# US 8,568,899 B2 · Metal covered polyimide composite, process for producing the composite, and process for producing electronic circuit board > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,568,899 B2 - Document ID: US8568899B2 - Status: Granted - Kind: B2 - Application number: 12/738,098 - Filed: 2008-09-16 - Published: 2010-09-02 - Granted: 2013-10-29 - Earliest claimed: 2007-10-18 - Assignees: JX Nippon Mining & Metals Corporation - Applicants: Michiya Kohiki; Naonori Michishita; Nobuhito Makino - Inventors: Michiya Kohiki; Naonori Michishita; Nobuhito Makino - Web page: https://patentgrep.com/patent/US8568899B2 ## CPC - C25D 5/10: Electroplating with more than one layer of the same or of different metals (for bearings C25D7/10) - C23C 18/1653: {Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating} - C23C 28/021: {including at least one metal alloy layer} - C23C 28/023: {only coatings of metal elements only} - C23C 28/028: {Including graded layers in composition or in physical properties, e.g. density, porosity, grain size} - C25D 5/56: of plastics - C25D 7/06: Wires; Strips; Foils - H05K 1/09: Use of materials for the {conductive, e.g. } metallic pattern - H05K 3/388: {by the use of a metallic or inorganic thin film adhesion layer} - H05K 1/0393: {Flexible materials (H05K1/038 takes precedence; specific organic compositions are classified in H05K1/0313 and subgroups)} - H05K 2201/0154: Polyimide - H05K 2201/0338: Layered conductor, e.g. layered metal substrate, layered finish layer or layered thin film adhesion layer - H05K 2203/0723: Electroplating, e.g. finish plating - Y10T 428/12569: Synthetic resin - Y10T 428/12847: Cr-base component - Y10T 428/12903: Cu-base component - Y10T 428/1291: Next to Co-, Cu-, or Ni-base component - Y10T 428/265: 1 mil or less - Y10T 428/31681: Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.] - Y10T 428/31721: Of polyimide - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Provided is a metal covered polyimide composite comprising a tie-coat layer and a metal seed layer formed on a surface of a polyimide film by electroless plating or a drying method, and a copper layer or a copper alloy layer formed thereon by electroplating, wherein the copper plated layer or copper alloy plated layer comprises three layers to one layer of the copper layer or copper alloy layer, and there is a concentrated portion of impurities at the boundary of the copper layer or copper alloy layer when the copper layer or copper alloy layer is three layers to two layers, and there is no concentrated portion of impurities when the copper layer or copper alloy layer is a single layer. Additionally provided are a method of producing the composite and a method of producing an electronic circuit board. ## Claims ### Claim 1 A metal covered polyimide composite obtained by feeding around one or two plating drums in one or two plating baths a polyimide film comprising a tie-coat layer and a metal seed layer formed on a surface of a polyimide film by electroless plating or a dry method, and a copper layer or a copper alloy layer directly formed on the metal seed layer by electroplating in the one or two plating baths, wherein the copper layer or copper alloy layer consists of two or three separately-applied plating layers of copper or copper alloy with a boundary being formed and located between each adjacent pair of the separately-applied plating layers, including a concentrated portion of impurities at the boundary or boundaries, wherein each of said two or three separately-applied plating layers of copper or copper alloy has a thickness within a range of 2.07 μm to 8.50 μm without a boundary containing concentrated impurities extending therein, and wherein no further layers of copper or copper alloy are plated on said two or three separately-applied plating layers of copper or copper alloy of the metal covered polyimide composite. ### Claim 2 (depends on 1) The metal covered polyimide composite according to claim 1, wherein the tie-coat layer is made of a metal or an alloy selected from the group consisting of nickel, chromium, cobalt, nickel alloy, chromium alloy, and cobalt alloy, and the metal seed layer is made of copper or copper alloy. ### Claim 3 (depends on 2) The metal covered polyimide composite according to claim 2, wherein said copper layer or copper alloy layer consists of two separately-applied plating layers and a single boundary between said two separately applied plating layers, and wherein the thickness of each of said two separately-applied plating layers is within a range of 3.90 μm to 4.27 μm. ### Claim 4 (depends on 2) The metal covered polyimide composite according to claim 2, wherein said copper layer or copper alloy layer consists of three separately-applied plating layers and two boundaries, and wherein the thickness of each of said three separately-applied plating layers is within a range of 2.07 μm to 3.90 μm. ### Claim 5 (depends on 1) The metal covered polyimide composite according to claim 1, wherein the thickness of each of said two or three separately-applied plating layers is within a range of 2.07 μm to 4.27 μm. ### Claim 6 (depends on 1) A method of producing an electronic circuit board, wherein, after forming a copper circuit or copper alloy circuit by way of etching the metal covered polyimide composite according to claim 1, tin plating to the copper circuit or copper alloy circuit is performed. ### Claim 7 A metal covered polyimide composite, comprising: a polyimide film; a tie-coat layer formed on a surface of said polyimide film; a metal seed layer formed on said tie-coat layer; and a copper or copper alloy layer directly formed on said metal seed layer by electroplating, said copper or copper alloy layer consisting of two or three separately-applied plating layers with a boundary only being formed and located between each adjacent pair of plating layers and a concentrated portion of impurities being present only within the boundary between each adjacent pair of plating layers and not within the two or three separately-applied plating layers; each of said two or three separately-applied plating layers having a thickness within a range of 2.07 μm to 8.50 