WO2014136763A1 - Feuille de cuivre pour un traitement par laser, feuille de cuivre soutenue par une feuille de support pour un traitement par laser, stratifié plaqué de cuivre et procédé de fabrication d'une carte de circuits imprimés - Google Patents

Feuille de cuivre pour un traitement par laser, feuille de cuivre soutenue par une feuille de support pour un traitement par laser, stratifié plaqué de cuivre et procédé de fabrication d'une carte de circuits imprimés Download PDF

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Publication number
WO2014136763A1
WO2014136763A1 PCT/JP2014/055446 JP2014055446W WO2014136763A1 WO 2014136763 A1 WO2014136763 A1 WO 2014136763A1 JP 2014055446 W JP2014055446 W JP 2014055446W WO 2014136763 A1 WO2014136763 A1 WO 2014136763A1
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WIPO (PCT)
Prior art keywords
copper
copper foil
layer
foil
laser processing
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PCT/JP2014/055446
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English (en)
Japanese (ja)
Inventor
光由 松田
吉川　和広
保次 原
宣男 藤本
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 CN201480011975.2A priority Critical patent/CN105008594A/zh
Priority to JP2015504326A priority patent/JP6304829B2/ja
Priority to KR1020157023938A priority patent/KR102356407B1/ko
Publication of WO2014136763A1 publication Critical patent/WO2014136763A1/fr

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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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • 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
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
    • H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
    • H05K3/0038—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material combined with laser drilling through a metal layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09209—Shape and layout details of conductors
    • H05K2201/095—Conductive through-holes or vias
    • H05K2201/09509—Blind vias, i.e. vias having one side closed

Definitions

  • the present invention relates to a copper foil for laser processing, and in particular, relates to a copper foil for laser processing suitable for a printed wiring board manufacturing material, a copper foil for laser processing with a carrier foil, a copper clad laminate, and a method for manufacturing a printed wiring board.
  • a multilayer printed wiring board is obtained by laminating three or more wiring layers via an insulating layer, and electrically connecting each wiring layer by an interlayer connection means such as a via hole or a through hole.
  • a build-up method is known as a method for manufacturing a printed wiring board.
  • the build-up method is a manufacturing method in which a wiring layer is laminated on an inner layer circuit via an insulating layer, and multilayered while performing interlayer connection. For example, when an ultrahigh-definition wiring pattern is formed by the modified-semi-additive method (MSAP method) or the like, a build-up printed wiring board is manufactured by the following procedure.
  • MSAP method modified-semi-additive method
  • a copper foil is laminated via an insulating layer on a core substrate or the like provided with an inner layer circuit, via holes are formed by laser processing or the like, and interlayer connection is performed by an electroless plating method.
  • the seed layer under the plating resist is removed by etching together with the plating resist.
  • micro via holes having a top diameter of 100 ⁇ m or less.
  • Such micro via holes are generally drilled by laser processing using a carbon dioxide laser or the like.
  • a Cu direct method is often employed in which a carbon dioxide laser or the like is directly irradiated from above the copper foil to simultaneously perforate the copper foil and the insulating layer.
  • copper has a very low absorptivity of laser light in the far-infrared to infrared wavelength region such as a carbon dioxide laser, so when forming micro via holes by the Cu direct method, copper such as blackening treatment is used in advance. It was necessary to perform a pretreatment to increase the absorption rate of the laser beam on the foil surface.
  • Patent Document 1 describes a copper foil in which an alloy layer mainly composed of Sn and Cu is provided on the surface of the copper foil as a technique that eliminates the need for pretreatment during laser processing.
  • Sn has a laser absorption rate that is twice or more higher than that of Cu, so an alloy layer mainly composed of Sn and Cu is provided on the copper foil surface.
  • a via hole having a diameter of 100 ⁇ m can be formed by directly irradiating the surface of the copper foil with laser light without performing a pretreatment such as a blackening treatment.
  • the copper foil for laser drilling described in Patent Document 1 is provided with a metal Sn layer by vapor deposition or plating on the surface of the copper foil, and then Sn and Cu on the surface of the copper foil by heat diffusion treatment. Is used as an alloy layer. For this reason, in the said alloy layer, distribution will arise in Sn content in the thickness direction, and it will be thought that the etching rate in the thickness direction of the said copper foil varies. Further, the outermost surface of the copper foil has a very high Sn content, and the copper foil described in Patent Document 1 is considered to have a three-layer structure of an Sn layer, an alloy layer of Sn and Cu, and a copper layer in order from the surface layer. It is done.
  • the metal Sn layer is not soluble in an etching solution for a general copper foil, when the copper foil described in Patent Document 1 is used, it is difficult to dissolve and remove the outermost surface by etching. Therefore, when the copper foil described in Patent Document 1 is used, in the etching process, after removing the outermost surface of the copper foil with a metal Sn layer etching solution capable of dissolving Sn in advance, The lower layer needs to be etched, and the etching process becomes complicated. Further, since the alloy layer of Sn and Cu described in Patent Document 1 is an alloyed layer by thermal diffusion, it is considered that the metal composition in the thickness direction is not uniform, and the etching rate in the thickness direction varies. Can occur.
  • the copper foil cannot be etched with a uniform thickness, and the thickness of the copper foil may vary. Furthermore, it is considered that the etching rate of the surface of the alloy layer is slower than that of the wiring pattern portion formed by electrolytic copper plating when the Sn content is high. For this reason, when the seed layer is removed, the wiring pattern portion is etched faster, the line width becomes narrower, and it is difficult to obtain a good wiring pattern.
  • the present invention provides a copper foil for laser processing, a copper foil for laser processing with a carrier foil, a copper-clad laminate, and a method for producing a printed wiring board that is excellent in laser processability and capable of forming a wiring pattern satisfactorily.
