copper foil, and the cobalt or cobalt-nickel layer as the secondary particles formed thereon.
- the composition and particle shape is a problem of powder falling off.
- Patent Document 9 it is difficult to say that the essential problem of powder falling is solved only by forming a smooth layer as the outermost layer.
- JP-A-52-145769 Japanese Patent Publication No.63-2158 Japanese Patent Application No. 1-112227 Japanese Patent Application No. 1-112226 Japanese Patent Publication No. 6-54831 Japanese Patent No. 2849059 Japanese Patent Laid-Open No. 4-96395 JP-A-10-18075 JP 2004-260068 A
- the problem of the present invention is that a roughening treatment consisting of copper-cobalt-nickel alloy plating, which is the most basic, causes the dendritic coarsening particles to fall off from the surface of the copper foil and is generally referred to as powdering.
- the present invention provides a printed circuit copper foil capable of suppressing processing unevenness, increasing peel strength, and improving heat resistance. Along with the development of electronic devices, the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. It is an object of the present invention to provide a technique that meets these requirements.
- the present invention provides the following inventions.
- the foil has a primary particle layer with an average particle diameter of 0.25 to 0.45 ⁇ m, and a secondary particle layer made of a ternary alloy composed of copper, cobalt and nickel has an average particle diameter of 0.05-0.
- a copper foil for printed circuit characterized in that it is 25 ⁇ m.
- a copper foil for a circuit can be provided.
- the cobalt-nickel alloy plating layer may have a cobalt adhesion amount of 200 to 3000 ⁇ g / dm 2 and a cobalt ratio of 60 to 66 mass%.
- the zinc-nickel alloy plating layer has a total amount in the range of 150 to 500 ⁇ g / dm 2 , a nickel amount in the range of 50 ⁇ g / dm 2 or more, and a nickel ratio in the range of 0.16 to 0.40.
- -A nickel alloy plating layer can be formed.
- a rust prevention treatment layer can be formed on the zinc-nickel alloy plating layer.
- the independent film processing of chromium oxide or the mixed film processing layer of chromium oxide, zinc, and / or zinc oxide can be formed, for example.
- a silane coupling layer can be formed on the mixed film treatment layer.
- the printed circuit copper foil can produce a copper-clad laminate bonded to a resin substrate by thermocompression bonding without using an adhesive.
- the roughened particles formed in a dendritic shape are peeled off from the surface of the copper foil.
- the present invention provides a copper foil for a printed circuit that can suppress a phenomenon called powder fall, increase peel strength, and improve heat resistance. Further, abnormally grown particles are reduced, the particle diameters are uniform, and the entire surface is covered, so that the etching property is good and a highly accurate circuit can be formed.
- the miniaturization and high integration of semiconductor devices have further progressed, and the processing performed in the manufacturing process of these printed circuits has been made more severe. Has a technical effect to answer.
- FIG. It is the microscope picture of the surface at the time of performing the roughening process which consists of copper-cobalt-nickel alloy plating on the conventional copper foil.
- a primary particle layer is previously formed on a copper foil, and a secondary particle layer made of copper-cobalt-nickel alloy plating is formed on the primary particle layer. It is a micrograph.
- a primary particle layer is formed in advance on a copper foil, and a secondary particle layer made of copper-cobalt-nickel alloy plating is formed on the primary particle layer. It is the microscope picture of the surface at the time of improving roughness further.
- the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil.
- the surface of the copper foil that adheres to the resin base material that is, the roughened surface, has a “fisture” on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after lamination.
- a roughening treatment is performed to perform electrodeposition.
- the electrolytic copper foil has irregularities at the time of manufacture, the irregularities are further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment.
- the content of treatment may be somewhat different between the rolled copper foil and the electrolytic copper foil.
- a known treatment related to copper foil roughening is included as necessary, and is referred to as “roughening treatment”.
- This roughening treatment is performed by copper-cobalt-nickel alloy plating (in the following explanation, the roughening treatment of copper-cobalt-nickel alloy plating is performed to clarify the difference from the previous step. Is called a “secondary particle layer”), as described above, simply forming a copper-cobalt-nickel alloy plating layer on a copper foil causes problems such as powder falling as described above. To do.
- FIG. 3 shows a photomicrograph of the surface of the copper foil in which a copper-cobalt-nickel alloy plating layer is formed on the copper foil.
- fine particles developed in a dendritic shape can be seen.
- the fine particles developed in a dendritic shape shown in FIG. 3 are produced at a high current density.
- particle nucleation during initial electrodeposition is suppressed, and new particle nuclei are formed at the tip of the particle. Will grow. Therefore, in order to prevent this, when electroplating is performed at a reduced current density, sharp rising does not occur, particles increase, and rounded particles grow as shown in FIG.
- the powder falling is slightly improved, but it is not sufficient to achieve the object of the present invention.
- the state of powder falling when the copper-cobalt-nickel alloy plating layer as shown in FIG. 3 is formed is shown in the conceptual explanatory diagram of FIG.
- the cause of this powder fall is that fine particles are formed in a dendritic shape on the copper foil as described above.
- the dendritic particles are easily broken by an external force and fall off from the root.
- the fine dendritic particles cause peeling due to “rubbing” during the process, contamination of the roll with peeling powder, and etching residue due to peeling powder.
- a secondary particle layer made of a ternary alloy made of copper, cobalt and nickel is formed on the primary particle layer.
- FIG. 5 to 6 show micrographs of the surface on which the primary particles and secondary particles are formed on the copper foil (details will be described later). This eliminates peeling due to "rubbing" during processing, dirt on the roll due to peeling powder, etching residue due to peeling powder, that is, it can suppress the phenomenon called powder falling and processing unevenness, increase peel strength, and The copper foil for printed circuits which can improve heat resistance can be obtained.
- the average particle size of the primary particle layer is 0.25 to 0.45 ⁇ m
- the average particle size of the secondary particle layer made of a ternary alloy composed of copper, cobalt and nickel is 0.05 to 0.25 ⁇ m. As is clear from the examples shown below, this is the optimum condition for preventing powder falling off.
- the primary particle layer and the secondary particle layer are formed by an electroplating layer.
- the secondary particles are characterized by one or more dendritic particles grown on the primary particles.
- the average particle size of the secondary particle layer is as small as 0.05 to 0.25 ⁇ m, but this particle size can also be called the particle height. That is, it can be said that one of the features of the present invention is that the height of the secondary particles is suppressed and the separation (powder off) of the particles is suppressed.
- the primary particle layer and the secondary particle layer thus formed can achieve an adhesive strength of 0.80 kg / cm or more, and further an adhesive strength of 0.90 kg / cm or more. Further, when looking at the roughness of the surface on which the primary particle layer and the secondary particle layer are formed, Rz can be 1.5 or less, and further Rz can be 1.0 ⁇ m or less. Lowering the surface roughness is more effective in suppressing the powder falling phenomenon.
- This invention can provide the copper foil for printed circuits provided with said property and characteristic.
- Copper primary particle plating conditions An example of the plating conditions for the primary particles of copper is as follows. In addition, this plating condition shows a suitable example to the last, and the average particle diameter formed on copper foil plays the role of powder omission prevention in the primary particle of copper. Therefore, as long as the average particle diameter falls within the scope of the present invention, the plating conditions other than those indicated below are not disturbed. The present invention includes these. Moreover, you may give metal layer plating between copper foil and primary particle
- a heat-resistant layer can be further formed on the secondary particle layer.
