CN116209787A - Conductive film with excellent solder wettability - Google Patents
Conductive film with excellent solder wettability Download PDFInfo
- Publication number
- CN116209787A CN116209787A CN202180053398.3A CN202180053398A CN116209787A CN 116209787 A CN116209787 A CN 116209787A CN 202180053398 A CN202180053398 A CN 202180053398A CN 116209787 A CN116209787 A CN 116209787A
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- CN
- China
- Prior art keywords
- copper
- layer
- conductive film
- compounds
- solder wettability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910000679 solder Inorganic materials 0.000 title abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000007747 plating Methods 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 64
- 239000010949 copper Substances 0.000 claims abstract description 64
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 27
- -1 thiol compounds Chemical class 0.000 claims abstract description 21
- 230000004888 barrier function Effects 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical group 0.000 claims abstract description 17
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 150000003585 thioureas Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims 1
- 150000003852 triazoles Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 41
- 238000003860 storage Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 49
- 239000010408 film Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 7
- 239000002184 metal Chemical group 0.000 description 7
- 229910052751 metal Chemical group 0.000 description 7
- 238000005282 brightening Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004649 discoloration prevention Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical compound SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The purpose of the present invention is to manufacture a conductive film with low cost, which suppresses the reduction of solder wettability caused by long-term storage or the like, through a simple process. The surface of a copper layer and/or a copper alloy layer formed on a film substrate is provided with a barrier layer containing an organic compound bonded to copper, and a conductive film formed by stacking a tin plating layer on the barrier layer. The organic compound is preferably selected from heterocyclic compounds, thiourea compounds and thiol compounds.
Description
Technical Field
The present invention relates to a conductive film. More specifically, the present invention relates to a conductive film having excellent solder wettability and less reduction in solder wettability with time.
Background
A material in which tin plating is applied to the surface of copper and/or copper alloy material is used for various electronic components such as terminals and connectors for electrical connection. For the purpose of tin plating, the contact resistance value is lowered. In addition, in order to improve corrosion resistance of the surface of copper and/or copper alloy material, good solder wettability may be provided.
Conventionally, in the case of long-term storage after tin plating, there is known a problem of reduced solder wettability. When the storage conditions are high temperatures, the problem of reduced solder wettability becomes more remarkable. The reason for this is considered that copper atoms and other metal atoms diffuse from copper and/or copper alloy material into the tin plating layer and reach the surface of the tin plating layer.
In order to solve this problem, it has been proposed to form a diffusion barrier layer made of nickel plating between a copper base material (copper-based solder) and tin plating (patent document 1), or to provide an intermediate layer containing an intermetallic compound of nickel and tin (patent document 2). The diffusion coefficient from nickel to the tin-plated layer is much lower than that of copper. Further, there has been proposed a conductive material for a connection member, which comprises a surface plating layer comprising a nickel layer and a copper-tin alloy layer formed in this order on the surface of a base material comprising copper and/or a copper alloy, and a tin layer formed on the surface plating layer (patent document 3).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 10-302864
Patent document 2: japanese patent laid-open No. 04-329891
Patent document 3: japanese patent application laid-open No. 2004-068026
Disclosure of Invention
Problems to be solved by the invention
As proposed in patent documents 1 to 3, the method of providing a metal layer such as nickel between copper and/or copper alloy material and tin plating layer can obtain a certain effect in suppressing the reduction of solder wettability during long-term storage. However, since a plurality of metal layers need to be formed sequentially, the process becomes complicated and the cost becomes high.
In recent years, in electronic devices that are increasingly miniaturized and light-weighted, a flexible circuit board in which a circuit is formed on a flexible film and electronic components are mounted has become a mainstream. Further, in an electronic device called a so-called wearable device that is worn on the body and used, a flexible circuit board is bent at a high frequency. In a contact portion of a flexible circuit board or the like, there is a problem that a metal multilayer structure not only hinders flexibility but also is liable to peel between metal layers due to repeated bending.
Means for solving the problems
In order to solve the above problems, the present inventors have studied a novel method for suppressing diffusion of copper atoms from a copper layer and/or a copper alloy layer formed on a film substrate to a tin plating layer laminated on the surface thereof. As a result, it has been found that by forming a barrier layer in which copper and a specific organic compound are bonded to the surface of a copper layer and/or a copper alloy layer, and stacking a tin plating layer on the barrier layer, diffusion of copper atoms into the tin plating layer can be suppressed, and the present invention has been completed.
