CN108257783B - A kind of preparation method of the capacitor metalized film of automatic reduction type - Google Patents
A kind of preparation method of the capacitor metalized film of automatic reduction type Download PDFInfo
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- CN108257783B CN108257783B CN201711492490.1A CN201711492490A CN108257783B CN 108257783 B CN108257783 B CN 108257783B CN 201711492490 A CN201711492490 A CN 201711492490A CN 108257783 B CN108257783 B CN 108257783B
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- film
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- automatic reduction
- reduction type
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- 239000003990 capacitor Substances 0.000 title claims abstract description 61
- 239000011104 metalized film Substances 0.000 title claims abstract description 58
- 230000009467 reduction Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010408 film Substances 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229920001721 polyimide Polymers 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 50
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 40
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 238000007788 roughening Methods 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 8
- 229940071536 silver acetate Drugs 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 229940038773 trisodium citrate Drugs 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 4
- 238000001465 metallisation Methods 0.000 abstract description 3
- 239000009719 polyimide resin Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 1
- 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 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzenetetracarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011370 conductive nanoparticle Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
Abstract
The invention discloses a kind of preparation methods of capacitor metalized film of automatic reduction type, belong to metallized film preparation technical field.At work, temperature slowly increases the capacitor metalized film of the present invention, and cohesive force reduces between resin matrix, is improved the carrying current capacity of metallized film.The present invention is because conducting particles is evenly dispersed in polyimide resin matrix, very strong mechanical interlock can be generated between them, so-called " self-metallization " refers to during being heat-treated to film, the compound of its internal silver is not in the case where adding any reducing agent, the metal film formed in this way is uniformly fine and close, capacitor stability as composed by it is strong, conductive silver powder particle and nano graphite powder are discontinuous phases in metallized film, nano graphite powder thermal expansion character can be such that metallized film expands at work again, to in the heated generation miniature deformation of metallized film, can automatic reduction be original form and thickness, it has a extensive future.
Description
Technical field
The invention discloses a kind of preparation methods of capacitor metalized film of automatic reduction type, belong to metallized film system
Standby technical field.
Background technique
For capacitor in accordance with the difference of medium, there are many its type, such as: electrolyte capacitance, papery capacitor, thin-film capacitor,
Ceramic condenser, mica capacitor, air capacitor etc..But it is the most used in sound appliances, surely belong to electrolytic capacitor and thin
Membrane capacitance.Electrolytic capacitor is used in the place for needing capacitance very big, such as the filter capacitor of main power source part mostly, removes
Except filtering, and also serves as storage electric energy and be used.And thin-film capacitor is then used in the commissure of analog signal extensively, power supply noise
The places such as bypass.Thin film capacitor is to work as electrode with metal foil, by itself and poly- ethyl ester, polypropylene, and polystyrene or poly- carbonic acid
The plastic films such as ester are wound into the capacitor of cylindric construction after the overlapping of both ends.And divided according to the type of plastic film
It is also known as poly- ethyl ester capacitor, polypropylene capactive, polystyrene capacitor and poly- carbonic acid capacitor.
Its preparation method of common thin film capacitor is after being overlapped the metal foils such as aluminium as electrode and plastic film wound on one
It rises and is made.But in addition thin film capacitor has a kind of autofrettage again, is called metallized film, preparation method be on a plastic film with
One layer of very thin metal is as electrode in vacuum evaporation.The thickness of electrode foil can be so saved, capacitor unit is reduced and holds
The volume of amount, so thin film capacitor is easier to be made into small-sized, the big capacitor of capacity.Metallic film capacitor is used
Film have poly- ethyl ester, polypropylene, polycarbonate etc., other than winding-type, also there is lamination-type.This kenel of metallized film
Capacitor there is a kind of so-called I my reactivation, i.e. the minute portions of hypothesis electrode cause short because electric boundary matter is fragile
Lu Shi, causes the electrode metal of short-circuit peripheral portion, can cause because of the electrostatic energy or short circuit current of capacitor institute band at that time
It is greater area of to dissolve and evaporate and restore to insulate, so that capacitor is replied the effect of capacitor once again.