- the plating conditions are shown below.
- Liquid composition Nickel 5-20 g / L, Cobalt 1-8 g / L pH: 2-3
- the present invention can further form the following heat-resistant layer on the secondary particle layer.
- the plating conditions are shown below.
- Liquid composition Nickel 2-30 g / L, Zinc 2-30 g / L pH: 3-4
- the present invention can further form the following antirust layer.
- the plating conditions are shown below.
- conditions for the immersion chromate treatment are shown, but electrolytic chromate treatment may be used.
- Liquid composition potassium dichromate 1-10 g / L, zinc 0-5 g / L pH: 3-4
- Liquid temperature 50-60C
- Current density 0-2A / dm 2 (for immersion chromate treatment)
- Coulomb amount 0 to 2 As / dm 2 (for immersion chromate treatment)
- Copper as the secondary particles - cobalt - nickel alloy plating, by electrolytic plating, coating weight of 10 ⁇ 30mg / dm 2 of copper -100 ⁇ 3000 ⁇ g / dm 2 of cobalt -50 ⁇ 500 ⁇ g / dm 2 3 ternary alloy of nickel A layer can be formed.
- Co adhesion amount is less than 100 ⁇ g / dm 2 , the heat resistance is deteriorated and the etching property is also deteriorated.
- the amount of Co deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into consideration, etching spots occur, and deterioration of acid resistance and chemical resistance can be considered.
- Ni adhesion amount When the Ni adhesion amount is less than 50 ⁇ g / dm 2 , the heat resistance deteriorates. On the other hand, when the Ni adhesion amount exceeds 500 ⁇ g / dm 2 , the etching property is lowered. That is, although it is not at a level where etching remains and etching cannot be performed, it becomes difficult to form a fine pattern.
- Preferred Co deposition amount is 500 ⁇ 2000 ⁇ g / dm 2, and preferably nickel coating weight is 50 ⁇ 300 ⁇ g / dm 2.
- copper - cobalt - deposition of nickel alloy plating it may be desirable is 10 ⁇ 30mg / dm 2 of copper -100 ⁇ 3000 ⁇ g / dm 2 of cobalt -50 ⁇ 500 ⁇ g / dm 2 of nickel.
- Each adhesion amount of the ternary alloy layer is a desirable condition, and a range exceeding this amount is not denied.
- the etching stain means that Co remains without being dissolved when etched with copper chloride
- the etching residue means that Ni remains undissolved when alkaline etching is performed with ammonium chloride. It means to end.
- an alkaline etching solution and a copper chloride based etching solution as described in the following examples are used. Although this etching solution and etching conditions are versatile, it should be understood that they are not limited to these conditions and can be arbitrarily selected.
- a cobalt-nickel alloy plating layer can be formed on the roughened surface.
- the cobalt-nickel alloy plating layer preferably has a cobalt adhesion amount of 200 to 3000 ⁇ g / dm 2 and a cobalt ratio of 60 to 66 mass%.
- This treatment can be regarded as a kind of rust prevention treatment in a broad sense.
- This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially lowered.
- the amount of cobalt adhesion is less than 200 ⁇ g / dm 2 , the heat-resistant peel strength decreases, the oxidation resistance and chemical resistance deteriorate, and the treatment surface becomes reddish.
- the amount of cobalt deposition exceeds 3000 ⁇ g / dm 2 , it is not preferable when the influence of magnetism must be taken into consideration, etching spots occur, and deterioration of acid resistance and chemical resistance is considered.
- a preferable cobalt adhesion amount is 400 to 2500 ⁇ g / dm 2 .
- the cobalt ratio is preferably 60 to 66 mass%.
- the direct major cause of soft etching soaking is a heat-resistant rust-proof layer made of a zinc-nickel alloy plating layer, but cobalt can also cause the soaking of soft etching.
- the above adjustment is a more desirable condition.
- the nickel adhesion amount is small, the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance are lowered. Further, when the nickel adhesion amount is too large, the alkali etching property is deteriorated, so it is desirable to determine the balance with the cobalt content.
- a zinc-nickel alloy plating layer can be further formed on the cobalt-nickel alloy plating.
- the total amount of the zinc-nickel alloy plating layer is 150 to 500 ⁇ g / dm 2 and the nickel ratio is 16 to 40% by mass. This has a role of a heat-resistant rust-proof layer.
- This condition is also a preferable condition, and other known zinc-nickel alloy plating can be used. It will be understood that this zinc-nickel alloy plating is a preferred additional condition in the present invention.
- the processing performed in the manufacturing process of the printed circuit becomes much higher, and there is heat generation during use of the device after it has become a product.
- Nickel has an effect of suppressing penetration of an etching agent (etching aqueous solution of H 2 SO 4 : 10 wt%, H 2 O 2 : 2 wt%) used in soft etching.
- the total amount of the zinc-nickel alloy plating layer is 150 to 500 ⁇ g / dm 2
- the lower limit of the nickel ratio in the alloy layer is 16% by mass
- the upper limit is 40% by mass
- the nickel The content of 50 ⁇ g / dm 2 or more serves as a heat-resistant and rust-proof layer, suppresses the penetration of the etching agent used during soft etching, and prevents weakening of the joint strength of the circuit due to corrosion It has the effect that it can be done.
- the heat and rust prevention ability is lowered and it becomes difficult to play a role as a heat and rust prevention layer, and if the total amount exceeds 500 ⁇ g / dm 2 The hydrochloric acid resistance tends to deteriorate.
- the lower limit of the nickel ratio in the alloy layer is less than 16% by mass, the amount of penetration at the time of soft etching exceeds 9 ⁇ m, which is not preferable.
- the upper limit value of 40% by mass of the nickel ratio is a technical limit value at which a zinc-nickel alloy plating layer can be formed.
- a cobalt-nickel alloy plating layer and further a zinc-nickel alloy plating layer may be sequentially formed on the copper-cobalt-nickel alloy plating layer as the secondary particle layer as necessary. it can.
- the total amount of cobalt and nickel deposited in these layers can also be adjusted. It is desirable that the total deposition amount of cobalt is 300 to 4000 ⁇ g / dm 2 and the total deposition amount of nickel is 150 to 1500 ⁇ g / dm 2 .
- the total adhesion amount of cobalt is less than 300 ⁇ g / dm 2 , the heat resistance and chemical resistance are lowered, and when the total adhesion amount of cobalt exceeds 4000 ⁇ g / dm 2 , etching spots may occur. Moreover, if the total adhesion amount of nickel is less than 150 microgram / dm ⁇ 2 >, heat resistance and chemical resistance will fall. When the total adhesion amount of nickel exceeds 1500 ⁇ g / dm 2 , an etching residue is generated. Preferably, the total deposit of cobalt is 1500-3500 ⁇ g / dm 2 and the total deposit of nickel is 500-1000 ⁇ g / dm 2 . If the above conditions are satisfied, the conditions described in this paragraph need not be particularly limited.
- a rust prevention treatment is performed as necessary.