That is, the present invention is a conductive film in which a barrier layer containing an organic compound bonded to copper is provided on the surface of a copper layer and/or a copper alloy layer formed on a thin film substrate, and a tin plating layer is laminated on the barrier layer. Thus, diffusion of copper atoms from the copper layer and/or copper alloy layer to the tin plating layer can be effectively suppressed, and thus a conductive film with reduced change in solder wettability with time can be obtained.
The organic compound is preferably a mixture of 1 or more selected from heterocyclic compounds, thiourea compounds and thiol compounds. The heterocyclic compound is preferably selected from triazole compounds, pyrrole compounds, pyrazole compounds, thiazole compounds and imidazole compounds.
The arithmetic average roughness Ra of the surface of the tin-plated layer is preferably 0.02 to 0.3. Mu.m, more preferably 0.08 to 0.2. Mu.m. This can further suppress the decrease in solder wettability with time.
Effects of the invention
According to the present invention, a conductive film in which a decrease in solder wettability with time is suppressed can be produced at low cost by a simple process.
Detailed Description
The conductive film of the present invention is composed of a flexible film and a copper layer and/or a copper alloy layer formed on the film. As the flexible film, a film containing a synthetic resin is preferably used. The synthetic resin is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polyimide, and the like. Among them, polyimide films are preferable. The thickness of the film is preferably 4 to 100. Mu.m, more preferably 10 to 50. Mu.m.
As a method for forming the copper layer and/or the copper alloy layer on the film, a known method may be used without limitation. Examples of the method include a method of adhering a copper foil and/or a copper alloy foil using an adhesive, a dry film forming method such as a vacuum deposition method or a sputtering method, and a wet film forming method such as an electroless plating method or an electroplating method. In addition, these methods may be combined to form a copper layer and/or a copper alloy layer. The preferred method is a dry film forming method. Examples of other metals that can be used in the copper alloy include nickel, zinc, and tin.
The thickness of the copper layer and/or copper alloy layer is not particularly limited, but is preferably 0.5 to 5. Mu.m. If the thickness of the copper layer and/or the copper alloy layer is within this range, a conductive film having both excellent conductivity and flexibility can be obtained. More preferably, the thickness is in the range of 1 to 3. Mu.m. The copper layer and/or the copper alloy layer may be one layer only, or two or more layers having different properties may be stacked.
In the conductive film of the present invention, a barrier layer containing an organic compound bonded to copper is formed on the surface of the copper layer and/or the copper alloy layer. The organic compound is preferably an organic compound selected from the group consisting of heterocyclic compounds, thiourea compounds and thiol compounds. These organic compounds can form a thin film at a molecular level on the surface of the copper layer and/or the copper alloy layer by chemically bonding nitrogen atoms or sulfur atoms contained in the molecular structure thereof to copper atoms.
Examples of the heterocyclic compound include compounds selected from the group consisting of triazole compounds, pyrrole compounds, pyrazole compounds, thiazole compounds, imidazole compounds, thiadiazole compounds, oxazole compounds and thiazoline compounds.
Among them, benzotriazole, tolyltriazole, mercaptobenzothiazole, mercaptothiadiazole, benzimidazole mercaptan, benzoxazole mercaptan, methylbenzothiazole, mercaptothiazoline and the like are particularly preferable.
Examples of the thiourea compound include thiourea, diethylthiourea, dibutylthiourea, 1, 3-diethyl-2-thiourea, trimethylthiourea, 1, 3-dimethylthiourea, 1-acetylthiourea, N-allylthiourea, ethylenethiourea, and N-methylthiourea.
Examples of the thiol compound include methane dithiol, 1, 2-ethane dithiol, 1-propane dithiol, and triazine thiol.
The organic compound is preferably a heterocyclic compound, more preferably a triazole compound, and particularly preferably benzotriazole or a derivative thereof.
And forming a tin plating layer so as to be laminated on the barrier layer. The thickness of the tin plating layer is preferably 0.5 to 3.0. Mu.m. If the thickness of the tin plating layer is within this range, excellent solder wettability can be maintained for a long period of time. The tin plating layer may be formed by either electroless plating or electroplating, but is preferably formed by electroplating for reasons of easy control of film thickness or easy continuous processing.