  • the purpose is to provide.
  • the present inventors have achieved the above object by employing the following copper foil for laser processing.
  • the copper foil for laser processing according to the present invention has an etching property with respect to a copper etching solution, has an etching rate slower than that of the copper foil, and a hardly soluble laser absorbing layer that absorbs infrared laser light on the surface of the copper foil. It is characterized by having.
  • the hardly soluble laser absorbing layer is preferably an electrolytic copper-tin alloy layer formed by an electrolytic plating method with a tin content of 25 mass% or more and 50 mass% or less.
  • the thickness of the hardly soluble laser absorbing layer is preferably 3 ⁇ m or less.
  • the thickness of the copper foil is preferably 7 ⁇ m or less.
  • the other surface of the copper foil is provided with at least one of a roughening treatment layer and a primer resin layer.
  • the copper foil for laser processing with a carrier foil according to the present invention is characterized in that the carrier foil is detachably provided on the hardly soluble laser absorbing layer.
  • the copper foil for laser processing and the insulating layer constituting material are laminated so that the hardly soluble laser absorption layer is disposed on the side irradiated with the infrared laser light. It is characterized by that.
  • the method for manufacturing a printed wiring board according to the present invention has an etching property with respect to a copper etching solution, has an etching rate slower than that of the copper foil, and includes a laser absorption layer that absorbs infrared laser light on the surface of the copper foil.
  • a via hole for interlayer connection is formed by directly irradiating a poorly soluble laser absorption layer with infrared laser light on a laminate in which a copper foil for laser processing and another conductor layer are laminated via an insulating layer.
  • the micro-etching process as a pretreatment of the desmear process and / or the electroless plating process for removing smear in the via hole, the hardly soluble laser absorbing layer is removed from the surface of the copper foil.
  • the copper foil for laser processing according to the present invention is excellent in laser processability, and a uniform etching rate in the thickness direction can be obtained in the subsequent etching process.
  • the total manufacturing cost can be reduced.
  • the hardly soluble laser absorbing layer can function as an etching resist, the surface of the copper foil (layer) is dissolved in various etching steps before the formation of the wiring pattern, resulting in variations in the thickness of the copper foil (layer). Can be prevented. For this reason, a wiring pattern can be formed with a favorable etching factor.
  • FIG. 1 It is a figure which shows the relationship between the tin content of the electrolytic metal foil which concerns on this invention, and an etching rate. It is a figure for demonstrating an example of the manufacturing method of the printed wiring board which concerns on this invention. It is a figure for evaluating the etching property of the electrolytic copper foil in the copper clad laminated board produced by the Example and the comparative example 1.
  • FIG. 1 shows the relationship between the tin content of the electrolytic metal foil which concerns on this invention, and an etching rate. It is a figure for demonstrating an example of the manufacturing method of the printed wiring board which concerns on this invention. It is a figure for evaluating the etching property of the electrolytic copper foil in the copper clad laminated board produced by the Example and the comparative example 1.
  • Copper foil for laser processing The copper foil for laser processing according to the present invention has an etching property with respect to a copper etching solution, an etching rate that is slower than that of the copper foil, and a hardly soluble laser absorbing layer that absorbs infrared laser light. It is provided on the surface of the copper foil.
  • the copper foil for laser processing according to the present invention provides laser light to the surface of the copper foil for laser processing without performing pretreatment such as blackening treatment by the Cu direct method in the manufacturing process of the printed wiring board. By direct irradiation, micro holes such as micro via holes can be formed by laser processing.
  • the hardly soluble laser absorbing layer is, for example, a copper layer containing an infrared laser absorbing metal material having absorbability with respect to infrared laser light, and by containing the infrared absorbing material in the copper layer, It is preferable to use a copper layer containing an infrared laser-absorbing metal material capable of making the etching rate for the copper etching solution slower than the etching rate of the copper foil.
  • Specific examples of the hardly soluble laser absorbing layer include an electrolytic copper-tin alloy layer containing 25% by mass or more and 50% by mass or less of tin formed by an electrolytic plating method. In the present embodiment, the following description will be made mainly assuming that this electrolytic copper-tin alloy layer is used as the hardly soluble laser absorbing layer.
  • Electrolytic copper-tin alloy layer First, the electrolytic copper-tin alloy layer will be described. Tin has a higher absorption rate of laser light (carbon dioxide laser light, etc.) having a wavelength in the far-infrared to infrared wavelength range compared to copper. That is, the electrolytic copper-tin alloy layer can function as a laser light absorption layer, and as described above, the pretreatment at the time of drilling by the Cu direct method can be eliminated.
  • the electrolytic copper-tin alloy layer is etched on the surface of the copper foil in various etching processes performed in a desmear process, a micro-etching process, etc. performed after drilling and before forming a wiring pattern.
  • the electrolytic copper-tin alloy layer is etched in various etching processes performed before these wiring patterns are formed.
  • the timing at which the electrolytic copper-tin alloy layer is dissolved and removed can be controlled by its tin content and thickness. Therefore, it is possible to dissolve and remove only the electrolytic copper-tin alloy layer without dissolving the surface of the copper foil before the electroless plating step for interlayer connection. Therefore, for example, when a wiring pattern is formed by the MSAP method, an electroless plating film can be formed on a copper foil in which the original thickness is maintained, and a seed layer having a uniform thickness can be obtained. .