- a preferable antirust treatment is a coating treatment of chromium oxide alone or a mixture coating treatment of chromium oxide and zinc / zinc oxide.
- Chromium oxide and zinc / zinc oxide mixture film treatment is a method of forming zinc or zinc oxide comprising zinc oxide and chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. It is the process which coat
- At least one kind of dichromate such as K 2 Cr 2 O 7 and Na 2 Cr 2 O 7 and CrO 3 and a water-soluble zinc salt such as ZnO 4 and ZnSO 4 ⁇ 7H are used.
- a mixed aqueous solution of at least one kind such as 2 O and an alkali hydroxide is used.
- a typical plating bath composition and electrolysis conditions are as follows.
- the copper foil thus obtained has excellent heat resistance peel strength, oxidation resistance and hydrochloric acid resistance.
- a printed circuit having a pitch of 150 ⁇ m or less can be etched with a CuCl 2 etching solution, and alkali etching can be performed. In addition, penetration into the circuit edge portion during soft etching can be suppressed.
- the soft etching solution an aqueous solution of H 2 SO 4 : 10 wt% and H 2 O 2 : 2 wt% can be used. Processing time and temperature can be adjusted arbitrarily.
- alkaline etching liquids for example, liquids such as NH 4 OH: 6 mol / liter, NH 4 Cl: 5 mol / liter, CuCl 2 : 2 mol / liter (temperature: 50 ° C.) are known.
- the copper foil obtained in all the above steps has a black color as in the case of the Cu—Ni treatment.
- Black is meaningful in terms of alignment accuracy and high heat absorption rate.
- printed circuit boards including rigid boards and flexible boards are mounted with components such as ICs, resistors, and capacitors in an automatic process, and chip mounting is performed while reading circuits with sensors.
- alignment on the copper foil treated surface may be performed through a film such as Kapton.
- Kapton This also applies to positioning when forming a through hole.
- the closer the processing surface is to black the better the light absorption and the higher the positioning accuracy.
- the copper foil and the film are often cured and bonded together while applying heat. At this time, when heating is performed by using long waves such as far infrared rays and infrared rays, the heating efficiency is improved when the color tone of the treated surface is black.
- silane treatment for applying a silane coupling agent to at least the roughened surface on the rust preventive layer is performed mainly for the purpose of improving the adhesive force between the copper foil and the resin substrate.
- the silane coupling agent used for the silane treatment include olefin silane, epoxy silane, acrylic silane, amino silane, and mercapto silane, which can be appropriately selected and used.
- the application method may be any of spraying a silane coupling agent solution by spraying, coating with a coater, dipping, pouring and the like.
- 60-15654 describes that the adhesion between a copper foil and a resin substrate is improved by subjecting the rough surface of the copper foil to a chromate treatment followed by a silane coupling agent treatment. . Refer to this for details. Thereafter, if necessary, an annealing treatment may be performed for the purpose of improving the ductility of the copper foil.
- Example 1 to Example 9 A primary particle layer (Cu) and a secondary particle layer (copper-cobalt-nickel alloy plating) were formed on the rolled copper foil under the conditions shown below.
- the bath composition and plating conditions used are as follows. [Bath composition and plating conditions]
- the bath composition and plating conditions used are as follows.
- Table 1 shows the diameter, powder fall, peel strength, heat resistance, and roughness (Rz). Moreover, the same result is shown in Table 1 as a comparative example.
- Example 1 the current density for forming primary particles is 51 A / dm 2 and 2 A / dm 2 , and the coulomb amounts are 72 As / dm 2 and 8 As / dm 2. This is a case where 24 A / dm 2 and the coulomb amount are 34 As / dm 2 .
- the current density and the amount of Coulomb which form primary particles are two steps, when forming primary particles normally, two steps of electroplating are required. That is, the plating conditions for the first stage core particle formation and the electroplating for the second stage core particle growth.
- the first plating conditions are electroplating conditions for forming the first stage nucleating particles
- the second plating conditions are electroplating conditions for growing the second stage nucleating particles.
- the average particle diameter of the primary particles was 0.25 ⁇ m
- the average particle diameter of the secondary particles was 0.05 ⁇ m
- the normal peel strength was as high as 0.88 kg / cm
- the heat resistance 180 The peel strength after heating at 48 ° C. for 48 hours was as high as 0.71 kg / cm
- the surface roughness Rz was 0.98 ⁇ m.
- Example 2 the current density for forming the primary particles is 51 A / dm 2 and 2 A / dm 2 , and the coulomb amounts are 72 As / dm 2 and 8 As / dm 2. This is a case where 28 A / dm 2 and the coulomb amount are 39 As / dm 2 .
- the average particle diameter of the primary particles was 0.25 ⁇ m
- the average particle diameter of the secondary particles was 0.15 ⁇ m
- there was no powder falling the normal peel strength was as high as 0.90 kg / cm
- the heat resistance 180 The peel strength after heating at ° C for 48 hours was as high as 0.72 kg / cm
- the surface roughness Rz was 0.98 ⁇ m.
- Example 3 the current density for forming the primary particles is 51 A / dm 2 and 2 A / dm 2 , and the coulomb amounts are 72 As / dm 2 and 8 As / dm 2. This is a case where 31 A / dm 2 and the coulomb amount are 44 As / dm 2 .
- the average particle diameter of the primary particles was 0.25 ⁇ m
- the average particle diameter of the secondary particles was 0.25 ⁇ m
- the normal peel strength is as high as 0.92 kg / cm
- the heat resistance peel strength after heating at 180 ° C. for 48 hours
- the surface roughness Rz is 1.02 ⁇ m. It was.
- Example 4 the current density for forming primary particles is 55 A / dm 2 and 3 A / dm 2 , and the coulomb amounts are 77 As / dm 2 and 12 As / dm 2. This is a case where 24 A / dm 2 and the coulomb amount are 34 As / dm 2 .
- the average particle diameter of the primary particles was 0.35 ⁇ m
- the average particle diameter of the secondary particles was 0.05 ⁇ m
- there was no powder falling the normal peel strength was as high as 0.95 kg / cm
- the heat resistance 180 The peel strength after heating at 48 ° C. for 48 hours was as high as 0.73 kg / cm
- the surface roughness Rz was 1.20 ⁇ m.
- Example 5 the current density for forming the primary particles is 55 A / dm 2 and 3 A / dm 2 , and the coulomb amounts are 77 As / dm 2 and 12 As / dm 2. This is a case where 28 A / dm 2 and the coulomb amount are 39 As / dm 2 .
- the average particle diameter of the primary particles was 0.35 ⁇ m
- the average particle diameter of the secondary particles was 0.15 ⁇ m
- there was no powder falling the normal peel strength was as high as 0.96 kg / cm
- the heat resistance 180 The peel strength after 48 ° C heating for 48 hours was as high as 0.74 kg / cm
- the surface roughness Rz was 1.20 kg / cm.
- Example 6 the current density for forming the primary particles is 55 A / dm 2 and 3 A / dm 2 , and the coulomb amounts are 77 As / dm 2 and 12 As / dm 2. This is a case where 31 A / dm 2 and the coulomb amount are 44 As / dm 2 .