The arithmetic average roughness Ra of the surface of the tin-plated layer is preferably 0.02 to 0.3. Mu.m, more preferably 0.08 to 0.2. Mu.m. When the arithmetic average roughness Ra of the tin-plated layer surface is small, the solder wettability tends to be easily lowered. If the arithmetic average roughness Ra of the tin-plated layer surface is within the above range, a conductive film that further suppresses the decrease in solder wettability with time can be obtained. The arithmetic average roughness Ra of the tin-plated layer surface refers to the surface roughness of the outermost layer of the laminated conductive film, and may be determined in accordance with JIS B0601 after lamination: 2001.
The relationship between the arithmetic average roughness Ra of the tin plating layer surface and the decrease in solder wettability with time is considered to be caused by the organic matter contained in the tin plating layer. In particular, as a brightening agent to be added to a plating solution, there is a brightening agent whose wettability to solder is significantly reduced by oxidation. Therefore, it is preferable to carry out the tin plating treatment without excessively using such a brightening agent, and as a result, it is preferable to set the arithmetic average roughness Ra of the tin plating layer surface to be in the range of 0.02 to 0.3 μm. The arithmetic average roughness Ra of the tin-plated layer surface varies depending on the kind of the brightening agent, the current density, the plating thickness, and the like. In addition, it may also be affected by the surface roughness of the copper layer and/or copper alloy layer of the substrate.
The method for manufacturing a conductive film of the present invention comprises: a first step of bringing a treatment liquid in which an organic compound is dissolved into contact with a copper layer and/or a copper alloy layer formed on a film base material to form a barrier layer containing the organic compound bonded to copper; and a second step of stacking a tin plating layer on the barrier layer by an electroplating method.
The method for forming the copper layer on the film base material is not particularly limited, and a known method can be used. Specifically, a copper vapor deposition method, an electrolytic copper plating method, an electroless copper plating method, and the like can be cited. Among them, copper vapor deposition is preferably used. If the vapor deposition method is used for forming the copper layer, a copper layer having high surface smoothness can be formed.
In the copper layer formation, the copper layer may be formed by vapor deposition, and then further formed thereon by electroplating copper. In this way, a thick copper layer thickness can be formed more efficiently. In this case, a second copper layer by a copper electroplating method is laminated on the surface of the copper layer formed by the vapor deposition method.
In the step of forming a barrier layer as the first step, the film base material on which the copper layer and/or copper alloy layer is formed is brought into contact with a treatment liquid in which the organic compound is dissolved. Examples of the solvent that can be used for the treatment liquid include water and alcohols. A surfactant or the like for dispersing the organic compound may be added.
The concentration of the organic compound in the treatment liquid is preferably 0.1 to 10g/L. The temperature of the treatment solution is preferably 20 to 40 ℃ and the contact time is preferably 5 to 60 seconds. Thereby, the barrier layer can be formed on the surface of the copper layer and/or copper alloy layer with a thickness within the above-described range.
The second step is a step of forming a tin plating layer by a general electrolytic tin plating method. As the plating solution used in the electrolytic tin plating method, for example, an aqueous solution of stannous sulfate or the like may be used as a tin supply source, and commercially available electrolytic tin plating solutions may be used. The organic matter content in the tin plating layer formed in the second step is affected by the composition of the plating solution. Therefore, in order to control the organic matter content of the tin plating layer within a predetermined range, it is necessary to appropriately control the amount of organic matter to be blended in the plating solution.
Examples of the organic substances added to the plating solution include various surfactants, brighteners, antioxidants, and the like. It is important to appropriately design the amount of these organic matters contained in the plating solution and to appropriately control the content of the organic matters in the tin plating layer formed in the second step.
Among the above organic substances, eutectoid organic substances derived from brightening agents typified by aldehyde compounds and amine compounds are particularly preferred because they tend to form oxide films on the surface of tin plating layers, and thus the solder wettability is significantly reduced, and the addition thereof is preferably limited. However, the carboxylic acid and carboxylic acid ester are limited to acrylic acid, methyl acrylate and methyl methacrylate, and may be added in the range of 0.01 to 1g/L for the purpose of adjusting the appearance quality.
The conditions of the electrolytic tin plating method in the second step are not particularly limited, and may be set within a range in which a tin plating layer of a desired thickness can be formed. When the general conditions are exemplified, the temperature of the plating solution may be set to 20 to 40℃and the current density may be set to 0.5 to 5.0A/dm 2 The treatment time may be set to 20 to 200 seconds.
