CN112194815A - Double-sided copper-plated polyimide film and preparation method thereof - Google Patents
Double-sided copper-plated polyimide film and preparation method thereof Download PDFInfo
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- CN112194815A CN112194815A CN202010872548.0A CN202010872548A CN112194815A CN 112194815 A CN112194815 A CN 112194815A CN 202010872548 A CN202010872548 A CN 202010872548A CN 112194815 A CN112194815 A CN 112194815A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 78
- 238000002791 soaking Methods 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000012670 alkaline solution Substances 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 21
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 14
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000004642 Polyimide Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 24
- 238000005530 etching Methods 0.000 description 24
- 239000003513 alkali Substances 0.000 description 20
- 238000005342 ion exchange Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- -1 copper carboxylate Chemical class 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention relates to a double-sided copper-plated polyimide film and a preparation method thereof, wherein the preparation method comprises the following steps: s1, soaking the cleaned polyimide film in a strong alkaline solution for a preset time to etch the polyimide film, then cleaning to be neutral and airing to obtain a modified polyimide film; s2, soaking the modified polyimide film in a solution containing copper ions for a preset time, then cleaning to be neutral and airing to obtain the modified polyimide film with the surface containing the carboxylic acid copper functional groups; and S3, soaking the modified polyimide film with the surface containing the carboxylic acid copper functional groups obtained in the step S2 in a reducing solution for a preset time to reduce copper ions, so as to obtain the double-sided copper-plated polyimide film. The invention obtains the ultrathin double-sided copper-plated polyimide film with high cohesiveness between copper and a PI substrate and excellent electrical property.
Description
Technical Field
The invention belongs to the field of manufacturing non-adhesive type polyimide flexible copper clad laminates, and particularly relates to a double-sided copper-plated polyimide film and a preparation method thereof.
Background
The copper plating process of Polyimide (PI) resin is one of the main technologies for manufacturing printed circuit board base materials, and is the key point for manufacturing a flexible copper clad laminate (2L-FCCL) with a two-layer structure. However, in the whole flexible copper clad laminate industry, the high bonding and copper foil covering thickness of less than 3 microns on the surface of polyimide can not be realized at present. This is because the copper foil has a reduced ability to withstand external force when the copper foil is thin, is easily torn and deformed, and is very difficult to handle, which greatly affects further improvement of the line density of the printed wiring board. Conventional methods for preparing surface-metallized composite films are all formed by externally depositing a metal phase onto the surface of a substrate, such as: physical Vapor Deposition (PVD), thermally induced chemical vapor deposition, photo-induced chemical vapor deposition, plasma arc catalyzed chemical vapor deposition, electrical deposition, electroless chemical reduction and the like, wherein the external deposition methods are usually completed through 2-3 steps, the metal particles and the polyimide substrate are two separated individuals, no strong interaction exists between the metal particles and the polyimide substrate, the interface bonding force is poor, and the metal film is easy to fall off. In addition, high-temperature heat treatment is sometimes required, which can cause serious damage to the surface of the polyimide film, and even cause distortion and even decomposition of the polyimide substrate.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to overcome at least one of the technical defects, provides a double-sided copper-plated polyimide film and a preparation method thereof, and solves the problems that the existing copper-plating process flow of a polyimide two-layer type flexible copper-clad plate is complex, the adhesion force between copper and a polyimide matrix is insufficient, the copper and the polyimide matrix are easy to fall off, the surface of the polyimide film is damaged, the performance is reduced and the like.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of a double-sided copper-plated polyimide film comprises the following steps:
s1, soaking the cleaned polyimide film in a strong alkaline solution for a preset time to etch the polyimide film, then cleaning to be neutral and airing to obtain a modified polyimide film;
s2, soaking the modified polyimide film in a solution containing copper ions for a preset time, then cleaning to be neutral and airing to obtain the modified polyimide film with the surface containing the carboxylic acid copper functional groups;
and S3, soaking the modified polyimide film with the surface containing the carboxylic acid copper functional groups obtained in the step S2 in a reducing solution for a preset time to reduce copper ions, so as to obtain the double-sided copper-plated polyimide film.