- the average particle diameter of the primary particles was 0.35 ⁇ m
- the average particle diameter of the secondary particles was 0.25 ⁇ m
- the normal peel strength is as high as 0.98 kg / cm
- the heat resistance peel strength after heating at 180 ° C. for 48 hours
- the surface roughness Rz is 1.51 ⁇ m. I was prepared.
- Example 7 the current density for forming the primary particles is 58 A / dm 2 and 4 A / dm 2 , and the coulomb amounts are 81 As / dm 2 and 16 As / dm 2. This is a case where 24 A / dm 2 and the coulomb amount are 34 As / dm 2 .
- the average particle diameter of the primary particles was 0.45 ⁇ m
- the average particle diameter of the secondary particles was 0.05 ⁇ m
- there was no powder falling the normal peel strength was as high as 0.96 kg / cm
- the heat resistance 180 The peel strength after heating at 48 ° C for 48 hours was as high as 0.71 kg / cm
- the surface roughness Rz was 1.21 ⁇ m.
- Example 8 the current density for forming the primary particles is 58 A / dm 2 and 4 A / dm 2 , and the coulomb amounts are 81 As / dm 2 and 16 As / dm 2. This is a case where 28 A / dm 2 and the coulomb amount are 39 As / dm 2 .
- the average particle diameter of the primary particles was 0.45 ⁇ m
- the average particle diameter of the secondary particles was 0.15 ⁇ m
- there was no powder falling the normal peel strength was as high as 0.97 kg / cm
- the heat resistance 180 The peel strength after heating at 48 ° C. for 48 hours was as high as 0.72 kg / cm
- the surface roughness Rz was 1.54 ⁇ m.
- Example 9 the current density for forming the primary particles is 58 A / dm 2 and 4 A / dm 2 , and the coulomb amounts are 81 As / dm 2 and 16 As / dm 2. This is a case where 31 A / dm 2 and the coulomb amount are 44 As / dm 2 .
- the average particle diameter of the primary particles was 0.45 ⁇ m
- the average particle diameter of the secondary particles was 0.25 ⁇ m
- the normal peel strength was as high as 0.98 kg / cm
- the heat resistance 180 The peel strength after heating at 48 ° C. for 48 hours was as high as 0.74 kg / cm
- the surface roughness Rz was 1.60 ⁇ m.
- the comparative example has the following results.
- the current density for forming the primary particles is 47 A / dm 2 and 1 A / dm 2
- the coulomb amounts are 66 As / dm 2 and 4 As / dm 2.
- 24 A / dm 2 and the coulomb amount are 34 As / dm 2 .
- the average particle size of the primary particles was 0.15 ⁇ m
- the average particle size of the secondary particles was 0.05 ⁇ m
- there was no powder falling but the normal peel strength was as low as 0.75 kg / cm
- the heat resistance (Peel strength after heating at 180 ° C. for 48 hours) also decreased to 0.70 kg / cm.
- the surface roughness Rz was as low as 0.87 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming the primary particles is 47 A / dm 2 and 1 A / dm 2
- the coulomb amounts are 66 As / dm 2 and 4 As / dm 2.
- 28 A / dm 2 and the coulomb amount are 39 As / dm 2 .
- the average particle diameter of the primary particles was 0.15 ⁇ m
- the average particle diameter of the secondary particles was 0.15 ⁇ m
- there was no powder falling but the normal peel strength was as low as 0.75 kg / cm, and the heat resistance (Peel strength after heating at 180 ° C. for 48 hours) also decreased to 0.70 kg / cm.
- the surface roughness Rz was as low as 0.88 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming primary particles is 47 A / dm 2 and 1 A / dm 2
- the coulomb amounts are 66 As / dm 2 and 4 As / dm 2.
- 31 A / dm 2 and the coulomb amount are 44 As / dm 2 .
- the average particle diameter of the primary particles was 1.5 ⁇ m
- the average particle diameter of the secondary particles was 0.25 ⁇ m
- powder falling was observed
- the normal peel strength was as low as 0.83 kg / cm
- the heat resistance The peel strength after heating at 180 ° C. for 48 hours was 0.72 kg / cm, which was an example level.
- the surface roughness Rz was 0.90 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming the primary particles is 47 A / dm 2 and 1 A / dm 2
- the coulomb amounts are 66 As / dm 2 and 4 As / dm 2.
- the average particle diameter of the primary particles was 0.15 ⁇ m
- the average particle diameter of the secondary particles was as large as 0.35 ⁇ m
- the normal peel strength was as low as 0.85 kg / cm
- the heat resistance peel strength after heating at 180 ° C. for 48 hours
- was 0.72 kg / cm which was an example level.
- the surface roughness Rz was 0.91 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming the primary particles is 51 A / dm 2 and 2 A / dm 2
- the coulomb amounts are 72 As / dm 2 and 8 As / dm 2.
- the average particle diameter of the primary particles was 0.25 ⁇ m
- the average particle diameter of the secondary particles was as large as 0.35 ⁇ m
- the normal peel strength was 0.93 kg / cm, an example level
- the heat resistance peel strength after heating at 180 ° C. for 48 hours
- the surface roughness Rz was 1.15 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming the primary particles is 55 A / dm 2 and 3 A / dm 2 , and the coulomb amounts are 77 As / dm 2 and 12 As / dm 2. This is a case of 34 A / dm 2 and a coulomb amount of 48 As / dm 2 .
- the average particle diameter of primary particles was 0.35 ⁇ m
- the average particle diameter of secondary particles was as large as 0.35 ⁇ m
- the normal peel strength was 0.98 kg / cm, an example level
- the heat resistance peel strength after heating at 180 ° C. for 48 hours
- the surface roughness Rz was 1.50 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- the current density for forming the primary particles is 58 A / dm 2 and 4 A / dm 2
- the coulomb amounts are 81 As / dm 2 and 16 As / dm 2.
- the average particle diameter of the primary particles was 0.45 ⁇ m
- the average particle diameter of the secondary particles was as large as 0.35 ⁇ m
- the normal peel strength was 0.98 kg / cm, which was an example level, but the heat resistance (peel strength after heating at 180 ° C. for 48 hours) was also 0.77 kg / cm, an example level.
- the surface roughness Rz increased to 1.55 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- Comparative Example 8 is a case where the current density for forming primary particles on the copper foil is 51 A / dm 2 and 2 A / dm 2 and the coulomb amounts are 72 As / dm 2 and 8 As / dm 2, and only the primary particle layer Is formed, and there is no secondary particle size.
- the average particle diameter of the primary particles is 0.25 ⁇ m, there is no powder falling, and the normal peel strength is 0.94 kg / cm, which is an example level, but heat resistance (peel strength after heating at 180 ° C. for 48 hours) Was significantly worse at 0.54 kg / cm.
- the surface roughness Rz was 1.10 ⁇ m.
- the overall evaluation as a printed circuit copper foil was poor.
- Comparative Example 9 shows a conventional example in which there is no primary particle diameter and only a secondary particle layer. That is, the current density for forming the secondary particles is 50 A / dm 2 and the coulomb amount is 25 As / dm 2 . As a result, the average particle diameter of the secondary particles was as large as 0.60 ⁇ m, and a large amount of powder falling occurred.