The first process and the second process may be continuously performed. Further, the first step may be preceded by a step of forming the copper layer and/or the copper alloy layer on the film base material, and these steps may be performed continuously. As an example of the process for forming the copper layer and/or copper alloy layer on the film base material, the following process may be mentioned: the film substrate on which a thin copper film is formed in advance by a vacuum vapor deposition method is formed with a copper layer to a desired thickness by an electroless copper plating method or an electrolytic copper plating method. In addition, between these steps, a water washing step and a drying step may be appropriately performed.
Examples
The present invention will be described below by way of examples, but the present invention is not limited to these examples. In addition, the evaluation in examples was performed according to the following method.
[ evaluation of solder wettability ]
Solder paste (trade name "ECO SOLDER PASTE L-BLT 5-T7F", manufactured by Qianzhi metal industries, inc.) was printed and applied onto the surface of the sample in a manner of having a radius of 6mm and a thickness of 70 μm, and after heat treatment at 250 ℃ for 3 minutes using a constant temperature dryer (trade name "DRA630DA", manufactured by ADVANTEC east ocean Co., ltd.), the long diameter (n=3) of the wet spread "solder" was measured, and an average value was calculated.
[ evaluation of solder wettability Change with time ]
The above-mentioned solder wettability evaluation was performed on samples before and after treatment (assuming storage at 80 ℃ for 1 month) in an atmosphere of 155 ℃ for 5 hours, and the ratio R (%) of the solder length after treatment to the solder length before treatment was calculated and evaluated. 100% means that there is no decrease in solder wettability with time, and a higher value (%) indicates a smaller decrease in solder wettability with time.
[ measurement of arithmetic average roughness Ra ]
The arithmetic average roughness Ra is obtained by following "JIS B0601: 2001", are determined by the method of the invention.
Example 1 >
Copper vapor deposited polyimide film (thickness of polyimide film 25 μm, thickness of copper layer 1.5 μm) manufactured by Toli KP film Co., ltd was immersed in 1g/L aqueous solution of 1,2, 3-benzotriazole at room temperature (25 ℃) for 60 seconds to form a barrier layer (first step). Then, the following electrolytic tin plating solution a was used to perform electrolytic tin plating, and a tin plating layer was formed on the barrier layer (second step). The temperature of the electrolytic tin plating solution was 40℃and the current density was 1.5A/dm 2 A 140 second treatment was performed. Then, the mixture is washed with water, and the mixture is subjected to discoloration prevention using a known discoloration prevention agentAnd (5) color treatment.
[ electrolytic tin plating solution A ]
Tin alkylsulfonate-containing solution (trade name "UTB PF-SN15", manufactured by Shichen chemical Co., ltd.): 400g/L
Alkyl sulfonic acid-based pH adjustor (trade name "UTB PF-A", manufactured by Shichen chemical Co., ltd.): 80g/L
Alkyl sulfonic acid-based plating additive (trade name "UTB PF-095SA", manufactured by stone chemical Co., ltd., no brightening agent): 25mL/L
Then, annealing treatment was performed at 150℃for 1 hour using a constant temperature dryer (product name "DRA630DA" manufactured by ADVANTEC TOYOBO Co., ltd.) to obtain a conductive film. The thickness of the tin plating layer in the obtained conductive film was 1.7. Mu.m, and the arithmetic average roughness Ra of the surface thereof was 0.14. Mu.m. As a result of evaluation of the change in solder wettability with time, the solder wettability before treatment was 11.0mm, the solder wettability after treatment was 10.7mm, and the ratio R was 97.3%, which was good.
Example 2 >
A conductive film was obtained in the same manner as in example 1, except that a copper vapor deposited polyimide film (thickness of polyimide film 25 μm and thickness of copper layer 1.5 μm) was used instead of the copper vapor deposited polyimide film (thickness of polyimide film 25 μm and thickness of copper layer 0.3 μm), and the following electrolytic copper plating solution was used to deposit thereon further a polyimide film of copper layer 1.2 μm. The temperature of the electrolytic copper plating solution was 40℃and the current density was 3.0A/dm 2 A copper electroplating treatment was performed for 109 seconds.
