CN114231956B - Copper foil-free flexible circuit activation material, film, flexible circuit, preparation and application - Google Patents
Copper foil-free flexible circuit activation material, film, flexible circuit, preparation and application Download PDFInfo
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- CN114231956B CN114231956B CN202111550494.7A CN202111550494A CN114231956B CN 114231956 B CN114231956 B CN 114231956B CN 202111550494 A CN202111550494 A CN 202111550494A CN 114231956 B CN114231956 B CN 114231956B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 94
- 239000010949 copper Substances 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 46
- 230000004913 activation Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 64
- 239000007790 solid phase Substances 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000011282 treatment Methods 0.000 claims description 229
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 121
- 238000005406 washing Methods 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 79
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 239000008139 complexing agent Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000011889 copper foil Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 6
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000013532 laser treatment Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000006698 induction Effects 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000004642 Polyimide Substances 0.000 description 19
- 229920001721 polyimide Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Classifications
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention provides a copper foil-free flexible circuit activation material, a film, a flexible circuit, preparation and application, wherein the film material consists of a solid phase powder catalytic additive and a liquid phase material in a weight ratio of 1:8-10; the solid phase powder catalytic additive consists of the following raw materials: 7-15wt% of aluminum oxide, 80-90wt% of cobalt blue, 1-4wt% of aluminum oxide short fibers, 1-5wt% of fillers and 0.5-1wt% of rare earth oxide; the liquid phase material consists of PI and/or PAI and a diluent, wherein the weight ratio of the PI and/or PAI to the diluent is 8-12:1. the PI and/or PAI materials of the invention are adopted, so that the cost is saved; a self-opening solid phase catalyst and a liquid phase material containing PI and/or PAI are adopted to prepare a film which can be activated by laser, a circuit pattern is formed by laser induction, and finally, metal deposition is realized in an electroless copper plating system to obtain a circuit.
Description
Technical Field
The invention belongs to the technical field of flexible circuit preparation, and particularly relates to a copper foil-free flexible circuit activation material, a film, a flexible circuit, preparation and application.
Background
The FCCL is mainly prepared by laminating Polyimide (PI) film materials developed by Dupont in early stage and copper foils (RA copper foil and ED copper foil) with certain thickness to prepare flexible circuit materials, and the flexible circuit materials comprise two FCCL with or without glue and glue. The method realizes the circuit through the following pattern transfer steps: fccl surface desxidation. 2. A photosensitive material (dry film or wet film) is applied. 3 UV exposure using a negative or laser data. Developing with sodium carbonate or sodium bicarbonate in the concentration of 4.1-3% to eliminate the photosensitive film material without polymerization and expose partial copper surface. 5. Etching the surface copper foil to obtain the circuit.
The circuit is manufactured mainly by realizing pattern transfer through a photosensitive material, and obtaining the circuit through a material reduction (reduction) mode, wherein the circuit comprises a PI film and copper foil covering process, and 6 main processes are provided. The four main processes of copper foil lamination, surface oxidation removal, development and etching have pollution emission, and copper foil and PI materials with the thickness of less than 1/2 ounce (about 18 microns) are basically imported from the main materials. Therefore, there is an urgent need to provide a copper foil-free flexible circuit film.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the copper foil-free flexible circuit activating material, the film, the flexible circuit, the preparation and the application, which can shorten the preparation flow of the flexible circuit and reduce the pollution emission.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the copper foil-free flexible circuit activating material is prepared from a solid phase powder catalytic additive and a liquid phase material in a weight ratio of 1:8-10; the solid phase powder catalytic additive consists of the following raw materials: 7-15wt% of aluminum oxide, 80-90wt% of cobalt blue, 1-4wt% of aluminum oxide short fibers, 1-5wt% of fillers and 0.5-1wt% of rare earth oxide;
the liquid phase material consists of PI and/or PAI and a diluent, wherein the weight ratio of the PI and/or PAI to the diluent is 8-12:1, a step of;
the diluent is N-methyl pyrrolidone;
the solid phase powder catalytic additive has a normal distribution with a first peak particle size of 800nm-1 mu m, a normal distribution with a second peak of 2-3.5 mu m, and the areas of the two peak areas are basically 1:1, a step of; the filler is titanium dioxide or carbon black;
the length of the alumina short fiber is 5-10mm, and the diameter is as follows: 3-7 mu m;
the rare earth oxide is at least one of cerium oxide, lanthanum oxide, praseodymium oxide and neodymium oxide; the rare earth oxide is CS-type rare earth oxide.
