CN114231956A - 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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- CN114231956A CN114231956A CN202111550494.7A CN202111550494A CN114231956A CN 114231956 A CN114231956 A CN 114231956A CN 202111550494 A CN202111550494 A CN 202111550494A CN 114231956 A CN114231956 A CN 114231956A
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- flexible circuit
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000004913 activation Effects 0.000 title claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052802 copper Inorganic materials 0.000 claims abstract description 82
- 239000010949 copper Substances 0.000 claims abstract description 82
- 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
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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 249
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 101
- 238000005406 washing Methods 0.000 claims description 89
- 238000000034 method Methods 0.000 claims description 75
- 230000008569 process Effects 0.000 claims description 68
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000008139 complexing agent Substances 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 claims description 16
- 239000011889 copper foil Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 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
- 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
- 238000010438 heat treatment Methods 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
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 238000012545 processing Methods 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
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 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
- 238000002791 soaking 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
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000001465 metallisation Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 50
- 239000004642 Polyimide Substances 0.000 description 19
- 229920001721 polyimide Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 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
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000010030 laminating Methods 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
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 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
- 230000001419 dependent effect 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
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating 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
- 230000009467 reduction Effects 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
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)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention provides a copper foil-free flexible circuit activating 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: 7-15 wt% of aluminum oxide, 80-90 wt% of cobalt blue, 1-4 wt% of alumina short fiber, 1-5 wt% of filler and 0.5-1 wt% 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 material provided by the invention is adopted, so that the cost is saved; the self-opening solid-phase catalyst and the liquid-phase material containing PI and/or PAI are adopted to prepare a laser-activated film, a circuit pattern is formed through 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 activating material, a film, a flexible circuit, preparation and application.
Background
The FCCL is mainly prepared by laminating a Polyimide (PI) film material developed by earlier Dupont and Copper foils with certain thickness (RA Copper foil and ED Copper foil) to prepare a Flexible circuit material, and the FCCL has two types of materials, namely no glue and glue. The circuit is realized by the following pattern transfer steps: FCCL surface deoxidation. 2. A photosensitive material (dry film or wet film) is applied. 3 UV exposure using negative film or laser data. Developing with 4.1-3% sodium carbonate or sodium bicarbonate to remove unpolymerized photosensitive film material and expose partial copper surface. 5. And etching the surface copper foil to obtain the circuit.
The above circuit manufacturing mainly realizes pattern transfer through photosensitive material, and obtains the circuit through a material reduction (subtractive) mode, wherein the circuit comprises a PI film and copper foil laminating process, and 6 main processes are provided. The four main procedures of copper foil lamination, surface deoxidation, development and etching are all polluted, and among the above main materials, copper foil and PI material with the thickness of less than 1/2 ounces (about 18 microns) are basically dependent on import. Therefore, it is urgently needed 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, and can shorten the preparation process of the flexible circuit and reduce the pollution emission.
In order to achieve the purpose, the invention provides the following technical scheme:
a 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: 7-15 wt% of aluminum oxide, 80-90 wt% of cobalt blue, 1-4 wt% of alumina short fiber, 1-5 wt% of filler and 0.5-1 wt% 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 diluent is N-methyl pyrrolidone;
the first peak particle size of the solid phase powder catalytic additive is normal distribution of 800nm-1um, the second peak is normal distribution of 2-3.5um, and the areas of the two peak areas are basically 1: 1; 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 um;
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, high activation, short copper impact time and coarse copper layer crystallization; 1: 11 results in low activation, long copper strike times and poor adhesion. The liquid phase material is composed of PI and/or PAI, diluent, and PI and PAI have similar performance, so when PI and PAI are used in the liquid phase material, the proportion of PI and PAI is not particularly limited.
The second purpose of the invention is to provide a copper-foil-free flexible circuit film, which comprises a base material film layer and an activation film layer; the activating film layer is made of the activating material; the substrate film layer is made of any one of PET, PI and PAI. The thickness of the activated film layer is 50-150 um; the thickness of the base material film layer is 50-150 um.
Considering that the instant thermal effect of the flexible circuit material in the laser induction process can cause the local shrinkage of the film material, the total thickness of the copper foil flexible circuit film is not less than 100 microns; the film can be formed by adopting a single PI material with the thickness not less than 50um, or can be formed by compounding the PI material with PET and other materials, or can be formed by adopting other anti-shrinkage flexible film materials to reduce the overall thickness of the flexible material.