μm; and no further layers of copper or copper alloy are plated on said two or three separately-applied plating layers of copper or copper alloy of the metal covered polyimide composite. ### Claim 8 (depends on 7) The metal covered polyimide composite according to claim 7, wherein said tie-coat layer is made from a metal selected from the group consisting of nickel, chromium, cobalt, nickel alloy, chromium alloy, and cobalt alloy, and wherein said metal seed layer is made from copper or copper alloy. ### Claim 9 (depends on 8) The metal covered polyimide composite according to claim 8, wherein said copper or copper alloy layer is in the form of a circuit, and wherein a layer of tin is plated thereon. ### Claim 10 (depends on 8) The metal covered polyimide composite according to claim 8, wherein said copper or copper alloy layer consists of two separately-applied plating layers and a single boundary between said two separately-applied plating layers. ### Claim 11 (depends on 10) The metal covered polyimide composite according to claim 10, wherein the thickness of each of said two separately-applied plating layers is within a range of 3.90 μm to 4.27 μm. ### Claim 12 (depends on 8) The metal covered polyimide composite according to claim 8, wherein said copper or copper alloy layer consists of three separately-applied plating layers and a total of two boundaries. ### Claim 13 (depends on 12) The metal covered polyimide composite according to claim 12, wherein the thickness of each of said three separately-applied plating layers is within a range of 2.07 μm to 3.90 μm. ### Claim 14 (depends on 7) The metal covered polyimide composite according to claim 7, wherein the thickness of each of said two or three separately-applied plating layers is within a range of 2.07 μm to 4.27 μm. ### Claim 15 A method of producing a metal covered polyimide composite, wherein after forming a tie-coat layer and a metal seed layer on a surface of a polyimide film by electroless plating or a dry method, and further feeding the polyimide film around a plating drum,only two or three separately-applied layers of electroplated copper or copper alloy are formed on the metal seed layer with a boundary being formed between each adjacent pair of the two or three layers of electroplated copper or copper alloy, wherein formed from the two or three layers of electroplated copper or copper alloy is a copper layer or copper alloy layer including a concentrated portion of impurities at the boundary between each adjacent pair of the two or three layers of electroplated copper or copper alloy, wherein the two or three layers of electroplated copper or copper alloy are formed by dividing an electroplating zone into two to four zones when feeding the polyimide film with the tie-coat layer and metal seed layer formed thereon around the plating drum and performing electroplating thereto, and wherein a gap between at least two adjacent ones of the zones is equal to or less than half the distance between anodes of the at least two adjacent ones of the zones and the polyimide film traveling on the plating drum. ### Claim 16 (depends on 15) The method according to claim 15, further comprising the steps of: etching the copper layer or copper alloy layer to form a copper or copper alloy circuit; and plating the copper or copper alloy circuit with a layer of tin. ### Claim 17 A method of producing a metal-covered polyimide composite, comprising the steps of: forming a tie-coat layer on a surface of a polyimide film and a metal seed layer on the tie-coat layer; and feeding the polyimide film with the tie-coat layer and the metal seed layer around a plating drum within an electroplating bath to electroplate two or three plating layers of copper or copper alloy on the metal seed layer such that a boundary containing concentrated impurities is formed between each adjacent pair of the two or three plating layers of copper or copper alloy; wherein the electroplating bath has an electroplating area divided into a plurality of electroplating zones, a pre-determined one of the plurality of electroplating zones consisting of two adjacent anode plates which are electrically connected and which have a gap formed therebetween equal to or less than half a distance between surfaces of the two adjacent anode plates facing the plating drum and the polyimide film traveling on the plating drum; and wherein one of the two or three plating layers of copper or copper alloy being formed in the pre-determined one of the plurality of electroplating zones. ### Claim 18 A method of producing a metal-covered polyimide composite, comprising the steps of: forming a tie-coat layer on a surface of a polyimide film and a metal seed layer on the tie-coat layer; and feeding the polyimide film with the tie-coat layer and the metal seed layer around a first plating drum within a first electroplating bath and a second plating drum within a second electroplating bath to electroplate two or three plating layers of copper or copper alloy on the metal seed layer such that a boundary containing concentrated impurities is formed between each adjacent pair of the two or three plating layers of copper or copper alloy; wherein the first electroplating bath includes an electroplating zone consisting of two adjacent anode plates which are electrically connected and which have a gap formed therebetween equal to or less than half a distance between surfaces of the two adjacent anode plates facing the first plating drum and the polyimide film traveling on the first plating drum; wherein the second electroplating bath includes an electroplating zone consisting of two adjacent anode plates which are electrically connected and which have a gap formed therebetween equal to or less than half a distance between surfaces of the two adjacent anode plates facing the second plating drum and the polyimide film traveling on the second plating drum; and wherein one of the two or three plating layers of copper or copper alloy is formed in the electroplating zone of the first electroplating bath and another one of the two or three plating layers of copper or copper alloy is formed in the electroplating zone of the second electroplating bath.