The activating material is prepared from a solid-phase powder catalytic additive and a liquid-phase material in a weight ratio of 1:8-10, and the range mainly considers the processability of film coating and thickness control. 1:7, the activation degree is high, the copper impact time is short, and the copper layer is coarse in crystallization; 1:11 would result in low activation, long copper impact time and poor adhesion. The liquid phase material is composed of PI and/or PAI and a diluent, and the PI and PAI have similar properties, so that the ratio of PI and PAI is not particularly limited when they are used in the liquid phase material.
The second object of the invention is to provide a copper foil-free flexible circuit film, which comprises a substrate film layer and an activation film layer; the activation film layer is made of the activation material; the substrate film layer is made of any one of PET, PI, PAI. The thickness of the activated film layer is 50-150 mu m; the thickness of the substrate film layer is 50-150 mu m.
Considering that the instantaneous thermal effect of the flexible circuit material in the laser induction process can cause local shrinkage of the film material, and the total thickness of the copper foil-free flexible circuit film is not less than 100 micrometers; the film can be formed by adopting a single PI material with the thickness not smaller than 50 mu m, or can be compounded by adopting a PI material, PET and other materials, or adopts other anti-shrinkage flexible film materials to reduce the overall thickness of the flexible material.
The third object of the invention is to provide a copper foil-free flexible circuit, which comprises a substrate layer film and a metal plating layer, wherein the substrate layer film is the copper foil-free flexible circuit film; the metal plating layer comprises a copper plating layer, a nickel plating layer and a nickel plating gold layer; the activation film layer is sequentially provided with a copper plating layer, a nickel plating layer and a nickel-gold plating layer.
The thickness of the copper plating layer is 6-20 micrometers; the thickness of the nickel plating layer is 2-8 micrometers; the thickness of the nickel-plated gold layer is 0.05-0.15 micrometers.
The fourth object of the present invention is to provide a method for manufacturing the copper foil-free flexible circuit, comprising the following steps:
step 1, directly patterning a substrate layer film by laser;
step 2, carrying out ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, washing the film subjected to ultrasonic treatment by two times;
step 4, performing impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, washing the film subjected to the copper impact treatment in the step 4 by two times;
step 6, carrying out chemical plating thick copper treatment on the film subjected to the two water washing treatments in the step 5;
step 7, washing the film subjected to the chemical plating thick copper treatment in the step 6 by three pure water treatments;
step 8, pre-soaking the film subjected to the three-step pure water washing treatment by the middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-soaking treatment in the step 8;
step 10, washing the film subjected to the nickel pre-activation treatment in the step 9 by using two pure water;
step 11, performing post-leaching treatment on the film subjected to the two pure water washing treatments in the step 10;
step 12, performing three pure water washes on the film subjected to the immersion treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the three pure water washing treatments in the step 12;
step 14, performing two pure water washing treatments on the film subjected to the chemical nickel plating treatment in the step 13;
step 15, performing nickel-gold protection treatment on the film subjected to the two pure water washing treatments in the step 14;
step 16, performing three pure water washes on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, carrying out hot water washing treatment on the film subjected to the three pure water washing treatments in the step 16;
and step 18, drying the film subjected to the hot water treatment in the step 17 to obtain the copper foil-free flexible circuit.