- the normal peel strength was 0.90 kg / cm, an example level, and the heat resistance (peel strength after heating at 180 ° C. for 48 hours) was also 0.73 kg / cm, an example level. Furthermore, the surface roughness Rz was 0.78 ⁇ m. This is an example in which there are many problems with powder falling, and the overall evaluation as a copper foil for printed circuits was poor.
- a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer.
- the average particle size of the primary particle layer is 0.25 to 0.45 ⁇ m
- the present invention having a thickness of 0.05 to 0.25 ⁇ m has an excellent effect of suppressing the phenomenon called powder fall and processing unevenness, further increasing the peel strength and improving the heat resistance. It turns out that it has the outstanding effect that it can do.
- the roughened particles formed in a dendritic shape are peeled off from the surface of the copper foil and are generally referred to as powdering.
- the present invention provides a copper foil for a printed circuit which has an excellent effect of suppressing processing unevenness, can further increase peel strength, and can improve heat resistance.
- the number of abnormally grown particles is reduced, the particle diameter is uniform, and the entire surface is covered, so that the etching property is good and the circuit can be formed with high accuracy, so that the semiconductor device can be downsized and highly integrated. It is useful as a printed circuit material for advanced electronic equipment.
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Abstract
Description
本発明の印刷回路用銅箔は、例えばファインパターン印刷回路及び磁気ヘッド用FPC( Flexible Printed Circuit )に、特に適する。
最終的に、所要の素子が半田付けされて、エレクトロニクスデバイス用の種々の印刷回路板を形成する。印刷回路板用銅箔は、樹脂基材と接着される面(粗化面)と非接着面(光沢面)とで異なるが、それぞれ多くの方法が提唱されている。
銅箔の粗化処理は、銅箔と基材との接着性を決定するものとして、大きな役割を担っている。この粗化処理としては、当初銅を電着する銅粗化処理が採用されていたが、その後、様々な技術が提唱され、耐熱剥離強度、耐塩酸性及び耐酸化性の改善を目的として銅-ニッケル粗化処理が一つの代表的処理方法として定着するようになっている。
本件出願人は、銅-ニッケル粗化処理を提唱し(特許文献1参照)、成果を納めてきた。銅-ニッケル処理表面は黒色を呈し、特にフレキシブル基板用圧延処理箔では、この銅-ニッケル処理の黒色が商品としてのシンボルとして認められるに至っている。
そこで、ファインパターン用処理として、本件出願人は、先にCu-Co処理(特許文献2及び特許文献3参照)及びCu-Co-Ni処理(特許文献4参照)を開発した。
これら粗化処理は、エッチング性、アルカリエッチング性及び耐塩酸性については、良好であったが、アクリル系接着剤を用いたときの耐熱剥離強度が低下することが改めて判明し、また耐酸化性も所期程充分ではなくそして色調も黒色までには至らず、茶乃至こげ茶色であった。
好ましくは、前記コバルトめっき層或いはコバルト-ニッケル合金めっき層を形成した後に、クロム酸化物の単独皮膜処理或いはクロム酸化物と亜鉛及び(又は)亜鉛酸化物との混合皮膜処理を代表とする防錆処理が施される。
このようなことから、特許文献5において確立された銅箔の表面に銅-コバルト-ニッケル合金めっきによる粗化処理後、コバルトめっき層或いはコバルト-ニッケル合金めっき層を形成する印刷回路用銅箔の処理方法において、耐熱剥離性を改善する発明を行った。
銅箔回路は、一段と細線化されているが、基板上で一旦回路を形成した後、銅回路の上表面を硫酸と過酸化水素を含有するエッチング液によりソフトエッチングする工程が行われているが、この工程において、ポリイミド等の樹脂基板と銅箔の接着部のエッジ部にエッチング液が染み込むという問題が生じた。
これは、銅箔の処理面の一部が侵食されているとも言える。このような侵食は、微細な回路においては、銅箔と樹脂との接合力を低下させるので、重要な問題である。これを解決することも要求されている。
この粉落ち現象は厄介な問題であり、銅-コバルト-ニッケル合金めっきの粗化処理層は、樹脂層との密着性に優れており、耐熱性にも優れているという特徴を有しているにもかかわらず、上記の通り、外力により粒子が脱落し易く、処理中の「こすれ」による剥離、剥離粉によるロールの汚れ、剥離粉によるエッチング残渣が生ずるという問題を生じた。
この場合は、最外層にコバルト又はコバルト-ニッケル層の平滑層を設けることが粉落ち防止の主たる要件となっている。しかし、銅-コバルト-ニッケル合金めっきの粉落ちは、むしろ銅箔へ施される銅の一次粒子の層の粒子形状、そしてこの上に形成される二次粒子としてのコバルト又はコバルト-ニッケル層の組成と、粒子形状が、粉落ちの問題となるものである。しかし、特許文献9には、最外層に平滑層を形成するだけで、粉落ちの本質的な問題を解決しているとは言い難い。
1)銅箔の表面に、銅の一次粒子層を形成した後、該一次粒子層の上に、銅、コバルト及びニッケルからなる3元系合金からなる二次粒子層を形成した印刷回路用銅箔であって、一次粒子層の平均粒子径が0.25-0.45μmであり、銅、コバルト及びニッケルからなる3元系合金からなる二次粒子層の平均粒子径が0.05-0.25μmであることを特徴とする印刷回路用銅箔。
2)前記一次粒子層及び二次粒子層が、電気めっき層であることを特徴とする上記1)記載の印刷回路用銅箔。
3)二次粒子が、前記一次粒子の上に成長した1又は複数個の樹枝状の粒子であることを特徴とする上記1)又は2)記載の印刷回路用銅箔。
4)一次粒子層及び二次粒子層の接着強度が0.80kg/cm以上であることを特徴とする上記1)~3)のいずれか一項に記載の印刷回路用銅箔。
5)一次粒子層及び二次粒子層の接着強度が0.90kg/cm以上であることを特徴とする上記1)~3)のいずれか一項に記載の印刷回路用銅箔。
6)一次粒子層及び二次粒子層を形成した表面の粗さRzが1.5μm以下であることを特徴とする上記1)~5)のいずれか一項に記載の印刷回路用銅箔。
7)一次粒子層及び二次粒子層を形成した表面の粗さRzが1.0μm以下であることを特徴とする上記1)~5)のいずれか一項に記載の印刷回路用銅箔。
前記コバルト-ニッケル合金めっき層は、コバルトの付着量を200~3000μg/dm2とし、かつコバルトの比率が60~66質量%とすることができる。