As electronics and information industry and power industry are grown rapidly, thin film capacitor is to large capacity, micromation and height
The direction of security reliability is developed, and to indexs such as volume, the resistance to mild reliabilities of thin film capacitor, more stringent requirements are proposed.It is existing
Some polypropylene capacitor films, thickness is big, temperature tolerance is poor, percent thermal shrinkage is relatively higher, with this film roll capacitor made of
With the lengthening of its working time, internal temperature rise is very fast, causes the stability of capacitor sharply to decline, or even cause capacitor
Failure, brings serious security risk to power grid.
Therefore, inventing a kind of capacitor metalized film of automatic reduction type has product to metallized film preparation technical field
Pole meaning.
Summary of the invention
Present invention mainly solves the technical issues of, at work for current capacitor metalized film, internal heating
Comparatively fast, miniature deformation can occur for metallized film, cause the stability of capacitor sharply to decline, in addition metallized film compares
Thin, carrying current capacity is weak, and the defect of conductive capability difference provides a kind of preparation of capacitor metalized film of automatic reduction type
Method.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of the capacitor metalized film of automatic reduction type, it is characterised in that specific preparation step are as follows:
(1) aqueous solution of 20~25mL silver nitrate solution and 30~40mL trisodium citrate is fitted into single port bottle, uses magnetic
The stirring of power blender, then 2~3mL sodium borohydride solution is added into single port bottle, it is stirred to react, stands, obtain silver-colored crystal seed liquid；
(2) by 0.8~1.2g polyvinylpyrrolidone, 2~3g ascorbic acid, 1.0~1.5g cetyl trimethyl bromine
Change ammonium and be dissolved in deionized water and be added above-mentioned silver-colored crystal seed liquid, continuously adds deionized water dilution, obtain reproducibility dispersion liquid；
(3) it takes 100~120mLDMF to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, starting
Magnetic stirrer, 5~7g4,4 '-diaminodiphenyl ethers are added into beaker, and stirring adds 6~8g Pyromellitic Acid
Acid anhydride is stirred to react, and obtains polyamic acid colloidal sol；
(4) above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol are mixed, obtains mixed glue solution, will mixes
Glue is fitted into the four-hole boiling flask with blender and dropping funel, and the silver nitrate solution that mass fraction is 30% is packed into dropping liquid
In funnel, silver nitrate solution is added dropwise into four-hole boiling flask, after being added dropwise, reaction obtains polyimide precursor colloidal sol；
(5) glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and is stopped, lifted upwards, natural drying is placed on
Heat temperature raising in baking oven, isothermal holding tear the cured film of glass substrate surface, obtain carrying Ag films；
(6) aluminum steel is put into vacuum evaporating coating machine, heat temperature raising, Ag films will be carried and be put into vacuum chamber, it is silver-colored to carrying
Film is aluminized metal film, obtains metallized film, metallized film is put into silver acetate solution, is impregnated roughening, is roughened
Roughening film is put into baking oven by film, dry, obtains the capacitor metalized film of automatic reduction type.
The mass fraction of silver nitrate solution described in step (1) is 25%, and the aqueous solution mass fraction of trisodium citrate is
20%, magnetic stirring apparatus revolving speed is 600~700r/min, and the mass fraction of sodium borohydride solution is 10%, and being stirred to react the time is 2
~3min, time of repose are 2~3h.
Volume is after ascorbic acid described in step (2) is L-type ascorbic acid, addition deionized water dilutes silver-colored crystal seed liquid
100~120mL.
Control water bath temperature described in step (3) is 35~40 DEG C, and magnetic stirring apparatus revolving speed is 500~550r/min,
Mixing time is 10~15min, and being stirred to react the time is 3~4h.
The mass ratio that reproducibility dispersion liquid described in step (4), nano graphite powder, polyamic acid colloidal sol mix is 2 ︰, 1 ︰ 7,
The mass fraction of silver nitrate solution is 30%, and the drop rate of dropping funel is 4~5mL/min, and the reaction time is 30~35min.
It is 10~15min that glass substrate described in step (5), which is inserted perpendicularly into polyimide precursor colloidal sol the residence time,
The upward rate of pulling is 4cm/min, and the natural drying time is 20~25min, and temperature is 80~90 DEG C after heat temperature raising in baking oven,
The isothermal holding time is 30~40min.