Further, the laser processing parameters in step 1 are: filling space: <50 microns, scanning frequency: 40-100 khz, scanning speed: 1000-2500 mm/s, power: 7-10 watts, laser wavelength: 1064nm;
further, in the step 2, ultrasonic water washing treatment is carried out for 5-15 minutes, the water dripping time is 20-30 seconds, and the ultrasonic water washing treatment is carried out in an environment of 50-60 ℃;
further, in the step 3, the water washing treatment time is 1-2 minutes, the water dripping time is 15-30 seconds, the water washing treatment is carried out at normal temperature, and the water washing treatment process adopts mechanical swing or air stirring;
further, in the step 4, the treatment time is 10-30 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 50-62 ℃, and the treatment process adopts any mode of air stirring or mechanical pump circulation;
further, the water washing treatment time in the step 5 is 0.5-1 min, the water dripping time is 20-30 seconds, the water washing treatment is carried out at normal temperature, and air stirring is adopted in the water washing treatment process;
further, the treatment time in the step 6 is 60-180 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 50-56 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, in the step 7, the water washing treatment time is 30 minutes, the water dripping time is 20-30 seconds, the water washing treatment is carried out at normal temperature, and air stirring is adopted in the water washing treatment process;
further, the treatment time in the step 8 is 3-5 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the presoaking treatment process adopts air stirring;
further, the treatment time in the step 9 is 5-10 minutes, the dripping time is 20-30 seconds, the treatment is carried out at the temperature of 32-38 ℃, and the mechanical circulation is adopted in the treatment process;
further, in the step 10, the water washing treatment time is 1-2 minutes, the water dripping time is 20-30 seconds, the water washing treatment is carried out at normal temperature, and the air stirring is adopted in the water washing treatment process;
further, the treatment time in the step 11 is 2-5 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, the treatment time in the step 12 is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, the treatment time in the step 13 is 10-25 minutes, the dripping time is 20-30 seconds, the treatment is carried out under the environment of 60-85 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, the treatment time in the step 14 is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, in the step 15, the treatment time is 3-8 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 35-45 ℃, and the mechanical circulation is adopted in the treatment process;
further, in the step 16, the treatment time is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, the treatment time in the step 17 is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 60-70 ℃, and the air stirring is adopted in the treatment process;
further, the drying treatment time in step 18: 25-30 minutes at 60-70 ℃.
Further, the components of the solution used in the impact copper treatment process in the step 4 are as follows: 150-200 parts of copper complexing agent, 20-40 parts of copper sulfate, 1-5 parts of methanol, 25-35 parts of sodium hydroxide, 12-18 parts of formaldehyde and 700-1000 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the impact copper treatment process in the step 4 comprises the following steps:
a) Adding 350-500 parts of deionized water into the prepared clean plating tank;
b) Stirring air, and adding 150-200 parts of copper complexing agent;
c) Adding 20-40 parts of copper sulfate;
d) Adding 1-5 parts of methanol;
e) Adding 25-35 parts of sodium hydroxide;
f) Adding 350-500 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 54-62 ℃;
h) Adding 12-18 parts of formaldehyde;
i) And (3) after heating to the operating condition, analyzing the concentration of the complexing agent, copper ions, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range.
Further, the solution used in the treatment process of the electroless thick copper plating in the step 6 comprises the following components: 120-180 parts of copper complexing agent, 20-25 parts of copper sulfate, 0.4-0.8 part of methanol, 20-25 parts of sodium hydroxide, 8-12 parts of formaldehyde and 700-1000 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the process of treating the electroless thick copper plating in the step 6 comprises the following steps:
a) Adding 350-500 parts of deionized water into the prepared clean plating tank;
b) Starting air stirring, and adding 120-180 parts of copper complexing agent;
c) Adding 20-25 parts of copper sulfate;
d) Adding 0.4-0.8 part of methanol;
e) Adding 20-25 parts of sodium hydroxide;
f) Adding 350-500 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 50-56 ℃;
h) Adding 8-12 parts of formaldehyde;
i) And (3) after heating to the operating condition, analyzing the concentration of the complexing agent, copper ions, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range.
The invention firstly carries out impact copper treatment, and a compact copper layer is slowly deposited on the basis of approximately 2-3 microns of impact copper; copper deposition during thick copper plating can be realized rapidly by copper impact treatment;
the chemical nickel plating treatment can ensure certain corrosion resistance of the copper circuit, so that the circuit meets the reliability test such as salt spray test and the like; the 5% neutral salt spray test reaches more than 48 hours. The high temperature and high humidity test at 85% relative humidity and 85 ℃ reaches more than 72 hours.
The nickel-gold protection treatment is to strengthen the reliability, oxidation resistance and low contact resistance of the plating again; the high-temperature and high-humidity test at 85 ℃ for 96 hours with the relative humidity of 85 percent is completed, and the resistance value is not more than 0.5 ohm.