前記亜鉛-ニッケル合金めっき層においては、その総量を150~500μg/dm2の範囲とし、ニッケル量が50μg/dm2以上の範囲、かつニッケル比率が0.16~0.40の範囲にある亜鉛-ニッケル合金めっき層を形成することができる。
この防錆処理については、例えばクロム酸化物の単独皮膜処理若しくはクロム酸化物と亜鉛及び(又は)亜鉛酸化物との混合皮膜処理層を形成することができる。さらに、前記混合皮膜処理層上には、シランカップリング層を形成することができる。
上記の印刷回路銅箔は、接着剤を介さずに熱圧着により、樹脂基板と接着させた銅張積層板を製造することが可能である。
また、異常成長した粒子が少なくなり、粒子径が揃い、かつ全面を覆うことになるので、エッチング性が良好となり、精度の高い回路形成が可能となる。
電子機器の発展が進む中で、半導体デバイスの小型化、高集積化が更に進み、これらの印刷回路の製造工程で行われる処理が一段と厳しい要求がなされているが、本願発明をこれらの要求にこたえる技術的効果を有する。
圧延銅箔と電解銅箔とでは処理の内容を幾分異にすることもある。本発明においては、こうした前処理及び仕上げ処理をも含め、銅箔粗化と関連する公知の処理を必要に応じて含め、「粗化処理」と云っている。
このような高電流密度で処理された場合には、初期電着における粒子の核生成が抑制されるため、粒子先端に新たな粒子の核が形成されるため、次第に樹枝状に、細く長く粒子が成長することになる。
したがって、これを防止するために、電流密度を下げて電気めっきすると、図4に示すように、鋭い立ち上がりがなくなり、粒子が増加し、丸みを帯びた形状の粒子が成長する。しかし、この図4に示すような状況下においても、粉落ちはやや改善されるが、本願発明の目的を達成するためには十分でない。
これによって、処理中の「こすれ」による剥離、剥離粉によるロールの汚れ、剥離粉によるエッチング残渣が無くなり、すなわち粉落ちと言われる現象と処理ムラを抑制することができ、ピール強度を高め、かつ耐熱性を向上させることのできる印刷回路用銅箔を得ることができる。
上記一次粒子層及び二次粒子層は、電気めっき層により形成する。この二次粒子の特徴は、前記一次粒子の上に成長した1又は複数個の樹枝状の粒子である。
上記の通り、二次粒子層の平均粒子径を0.05-0.25μmと小さくしているが、この粒子径は粒子の高さと言い換えることもできる。すなわち、二次粒子の高さを抑制し、粒子の剥離(粉落ち)を抑制したのが、本願発明の特徴の一つとも言える。
また、一次粒子層及び二次粒子層を形成した表面の粗さを見ると、Rzを1.5以下さらには、Rzを1.0μm以下とすることができる。表面粗さを低くすることは、粉落ち現象を抑制するのにより有効である。本願発明は、上記の性状と特性を備えた印刷回路用銅箔を提供することができる。
銅の一次粒子のめっき条件の一例を挙げると、下記の通りである。
なお、このめっき条件はあくまで好適な例を示すものであり、銅の一次粒子は銅箔上に形成される平均粒子径が粉落ち防止の役割を担うものである。したがって、平均粒子径が本願発明の範囲に入るものであれば、下記に表示する以外のめっき条件であることは何ら妨げるものではない。本願発明はこれらを包含するものである。
また、一次粒子形成前に、銅箔と一次粒子の間に、金属層めっきを施してもよい。金属めっき層としては、銅めっき層、銅合金めっき層が代表的に考えられる。銅めっき層を行う場合には、硫酸銅と硫酸を主成分とする硫酸銅水溶液のみを使用する場合や、硫酸、メルカプト基を有する有機硫黄化合物、ポリエチレングリコールなどの界面活性剤、さらに塩化物イオンを組み合わせた硫酸銅水溶液を使用して、電気めっきにより銅めっき層を形成する方法が挙げられる。
液組成 :銅10~20g/L、硫酸50~100g/L
液温 :25~50C
電流密度 :1~58A/dm2
クーロン量:4~81As/dm2
なお、上記と同様に、このめっき条件はあくまで好適な例を示すものであり、二次粒子は一次粒子の上に形成されるものであり、平均粒子径が粉落ち防止の役割を担うものである。したがって、平均粒子径が本願発明の範囲に入るものであれば、下記に表示する以外のめっき条件であることは何ら妨げるものではない。本願発明はこれらを包含するものである。
液組成 :銅10~20g/L、ニッケル5~15g/L、コバルト5~15g/L
pH :2~3
液温 :30~50C
電流密度 :24~50A/dm2
クーロン量:34~48As/dm2
本願発明は、上記二次粒子層の上に、さらに耐熱層を形成することができる。このめっき条件を下記に示す。
液組成 :ニッケル5~20g/L、コバルト1~8g/L
pH :2~3
液温 :40~60C
電流密度 :5~20A/dm2
クーロン量:10~20As/dm2
本願発明は、上記二次粒子層の上に、さらに次の耐熱層を形成することができる。このめっき条件を下記に示す。
液組成 :ニッケル2~30g/L、亜鉛2~30g/L
pH :3~4
液温 :30~50C
電流密度 :1~2A/dm2
クーロン量:1~2As/dm2
本願発明は、さらに次の防錆層を形成することができる。このめっき条件を下記に示す。下記においては、浸漬クロメート処理の条件を示したが、電解クロメート処理でも良い。
液組成 :重クロム酸カリウム1~10g/L、亜鉛0~5g/L
pH :3~4
液温 :50~60C
電流密度 :0~2A/dm2(浸漬クロメート処理のため)
クーロン量:0~2As/dm2(浸漬クロメート処理のため)
一例として、エポキシシラン水溶液の塗布を挙げることができる。
Co付着量が100μg/dm2未満では、耐熱性が悪くなり、またエッチング性も悪くなる。Co付着量が3000μg/dm2を超えると、磁性の影響を考慮せねばならない場合には好ましくなく、エッチングシミが生じ、また、耐酸性及び耐薬品性の悪化が考慮され得る。
以上から、銅-コバルト-ニッケル合金めっきの付着量は、10~30mg/dm2銅-100~3000μg/dm2コバルト-50~500μg/dm2ニッケルであることが望ましいと言える。この3元系合金層の各付着量はあくまで、望ましい条件であり、この量を超える範囲を否定するものではない。
一般に、回路を形成する場合には、下記の実施例の中で説明するようなアルカリ性エッチング液及び塩化銅系エッチング液を用いて行われる。このエッチング液及びエッチング条件は、汎用性のあるものであるが、この条件に限定されることはなく、任意に選択できることは理解されるべきことである。
このコバルト-ニッケル合金めっき層は、コバルトの付着量が200~3000μg/dm2であり、かつコバルトの比率が60~66質量%とするのが望ましい。この処理は広い意味で一種の防錆処理とみることができる。
このコバルト-ニッケル合金めっき層は、銅箔と基板の接着強度を実質的に低下させない程度に行なう必要がある。コバルト付着量が200μg/dm2未満では、耐熱剥離強度が低下し、耐酸化性及び耐薬品性が悪くなり、また処理表面が赤っぽくなってしまうので好ましくない。
また、コバルト付着量が3000μg/dm2を超えると、磁性の影響を考慮せねばならない場合には好ましくなく、エッチングシミが生じ、また、耐酸性及び耐薬品性の悪化が考慮される。好ましいコバルト付着量は400~2500μg/dm2である。
後述するように、ソフトエッチングの染み込み発生の直接の大きな原因は、亜鉛-ニッケル合金めっき層からなる耐熱防錆層であるが、コバルトもソフトエッチングの際の染み発生の原因になることもあるので、上記に調整することが、より望ましいとする条件である。
一方、ニッケル付着量が少ない場合には、耐熱剥離強度が低下し、耐酸化性及び耐薬品性が低下する。また、ニッケル付着量が多すぎる場合には、アルカリエッチング性が悪くなるので、上記コバルト含有量とのバランスで決めることが望ましい。
印刷回路の製造工程で行われる処理が一段と高温となり、また製品となった後の機器使用中の熱発生がある。例えば、樹脂に銅箔を熱圧着で接合する、いわゆる二層材では、接合の際に300°C以上の熱を受ける。このような状況の中でも、銅箔と樹脂基材との間での接合力の低下を防止することが必要であり、この亜鉛-ニッケル合金めっきは有効である。
上記の通り、前記亜鉛-ニッケル合金めっき層の総量を150~500μg/dm2とすると共に、当該合金層中のニッケル比率の下限値を16質量%に、上限値を40質量%とし、かつニッケルの含有量を50μg/dm2以上とすることが、耐熱防錆層という役割を備えると共に、ソフトエッチングの際に使用するエッチング剤の染み込みを抑制し、腐食に回路の接合強度の弱体化を防止することができるという効果を有する。