Temperature is 700~800 DEG C when vacuum evaporating coating machine plated film described in step (6), and institute's metal-coated membrane is with a thickness of 0.1
~0.3mm, silver acetate liquid quality fraction are 20%, and immersion coarsening time is 3~4h, and baking oven set temperature is 80~90 DEG C dry
The dry time is 2~3h.
The beneficial effects of the present invention are:
(1) aqueous solution of silver nitrate solution, sodium citrate is mixed to join in sodium borohydride solution by the present invention, and stirring is anti-
Silver-colored crystal seed liquid should be obtained, polyvinylpyrrolidone, L-type ascorbic acid, cetyl trimethylammonium bromide and the brilliant solution of silver are mixed
Close, and be added deionized water dilution, obtain reproducibility dispersion liquid, using DMF as solvent, addition 4,4 '-diaminodiphenyl ethers and
Benzene tetracarboxylic acid acid anhydride is stirred to react to obtain polyamic acid colloidal sol, and reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol are pressed
Certain mass obtains mixed glue solution, silver nitrate solution is gradually added dropwise into mixed glue solution, gathered by being stirred to react than mixing
Acid imide precursor sol tears to obtain load Ag films after film solidification, finally with true by czochralski method to glass substrate plated film
Empty evaporation coating machine plates one layer of aluminium film to Ag films are carried, and obtains metallized film, is dried to obtain after metallized film is roughened certainly
The dynamic capacitor metalized film of reduced form, at work, temperature slowly increases the capacitor metalized film of the present invention, resin matrix
Between cohesive force reduce, the Brownian movement of conductive nano particle assembles it mutually, conductive cluster caused gradually to increase, and is formed conductive
Network, improves the conductivity of metallized film, wherein the silver salt adulterated can be restored, is covered in resin matrix table
Face, improves the conductivity of metal film, the expansion when nano graphite powder adulterated in resin matrix is heated, can by highly conductive silver powder from
Son is connected in series, and improves the electrical efficiency of resin matrix, is improved the carrying current capacity of metallized film；
(2) present invention can generate between them very strong because conducting particles is evenly dispersed in polyimide resin matrix
Mechanical interlock, simultaneously as silver is a kind of blunt metal, without very strong interaction between polymer substrate, so golden
Categoryization film will keep most of excellent properties such as high thermal stability of polyimide matrix, and metallized film of the invention can
Self-metallization, so-called " self-metallization " refer to that during being heat-treated to film, the compound of internal silver is not adding
In the case where any reducing agent, by thermal induction effect automatic reduction, the table of a part of Particle diffusion therein to polymer
Face, and certain aggregation occurs on the surface of polymer, forming one layer of particle size is nanoscale metal film on surface, such shape
At metal film uniformly and it is fine and close, capacitor stability as composed by it is strong, in metallized film conductive silver powder particle with receive
Rice graphite powder is discontinuous phase, and polyimide resin matrix is continuous phase, the discontinuous phase molecule of electric conductivity energy in continuous phase
The thermalization shrinking percentage of metallized film is enough reduced, nano graphite powder thermal expansion character can make metallized film swollen at work again
It is swollen, thus metallized film is heated miniature deformation occurs when, can automatic reduction be original form and thickness, application prospect is wide
It is wealthy.