A fifth object of the present invention is to provide an application of the copper foil-free flexible circuit, which is an application in a multilayer flexible circuit board, the copper foil-free flexible circuit or the copper foil-free flexible circuit manufactured by the manufacturing method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The PI and/or PAI material provided by the invention realizes the imported substitution of the PI and/or PAI material, and saves the cost;
(2) Preparing a laser activatable film by adopting an autonomous solid phase catalyst and a liquid phase material containing PI and/or PAI, forming a circuit pattern by laser induction, and finally realizing metal deposition in an electroless copper plating system to obtain a circuit;
(3) Compared with the existing manufacturing process, the process is shortened, only the electroless plating process involves pollution, and the pollution discharge is greatly reduced.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The copper foil-free flexible circuit activating material is prepared from a solid phase powder catalytic additive and a liquid phase material in a weight ratio of 1:8; the solid phase powder catalytic additive consists of the following raw materials: 10wt% of aluminum oxide, 85wt% of cobalt blue, 2wt% of aluminum oxide short fibers, 2.2wt% of fillers and 0.8wt% of rare earth oxides;
the liquid phase material consists of PI and a diluent, wherein the weight ratio of the PI to the diluent is 10:1, a step of;
the diluent is N-methyl pyrrolidone;
the solid phase powder catalytic additive has a normal distribution with a first peak particle size of 800nm-1 mu m, a normal distribution with a second peak of 2-3.5 mu m, and the areas of the two peak areas are basically 1:1, a step of; the filler is titanium dioxide or carbon black;
the length of the alumina short fiber is 5-10mm, and the diameter is as follows: 3-7 mu m;
the rare earth oxide is cerium oxide; the rare earth oxide is CS-type rare earth oxide.
Example 2
The copper foil-free flexible circuit film comprises a substrate film layer and an activation film layer; the activated film layer is made of the activated material in example 1; the substrate film layer is made of PET; the thickness of the activation film layer is 50 mu m; the thickness of the substrate film layer is 50 mu m.
Example 3
A copper foil-free flexible circuit comprising a substrate layer film and a metallization layer, the substrate layer film being the copper foil-free flexible circuit film of example 2; the metal plating layer comprises a copper plating layer, a nickel plating layer and a nickel plating gold layer; the activation film layer is sequentially provided with a copper plating layer, a nickel plating layer and a nickel-gold plating layer.
The thickness of the copper plating layer is 18 microns; the thickness of the nickel plating layer is 6 microns; the thickness of the nickel-plated gold layer is 0.1 micrometer.
Example 4
The method for preparing the copper foil-free flexible circuit in the embodiment 3 comprises the following steps:
step 1, directly patterning a substrate layer film by laser;
step 2, carrying out ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, washing the film subjected to ultrasonic treatment by two times;
step 4, performing impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, washing the film subjected to the copper impact treatment in the step 4 by two times;
step 6, carrying out chemical plating thick copper treatment on the film subjected to the two water washing treatments in the step 5;
step 7, washing the film subjected to the chemical plating thick copper treatment in the step 6 by three pure water treatments;
step 8, pre-soaking the film subjected to the three-step pure water washing treatment by the middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-soaking treatment in the step 8;
step 10, washing the film subjected to the nickel pre-activation treatment in the step 9 by using two pure water;
step 11, performing post-leaching treatment on the film subjected to the two pure water washing treatments in the step 10;
step 12, performing three pure water washes on the film subjected to the immersion treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the three pure water washing treatments in the step 12;
step 14, performing two pure water washing treatments on the film subjected to the chemical nickel plating treatment in the step 13;
step 15, performing nickel-gold protection treatment on the film subjected to the two pure water washing treatments in the step 14;
step 16, performing three pure water washes on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, carrying out hot water washing treatment on the film subjected to the three pure water washing treatments in the step 16;
and step 18, drying the film subjected to the hot water treatment in the step 17 to obtain the copper foil-free flexible circuit.