The third purpose of the invention is to provide a copper-foil-free flexible circuit, which comprises a substrate layer film and a metal-plated 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-gold plating layer; and 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 microns; the thickness of the nickel plating layer is 2-8 microns; the thickness of the nickel-gold plating layer is 0.05-0.15 micrometer.
The fourth purpose of the present invention is to provide a method for preparing the above copper-foil-free flexible circuit, which comprises the following steps:
step 1, directly carrying out graphical treatment on a substrate layer film through laser;
step 2, performing ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, performing two washing treatments on the film subjected to the ultrasonic treatment;
step 4, carrying out impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, performing two washing treatments on the film subjected to the copper impact treatment in the step 4;
step 6, performing chemical thick copper plating treatment on the film subjected to the two washing treatments in the step 5;
step 7, performing three-step pure water washing treatment on the film after the thick copper chemical plating treatment in the step 6;
step 8, performing pre-dipping treatment on the film subjected to the three pure water washing treatments in the step 7 through a middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-immersion treatment in the step 8;
step 10, performing two times of pure water washing treatment on the film subjected to the nickel pre-activation treatment in the step 9;
step 11, carrying out post-dipping treatment on the film subjected to the pure water washing treatment in the step 10;
step 12, performing three times of pure water washing treatment on the film subjected to post-dipping treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the pure water washing treatment in the step 12;
step 14, performing two times of pure water washing treatment 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 pure water washing treatment in the step 14;
step 16, performing three pure water washing treatments on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, performing 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 as follows: filling the space: <50 μm, scanning frequency: 40-100 khz, scan speed: 1000-: 7-10 watts, laser wavelength: 1064 nm;
further, in the step 2, ultrasonic water washing treatment is carried out for 5-15 minutes, the dripping time is 20-30 seconds, and the ultrasonic water washing treatment is carried out in an environment of 50-60 ℃;
further, the washing treatment in the step 3 is carried out at normal temperature for 1-2 minutes and 15-30 seconds, and mechanical swing or air stirring is adopted in the washing treatment process;
further, the treatment time in the step 4 is 10-30 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 50-62 ℃, and the treatment process adopts any one of air stirring or mechanical pump circulation;
further, the washing treatment time in the step 5 is 0.5-1 minute, the dripping time is 20-30 seconds, the washing treatment is carried out at the normal temperature, and air stirring is adopted in the washing treatment process;
further, 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 one of air stirring or mechanical circulation;
further, the washing treatment time in the step 7 is 30 minutes, the water dripping time is 20-30 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
further, the treatment time in the step 8 is 3-5 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the pre-soaking treatment process is carried out by adopting air stirring;
further, the treatment time in the step 9 is 5-10 minutes, the water 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, the washing treatment time in the step 10 is 1-2 minutes, the water dripping time is 20-30 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
further, the treatment time in the step 11 is 2-5 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any one of air stirring or mechanical circulation;
further, the treatment time in the step 12 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, in the step 13, the treatment time is 10-25 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at the temperature of 60-85 ℃, and the treatment process adopts any one of air stirring or mechanical circulation;
further, in the step 14, the treatment time is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, the treatment time in the step 15 is 3-8 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 35-45 ℃, and the mechanical cycle is adopted in the treatment process;
further, the treatment time in the step 16 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, the treatment time in the step 17 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 60-70 ℃, and air stirring is adopted in the treatment process;
further, the drying processing time in step 18: 25-30 minutes at a temperature of 60-70 ℃.
Further, the solution used in the impact copper treatment process of step 4 comprises the following components: 200 parts of copper complexing agent 150-; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the step 4 impact copper treatment process comprises the following steps:
a) adding 350-500 parts of deionized water into a prepared clean plating bath;
b) starting air stirring, and adding 150 and 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) then 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 the temperature is raised to the operating condition, analyzing the concentrations of the complexing agent, the copper ions, the formaldehyde and the sodium hydroxide, and adjusting the feeding in the process range for trial production.