  • Tin content in the present invention when an electrolytic copper-tin alloy layer is used as the hardly soluble laser absorption layer, the tin content in the electrolytic copper-tin alloy layer is 25% by mass or more as described above. This is because the function as an etching resist is exhibited. As shown in FIG. 1, when the tin content in the electrolytic copper-tin alloy layer is less than 25% by mass, the etching rate of the electrolytic copper-tin alloy layer is compared with that of the electrolytic copper foil having a tin content of 0% by mass. Then it will be faster.
  • the etching rate is slow as compared with a normal electrolytic copper foil containing no tin. Therefore, by setting the tin content in the electrolytic copper-tin alloy layer to 25% by mass or more, as described above, the electrolytic copper-tin alloy layer can function as an etching resist, and before the wiring pattern is formed, It is possible to prevent the copper foil from being melted and causing variations in the thickness of the copper foil during various etching processes to be performed.
  • This specification describes an invention relating to specific tin mass% when the total content of copper and tin in the copper-tin alloy layer is 100 mass%.
  • the electrolytic copper-tin alloy layer is composed of the obtained copper-tin alloy deposited on the surface of the copper foil by the electrolytic plating method, the metal composition in the thickness direction becomes uniform, and the electrolytic copper-tin alloy The etching rate of the layer can be made uniform in the thickness direction. Therefore, the electrolytic copper-tin alloy layer can be dissolved at a uniform rate in the thickness direction in various etching processes performed before the wiring pattern is formed. As shown in FIG. 1, the etching rate decreases as the tin content increases. Therefore, as described above, the electrolytic copper-tin alloy layer can be dissolved and removed at an appropriate timing by adjusting the tin content and thickness in the electrolytic copper-tin alloy layer.
  • an electroless plating film is formed on the surface of the copper foil with the original thickness maintained. Can do. Therefore, for example, when a wiring pattern is formed by the MSAP method, a seed layer having a uniform thickness can be formed. Therefore, when the seed layer is removed in a flash etching process after the wiring pattern is formed, Since it has a uniform composition in the thickness direction, the seed layer can be dissolved and removed at a uniform etching rate. As described above, it is possible to form a wiring pattern having a good etching factor.
  • the wiring pattern is formed not only by the MSAP method but also by a method including an etching process such as a subtractive method.
  • the electrolytic copper-tin alloy layer can be removed to expose the copper foil (layer) with the initial thickness maintained. A layer can be obtained, and a wiring pattern having a good etching factor can be formed.
  • the etching rate of the electrolytic copper foil not containing tin is 100
  • the etching rate of the electrolytic copper-tin alloy foil having a tin content exceeding 50% by mass is less than 3. Accordingly, if the tin content in the electrolytic copper-tin alloy layer exceeds 50% by mass, the etching rate with respect to the copper etching solution becomes too slow. Therefore, during various etching processes performed before the wiring pattern is formed. It becomes difficult to dissolve and remove the electrolytic copper-tin alloy layer. In particular, as shown in FIG.
  • the tin content in the electrolytic copper-tin alloy layer is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
  • the etching rates of the electrolytic copper-tin alloy foil are 4 (tin content: 45 mass%) and 13 (tin content: 40 mass), respectively. %), 25 (tin content: 35 mass%).
  • the etching rate of the electrolytic copper-tin alloy foil with respect to the copper etching solution is faster than the etching rate of the copper foil not containing tin.
  • the etching rate shown in FIG. 1 is that electrolytic copper-tin alloy foils (thickness: 3 ⁇ m) having different tin contents (mass%) were prepared, and each electrolytic copper-tin alloy foil was subjected to a sulfuric acid-hydrogen peroxide etching solution.
  • etching amount ( ⁇ m) per unit time obtained by immersing in 30 seconds, washing with water and drying, then measuring the thickness by cross-sectional observation, and obtaining the thickness reduced by etching.
  • the tin content here can be measured by the following method.
  • a solution in which the copper foil for laser processing as a sample is completely dissolved is subjected to ICP analysis, fluorescent X-ray apparatus, titration determination
  • the amount of copper contained in the electrolytic copper-tin alloy layer was calculated by measuring the total copper content using a method, etc., and subtracting the “copper amount converted from the cross-sectional thickness of the copper foil” from this total copper content.
  • tin content (% by mass) can be calculated.
  • the thickness of the copper foil is known in advance by cross-sectional observation, etc., using a fluorescent X-ray film thickness measuring instrument, perform a composition analysis of the foil defined as a two-layer foil, and in the electrolytic copper-tin alloy layer The tin content (% by mass) can be calculated.
  • the thickness of the electrolytic copper-tin alloy layer can be set to an appropriate value depending on the thickness and use of the laser processing copper foil. However, in consideration of dissolving and removing the electrolytic copper-tin alloy layer by etching at an appropriate stage before forming the wiring pattern, it is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less. On the other hand, if the thickness of the electrolytic copper-tin alloy layer is less than 0.1 ⁇ m, it is difficult to achieve the purpose of improving the absorption rate of the laser beam, and in various etching processes performed before forming the wiring pattern. In some cases, the electrolytic copper-tin alloy layer cannot function sufficiently as an etching resist for copper foil.
  • the thickness of the electrolytic copper-tin alloy layer is preferably 0.3 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the etching rate for the copper etching solution varies depending on the tin content in the electrolytic copper-tin alloy layer. Therefore, the thickness of the electrolytic copper-tin alloy layer is appropriately determined according to the tin content. An appropriate value is preferable.
  • any copper etchant can be used without particular limitation as long as it is an etchant generally used as an etchant for copper.
  • various copper etching solutions such as copper chloride etching solution, iron chloride etching solution, sulfuric acid-hydrogen peroxide etching solution, sodium persulfate etching solution, ammonium persulfate etching solution, potassium persulfate etching solution, etc. Can be used.
  • the copper foil refers to a metal foil having a copper content of 99% by mass or more, and refers to a tin-free copper foil that does not contain tin except for inevitable impurities.