また、合金層中のニッケル比率の下限値が16質量%未満では、ソフトエッチングの際の染み込み量が9μmを超えるので、好ましくない。ニッケル比率の上限値40質量%については、亜鉛-ニッケル合金めっき層を形成できる技術上の限界値である。
コバルトの合計付着量が300μg/dm2未満では、耐熱性及び耐薬品性が低下し、コバルトの合計付着量が4000μg/dm2 を超えると、エッチングシミが生じることがある。また、ニッケルの合計付着量が150μg/dm2未満では、耐熱性及び耐薬品性が低下する。ニッケルの合計付着量が1500μg/dm2を超えると、エッチング残が生じる。
好ましくは、コバルトの合計付着量は1500~3500μg/dm2であり、そしてニッケルの合計付着量は500~1000μg/dm2である。上記の条件を満たせば、特にこの段落に記載する条件に制限される必要はない。
めっき浴としては、代表的には、K2Cr2O7、Na2Cr2O7等の重クロム酸塩やCrO3等の少なくとも一種と、水溶性亜鉛塩、例えばZnO 、ZnSO4・7H2Oなど少なくとも一種と、水酸化アルカリとの混合水溶液が用いられる。代表的なめっき浴組成と電解条件例は次の通りである。
ソフトエッチング液には、H2SO4:10wt%、H2O2:2wt%の水溶液が使用できる。処理時間と温度は任意に調節できる。
アルカリエッチング液としては、例えば、NH4OH:6モル/リットル、NH4Cl:5モル/リットル、CuCl2:2モル/リットル(温度50°C)等の液が知られている。
処理面が黒に近い程、光の吸収が良いため、位置決めの精度が高くなる。更には、基板を作製する際、銅箔とフィルムとを熱を加えながらキュワリングして接着させることが多い。このとき、遠赤外線、赤外線等の長波を用いることにより加熱する場合、処理面の色調が黒い方が、加熱効率が良くなる。
このシラン処理に使用するシランカップリング剤としては、オレフィン系シラン、エポキシ系シラン、アクリル系シラン、アミノ系シラン、メルカプト系シランを挙げることができるが、これらを適宜選択して使用することができる。
塗布方法は、シランカップリング剤溶液のスプレーによる吹付け、コーターでの塗布、浸漬、流しかけ等いずれでもよい。例えば、特公昭60-15654号は、銅箔の粗面側にクロメート処理を施した後シランカップリング剤処理を行なうことによって銅箔と樹脂基板との接着力を改善することを記載している。詳細はこれを参照されたい。この後、必要なら、銅箔の延性を改善する目的で焼鈍処理を施すこともある。
圧延銅箔に、下記に示す条件範囲で、一次粒子層(Cu)、二次粒子層(銅-コバルト-ニッケル合金めっき)形成した。
使用した浴組成及びめっき条件は、次の通りである。
[浴組成及びめっき条件]
液組成 :銅15g/L、硫酸75g/L
液温 :35°C
電流密度 :2~58A/dm2
クーロン量:8~81As/dm2
(B)二次粒子層の形成(Cu-Co-Ni合金めっき)
液組成 :銅15g/L、ニッケル8g/L、コバルト8g/L
pH :2
液温 :40°C
電流密度 :24~31A/dm2
クーロン量:34~44As/dm2
比較例において、使用した浴組成及びめっき条件は、次の通りである。
[浴組成及びめっき条件]
(A)一次粒子層の形成(銅めっき)
液組成 :銅15g/L、硫酸75g/L
液温 :35°C
電流密度 :1~58A/dm2
クーロン量:4~81As/dm2
(B)二次粒子層の形成(Cu-Co-Ni合金めっき条件)
液組成 :銅15g/L、ニッケル8g/L、コバルト8g/L
pH :2
液温 :40°C
電流密度 :24~50A/dm2
クーロン量:34~48As/dm2
また、比較例として、同様の結果を表1に示す。
実施例1は、一次粒子を形成する電流密度を51A/dm2と2A/dm2とし、クーロン量を72As/dm2と8As/dm2とした場合で、二次粒子を形成する電流密度を24A/dm2とし、クーロン量を34As/dm2とした場合である。
なお、一次粒子を形成する電流密度とクーロン量が2段階になっているが、通常一次粒子を形成する場合には、2段階の電気めっきが必要となる。すなわち、第1段階の核粒子形成のめっき条件と第2段階の核粒子の成長の電気めっきである。最初のめっき条件は、第1段階の核形成粒子形成のための電気めっき条件であり、次のめっき条件は、第2段階の核粒子の成長のための電気めっき条件である。以下の実施例及び比較例についても同様なので、説明は省略する。
この結果、一次粒子の平均粒子径が0.25μmで、二次粒子の平均粒子径が0.05μmであり、粉落ちがなく、常態ピール強度が0.88kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.71kg/cmと高く、さらに表面粗さRzが0.98μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.25μmで、二次粒子の平均粒子径が0.15μmであり、粉落ちがなく、常態ピール強度が0.90kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.72kg/cmと高く、さらに表面粗さRzが0.98μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.25μmで、二次粒子の平均粒子径が0.25μmであり、若干粉落ちが見られたが、問題となるレベルではなかった。常態ピール強度が0.92kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.73kg/cmと高く、さらに表面粗さRzが1.02μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.35μmで、二次粒子の平均粒子径が0.05μmであり、粉落ちがなく、常態ピール強度が0.95kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.73kg/cmと高く、さらに表面粗さRzが1.20μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.35μmで、二次粒子の平均粒子径が0.15μmであり、粉落ちがなく、常態ピール強度が0.96kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.74kg/cmと高く、さらに表面粗さRzが1.20kg/cmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.35μmで、二次粒子の平均粒子径が0.25μmであり、粉落ちが若干見られたが、特に問題となるレベルではなかった。また、常態ピール強度が0.98kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.75kg/cmと高く、さらに表面粗さRzが1.51μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.45μmで、二次粒子の平均粒子径が0.05μmであり、粉落ちがなく、常態ピール強度が0.96kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.71kg/cmと高く、さらに表面粗さRzが1.21μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.45μmで、二次粒子の平均粒子径が0.15μmであり、粉落ちがなく、常態ピール強度が0.97kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.72kg/cmと高く、さらに表面粗さRzが1.54μmであるという特徴を備えていた。
この結果、一次粒子の平均粒子径が0.45μmで、二次粒子の平均粒子径が0.25μmであり、粉落ちがなく、常態ピール強度が0.98kg/cmと高く、耐熱性(180°C48時間加熱後のピール強度)が0.74kg/cmと高く、さらに表面粗さRzが1.60μmであるという特徴を備えていた。
比較例1は、一次粒子を形成する電流密度を47A/dm2と1A/dm2とし、クーロン量を66As/dm2と4As/dm2とした場合で、二次粒子を形成する電流密度を24A/dm2とし、クーロン量を34As/dm2とした場合である。