Further, the solution used in the chemical thick copper plating treatment process in the step 6 comprises the following components: 180 portions of copper complexing agent 120, 20 to 25 portions of copper sulfate, 0.4 to 0.8 portion of methanol, 20 to 25 portions of sodium hydroxide, 8 to 12 portions of formaldehyde and 1000 portions of deionized water 700; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the step 6 of the thick copper electroless plating treatment process comprises the following steps:
a) adding 350-500 parts of deionized water into a prepared clean plating bath;
b) starting air stirring, and adding 120 and 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) then 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 the temperature is raised to the operating condition, analyzing the concentrations of the complexing agent, the copper ions, the formaldehyde and the sodium hydroxide, and adjusting the feeding in the process range for trial production.
According to the invention, impact copper treatment is firstly carried out, and a compact copper layer is slowly deposited on the basis of impact copper of about 2-3 microns; copper is impacted, so that the deposition of copper during thick copper plating can be quickly realized;
the chemical nickel plating treatment can ensure a certain corrosion resistance effect of the copper line, so that the line can meet reliability tests such as salt spray tests and the like; the 5% neutral salt spray test reaches more than 48 hours. 85% relative humidity, and over 72 hours under 85 ℃ high temperature and high humidity test.
The nickel-gold protection treatment is to enhance the reliability, oxidation resistance and low contact resistance of the plating layer again; after 96 hours of 85 percent relative humidity and 85 ℃ high temperature and high humidity test, the resistance value is not more than 0.5 ohm.
The fifth purpose of the invention is to provide an application of the copper-foil-free flexible circuit, wherein the copper-foil-free flexible circuit or the copper-foil-free flexible circuit prepared by the preparation method is applied to a multilayer flexible circuit board.
Compared with the prior art, the invention has the beneficial effects that:
(1) by adopting the PI and/or PAI material, the import substitution of the PI and/or PAI material is realized, and the cost is saved;
(2) preparing a laser-activatable film by adopting an independently opened solid-phase catalyst and a liquid-phase material containing PI and/or PAI, forming a circuit pattern through laser induction, and finally realizing metal deposition in a chemical copper plating system to obtain a circuit;
(3) compared with the existing manufacturing process, the process is shortened, only the chemical plating process is related to pollution, and the pollution emission 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 illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A 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: 10 wt% of aluminum oxide, 85 wt% of cobalt blue, 2 wt% of alumina short fiber, 2.2 wt% of filler and 0.8 wt% of rare earth oxide;
the liquid phase material consists of PI and a diluent, wherein the weight ratio of the PI to the diluent is 10: 1;
the diluent is N-methyl pyrrolidone;
the first peak particle size of the solid phase powder catalytic additive is normal distribution of 800nm-1um, the second peak is normal distribution of 2-3.5um, and the areas of the two peak areas are basically 1: 1; 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 um;
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 base material film layer and an activation film layer; the activated film layer is made of the activated material of example 1; the base material film layer is made of PET; the thickness of the activated film layer is 50 um; the thickness of the base material film layer is 50 um.
Example 3
A copper foil-free flexible circuit, wherein the flexible circuit comprises a substrate layer film and a metal-plated layer, and the substrate layer film is the copper foil-free flexible circuit film in embodiment 2; the metal plating layer comprises a copper plating layer, a nickel plating layer and a nickel-gold plating layer; and 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-gold plating 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 carrying out graphical treatment on a substrate layer film through laser;
step 2, performing ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, performing two washing treatments on the film subjected to the ultrasonic treatment;
step 4, carrying out impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, performing two washing treatments on the film subjected to the copper impact treatment in the step 4;
step 6, performing chemical thick copper plating treatment on the film subjected to the two washing treatments in the step 5;
step 7, performing three-step pure water washing treatment on the film after the thick copper chemical plating treatment in the step 6;
step 8, performing pre-dipping treatment on the film subjected to the three pure water washing treatments in the step 7 through a middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-immersion treatment in the step 8;
step 10, performing two times of pure water washing treatment on the film subjected to the nickel pre-activation treatment in the step 9;
step 11, carrying out post-dipping treatment on the film subjected to the pure water washing treatment in the step 10;
step 12, performing three times of pure water washing treatment on the film subjected to post-dipping treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the pure water washing treatment in the step 12;