Specific embodiment
By 20~25mL mass fraction be 25% silver nitrate solution and 30~40mL mass fraction be 20% citric acid three
The aqueous solution of sodium is fitted into single port bottle, starts to stir with the revolving speed of 600~700r/min with magnetic stirring apparatus, then into single port bottle
The sodium borohydride solution that 2~3mL mass fraction is 10% is added, is stirred to react 2~3min, stands 2~3h, obtains silver-colored crystal seed liquid；
0.8~1.2g polyvinylpyrrolidone, 2~3gL type ascorbic acid, 1.0~1.5g cetyl trimethylammonium bromide are dissolved in
In deionized water and above-mentioned silver-colored crystal seed liquid is added, continuously adds deionized water and is diluted to 100~120mL, obtain reproducibility dispersion
Liquid；It takes 100~120mLDMF to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, water-bath pot temperature is controlled
Degree is 35~40 DEG C, starts magnetic stirring apparatus, is stirred with the revolving speed of 500~550r/min, 5~7g4 of addition into beaker, 4 '-
Diaminodiphenyl ether stirs 10~15min, adds 6~8g pyromellitic dianhydride, be stirred to react 3~4h, obtain polyamic acid
Colloidal sol；In mass ratio it is that 2 ︰, 1 ︰ 7 is mixed by above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol, obtains epoxy glue
Mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel, the silver nitrate solution for being 30% by mass fraction by liquid
It is fitted into dropping funel, silver nitrate solution is added dropwise with the drop rate of 4~5mL/min, after being added dropwise, react 30~35min,
Obtain polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into 10~15min of stop in polyimide precursor colloidal sol, with
The rate of 4cm/min lifts upwards, and 20~25min of natural drying, which is placed in baking oven, is heated to 80~90 DEG C, at heat preservation
30~40min is managed, the cured film of glass substrate surface is torn, obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine
In, 700~800 DEG C are heated to, Ag films will be carried and be put into vacuum chamber, aluminized metal film to Ag films are carried, control is plated
Thickness of metal film is 0.1~0.3mm, obtains metallized film, and it is molten that metallized film is put into the silver acetate that mass fraction is 20%
In liquid, 3~4h of roughening is impregnated, obtains roughening film, film will be roughened and be put into the baking oven that set temperature is 80~90 DEG C, dry 2~
3h obtains the capacitor metalized film of automatic reduction type.
Example 1
By 20mL mass fraction be 25% silver nitrate solution and 30mL mass fraction be 20% trisodium citrate it is water-soluble
Liquid is fitted into single port bottle, starts to stir with the revolving speed of 600r/min with magnetic stirring apparatus, then 2mL mass point is added into single port bottle
The sodium borohydride solution that number is 10% is stirred to react 2min, stands 2h, obtains silver-colored crystal seed liquid；By 0.8g polyvinylpyrrolidone,
2gL type ascorbic acid, 1.0g cetyl trimethylammonium bromide are dissolved in deionized water and are added above-mentioned silver-colored crystal seed liquid, continue to add
Enter deionized water and be diluted to 100mL, obtains reproducibility dispersion liquid；It takes 100mLDMF to be put into beaker, beaker is moved into and has magnetic
In the water-bath of power blender, control water bath temperature is 35 DEG C, starts magnetic stirring apparatus, is stirred with the revolving speed of 500r/min,
5g4 is added into beaker, 4 '-diaminodiphenyl ethers stir 10min, add 6g pyromellitic dianhydride, be stirred to react 3h, obtain
To polyamic acid colloidal sol；It is in mass ratio that 2 ︰, 1 ︰ 7 is mixed by above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol,
Mixed glue solution is obtained, mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel, is 30% by mass fraction
Silver nitrate solution is fitted into dropping funel, and silver nitrate solution is added dropwise with the drop rate of 4mL/min, after being added dropwise, reaction
30min obtains polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and stops 10min,
It is lifted upwards with the rate of 4cm/min, natural drying 20min, which is placed in baking oven, is heated to 80 DEG C, isothermal holding
30min tears the cured film of glass substrate surface, obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine, is heated
Be warming up to 700 DEG C, Ag films will be carried and be put into vacuum chamber, aluminized metal film to Ag films are carried, control institute's metal-coated membrane with a thickness of
0.1mm obtains metallized film, metallized film is put into the silver acetate solution that mass fraction is 20%, impregnates roughening 3h,
Roughening film is obtained, film will be roughened and be put into the baking oven that set temperature is 80 DEG C, dry 2h obtains automatic reduction type capacitor metal
Change film.