  • the copper foil may be either an electrolytic copper foil or a rolled copper foil. However, in view of economy and production efficiency, an electrolytic copper foil is more preferable.
  • the copper foil is a layer that is bonded to an insulating layer constituting material and constitutes a part of a seed layer or the like when a multilayer printed wiring board is manufactured.
  • the thickness of the copper foil can be the same as that of a commercially available copper foil as a general printed wiring board material.
  • the copper foil is preferably thin from the viewpoint of obtaining a better etching factor, and is 7 ⁇ m or less. Is preferred.
  • the thickness of the copper foil is 3 ⁇ m or less from the viewpoint of forming a finer wiring pattern with a good etching factor. It is more preferably a thin electrolytic copper foil, and further preferably 2 ⁇ m or less. However, when the copper foil has a thickness of 7 ⁇ m or less, it is preferably used in the form of a copper foil for laser processing with a carrier foil, which will be described later, so as not to cause problems such as wrinkles and tearing during handling.
  • the surface of the copper foil that is bonded to the interlayer insulating layer that is, the surface opposite to the surface on which the electrolytic copper-tin alloy layer is provided (hereinafter referred to as the bonding surface) It is preferably smooth.
  • the surface roughness (Rzjis) of the adhesion surface is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • the surface roughness of the said adhesion surface points out the surface roughness of the adhesion surface after forming a roughening process layer.
  • a roughening treatment layer is provided on the adhesive surface of the copper foil, that is, the surface opposite to the surface on which the electrolytic copper-tin alloy layer is provided. Also good.
  • the roughening treatment layer can be formed by a method of depositing and forming fine metal particles on the surface (bonding surface) of the copper foil, a method of forming a roughened surface by an etching method, or the like.
  • the method for forming the roughened layer may be any method as long as the adhesion between the copper foil and the insulating layer can be physically improved. Can be adopted.
  • Primer resin layer In the copper foil for laser processing according to the present invention, a primer resin layer may be provided on the adhesive surface of the copper foil.
  • the primer resin layer is an adhesive layer having good adhesion to both the copper foil and the insulating layer constituting material.
  • the primer resin layer can be a layer made of a resin composition containing an epoxy resin or an aromatic polyamide resin.
  • the thickness of the primer resin layer is not particularly limited as long as the adhesion between the copper foil and the insulating layer constituting material can be improved.
  • the thickness of the primer resin layer can be in the range of 0.5 ⁇ m to 10 ⁇ m.
  • the roughening process layer and the primer resin layer may be simultaneously provided in the adhesive surface of copper foil.
  • the hardly soluble laser absorbing layer is the above-mentioned electrolytic copper-tin alloy layer
  • an electrolytic solution containing copper ions and tin ions is used.
  • the copper foil for laser processing can be obtained by laminating an electrolytic copper-tin alloy layer having a tin content of 25 mass% or more and 50 mass% or less on the copper foil by an electrolytic plating method, its production method is particularly limited. It is not something.
  • various surface treatment layers such as a rust prevention treatment layer and a silane coupling treatment layer may be provided on the adhesive surface of the copper foil as required. It is.
  • the copper foil for laser processing with carrier foil is provided with the carrier foil peelable on the hardly soluble laser absorbing layer of the copper foil for laser processing, and the carrier foil / peeling layer / copper foil for laser processing (difficulty Each layer is laminated like a soluble laser absorption layer / copper foil).
  • the copper foil for laser processing with carrier foil since the same configuration as the above-described copper foil for laser processing can be adopted except for the configuration related to the carrier foil, only the configuration related to the carrier foil will be described here.
  • Carrier foil is a metal foil that is detachably provided on a copper foil for laser processing.
  • the copper foil for laser processing is an ultrathin copper foil having a thickness of 7 ⁇ m or less as described above, By supporting the processing copper foil, it is possible to prevent wrinkles and tears and to improve the handling properties.
  • the material constituting the carrier foil is not particularly limited, but it is possible to form the electrolytic copper-tin alloy layer and the copper foil on the carrier foil by electrodeposition through a release layer. It is preferable that it is the metal material which has.
  • a copper foil, a copper alloy foil, an aluminum foil, a composite foil in which a metal plating layer such as copper or zinc is provided on the surface of the aluminum foil, a stainless steel foil, a resin film whose surface is metal-coated, or the like can be used.
  • a copper foil can be suitably used as a carrier foil.
  • the carrier foil can be reused as a copper raw material after being peeled from the laser processing copper foil, and therefore, it is preferable from the viewpoint of resource conservation.
  • the thickness of the carrier foil is not particularly limited, but can be, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the carrier foil is less than 5 ⁇ m, the thickness of the carrier foil is thin, and the original purpose of the carrier foil to improve the handling property of the copper foil for ultrathin laser processing having a thickness of 7 ⁇ m or less cannot be achieved, It is not preferable.
  • the thickness of the carrier foil is preferably 100 ⁇ m or less, and a thickness of 35 ⁇ m or less is also applicable.
  • the copper foil for laser processing with carrier foil is a so-called peelable type copper foil for laser processing with carrier foil.
  • the release layer allows the carrier foil to be easily peeled from the copper foil for laser processing by hand, and the adhesive strength between the carrier foil and the copper foil for laser processing is appropriate until the carrier foil is peeled off. It is required to be in close contact.
  • the inorganic peeling layer comprised from an inorganic agent and the organic peeling layer comprised from an organic agent are mentioned, for example.
  • Inorganic release layer As an inorganic agent constituting the inorganic release layer, for example, one or more selected from chromium, nickel, molybdenum, tantalum, vanadium, tungsten, cobalt, and oxides thereof are mixed and used. be able to.