step 14, performing two times of pure water washing treatment 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 pure water washing treatment in the step 14;
step 16, performing three pure water washing treatments on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, performing 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 as follows: filling the space: 30 μm, scanning frequency: 80 khz, scan speed: 1500 mm/sec, power: 8W, laser wavelength: 1064 nm;
further, in the step 2, ultrasonic water washing treatment is carried out for 10 minutes, the dripping time is 25 seconds, and the ultrasonic water washing treatment is carried out in an environment of 55 ℃;
further, the washing treatment time in the step 3 is 1 minute, the dripping time is 20 seconds, the washing treatment is carried out at normal temperature, and the washing treatment process adopts mechanical swing or air stirring;
further, the treatment time in the step 4 is 25 minutes, the water dripping time is 25 seconds, the treatment is carried out at 55 ℃, and the treatment process adopts any one of air stirring or mechanical pump circulation;
further, the washing treatment time in the step 5 is 0.8 minute, the dripping time is 25 seconds, the washing treatment is carried out at the normal temperature, and air stirring is adopted in the washing treatment process;
further, the treatment time in the step 6 is 150 minutes, the water dripping time is 25 seconds, the treatment is carried out at 55 ℃, and the treatment process adopts any one of air stirring or mechanical circulation;
further, the washing treatment time in the step 7 is 30 minutes, the dripping time is 25 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
further, the treatment time in the step 8 is 4 minutes, the water dripping time is 25 seconds, the treatment is carried out at normal temperature, and the pre-soaking treatment process adopts air stirring;
further, the treatment time in the step 9 is 8 minutes, the water 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, the washing treatment time in the step 10 is 1.5 minutes, the dripping time is 25 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
further, the treatment time in the step 11 is 3 minutes, the water dripping time is 25 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any one of air stirring or mechanical circulation;
further, the treatment time in the step 12 is 1 minute, the water dripping time is 25 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, the treatment time in the step 13 is 15 minutes, the water dripping time is 25 seconds, the treatment is carried out in an environment of 75 ℃, and the treatment process adopts any one of air stirring or mechanical circulation;
further, the treatment time in the step 14 is 1 minute, the water dripping time is 25 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, the treatment time in the step 15 is 5 minutes, the water dripping time is 25 seconds, the treatment is carried out at 38 ℃, and the mechanical circulation is adopted in the treatment process;
further, the treatment time in the step 16 is 1 minute, the water dripping time is 25 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
further, the treatment time in the step 17 is 1 minute, the water dripping time is 25 seconds, the treatment is carried out at 65 ℃, and air stirring is adopted in the treatment process;
further, the drying processing time in step 18: for 25 minutes at a temperature of 65 ℃.
Further, the solution used in the impact copper treatment process of step 4 comprises the following components: 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 sodium potassium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the step 4 impact copper treatment process comprises the following steps:
a) adding 450 parts of deionized water into the prepared clean plating tank;
b) starting air to stir, and adding 180 parts of copper complexing agent;
c) adding 30 parts of copper sulfate;
d) 3 parts of methanol are added;
e) adding 30 parts of sodium hydroxide;
f) adding 450 parts of deionized water to the liquid preparation amount;
g) heating the plating bath to 58 ℃;
h) adding 16 parts of formaldehyde;
i) and (3) after the temperature is raised to the operating condition, analyzing the concentrations of the complexing agent, the copper ions, the formaldehyde and the sodium hydroxide, and adjusting the feeding in the process range for trial production.
Further, the solution used in the chemical thick copper plating treatment process 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 sodium potassium tartrate according to the weight ratio of 1: 1.
Further, the preparation method of the solution used in the step 6 of the thick copper electroless plating treatment process comprises the following steps:
a) adding 450 parts of deionized water into the prepared clean plating tank;
b) starting air to stir, and adding 160 parts of copper complexing agent;
c) adding 23 parts of copper sulfate;
d) 0.6 part of methanol was added;
e) 23 parts of sodium hydroxide are added;
f) adding 450 parts of deionized water to the liquid preparation amount;
g) heating the plating bath to 53 ℃;
h) adding 10 parts of formaldehyde;
i) and (3) after the temperature is raised to the operating condition, analyzing the concentrations of the complexing agent, the copper ions, the formaldehyde and the sodium hydroxide, and adjusting the feeding in the process range for trial production.
Example 5
The copper foil-free flexible circuit is applied to a multilayer flexible circuit board, wherein the copper foil-free flexible circuit in embodiment 3 or the copper foil-free flexible circuit prepared by the preparation method in embodiment 4 is applied to the copper foil-free flexible circuit.