Preferably, the strong alkaline solution in the step S1 is one of a potassium hydroxide solution and a sodium hydroxide solution, and the concentration is 3-8 mol/L.
Preferably, the copper ion-containing solution in the step S2 is one of a copper sulfate solution, a copper chloride solution and a copper bromide solution, and the concentration is 0.01-0.5 mol/L.
Preferably, the reducing solution in step S3 is one of hydrogen peroxide, an acetaldehyde solution and a dimethylamine borane solution, and the concentration is 0.01 to 0.5 mol/L.
Preferably, the strongly alkaline solution in the step S1 is a sodium hydroxide solution with a concentration of 5mol/L, the solution containing copper ions in the step S2 is a copper sulfate solution with a concentration of 0.5mol/L, and the solution with reducibility in the step S3 is a dimethylamine borane solution with a concentration of 0.2 mol/L.
Preferably, the soaking in the step S1 is soaking at 50 ℃ for 1-15 min.
Preferably, the soaking in the step S2 is soaking at 50 ℃ for 1-35 min.
Preferably, the soaking in the step S3 is soaking at 50 ℃ for 1-10 min.
Preferably, the strongly alkaline solution in the step S1 is a sodium hydroxide solution, the concentration is 5mol/L, the soaking temperature is 50 ℃, and the soaking time is 9 min; the solution containing copper ions in the step S2 is a copper sulfate solution, the concentration of the copper ions is 0.5mol/L, the soaking temperature is 50 ℃, and the soaking time is 30 min.
The double-sided copper-plated polyimide film is prepared by the preparation method, copper is plated on both sides of the polyimide film, and the thickness of a copper layer is 0.7-2.0 mu m.
Compared with the prior art, the invention has the advantages that:
according to the invention, the Cu/PI/Cu composite film is prepared by directly electroplating on the surface of PI resin by an ion exchange method, so that the ultrathin double-sided copper-plated polyimide film with high cohesiveness between copper and a PI substrate and excellent electrical property is obtained, a circuit pattern can be directly formed on the basis of the ultrathin double-sided copper-plated polyimide film, and the method has important practical significance for solving the technical bottleneck that the thickness of a metal layer in the current flexible copper-clad plate industry cannot be less than 3 mu m; compared with the prior art for manufacturing the PI double-sided copper-clad plate by a hot-pressing laminating method, the preparation method is simple, quick and energy-saving, the double-sided copper-plated polyimide film can be directly obtained at one time, the copper-plated film has good bonding force with a PI resin matrix and controllable thickness, the PI resin keeps the original mechanical property, and the preparation method is green, environment-friendly, low in cost and the like; the Cu/PI/Cu composite film obtained by the invention is mainly applied to a double-sided FPC substrate-polyimide double-sided adhesive-free copper clad plate.
Detailed Description
The present invention will be further described with reference to preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The specific embodiment of the invention provides a preparation method of a double-sided copper-plated polyimide film, which comprises the following steps:
s1, soaking the cleaned polyimide film in a strong alkaline solution for a preset time to etch the polyimide film, then cleaning to be neutral and airing to obtain a modified polyimide film;
s2, soaking the modified polyimide film in a solution containing copper ions for a preset time, then cleaning to be neutral and airing to obtain the modified polyimide film with the surface containing the carboxylic acid copper functional groups;
and S3, soaking the modified polyimide film with the surface containing the carboxylic acid copper functional groups obtained in the step S2 in a reducing solution for a preset time to reduce copper ions, so as to obtain the double-sided copper-plated polyimide film.
In some preferred embodiments, the strongly alkaline solution in the step S1 is one of a potassium hydroxide solution and a sodium hydroxide solution, and the concentration is 3 to 8 mol/L.
In some preferred embodiments, the copper ion-containing solution in step S2 is one of a copper sulfate solution, a copper chloride solution and a copper bromide solution, and the concentration is 0.01 to 0.5 mol/L.
In some preferred embodiments, the reducing solution in step S3 is one of hydrogen peroxide, acetaldehyde solution and dimethylamine borane solution, and the concentration is 0.01 to 0.5 mol/L.