  • Organic release layer As an organic agent constituting the organic release layer, for example, one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids can be mixed and used. .
  • the release layer may be either an inorganic release layer or an organic release layer, but is preferably an organic release layer from the viewpoint that the peeling properties of the carrier foil are stabilized.
  • the nitrogen-containing organic compound More specifically, it is preferable to employ the following compounds as the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid.
  • the nitrogen-containing compound include orthotriazoles, aminotriazoles, imidazoles, salts thereof, and derivatives thereof.
  • orthotriazoles such as carboxybenzotriazole, aminotriazoles such as 3-amino-1H-1,2,4-triazole, and triazole derivatives N ′, N′-bis (benzotriazolylmethyl) urea Can be mentioned. Any one or more of these can be used to form an organic release layer composed of a nitrogen-containing compound.
  • sulfur-containing compound examples include thiazole, mercaptobenzothiazole, dibenzoazyl disulfide, cyclohexylamine salt of mercaptobenzothiazole, dicyclohexylamine salt of mercaptobenzothiazole, thiocyanuric acid and 2-benzimidazolethiol.
  • thiazole mercaptobenzothiazole, dibenzoazyl disulfide
  • cyclohexylamine salt of mercaptobenzothiazole dicyclohexylamine salt of mercaptobenzothiazole
  • 2-benzimidazolethiol 2-benzimidazolethiol.
  • carboxylic acids examples include high molecular weight carboxylic acids.
  • high molecular weight carboxylic acids it is particularly preferable to use a fatty acid that is a long-chain hydrocarbon monocarboxylic acid.
  • the fatty acid may be a saturated fatty acid, but it is particularly preferable to use an unsaturated fatty acid such as oleic acid or linolenic acid.
  • the thickness of the release layer is preferably 100 nm or less, and more preferably 50 nm or less.
  • a release layer is provided on the surface of the carrier foil, and copper is deposited on the carrier foil via the release layer by a method such as electrolysis to form an electrolytic copper foil.
  • the thickness of the release layer exceeds 100 nm, particularly in the case of an organic release layer, it becomes difficult to form an electrolytic copper foil on the release layer.
  • the adhesion strength between the carrier foil and the electrolytic copper foil is lowered. Accordingly, the thickness of the release layer is preferably 100 nm or less.
  • the lower limit value of the thickness of the release layer is not particularly limited. However, when the thickness is less than 1 nm, it becomes difficult to form a release layer with a uniform thickness, and the thickness varies. For this reason, it is preferable that the thickness of a peeling layer is 1 nm or more, and it is more preferable that it is 2 nm or more.
  • the heat-resistant metal layer The copper foil for laser processing with the carrier foil forms a heat-resistant metal layer between the carrier foil and the release layer, or between the release layer and the electrolytic copper-tin alloy layer of the copper foil for laser processing, It is also preferable to have a layer configuration of carrier foil / heat-resistant metal layer / release layer / copper foil for laser processing or a layer configuration of carrier foil / release layer / heat-resistant metal layer / copper foil for laser processing.
  • the manufacturing method of the copper foil for laser processing with a carrier foil is not specifically limited. For example, after forming a release layer on the surface of the carrier foil, the electrolytic copper-tin alloy layer and the copper foil are electrolytically deposited on the carrier foil through the release layer. Any method may be used as long as the foil can be obtained.
  • the peeling layer at this time is comprised with the above-mentioned component, it does not affect the measurement of the tin content of the electrolytic copper-tin alloy layer. Therefore, the total copper content is measured using ICP analysis method, fluorescent X-ray apparatus, titration quantitative method, etc. for a solution in which the sample of layer structure of “peeling layer / electrolytic copper-tin alloy layer / copper foil” is completely dissolved. And “the amount of copper contained in the electrolytic copper-tin alloy layer” calculated by subtracting "the amount of copper converted from the cross-sectional thickness of the copper foil” from this total copper content and "the tin content in the solution” From this, the tin content (% by mass) can be calculated.
  • the thickness of the copper foil is known in advance by cross-sectional observation, etc., using a fluorescent X-ray film thickness measuring instrument, perform a composition analysis of the foil defined as a two-layer foil, and in the electrolytic copper-tin alloy layer The tin content (% by mass) can be calculated.
  • the copper clad laminate according to the present invention will be described.
  • the copper foil for laser processing and the insulating layer constituting material are laminated so that the hardly soluble laser absorption layer is disposed on the side irradiated with the infrared laser light. It is characterized by that. That is, the copper-clad laminate according to the present invention is formed by laminating the insulating layer constituent material and the copper foil for laser processing, and the insulating layer constituent material / copper foil / slightly soluble laser absorbing layer (electrolytic copper-tin alloy layer). Any structure may be used as long as it has a layer structure stacked in the order of).
  • the said copper clad laminated body can be obtained, there will be no limitation in particular in the manufacturing method.
  • the copper foil side of the copper foil for laser processing or the copper foil with carrier foil is laminated on the insulating resin base material or insulating resin layer of the so-called B stage, and heated and pressed on the insulating resin base material or insulating resin layer.
  • a copper clad laminate in which a copper foil for laser processing is laminated can be obtained.
  • the carrier foil may be removed at an appropriate stage.
  • the copper foil 10 for laser processing used here has a layer structure of primer resin layer 11 / copper foil (electrolytic copper foil layer) 12 / electrolytic copper-tin alloy layer 13 (slightly soluble laser absorbing layer), It is assumed that no roughening treatment layer is provided on the bonding surface of the copper foil 12.
  • a method for manufacturing a multilayer printed wiring board in which three or more wiring layers are laminated via an insulating layer will be described.