Comparative example 1
Comparative example 1 is a flexible circuit made of FNC film of a certain brand abroad;
the following table shows the flexible circuit of example 3 of the present invention in comparison with the flexible circuit of comparative example 1
TABLE 1
| Specification of | Comparative example 1 | Example 2 |
| Copper layer/copper foil thickness (mum) | 18 | 18 |
| Thickness of adhesive layer (μm) | 12 | NA |
| Film thickness of base layer (μm) | 12.5 | 100 |
| UL test | ||
| Grade of combustion | 94V-0,94VTM-0 | 94V-0,94VTM-0 |
| Resistance to weldability | 260℃ 10sec | 260℃ 10sec |
TABLE 2 characteristic index test results
It can be seen from tables 1 and 2 that the PI film of the invention is applied to flexible circuits, basically reaches the level of foreign similar products, reduces the consumption of copper foil, reduces the production cost and 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 um.
Comparative example 3
Comparative example 3 differs from example 2 in that the thickness of the activated film layer was 45 um.
Comparative example 4
Comparative example 4 is different from example 2 in that the thickness of the activated film layer is 40 um.
TABLE 3
| Examples | Observation with naked eyes |
| Example 2 | Without wrinkling |
| Comparative example 2 | Slight wrinkling |
| Comparative example 3 | Slight wrinkling |
| Comparative example 4 | Significant wrinkling |
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. The 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: 7-15 wt% of aluminum oxide, 80-90 wt% of cobalt blue, 1-4 wt% of alumina short fiber, 1-5 wt% of filler and 0.5-1 wt% 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.
2. the copper-foil-free flexible circuit activating material as claimed in claim 1, wherein: the diluent is N-methyl pyrrolidone;
the first peak particle size of the solid phase powder catalytic additive is normal distribution of 800nm-1um, the second peak is normal distribution of 2-3.5um, and the areas of the two peak areas are basically 1: 1; 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 um;
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.
3. The utility model provides a exempt from copper foil flexible line film which characterized in that: comprises a substrate film layer and an activation film layer; the activated film layer is made of the activated material of any one of claims 1-2; the substrate film layer is made of any one of PET, PI and PAI.
4. 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-plated layer, wherein the substrate layer film is the copper-foil-free flexible circuit film in claim 3; the metal plating layer comprises a copper plating layer, a nickel plating layer and a nickel-gold plating layer; and the activation film layer is sequentially provided with a copper plating layer, a nickel plating layer and a nickel-gold plating layer.
5. The copper-foil-free flexible circuit of claim 4, wherein:
the thickness of the copper plating layer is 6-20 microns; the thickness of the nickel plating layer is 2-8 microns; the thickness of the nickel-gold plating layer is 0.05-0.15 micrometer; the thickness of the activated film layer is 50-150 um;
the thickness of the base material film layer is 50-150 um.
6. The method for preparing a copper-foil-free flexible circuit according to any one of claims 4 to 5, wherein: the method comprises the following steps:
step 1, directly carrying out graphical treatment on a substrate layer film through laser;
step 2, performing ultrasonic water washing on the film subjected to the laser treatment in the step 1;
step 3, performing two washing treatments on the film subjected to the ultrasonic treatment;
step 4, carrying out impact copper treatment on the film subjected to the water washing treatment in the step 3;
step 5, performing two washing treatments on the film subjected to the copper impact treatment in the step 4;
step 6, performing chemical thick copper plating treatment on the film subjected to the two washing treatments in the step 5;
step 7, performing three-step pure water washing treatment on the film after the thick copper chemical plating treatment in the step 6;
step 8, performing pre-dipping treatment on the film subjected to the three pure water washing treatments in the step 7 through a middle conversion hanger;
step 9, performing nickel pre-activation treatment on the film subjected to the pre-immersion treatment in the step 8;
step 10, performing two times of pure water washing treatment on the film subjected to the nickel pre-activation treatment in the step 9;
step 11, carrying out post-dipping treatment on the film subjected to the pure water washing treatment in the step 10;
step 12, performing three times of pure water washing treatment on the film subjected to post-dipping treatment in the step 11;
step 13, carrying out chemical nickel plating treatment on the film subjected to the pure water washing treatment in the step 12;
step 14, performing two times of pure water washing treatment 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 pure water washing treatment in the step 14;
step 16, performing three pure water washing treatments on the film subjected to the nickel-gold protection treatment in the step 15;
step 17, performing 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.