In some preferred embodiments, the strongly alkaline solution in the step S1 is a sodium hydroxide solution with a concentration of 5mol/L, the solution containing copper ions in the step S2 is a copper sulfate solution with a concentration of 0.5mol/L, and the solution with reducibility in the step S3 is a dimethylamine borane solution with a concentration of 0.2 mol/L.
In some preferred embodiments, the soaking in step S1 is at 50 ℃ for 1-15 min.
In some preferred embodiments, the soaking in step S2 is at 50 ℃ for 1-35 min.
In some preferred embodiments, the soaking in step S3 is soaking at 50 ℃ for 1-10 min.
In some preferred embodiments, the strongly alkaline solution in step S1 is a sodium hydroxide solution with a concentration of 5mol/L, a soaking temperature of 50 ℃, and a soaking time of 9 min; the solution containing copper ions in the step S2 is a copper sulfate solution, the concentration of the copper ions is 0.5mol/L, the soaking temperature is 50 ℃, and the soaking time is 30 min.
The specific embodiment of the invention also provides a double-sided copper-plated polyimide film, which is prepared by adopting the preparation method, wherein both sides of the polyimide film are plated with copper, and the thickness of a copper layer is 0.7-2.0 μm.
The present application is further illustrated by the following more specific examples.
The preparation method of the double-sided copper-plated polyimide film comprises the following steps:
s1: preparing a sodium hydroxide solution, a copper ion-containing solution and a dimethylamine borane solution with required concentrations; specifically, the method comprises the following steps:
(1) accurately weighing 100ml of deionized water in a clean beaker, weighing a proper amount of sodium hydroxide, pouring the sodium hydroxide into the beaker, and stirring until the sodium hydroxide is completely dissolved to prepare an alkali solution with the concentration gradient of 3, 5, 7 and 8 mol/L;
(2) the completely dissolved sodium hydroxide solution is placed in a constant temperature water bath and heated to 50 ℃.
(3) Copper sulfate solution, copper chloride solution and copper bromide solution with the concentration of 0.5mol/L are respectively prepared according to the steps similar to the steps (1) and (2), and are placed in a constant temperature water bath to be heated to 50 ℃.
(4) Preparing dimethylamine borane solution with the concentration of 0.5mol/L according to the steps similar to the steps (1) and (2), and placing the dimethylamine borane solution in a constant temperature water bath to heat to 50 ℃.
S2: preparing a polyimide film; the method comprises the following specific steps:
(1) cutting the polyimide film into regular sizes of 135mm multiplied by 75mm, and marking the polyimide film so as to distinguish the films under different experimental conditions;
(2) and respectively putting the cut and marked polyimide films into distilled water for ultrasonic cleaning for 10 min.
S3: etching the polyimide film; the method comprises the following specific steps:
soaking the prepared polyimide film in a sodium hydroxide aqueous solution for 1-15min to ensure that the surface of the polyimide film is completely immersed in the sodium hydroxide aqueous solution, opening the imide ring of the polyimide under the action of the sodium hydroxide aqueous solution to form polyimide with a sodium polyamic acid functional group on the surface to obtain a modified polyimide film with a sodium carboxylate functional group on the surface, and subsequently exchanging sodium ions in the sodium polyamic acid functional group on the surface with copper ions in the aqueous solution containing the copper ions (step S4).
S4: performing copper ion exchange on the modified polyimide film obtained in the step S3; the method comprises the following specific steps:
(1) washing the modified polyimide film obtained by the step S3 with deionized water to be neutral and airing;
(2) and soaking the dried modified polyimide film in a copper sulfate aqueous solution for 1-35 min. In the process, copper ions and sodium ions are exchanged to obtain the modified polyimide film with the surface containing the functional group of the copper carboxylate.
S5: carrying out copper ion reduction on the modified polyimide film obtained in the step S4; the method comprises the following specific steps:
(1) cleaning the modified polyimide film obtained in the step S4 to be neutral by using deionized water and airing;
(2) soaking the polyimide film in dimethylamine borane aqueous solution for 1-10min, reducing copper ions, converting the copper ions into corresponding metal particles, diffusing the metal particles to the surface of polyimide to generate aggregation, thereby forming a copper coating film and obtaining the polyimide film plated with copper on two sides.