この結果、一次粒子の平均粒子径が0.15μmで、二次粒子の平均粒子径が0.05μmであり、粉落ちはなかったが、常態ピール強度が0.75kg/cmと低く、耐熱性(180°C48時間加熱後のピール強度)も0.70kg/cmと低下した。さらに表面粗さRzが0.87μmと低かった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.15μmで、二次粒子の平均粒子径が0.15μmであり、粉落ちはなかったが、常態ピール強度が0.75kg/cmと低く、耐熱性(180°C48時間加熱後のピール強度)も0.70kg/cmと低下した。さらに表面粗さRzが0.88μmと低かった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が1.5μmで、二次粒子の平均粒子径が0.25μmであり、粉落ちが見られ、常態ピール強度が0.83kg/cmと低く、耐熱性(180°C48時間加熱後のピール強度)は0.72kg/cmと実施例レベルであった。さらに表面粗さRzが0.90μmであった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.15μmで、二次粒子の平均粒子径が0.35μmと大きくなり、粉落ちが多量に発生した。常態ピール強度が0.85kg/cmと低く、耐熱性(180°C48時間加熱後のピール強度)は0.72kg/cmと実施例レベルであった。さらに表面粗さRzが0.91μmであった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.25μmで、二次粒子の平均粒子径が0.35μmと大きくなり、粉落ちが多量に発生した。常態ピール強度が0.93kg/cmと実施例レベルであり、耐熱性(180°C48時間加熱後のピール強度)も0.72kg/cmと実施例レベルであった。さらに表面粗さRzが1.15μmであった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.35μmで、二次粒子の平均粒子径が0.35μmと大きくなり、粉落ちが多量に発生した。常態ピール強度が0.98kg/cmと実施例レベルであり、耐熱性(180°C48時間加熱後のピール強度)も0.73kg/cmと実施例レベルであった。さらに表面粗さRzが1.50μmであった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.45μmで、二次粒子の平均粒子径が0.35μmと大きくなり、粉落ちが多量に発生した。常態ピール強度が0.98kg/cmと実施例レベルであるが、耐熱性(180°C48時間加熱後のピール強度)も0.77kg/cmと実施例レベルであった。さらに表面粗さRzが1.55μmと大きくなった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、一次粒子の平均粒子径が0.25μmで、粉落ちはなく、常態ピール強度が0.94kg/cmと実施例レベルであるが、耐熱性(180°C48時間加熱後のピール強度)が0.54kg/cmと著しく悪くなった。さらに表面粗さRzが1.10μmであった。全体的な印刷回路用銅箔としての評価は、不良であった。
この結果、二次粒子の平均粒子径が0.60μmと大きくなり、粉落ちが多量に発生した。常態ピール強度が0.90kg/cmと実施例レベルであり、耐熱性(180°C48時間加熱後のピール強度)も0.73kg/cmと実施例レベルであった。さらに表面粗さRzが0.78μmであった。粉落ちが多く問題がある例であり、全体的な印刷回路用銅箔としての評価は、不良であった。
Claims (7)
- 銅箔の表面に、銅の一次粒子層を形成した後、該一次粒子層の上に、銅、コバルト及びニッケルからなる3元系合金からなる二次粒子層を形成した印刷回路用銅箔であって、一次粒子層の平均粒子径が0.25-0.45μmであり、銅、コバルト及びニッケルからなる3元系合金からなる二次粒子層の平均粒子径が0.05-0.25μmであることを特徴とする印刷回路用銅箔。
- 前記一次粒子層及び二次粒子層が、電気めっき層であることを特徴とする請求項1記載の印刷回路用銅箔。
- 二次粒子が、前記一次粒子の上に成長した1又は複数個の樹枝状の粒子であることを特徴とする請求項1又は2記載の印刷回路用銅箔。
- 一次粒子層及び二次粒子層の接着強度が0.80kg/cm以上であることを特徴とする請求項1~3のいずれか一項に記載の印刷回路用銅箔。
- 一次粒子層及び二次粒子層の接着強度が0.90kg/cm以上であることを特徴とする請求項1~3のいずれか一項に記載の印刷回路用銅箔。
- 一次粒子層及び二次粒子層を形成した表面の粗さRzが1.5μm以下であることを特徴とする請求項1~5のいずれか一項に記載の印刷回路用銅箔。
- 一次粒子層及び二次粒子層を形成した表面の粗さRzが1.0μm以下であることを特徴とする請求項1~5のいずれか一項に記載の印刷回路用銅箔。
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JP2012513775A JP5654581B2 (ja) | 2010-05-07 | 2011-02-03 | 印刷回路用銅箔、銅張積層板、印刷回路基板、印刷回路及び電子機器 |
EP11777395A EP2557204A1 (en) | 2010-05-07 | 2011-02-03 | Copper foil for printed circuit |
KR1020127020693A KR101328235B1 (ko) | 2010-05-07 | 2011-02-03 | 인쇄 회로용 동박 |
SG2012060117A SG183311A1 (en) | 2010-05-07 | 2011-02-03 | Copper foil for printed circuit |
CN201180022507.1A CN102884228B (zh) | 2010-05-07 | 2011-02-03 | 印刷电路用铜箔 |
US13/635,147 US9580829B2 (en) | 2010-05-07 | 2011-02-03 | Copper foil for printed circuit |
US15/178,620 US10472728B2 (en) | 2010-05-07 | 2016-06-10 | Copper foil for printed circuit |
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US15/178,620 Continuation US10472728B2 (en) | 2010-05-07 | 2016-06-10 | Copper foil for printed circuit |
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- 2011-02-03 JP JP2012513775A patent/JP5654581B2/ja active Active
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Also Published As
Publication number | Publication date |
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JP5654581B2 (ja) | 2015-01-14 |
CN102884228B (zh) | 2015-11-25 |
TW201211326A (en) | 2012-03-16 |
SG183311A1 (en) | 2012-09-27 |
US20130011690A1 (en) | 2013-01-10 |
EP2557204A1 (en) | 2013-02-13 |
US10472728B2 (en) | 2019-11-12 |
KR101328235B1 (ko) | 2013-11-14 |
CN102884228A (zh) | 2013-01-16 |
TWI532887B (zh) | 2016-05-11 |
MY161040A (en) | 2017-04-14 |
US20160286665A1 (en) | 2016-09-29 |
KR20120112770A (ko) | 2012-10-11 |
US9580829B2 (en) | 2017-02-28 |
JPWO2011138876A1 (ja) | 2013-07-22 |
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