7. The method for preparing a copper-foil-free flexible circuit according to claim 6, wherein: the laser processing parameters in the step 1 are as follows: filling the space: <50 μm, scanning frequency: 40-100 khz, scan speed: 1000-: 7-10 watts, laser wavelength: 1064 nm;
in the step 2, ultrasonic water washing treatment is carried out for 5-15 minutes, the dripping time is 20-30 seconds, and the ultrasonic water washing treatment is carried out in an environment of 50-60 ℃;
the washing treatment time in the step 3 is 1-2 minutes, the dripping time is 15-30 seconds, the washing treatment is carried out at normal temperature, and mechanical swing or air stirring is adopted in the washing treatment process;
the treatment time in the step 4 is 10-30 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 50-62 ℃, and the treatment process adopts any one of air stirring or mechanical pump circulation;
the washing treatment time in the step 5 is 0.5-1 minute, the dripping time is 20-30 seconds, the washing treatment is carried out at the normal temperature, and air stirring is adopted in the washing treatment process;
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 one of air stirring or mechanical circulation;
in the step 7, the washing treatment time is 30 minutes, the water dripping time is 20-30 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
the treatment time in the step 8 is 3-5 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the pre-soaking treatment process is carried out by adopting air stirring;
the treatment time in the step 9 is 5-10 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at the temperature of 32-38 ℃, and the mechanical cycle is adopted in the treatment process;
the washing treatment time in the step 10 is 1-2 minutes, the water dripping time is 20-30 seconds, the washing treatment is carried out at normal temperature, and air stirring is adopted in the washing treatment process;
the treatment time in the step 11 is 2-5 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and the treatment process adopts any one of air stirring or mechanical circulation;
the treatment time in the step 12 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
in the step 13, the treatment time is 10-25 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at the temperature of 60-85 ℃, and the treatment process adopts any one of air stirring or mechanical circulation;
in the step 14, the treatment time is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
the treatment time in the step 15 is 3-8 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at 35-45 ℃, and the mechanical cycle is adopted in the treatment process;
the treatment time in the step 16 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at normal temperature, and air stirring is adopted in the treatment process;
the treatment time in the step 17 is 1-2 minutes, the water dripping time is 20-30 seconds, the treatment is carried out at the temperature of 60-70 ℃, and air stirring is adopted in the treatment process;
drying treatment time in step 18: 25-30 minutes at a temperature of 60-70 ℃.
8. The method for preparing a copper-foil-free flexible circuit according to claim 6, wherein: step 4 the impact copper treatment process uses a solution comprising the following components: 200 parts of copper complexing agent 150-; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1, preparing a composition;
the solution used in the chemical thick copper plating treatment process in the step 6 comprises the following components: 180 portions of copper complexing agent 120, 20 to 25 portions of copper sulfate, 0.4 to 0.8 portion of methanol, 20 to 25 portions of sodium hydroxide, 8 to 12 portions of formaldehyde and 1000 portions of deionized water 700; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
9. The method of manufacturing a copper foil-free flexible circuit according to claim 8, 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 a prepared clean plating bath;
b) starting air stirring, and adding 150 and 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) then 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 the temperature is raised to the operating condition, the concentrations of the complexing agent, copper ions, formaldehyde and sodium hydroxide are analyzed, and the feeding trial production is adjusted within the process range;
the preparation method of the solution used in the chemical thick copper plating treatment process in the step 6 comprises the following steps:
a) adding 350-500 parts of deionized water into a prepared clean plating bath;
b) starting air stirring, and adding 120 and 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) then 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 the temperature is raised to the operating condition, analyzing the concentrations of the complexing agent, the copper ions, the formaldehyde and the sodium hydroxide, and adjusting the feeding in the process range for trial production.
10. The application of the copper foil-free flexible circuit is characterized in that the copper foil-free flexible circuit is the copper foil-free flexible circuit of any one of claims 4 to 5 or the copper foil-free flexible circuit prepared by the preparation method of any one of claims 6 to 9, and the application is the application in a multilayer flexible circuit board.
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| CN115466943A (en) * | 2022-10-05 | 2022-12-13 | 复旦大学义乌研究院 | Flexible ultrahigh frequency radio frequency tag system based on polyether-ether-ketone film |
| CN115846646A (en) * | 2022-12-09 | 2023-03-28 | 开封夸克新材料有限公司 | Modified PET flexible circuit board, preparation method and application thereof |
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| CN114231956B (en) | 2023-11-17 |
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