  • the method for producing a printed wiring board according to the present invention is not limited to the method for producing a multilayer printed wiring board, and can also be applied when producing a double-sided printed wiring board.
  • the bonding surface side of the copper foil 10 for laser processing with a carrier foil is laminated on the bonding surface via a so-called B-stage insulating layer constituting material 20.
  • the laminated body shown to Fig.2 (a) is obtained by closely_contact
  • the surface of the electrolytic copper-tin alloy layer 13 which is the outermost layer is directly irradiated with infrared laser light by a carbon dioxide laser or the like to form the micro via hole 40 having the conductor pattern portion 30a of the inner layer circuit 30 as the bottom (FIG. 2 (b)).
  • a desmear process for removing smear remaining at the bottom of the micro via hole 40 using a desmear liquid is performed (see FIG. 2C).
  • the desmear process after immersing the laminate 100 in a swelling solution, the laminate 100 is immersed in a so-called desmear solution (for example, an alkaline permanganate aqueous solution) to remove smear, and then immersed in a neutralization solution (reducing agent).
  • desmear solution for example, an alkaline permanganate aqueous solution
  • a neutralization solution reducing agent
  • a microetching process is performed as a pretreatment for the electroless plating process.
  • the splash and the like attached around the micro via hole 40 is removed using a microetching solution (for example, sulfuric acid-hydrogen peroxide etchant or ammonium persulfate aqueous solution). If smear remains at the bottom of the micro via hole 40, it is removed (see FIG. 2D).
  • the surface of the laminate 100 comes into contact with a processing solution having etching properties with respect to copper, such as a neutralizing solution and a microetching solution. Since the electrolytic copper-tin alloy layer 13 has an etching property with respect to the copper etching solution, the surface thereof is etched in these steps. Since the etching rate with respect to the copper etching solution varies depending on the thickness and tin content of the electrolytic copper-tin alloy layer 13, the timing for dissolving the electrolytic copper-tin alloy layer 13 can be controlled by adjusting these. it can.
  • the electrolytic copper-tin is used in the desmear process by adjusting the thickness and material of the electrolytic copper-tin alloy layer 13. It is preferable to completely dissolve and remove the alloy layer 13.
  • the electrolytic copper-tin alloy layer 13 is left without being completely dissolved in the desmear process, and in the subsequent microetching process.
  • the electrolytic copper-tin alloy layer 13 may be completely dissolved and removed.
  • the timing for dissolving and removing the electrolytic copper-tin alloy layer 13 may be set appropriately according to the characteristics required for the printed wiring board.
  • an electroless plating film is formed on the inside of the micro via hole 40 and on the copper foil layer 12 to perform interlayer connection (not shown).
  • a plating resist is provided on the seed layer (copper foil + electroless plating film), a wiring pattern is formed by an electrolytic plating method, and the via hole is filled and plated.
  • the seed layer under the plating resist is removed together with the plating resist by flash etching.
  • the steps after the electroless plating step are not shown.
  • the reference numerals for the respective constituent elements are omitted.
  • the copper foil for laser processing it is possible to directly irradiate the laser beam without performing pretreatment for increasing the absorption rate of the laser beam such as blackening treatment. Processing can be performed. For this reason, the frequency
  • an electrolytic copper-tin alloy layer is used as the poorly soluble laser absorption layer, by adjusting the tin content and the thickness of the electrolytic copper-tin alloy layer as appropriate, The timing for dissolving and removing the tin alloy layer can be controlled.
  • FIG. 2 the case where the tin content in the electrolytic copper-tin alloy layer is relatively large and the electrolytic copper-tin layer is not dissolved in the desmear process is shown.
  • the present invention is not limited to the illustrated example, and the electrolytic copper-tin alloy is adjusted in the desmear process by adjusting the amount and thickness of tin in the electrolytic copper-tin alloy layer according to the characteristics required for the printed wiring board. The layer may be removed by dissolution.
  • a copper foil for carrier foil laser processing is prepared by the method described below, and then a copper-clad laminate is manufactured, and laser hole drilling processability evaluation using a carbon dioxide gas laser is performed, and a printed wiring board manufacturing process is performed.
  • the evaluation of the variation in the thickness of the copper foil (electrolytic copper foil layer) when subjected to the etching treatment performed before forming the wiring pattern was performed. Hereinafter, it will be described in order. The evaluation method will be described later.
  • Step A An electrolytic copper foil having a surface roughness (Rzjis) on one side of 0.6 ⁇ m and a thickness of 18 ⁇ m was used as a carrier foil, and a release layer was formed on the surface of the carrier foil as follows.
  • the surface roughness (Rzjis) is a value measured with a stylus type surface roughness meter using a diamond stylus having a tip radius of curvature of 2 ⁇ m in accordance with JIS B 0601.
  • This carrier foil was immersed in a dilute sulfuric acid aqueous solution containing carboxybenzotriazole having a free sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, a carboxybenzotriazole concentration of 800 ppm, and a liquid temperature of 30 ° C. for 30 seconds. Then, by picking up the carrier foil, the contaminated components adhering to the surface of the carrier foil are pickled and removed, and carboxybenzotriazole is adsorbed on the surface to form a release layer on the surface of the carrier foil.
  • the carrier foil provided.
  • Step B Next, in the metal component-containing electrolyte, the carrier foil provided with the release layer is cathode-polarized to form a heat-resistant metal layer on the surface of the release layer, and the carrier foil provided with the heat-resistant metal layer and the release layer; did.
  • nickel electrolyte nickel sulfate (NiSO 4 ⁇ 6H 2 O) and 330 g / l, nickel chloride (NiCl 2 ⁇ 6H 2 O) and 45 g / l, containing boric acid 30 g / l
  • the bath pH is 3 A watt bath, electrolysis at a liquid temperature of 45 ° C.