Example 2
By 22mL mass fraction be 25% silver nitrate solution and 35mL mass fraction be 20% trisodium citrate it is water-soluble
Liquid is fitted into single port bottle, starts to stir with the revolving speed of 650r/min with magnetic stirring apparatus, then 2mL mass point is added into single port bottle
The sodium borohydride solution that number is 10% is stirred to react 2min, stands 2.5h, obtains silver-colored crystal seed liquid；By 1.0g polyvinylpyrrolidine
Ketone, 2gL type ascorbic acid, 1.2g cetyl trimethylammonium bromide are dissolved in deionized water and are added above-mentioned silver-colored crystal seed liquid, after
The continuous deionized water that is added is diluted to 110mL, obtains reproducibility dispersion liquid；It takes 110mLDMF to be put into beaker, beaker is moved into band
Have in the water-bath of magnetic stirring apparatus, control water bath temperature is 37 DEG C, starts magnetic stirring apparatus, is stirred with the revolving speed of 520r/min
It mixes, 6g4 is added into beaker, 4 '-diaminodiphenyl ethers stir 12min, add 7g pyromellitic dianhydride, be stirred to react
3.5h obtains polyamic acid colloidal sol；It is in mass ratio 2 ︰ by above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol
1 ︰ 7 mixing, obtains mixed glue solution, and mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel, by quality point
Number is fitted into dropping funel for 30% silver nitrate solution, and silver nitrate solution is added dropwise with the drop rate of 4mL/min, is added dropwise
Afterwards, 32min is reacted, polyimide precursor colloidal sol is obtained；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and is stopped
12min is stayed, is lifted upwards with the rate of 4cm/min, natural drying 22min, which is placed in baking oven, is heated to 85 DEG C, heat preservation
35min is handled, the cured film of glass substrate surface is torn, obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine,
750 DEG C are heated to, Ag films will be carried and be put into vacuum chamber, aluminize metal film to Ag films are carried, control institute's plating metal film thickness
Degree is 0.2mm, obtains metallized film, metallized film is put into the silver acetate solution that mass fraction is 20%, and roughening is impregnated
3.5h obtains roughening film, will be roughened film and is put into the baking oven that set temperature is 85 DEG C, and dry 2.5h obtains automatic reduction type electricity
Canister metals film.
Example 3
By 25mL mass fraction be 25% silver nitrate solution and 40mL mass fraction be 20% trisodium citrate it is water-soluble
Liquid is fitted into single port bottle, starts to stir with the revolving speed of 700r/min with magnetic stirring apparatus, then 3mL mass point is added into single port bottle
The sodium borohydride solution that number is 10% is stirred to react 3min, stands 3h, obtains silver-colored crystal seed liquid；By 1.2g polyvinylpyrrolidone,
3gL type ascorbic acid, 1.5g cetyl trimethylammonium bromide are dissolved in deionized water and are added above-mentioned silver-colored crystal seed liquid, continue to add
Enter deionized water and be diluted to 120mL, obtains reproducibility dispersion liquid；It takes 120mLDMF to be put into beaker, beaker is moved into and has magnetic
In the water-bath of power blender, control water bath temperature is 40 DEG C, starts magnetic stirring apparatus, is stirred with the revolving speed of 550r/min,
7g4 is added into beaker, 4 '-diaminodiphenyl ethers stir 15min, add 8g pyromellitic dianhydride, be stirred to react 4h, obtain
To polyamic acid colloidal sol；It is in mass ratio that 2 ︰, 1 ︰ 7 is mixed by above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol,
Mixed glue solution is obtained, mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel, is 30% by mass fraction
Silver nitrate solution is fitted into dropping funel, and silver nitrate solution is added dropwise with the drop rate of 5mL/min, after being added dropwise, reaction
35min obtains polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and stops 15min,
It is lifted upwards with the rate of 4cm/min, natural drying 25min, which is placed in baking oven, is heated to 90 DEG C, isothermal holding
40min tears the cured film of glass substrate surface, obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine, is heated
Be warming up to 800 DEG C, Ag films will be carried and be put into vacuum chamber, aluminized metal film to Ag films are carried, control institute's metal-coated membrane with a thickness of
0.3mm obtains metallized film, metallized film is put into the silver acetate solution that mass fraction is 20%, impregnates roughening 4h,
Roughening film is obtained, film will be roughened and be put into the baking oven that set temperature is 90 DEG C, dry 3h obtains automatic reduction type capacitor metal
Change film.
Comparative example
With the capacitor metalized film of automatic reduction type of Dongguan company production as a comparison case to produced by the present invention
The capacitor metalized film of automatic reduction type in the capacitor metalized film of automatic reduction type and comparative example carries out performance detection,
Testing result is as shown in table 1:
1, test method:
Lateral shrinkage test is detected by 15585 standard of GB/T；
The test of longitudinal contraction rate is detected by 15585 standard of GB/T；
Transverse tensile strength test is detected by GBT228-2002 standard；
Longitudinal tensile strength test is detected by GBT228-2002 standard；
Minimum breakdown voltage test is detected by 3333 standard of GB/T.