[ electrolytic copper plating solution ]
Copper sulfate pentahydrate: 200g/L
Sulfuric acid: 55mL/L
Sodium chloride: 85mg/L
Matte bright copper plating additive (trade name "CU-SOFT", manufactured by JCU, inc.): 20mL/L
The thickness of the tin plating layer in the obtained conductive film was 1.8. Mu.m, and the arithmetic average roughness Ra of the surface thereof was 0.16. Mu.m. As a result of evaluation of the change in solder wettability with time, the solder wettability before treatment was 11.5mm, the solder wettability after treatment was 11.3mm, and the ratio R was 98.3%, which was good.
Example 3 >
A conductive film was obtained in the same manner as in example 1, except that the following electrolytic tin plating solution B was used instead of the electrolytic tin plating solution a at a liquid temperature of 21 ℃.
[ electrolytic tin plating solution B ]
Stannous sulfate: 50g/L
Sulfuric acid: 110mL/L
Methyl acrylate: 0.6g/L
Other additives: proper amount (containing antioxidant and surfactant)
The thickness of the tin plating layer in the obtained conductive film was 2.0. Mu.m, and the arithmetic average roughness Ra of the surface thereof was 0.03. Mu.m. As a result of evaluation of the change in solder wettability with time, the solder wettability before treatment was 10.3mm, the solder wettability after treatment was 8.3mm, and the ratio R was 80.6%, which was good.
Comparative example 1 >
A conductive film was obtained in the same manner as in example 1, except that the first step (formation of a barrier layer) was not performed. The thickness of the tin plating layer in the obtained conductive film was 1.7. Mu.m, and the arithmetic average roughness Ra of the surface thereof was 0.10. Mu.m. As a result of evaluation of the change in solder wettability with time, the solder wettability before treatment was 11.6mm, and the solder wettability after treatment was reduced to 7.7mm. The ratio R was 66.4%, which was a disadvantage.
Comparative example 2 >
A conductive film was obtained in the same manner as in example 2, except that the first step (formation of a barrier layer) was not performed. The thickness of the tin plating layer in the obtained conductive film was 1.7. Mu.m, and the arithmetic average roughness Ra of the surface thereof was 0.16. Mu.m. As a result of evaluation of the change in solder wettability with time, the solder wettability before treatment was 12.0mm, and the solder wettability after treatment was reduced to 9.0mm. The ratio R was 75.0%, which was a disadvantage.
Industrial applicability
The conductive film of the present invention is a conductive film that suppresses a decrease in solder wettability with time, and can be produced in a simple process as compared with conventional techniques. Thus, the method can be used for wearable devices and parts of various electronic devices, which need to be electrically connected. Further, a spacer material may be used for grounding the electronic device case by winding the spacer material around an elastic material or the like.
Claims (4)
1. And a conductive film having a barrier layer containing an organic compound bonded to copper on the surface of the copper layer and/or copper alloy layer formed on the film substrate, wherein a tin plating layer is laminated on the barrier layer.
2. The conductive film according to claim 1, wherein the organic compound is a mixture of 1 or more selected from the group consisting of heterocyclic compounds, thiourea compounds, thiol compounds.
3. The conductive film according to claim 2, wherein the heterocyclic compound is selected from the group consisting of triazole-based compounds, pyrrole-based compounds, pyrazole-based compounds, thiazole-based compounds, and imidazole-based compounds.
4. The conductive film according to claim 1, wherein the tin-plated layer surface has an arithmetic average roughness Ra of 0.02 to 0.3 μm.
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| JP2020-176078 | 2020-10-20 | ||
| JP2020176078 | 2020-10-20 | ||
| PCT/JP2021/035472 WO2022085374A1 (en) | 2020-10-20 | 2021-09-27 | Conductive film having excellent solder wettability |
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| JP2801793B2 (en) | 1991-04-30 | 1998-09-21 | 株式会社神戸製鋼所 | Tin-plated copper alloy material and method for producing the same |
| JP3286560B2 (en) | 1997-04-28 | 2002-05-27 | 株式会社オートネットワーク技術研究所 | Mating connection terminal |
| JP4090302B2 (en) | 2001-07-31 | 2008-05-28 | 株式会社神戸製鋼所 | Conductive material plate for forming connecting parts |
| JP5717289B2 (en) * | 2011-06-23 | 2015-05-13 | アキレス株式会社 | Conductive film for circuit |
| JP5286443B1 (en) * | 2012-11-20 | 2013-09-11 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
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