The method of the invention uses finished PI resin as a substrate, does not need to carry out the synthesis work of early polyamic acid, greatly simplifies the preparation process, and the hydrolysis and ion exchange processes of the PI film are both generated in a hydrolysis layer with a certain thickness on the surface of the film, and the substrate inside the PI film is kept intact and not damaged, so that the prepared composite film can maintain the excellent mechanical property and thermal stability of the original film. In addition, the metal ion solution used in the ion exchange process is prepared from cheap inorganic metal salt, and the metal ion solution can be recycled, so that the preparation cost is low, and the preparation method has a good development prospect in the aspect of preparing the double-sided copper-plated polyimide film.
The invention adopts an ion exchange method to prepare a copper/polyimide/copper composite film, and researches the factors of different alkali liquor etching time, alkali liquor concentration, ion exchange time, copper ion exchange solution types and the like on a double-sided copper-plated polyimide film (hereinafter called a composite film).
Influence of alkali liquor concentration on composite film performance
TABLE 1 Properties of composite films obtained by etching with NaOH of different concentrations
a) The method comprises the following steps The Cu accounts for C, O, Cu number percentage of three elements on the surface of the composite film.
As can be seen from the electrical property tests in Table 1, when the alkali liquor etching concentration is 5mol/L, the resistance of the prepared film is lower, which indicates that the conductivity is better, and as the alkali liquor etching concentration increases, the resistance decreases first and then increases, and the conductivity increases first and then decreases. With the increase of the alkali etching concentration, the content of copper element is increased and then decreased, and therefore, the alkali etching concentration is preferably 5 mol/L.
Secondly, the influence of the etching time of alkali liquor (5mol/L NaOH solution) on the performance of the composite film
TABLE 2 Properties of the composite films obtained at different etching times
a) Conductivity is here expressed in sheet resistance per cm.
b) The Cu accounts for C, O, N, Cu number percentage of four elements on the surface of the composite film.
As can be seen from the electrical property tests in Table 2, with the extension of the etching time of the alkali liquor, the resistance of the composite film is firstly reduced and then increased, that is, the electrical conductivity is firstly improved and then reduced, and when the etching time of the alkali liquor is 9-12 minutes, the resistance of the obtained composite film is lower, which indicates that the electrical conductivity is better. From the mechanical property test results in table 2, it can be seen that the mechanical strength is first decreased and then increased along with the increase of the etching time of the alkali solution, and the decrease occurs again when the etching time is continued to be increased, so that it can be seen that the mechanical property of the composite film is improved by the proper etching of the alkali solution, but there is a turning point, that is, about 9min, and the mechanical property is again decreased after the turning point. The alkali liquor etching time is about 9min, the surface metal layer of the obtained composite film is compact and uniform, and the conductivity of the obtained composite film is strong. Therefore, under the condition of 50 ℃, 5mol/L NaOH is etched for 9min, and the mechanical property and the electrical property are excellent.
Third, the influence of the ion exchange time on the performance of the composite film
Under the preferred conditions of the first and second steps, namely, under the conditions that the alkali liquor etching temperature is 50 ℃, the etching time is 9min and the alkali liquor etching concentration is 5mol/L, ion exchange is carried out by adopting 0.5mol/L copper sulfate solution, and the electrical properties of the composite film obtained under different ion exchange times are shown in Table 3.
From the conductivity of table 3, the conductivity was improved and then reduced. Therefore, the alkali liquor etching temperature is 50 ℃, the etching time is 9min, the ion exchange is carried out under the condition that the alkali liquor etching concentration is 5mol/L, and the copper sulfate exchange time is about 30 min.
Influence of copper salt exchange liquid kind on composite membrane performance
Under the preferred conditions of the first and the second, namely, the alkali liquor etching temperature is 50 ℃, the etching time is 9min, and the alkali liquor etching concentration is 5mol/L, the ion exchange is carried out, and 0.5mol/L copper sulfate solution and 0.5mol/L CuCl are respectively adopted2Solution, 0.5mol/LCuBr2The solution, ion exchange time was 30min, and the electrical properties of the composite films obtained in different copper ion-containing solutions are shown in table 4.