The capacitor metalized film performance measurement result of table 1
It is shunk at high temperature according to the capacitor metalized film of automatic reduction type produced by the present invention of data among the above
Rate is low, and performance is stablized, i.e., high-temperature stability is preferable, and minimum breakdown voltage reaches 600V/um, is able to bear heavy current impact, leads
Electric energy power is strong, has broad application prospects.
Claims (7)
1. a kind of preparation method of the capacitor metalized film of automatic reduction type, it is characterised in that specific preparation step are as follows:
(1) aqueous solution of 20~25mL silver nitrate solution and 30~40mL trisodium citrate is fitted into single port bottle, is stirred with magnetic force
Device stirring is mixed, then 2~3mL sodium borohydride solution is added into single port bottle, is stirred to react, stands, obtains silver-colored crystal seed liquid；
(2) by 0.8~1.2g polyvinylpyrrolidone, 2~3g ascorbic acid, 1.0~1.5g cetyl trimethylammonium bromide
It is dissolved in deionized water and is added above-mentioned silver-colored crystal seed liquid, deionized water dilution is continuously added, obtains reproducibility dispersion liquid；
(3) it takes 100~120mLDMF to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, magnetic force is started
5~7g4,4 '-diaminodiphenyl ethers are added into beaker for blender stirring, and stirring adds 6~8g pyromellitic dianhydride,
It is stirred to react, obtains polyamic acid colloidal sol；
(4) above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol are mixed, mixed glue solution is obtained, by mixed glue solution
It is fitted into the four-hole boiling flask with blender and dropping funel, the silver nitrate solution that mass fraction is 30% is packed into dropping funel
In, silver nitrate solution is added dropwise into four-hole boiling flask, after being added dropwise, reaction obtains polyimide precursor colloidal sol；
(5) glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and is stopped, lifted upwards, natural drying is placed on baking oven
Middle heat temperature raising, isothermal holding tear the cured film of glass substrate surface, obtain carrying Ag films；
(6) aluminum steel is put into vacuum evaporating coating machine, heat temperature raising, Ag films will be carried and be put into vacuum chamber, to load Ag films
It aluminizes metal film, obtains metallized film, metallized film is put into silver acetate solution, impregnate roughening, obtain roughening film, it will
Roughening film is put into baking oven, dry, obtains the capacitor metalized film of automatic reduction type.
2. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
The mass fraction of silver nitrate solution described in step (1) is 25%, and the aqueous solution mass fraction of trisodium citrate is 20%, and magnetic force stirs
Mixing device revolving speed is 600~700r/min, and the mass fraction of sodium borohydride solution is 10%, and being stirred to react the time is 2~3min, quiet
Setting the time is 2~3h.
3. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
Ascorbic acid described in step (2) be L-type ascorbic acid, be added deionized water by volume after the dilution of silver-colored crystal seed liquid be 100~
120mL。
4. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
Control water bath temperature described in step (3) is 35~40 DEG C, and magnetic stirring apparatus revolving speed is 500~550r/min, mixing time
For 10~15min, being stirred to react the time is 3~4h.
5. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
The mass ratio that reproducibility dispersion liquid described in step (4), nano graphite powder, polyamic acid colloidal sol mix is 2 ︰, 1 ︰ 7, and silver nitrate is molten
The mass fraction of liquid is 30%, and the drop rate of dropping funel is 4~5mL/min, and the reaction time is 30~35min.
6. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
It is 10~15min that glass substrate described in step (5), which is inserted perpendicularly into polyimide precursor colloidal sol the residence time, is lifted upwards
Rate is 4cm/min, and the natural drying time is 20~25min, and temperature is 80~90 DEG C after heat temperature raising in baking oven, isothermal holding
Time is 30~40min.
7. a kind of preparation method of capacitor metalized film of automatic reduction type according to claim 1, it is characterised in that:
Temperature is 700~800 DEG C when vacuum evaporating coating machine plated film described in step (6), institute's metal-coated membrane with a thickness of 0.1~0.3mm,
Silver acetate liquid quality fraction is 20%, and immersion coarsening time is 3~4h, and it is 2 that baking oven set temperature, which is 80~90 DEG C of drying times,
~3h.
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