Further, the laser processing parameters in step 1 are: filling space: 30 microns, scanning frequency: 80 khz, scan speed: 1500 mm/s, power: 8 watts, laser wavelength: 1064nm;
further, in the step 2, ultrasonic water washing treatment is carried out for 10 minutes, the water dripping time is 25 seconds, and the ultrasonic water washing treatment is carried out in an environment of 55 ℃;
further, in the step 3, the water washing treatment time is 1 minute, the water dripping time is 20 seconds, the water washing treatment is carried out at normal temperature, and the water washing treatment process adopts mechanical swing or air stirring;
further, in the step 4, the treatment time is 25 minutes, the dripping time is 25 seconds, the treatment is carried out at 55 ℃, and the treatment process adopts any mode of air stirring or mechanical pump circulation;
further, in the step 5, the water washing treatment time is 0.8 minute, the water dripping time is 25 seconds, the water washing treatment is carried out at normal temperature, and air stirring is adopted in the water washing treatment process;
further, in the step 6, the treatment time is 150 minutes, the dripping time is 25 seconds, the treatment is carried out at 55 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, in the step 7, the water washing treatment time is 30 minutes, the water dripping time is 25 seconds, the water washing treatment is carried out at normal temperature, and air stirring is adopted in the water washing treatment process;
further, in the step 8, the treatment time is 4 minutes, the dripping time is 25 seconds, the treatment is carried out at normal temperature, and the presoaking treatment process adopts air stirring;
further, in the step 9, the treatment time is 8 minutes, the dripping time is 25 seconds, the treatment is carried out at the temperature of 35 ℃, and the mechanical circulation is adopted in the treatment process;
further, in the step 10, the water washing treatment time is 1.5 minutes, the water dripping time is 25 seconds, the water washing treatment is carried out at normal temperature, and the air stirring is adopted in the water washing treatment process;
further, in the step 11, the treatment time is 3 minutes, the dripping time is 25 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, in the step 12, the treatment time is 1 minute, the dripping time is 25 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, in the step 13, the treatment time is 15 minutes, the dripping time is 25 seconds, the treatment is carried out at 75 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
further, in the step 14, the treatment time is 1 minute, the dripping time is 25 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, in the step 15, the treatment time is 5 minutes, the dripping time is 25 seconds, the treatment is performed at 38 ℃, and the mechanical circulation is adopted in the treatment process;
further, in the step 16, the treatment time is 1 minute, the dripping time is 25 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
further, in the step 17, the treatment time is 1 minute, the dripping time is 25 seconds, the treatment is carried out at 65 ℃, and the air stirring is adopted in the treatment process;
further, the drying treatment time in step 18: 25 minutes, at a temperature of 65 ℃.
Further, the components of the solution used in the impact copper treatment process in the step 4 are as follows: 180 parts of copper complexing agent, 30 parts of copper sulfate, 3 parts of methanol, 30 parts of sodium hydroxide, 16 parts of formaldehyde and 800 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the impact copper treatment process in the step 4 comprises the following steps:
a) Adding 450 parts of deionized water into the prepared clean plating tank;
b) Stirring by starting air, and adding 180 parts of copper complexing agent;
c) Adding 30 parts of copper sulfate;
d) Adding 3 parts of methanol;
e) Adding 30 parts of sodium hydroxide;
f) Adding 450 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 58 ℃;
h) Adding 16 parts of formaldehyde;
i) And (3) after heating to the operating condition, analyzing the concentration of the complexing agent, copper ions, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range.
Further, the solution used in the treatment process of the electroless thick copper plating in the step 6 comprises the following components: 150 parts of copper complexing agent, 23 parts of copper sulfate, 0.6 part of methanol, 23 parts of sodium hydroxide, 10 parts of formaldehyde and 850 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the process of treating the electroless thick copper plating in the step 6 comprises the following steps:
a) Adding 450 parts of deionized water into the prepared clean plating tank;
b) Stirring air, and adding 160 parts of copper complexing agent;
c) 23 parts of copper sulfate is added;
d) Adding 0.6 part of methanol;
e) Adding 23 parts of sodium hydroxide;
f) Adding 450 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 53 ℃;
h) Adding 10 parts of formaldehyde;
i) And (3) after heating to the operating condition, analyzing the concentration of the complexing agent, copper ions, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range.
Example 5
The use of the copper foil free flex circuit of example 3 or the copper foil free flex circuit made by the method of preparation of example 4, which is in a multilayer flex circuit board.
Comparative example 1
Comparative example 1 is a flexible circuit made of FNC film of a brand abroad;
the following table shows a comparison of the flexible circuit in example 3 of the present invention with the flexible circuit of comparative example 1
TABLE 1
TABLE 2 results of Property index test
The PI film of the invention can be seen from tables 1 and 2, and is applied to flexible circuits, so that the level of similar products abroad is basically achieved, the use amount of copper foil is reduced, the production cost is reduced, and the PI film has extremely high application value.
Comparative example 2
Comparative example 2 differs from example 2 in that the thickness of the activated film layer was 48 μm.
Comparative example 3
Comparative example 3 differs from example 2 in that the thickness of the activated film layer is 45 μm.