  • a nickel layer having a thickness of 0.01 ⁇ m is formed on the surface of the release layer, and a carrier having a heat-resistant metal layer and a release layer A foil was prepared.
  • Step C Next, in a copper-tin plating bath having the following composition, a carrier foil comprising the refractory metal layer and a release layer is cathodically polarized under the following electrolysis conditions, and a thickness of 0.7 ⁇ m is formed on the surface of the refractory metal layer. An electrolytic copper-tin alloy layer was formed.
  • Step D Next, a carrier foil provided with an electrolytic copper-tin alloy layer and the like is cathodic polarized in a copper plating bath having the following composition under the following conditions, and an electrolytic copper foil having a thickness of 2 ⁇ m on the surface of the electrolytic copper-tin metal layer.
  • the copper foil for laser processing with a carrier foil which concerns on this invention was obtained.
  • Step E In this example, a zinc-nickel alloy rust preventive layer is further formed on the surface of the copper foil for laser processing with a carrier foil on the side of the electrolytic copper foil, and subjected to electrolytic chromate treatment and amino silane coupling agent treatment.
  • the copper foil for surface treatment laser processing with a carrier foil was obtained.
  • the tin content in the electrolytic copper-tin alloy layer was 27.5% by mass.
  • the tin content in the examples was measured as follows. An electrolytic copper-tin alloy layer is formed at a stage where a release layer is formed on the surface of the carrier foil, a heat-resistant metal layer is formed on the surface of the release layer, and an electrolytic copper-tin alloy layer is formed on the surface of the heat-resistant metal layer. A tin content measurement sample was used. Thereafter, the electrolytic copper-tin alloy layer of the sample is peeled from the carrier foil, and the composition analysis of the foil is performed using a fluorescent X-ray film thickness measuring device XDAL-FD (manufactured by Fisher Instruments). The tin content (% by mass) was calculated. In the following comparative examples, the tin content is measured by the same method.
  • Comparative Example 1 In Comparative Example 1, a peelable type electrolytic copper foil with a carrier foil was produced in the same manner as in the Example except that the electrolytic copper-tin alloy layer was not provided. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
  • Comparative Example 2 In Comparative Example 2, in Step C, the carrier foil was cathodically polarized under the following electrolysis conditions in a copper-tin plating bath having the following composition, and the thickness of 0.7 ⁇ m was interposed on the carrier foil with a release layer and a heat-resistant metal layer.
  • An electrolytic copper foil with a carrier foil was produced in the same manner as in Example except that the electrolytic copper-tin alloy layer was formed. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
  • the tin content in the electrolytic copper-tin alloy layer was 12.9% by mass.
  • Comparative Example 3 In Comparative Example 3, using the electrolytic copper foil with carrier foil of Comparative Example 1, a copper clad laminate was produced in the same manner as in the example. Then, a metal tin layer having a thickness of 0.4 ⁇ m was formed on the surface of the copper foil of the copper clad laminate using a commercially available electroless tin plating solution. Then, the copper clad laminate on which the metal tin layer is formed is heat-treated at 200 ° C. for 30 minutes to cause mutual diffusion between the copper component of the electrolytic copper foil and the tin component of the metal tin layer, A copper-clad laminate having a diffusion alloy layer mainly composed of tin-copper on the surface layer of the copper foil was obtained.
  • Desmear process First, in the desmear process, swelling treatment (swelling solution: Rohm & Haas, MLB-211, liquid temperature: 75 ° C., treatment time: 15 minutes), oxidation treatment with an alkaline aqueous solution of potassium permanganate (oxidation treatment solution: Each treatment of Rohm & Haas, MLB-213, liquid temperature: 80 ° C., treatment time: 15 minutes, neutralization treatment (neutralization treatment liquid: Rohm & Haas, MLB-216, liquid temperature: 40 ° C., treatment time: 15 minutes) After that, after washing and drying, the thickness was measured by cross-sectional observation.
  • swelling treatment swelling solution: Rohm & Haas, MLB-211, liquid temperature: 75 ° C., treatment time: 15 minutes
  • oxidation treatment with an alkaline aqueous solution of potassium permanganate oxidation treatment solution: Each treatment of Rohm & Haas, MLB-213, liquid temperature: 80 ° C., treatment time: 15 minutes
  • neutralization treatment neutral
  • Micro-etching process Next, in the micro-etching process, each copper clad laminate after the desmear process is immersed in a sulfuric acid-hydrogen peroxide etching solution (CPE800 manufactured by Mitsubishi Gas Chemical Co., Ltd.) at a liquid temperature of 30 ° C. for 60 seconds. After washing with water and drying, the thickness was measured by cross-sectional observation. For cross-sectional observation, VE-9800 manufactured by Keyence Corporation was used.
  • CPE800 sulfuric acid-hydrogen peroxide etching solution
  • Table 1 shows the top diameter when via holes are formed under the above processing conditions for each copper-clad laminate.
  • the top diameter refers to the opening diameter of the via hole as shown in FIG.
  • the electrolytic copper-tin alloy layer containing tin is the outermost layer, and this electrolytic copper-tin alloy layer
  • drilling was possible by laser processing without performing pretreatment for increasing the absorption rate of laser light such as blackening treatment.
  • the copper-clad laminate produced in Comparative Example 1 cannot be directly drilled by laser processing, and if no pretreatment for increasing the laser light absorption rate, such as blackening treatment, is performed, the laser It was confirmed that micro via holes cannot be formed by processing.
  • the electrolytic copper foil of Comparative Example 3 includes a diffusion alloy layer obtained by interdiffusing copper and tin with a metal tin layer formed by electroless plating on the surface thereof by thermal diffusion.