TABLE 4 Properties of the composite films obtained after ion exchange of different copper salts
The results of the surface roughness, particle size and copper content tests in Table 4 are combined to show that CuSO4The composite film obtained after ion exchange has the most excellent conductivity, which is consistent with the previous conductivity test result, so that CuSO4Copper salts are most suitable as ion-exchange salts.
The thickness of the copper layer of the composite film prepared under the optimized experimental conditions is about 0.7-2.0 μm, the adhesion test is carried out through a Baige experiment, the test result shows that the adhesive tape does not have any shedding metal, and the adhesion degree of the metal coating and the film is ISO grade: 0, excellent performance and capability of meeting the application requirement of finished products.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (10)
1. The preparation method of the double-sided copper-plated polyimide film is characterized by comprising the following steps:
s1, soaking the cleaned polyimide film in a strong alkaline solution for a preset time to etch the polyimide film, then cleaning to be neutral and airing to obtain a modified polyimide film;
s2, soaking the modified polyimide film in a solution containing copper ions for a preset time, then cleaning to be neutral and airing to obtain the modified polyimide film with the surface containing the carboxylic acid copper functional groups;
and S3, soaking the modified polyimide film with the surface containing the carboxylic acid copper functional groups obtained in the step S2 in a reducing solution for a preset time to reduce copper ions, so as to obtain the double-sided copper-plated polyimide film.
2. The method according to claim 1, wherein the strongly alkaline solution in step S1 is one of a potassium hydroxide solution and a sodium hydroxide solution, and has a concentration of 3 to 8 mol/L.
3. The method of claim 1, wherein the copper ion-containing solution in step S2 is one of a copper sulfate solution, a copper chloride solution and a copper bromide solution, and has a concentration of 0.01 to 0.5 mol/L.
4. The method according to claim 1, wherein the reducing solution in step S3 is one of hydrogen peroxide, acetaldehyde solution and dimethylamine borane solution, and the concentration is 0.01 to 0.5 mol/L.
5. The method according to claim 1, wherein the strongly alkaline solution in the step S1 is a sodium hydroxide solution having a concentration of 5mol/L, the solution containing copper ions in the step S2 is a copper sulfate solution having a concentration of 0.5mol/L, and the solution having reducibility in the step S3 is a dimethylamine borane solution having a concentration of 0.2 mol/L.
6. The method according to any one of claims 1 to 5, wherein the soaking in step S1 is at 50 ℃ for 1 to 15 min.
7. The method according to any one of claims 1 to 5, wherein the soaking in step S2 is at 50 ℃ for 1 to 35 min.
8. The method according to any one of claims 1 to 5, wherein the soaking in step S3 is at 50 ℃ for 1 to 10 min.
9. The production method according to any one of claims 1 to 5, wherein the strongly alkaline solution in the step S1 is a sodium hydroxide solution with a concentration of 5mol/L, a soaking temperature of 50 ℃, and a soaking time of 9 min; the solution containing copper ions in the step S2 is a copper sulfate solution, the concentration of the copper ions is 0.5mol/L, the soaking temperature is 50 ℃, and the soaking time is 30 min.
10. A double-sided copper-plated polyimide film characterized in that it is produced by the production method as claimed in any one of claims 1 to 9, both sides of the polyimide film are plated with copper, and the thickness of the copper layer is 0.7 μm to 2.0 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112982022A (en) * | 2021-02-05 | 2021-06-18 | 南京信息工程大学 | Preparation method of copper-plated reduced graphene oxide wave-absorbing paper |
| CN113896931A (en) * | 2021-09-28 | 2022-01-07 | 华中科技大学 | Decontamination heat-resistant composite polymer film and preparation method and application thereof |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112982022A (en) * | 2021-02-05 | 2021-06-18 | 南京信息工程大学 | Preparation method of copper-plated reduced graphene oxide wave-absorbing paper |
| CN112982022B (en) * | 2021-02-05 | 2022-03-11 | 南京信息工程大学 | Preparation method of copper-plated reduced graphene oxide wave-absorbing paper |
| CN113896931A (en) * | 2021-09-28 | 2022-01-07 | 华中科技大学 | Decontamination heat-resistant composite polymer film and preparation method and application thereof |
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Application publication date: 20210108 |