Comparative example 4
Comparative example 4 differs from example 2 in that the thickness of the activated film layer is 40 μm.
TABLE 3 Table 3
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A copper foil-free flexible circuit activating material is characterized in that: the activating material is prepared from a solid-phase powder catalytic additive and a liquid-phase material in a weight ratio of 1:8-10; the solid phase powder catalytic additive consists of the following raw materials: 7-15wt% of aluminum oxide, 80-90wt% of cobalt blue, 1-4wt% of aluminum oxide short fibers, 1-5wt% of fillers and 0.5-1wt% of rare earth oxide; the liquid phase material consists of PI and/or PAI and a diluent, wherein the weight ratio of the PI and/or PAI to the diluent is 8-12:1, a step of;
the diluent is N-methyl pyrrolidone;
the solid phase powder catalytic additive has a normal distribution with a first peak particle size of 800nm-1 mu m, a normal distribution with a second peak of 2-3.5 mu m, and the areas of the two peak areas are basically 1:1, a step of; the filler is titanium dioxide or carbon black;
the length of the alumina short fiber is 5-10mm, and the diameter is as follows: 3-7 mu m;
the rare earth oxide is at least one of cerium oxide, lanthanum oxide, praseodymium oxide and neodymium oxide; the rare earth oxide is CS-type rare earth oxide.
2. A copper foil-free flexible circuit film is characterized in that: comprises a substrate film layer and an activation film layer; the activated film layer is made of the activated material of claim 1; the substrate film layer is made of any one of PET, PI, PAI.
3. The utility model provides a exempt from copper foil flexible line which characterized in that: the flexible circuit comprises a substrate layer film and a metal plating layer, wherein the substrate layer film is the copper foil-free flexible circuit film in claim 2; the metal plating layer comprises a copper plating layer, a nickel plating layer and a nickel plating gold layer; the activation film layer is sequentially provided with a copper plating layer, a nickel plating layer and a nickel-gold plating layer.
4. A copper foil free flex circuit according to claim 3 wherein:
the thickness of the copper plating layer is 6-20 micrometers; the thickness of the nickel plating layer is 2-8 micrometers; the thickness of the nickel-plated gold layer is 0.05-0.15 micrometers; the thickness of the activated film layer is 50-150 mu m;
the thickness of the substrate film layer is 50-150 mu m.
5. The method for manufacturing a copper foil-free flexible circuit according to any one of claims 3 to 4, wherein: the method comprises the following steps:
step 1, directly patterning a substrate layer film by laser;
step 2, carrying out ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, washing the film subjected to ultrasonic treatment by two times;
step 4, performing impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, washing the film subjected to the copper impact treatment in the step 4 by two times;
step 6, carrying out chemical plating thick copper treatment on the film subjected to the two water washing treatments in the step 5;
step 7, washing the film subjected to the chemical plating thick copper treatment in the step 6 by three pure water treatments;
step 8, pre-soaking the film subjected to the three-step pure water washing treatment by the middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-soaking treatment in the step 8;
step 10, washing the film subjected to the nickel pre-activation treatment in the step 9 by using two pure water;
step 11, performing post-leaching treatment on the film subjected to the two pure water washing treatments in the step 10;
step 12, performing three pure water washes on the film subjected to the immersion treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the three pure water washing treatments in the step 12;
step 14, performing two pure water washing treatments on the film subjected to the chemical nickel plating treatment in the step 13;
step 15, performing nickel-gold protection treatment on the film subjected to the two pure water washing treatments in the step 14;
step 16, performing three pure water washes on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, carrying out hot water washing treatment on the film subjected to the three pure water washing treatments in the step 16;
and step 18, drying the film subjected to the hot water treatment in the step 17 to obtain the copper foil-free flexible circuit.