  • the diffusion alloy layer the distribution of tin in the thickness direction is nonuniform, and the closer to the surface, the greater the distribution of tin.
  • FIG. 3 shows FIB-SIM images showing cross sections of the copper clad laminates of Example and Comparative Example 1.
  • the copper clad laminate produced in the example is provided with a 0.7 ⁇ m electrolytic copper-tin alloy layer on a 2 ⁇ m thick electrolytic copper foil layer.
  • the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.21 ⁇ m.
  • the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.38 ⁇ m.
  • the presence of the electrolytic copper-tin alloy layer does not change the thickness of the copper foil, and the initial The thickness (2 ⁇ m) can be maintained.
  • the copper clad laminate produced in Comparative Example 1 does not have an electrolytic copper-tin alloy layer on the electrolytic copper foil layer, so that it is 0.10 ⁇ m in the desmear process, and in the microetching process.
  • the thickness is reduced to 1.03 ⁇ m.
  • the tin content in the electrolytic copper-tin alloy layer is 27.5% by mass, and as shown in FIG. 1, the etching rate is slower than that of the electrolytic copper foil not containing tin.
  • the amount of etchings also becomes large and there exists a possibility that variation may arise in the thickness of copper foil.
  • the copper clad laminate of Comparative Example 2 includes an electrolytic copper-tin alloy layer having a tin content of 12.9% by mass, and as shown in FIG.
  • the etching rate of the layer is faster than that of the electrolytic copper foil containing no tin. Therefore, the copper-clad laminate of Comparative Example 2 has an electrolytic copper-tin alloy layer on the surface of the electrolytic copper foil layer, but the etching amount in the desmear process is 0.20 ⁇ m, and the etching amount in the microetching process is 1.25 ⁇ m. Also in this case, the surface of the electrolytic copper foil layer is dissolved, and the thickness of the electrolytic copper foil layer may vary.
  • the diffusion alloy layer mainly composed of tin-copper has a two-layer structure of a tin layer and a tin-copper diffusion alloy layer as described above. And the etching rate with respect to each etching liquid differs in a tin copper diffusion alloy layer, respectively. In particular, it is difficult to dissolve the metal tin layer as the outermost layer with a general etching treatment liquid for copper foil (see FIG. 1).
  • the total amount of etching after the desmear process and the micro-etching process is as small as 0.05 ⁇ m and functions as an etching resist layer, but the seed layer is removed by etching in the subsequent flash etching process after the wiring pattern is formed.
  • the said copper foil it thinks that an etching rate differs in each layer of a metal tin layer, a tin copper diffusion alloy layer, and an electrolytic copper foil layer, and it becomes difficult to etch uniformly in the thickness direction.
  • the etching rate of the wiring pattern portion formed by electrolytic copper plating is higher than that of the metal tin layer that is the outermost layer. Therefore, the etching factor is reduced, and it becomes difficult to form a wiring pattern with a good line width.
  • the electrolytic copper-tin alloy layer can be dissolved and removed in the desmear process and the microetching process. What is necessary is just to remove the layer and the electroless copper plating film formed on this electrolytic copper foil layer. Since these are all copper layers, there is no significant difference in the etching rate. Further, no great difference appears with the etching rate of the wiring pattern portion formed by electrolytic copper plating. Therefore, according to the copper foil for laser processing according to the present invention, it is possible to form a wiring pattern with a good etching factor.
  • the laser processability is excellent, and a uniform etching rate in the thickness direction can be obtained in the subsequent etching process.
  • the electrolytic copper-tin alloy layer can function as an etching resist, it is possible to prevent the copper foil surface from being melted and causing variations in the thickness of the copper foil in various etching processes before forming the wiring pattern. it can. Further, when removing the seed layer, only the copper foil portion needs to be dissolved and removed, so that a wiring pattern can be formed with a good etching factor.

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Abstract

La présente invention a pour but de proposer : une feuille de cuivre pour un traitement par laser qui présente une excellente aptitude au traitement par laser et à partir de laquelle un motif de câblage peut être formé de façon satisfaisante ; une feuille de cuivre soutenue par une feuille de support pour un traitement par laser, un stratifié plaqué de cuivre et un procédé de fabrication d'une carte de circuits imprimés. Cette feuille de cuivre pour un traitement par laser comprend une feuille de cuivre et, formée sur la surface de celle-ci, une couche d'absorption de lumière laser modérément soluble dans l'eau qui peut être gravée par des agents d'attaque de cuivre mais qui a une vitesse d'attaque chimique inférieure à la feuille de cuivre et qui absorbe de la lumière laser infrarouge.
PCT/JP2014/055446 2013-03-05 2014-03-04 Feuille de cuivre pour un traitement par laser, feuille de cuivre soutenue par une feuille de support pour un traitement par laser, stratifié plaqué de cuivre et procédé de fabrication d'une carte de circuits imprimés WO2014136763A1 (fr)

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CN201480011975.2A CN105008594A (zh) 2013-03-05 2014-03-04 激光加工用铜箔、带有载体箔的激光加工用铜箔、覆铜层压体及印刷线路板的制造方法
JP2015504326A JP6304829B2 (ja) 2013-03-05 2014-03-04 レーザー加工用銅箔、キャリア箔付レーザー加工用銅箔、銅張積層体及びプリント配線板の製造方法
KR1020157023938A KR102356407B1 (ko) 2013-03-05 2014-03-04 레이저 가공용 구리 박, 캐리어 박 구비 레이저 가공용 구리 박, 구리클래드 적층체 및 프린트 배선판의 제조 방법

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KR102356407B1 (ko) 2022-01-28
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