6. The method for manufacturing a copper foil-free flexible circuit according to claim 5, wherein: the laser processing parameters in the step 1 are as follows: filling space: scanning frequency <50 microns: 40-100 khz, scanning speed: 1000-2500 mm/s, power: 7-10 watts, laser wavelength: 1064nm;
in the step 2, ultrasonic water washing treatment is carried out for 5-15 minutes, the water dripping time is 20-30 seconds, and the ultrasonic water washing treatment is carried out in an environment of 50-60 ℃;
the water washing treatment time in the step 3 is 1-2 minutes, the water dripping time is 15-30 seconds, the water washing treatment is carried out at normal temperature, and the water washing treatment process adopts mechanical swing or air stirring;
in the step 4, the treatment time is 10-30 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 50-62 ℃, and the treatment process adopts any mode of air stirring or mechanical pump circulation;
the water washing treatment time in the step 5 is 0.5-1 min, the water dripping time is 20-30 seconds, the water washing treatment process is carried out at normal temperature, and air stirring is adopted;
in the step 6, the treatment time is 60-180 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 50-56 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
in the step 7, the water washing treatment time is 30 minutes, the water dripping time is 20-30 seconds, the water washing treatment is carried out at normal temperature, and the air stirring is adopted in the water washing treatment process;
in the step 8, the treatment time is 3-5 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the presoaking treatment process adopts air stirring;
in the step 9, the treatment time is 5-10 minutes, the dripping time is 20-30 seconds, the treatment is carried out at the temperature of 32-38 ℃, and the mechanical circulation is adopted in the treatment process;
the water washing treatment time in the step 10 is 1-2 minutes, the water dripping time is 20-30 seconds, the water washing treatment process is carried out at normal temperature, and air stirring is adopted in the water washing treatment process;
the treatment time in the step 11 is 2-5 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any mode of air stirring or mechanical circulation;
the treatment time in the step 12 is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
the treatment time in the step 13 is 10-25 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 60-85 ℃, and the treatment process adopts any mode of air stirring or mechanical circulation;
the treatment time in the step 14 is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
in the step 15, the treatment time is 3-8 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 35-45 ℃, and the mechanical circulation is adopted in the treatment process;
in the step 16, the treatment time is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the air stirring is adopted in the treatment process;
in the step 17, the treatment time is 1-2 minutes, the dripping time is 20-30 seconds, the treatment is carried out at 60-70 ℃, and the air stirring is adopted in the treatment process;
drying treatment time in step 18: 25-30 minutes at 60-70 ℃.
7. The method for manufacturing a copper foil-free flexible circuit according to claim 6, wherein: the components of the solution used in the impact copper treatment process in the step 4 are as follows: 150-200 parts of copper complexing agent, 20-40 parts of copper sulfate, 1-5 parts of methanol, 25-35 parts of sodium hydroxide, 12-18 parts of formaldehyde and 700-1000 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1:1, the composition is as follows;
the solution used in the step 6 of electroless thick copper plating treatment comprises the following components: 120-180 parts of copper complexing agent, 20-25 parts of copper sulfate, 0.4-0.8 part of methanol, 20-25 parts of sodium hydroxide, 8-12 parts of formaldehyde and 700-1000 parts of deionized water; wherein the copper complexing agent is EDTA and potassium sodium tartrate according to the weight ratio of 1: 1.
8. The method for manufacturing a copper foil-free flexible circuit according to claim 7, wherein: the preparation method of the solution used in the impact copper treatment process in the step 4 comprises the following steps:
a) Adding 350-500 parts of deionized water into the prepared clean plating tank;
b) Stirring air, and adding 150-200 parts of copper complexing agent;
c) Adding 20-40 parts of copper sulfate;
d) Adding 1-5 parts of methanol;
e) Adding 25-35 parts of sodium hydroxide;
f) Adding 350-500 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 54-62 ℃;
h) Adding 12-18 parts of formaldehyde;
i) After heating to the operation condition, analyzing the concentration of complexing agent, copper ion, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range;
the preparation method of the solution used in the treatment process of the electroless thick copper plating in the step 6 comprises the following steps:
a) Adding 350-500 parts of deionized water into the prepared clean plating tank;
b) Starting air stirring, and adding 120-180 parts of copper complexing agent;
c) Adding 20-25 parts of copper sulfate;
d) Adding 0.4-0.8 part of methanol;
e) Adding 20-25 parts of sodium hydroxide;
f) Adding 350-500 parts of deionized water to the liquid preparation amount;
g) Heating the plating tank to 50-56 ℃;
h) Adding 8-12 parts of formaldehyde;
i) And (3) after heating to the operating condition, analyzing the concentration of the complexing agent, copper ions, formaldehyde and sodium hydroxide, and adjusting the feeding test production within the process range.
9. Use of the copper foil free flex circuit according to any one of claims 3-4 or the copper foil free flex circuit produced by the method of any one of claims 5-8 in a multilayer flex circuit board.
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