CN108257783A - 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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- CN108257783A CN108257783A CN201711492490.1A CN201711492490A CN108257783A CN 108257783 A CN108257783 A CN 108257783A CN 201711492490 A CN201711492490 A CN 201711492490A CN 108257783 A CN108257783 A CN 108257783A
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- Prior art keywords
- film
- capacitor
- automatic reduction
- silver
- reduction type
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- 239000011104 metalized film Substances 0.000 title claims abstract description 59
- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 230000009467 reduction Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229920001721 polyimide Polymers 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 52
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 36
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 22
- 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 20
- 239000011521 glass Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 15
- 239000013078 crystal Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- 238000007788 roughening Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 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
- 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
- 238000001704 evaporation 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 235000019263 trisodium citrate Nutrition 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000007654 immersion Methods 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 6
- 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
- 239000010409 thin film Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 5
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005269 aluminizing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001408 amides Chemical class 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
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 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
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000007420 reactivation Effects 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
- 235000011083 sodium citrates Nutrition 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
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone 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
- 238000010792 warming 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 the capacitor metalized film of automatic reduction type, belong to metallized film preparing 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 uniformly disperses 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 plus in the case of any reducing agent, the metal film formed in this way is uniformly fine and close, the capacitor stability being made of 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, so as to when metallized film is heated generation miniature deformation, 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 the capacitor metalized film of automatic reduction type, belong to metallized film system
Standby technical field.
Background technology
For capacitor in accordance with the difference of medium, there are many its type, such as：Electrolyte capacitance, papery capacitance, thin-film capacitor,
Ceramic condenser, mica capacitor, air capacitance 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 serve 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 after being overlapped from both ends, are wound into the capacitor of cylindric construction.And divided according to the type of plastic film
Also known as it is poly- ethyl ester capacitance, polypropylene capactive, polystyrene capacitance and poly- carbonic acid capacitance.
Its preparation method of common thin film capacitor is wound on one after the metal foils such as aluminium are overlapped as electrode and plastic film
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
The very thin metal of vacuum evaporation last layer is with as electrode.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 make small-sized, the big capacitor of capacity.Metallic film capacitor is used
Film have poly- ethyl ester, polypropylene, makrolon etc., other than convoluted, also there is lamination-type.This kenel of metallized film
Capacitor there is a kind of so-called I my reactivation, that is, assume the minute portions of electrode and cause short because electric boundary matter is fragile
Lu Shi, causes the electrode metal of short-circuit peripheral portion, can be because of the electrostatic energy or short circuit current of capacitor institute band at that time, and causes
It is greater area of to dissolve and evaporate and restore to insulate, capacitor is made to reply 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 the indexs such as volume, resistance to mild reliability to thin film capacitor propose higher requirement.It is existing
Some polypropylene capacitor films, thickness is big, temperature tolerance is poor, percent thermal shrinkage is relatively higher, with this film roll around into capacitor
With the lengthening of its working time, internal temperature rise is very fast, and the stability of capacitor is caused drastically to decline or even cause capacitor
Failure, serious security risk is brought to power grid.
Therefore, invent a kind of capacitor metalized film of automatic reduction type has product to metallized film preparing technical field
Pole meaning.
Invention content
Present invention mainly solves the technical issues of, it is for current capacitor metalized film at work, internal to heat up
Comparatively fast, miniature deformation can occur for metallized film, the stability of capacitor be caused drastically to decline, in addition metallized film compares
It is thin, the defects of current capacity is weak, and conductive capability is poor is carried, provides a kind of preparation of the capacitor metalized film of automatic reduction type
Method.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of the capacitor metalized film of automatic reduction type, it is characterised in that specifically preparation process is：
（1）The aqueous solution of 20~25mL silver nitrate solutions and 30~40mL trisodium citrates is fitted into single port bottle, is stirred with magnetic force
Device stirring is mixed, then 2~3mL sodium borohydride solutions are added in into single port bottle, is stirred to react, stands, obtains silver-colored crystal seed liquid；
（2）By 0.8~1.2g polyvinylpyrrolidones, 2~3g ascorbic acid, 1.0~1.5g cetyl trimethylammonium bromides
It is dissolved in deionized water and adds in above-mentioned silver-colored crystal seed liquid, continuously add deionized water dilution, obtain reproducibility dispersion liquid；
（3）100~120mLDMF is taken to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, starts magnetic force
Blender stirs, and 5~7g4,4 '-diaminodiphenyl ether are added in into beaker, and stirring adds 6~8g pyromellitic dianhydrides,
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, polyimide precursor colloidal sol is obtained by the reaction；
（5）Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and is stopped, is 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 carrying 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.
Step（1）The mass fraction of the silver nitrate solution is 25%, and the aqueous solution mass fraction of trisodium citrate is
20%, magnetic stirring apparatus rotating speed is 600~700r/min, and the mass fraction of sodium borohydride solution is 10%, and it is 2 to be stirred to react the time
~3min, time of repose are 2~3h.
Step（2）Volume is after the ascorbic acid is L-type ascorbic acid, addition deionized water dilutes silver-colored crystal seed liquid
100~120mL.
Step（3）The control water-bath pot temperature is 35~40 DEG C, and magnetic stirring apparatus rotating speed is 500~550r/min,
Mixing time is 10~15min, is stirred to react the time as 3~4h.
Step（4）The reproducibility dispersion liquid, nano graphite powder, the mixing of polyamic acid colloidal sol mass ratio be 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.
Step（5）It is 10~15min that the glass substrate, which is inserted perpendicularly into polyimide precursor colloidal sol the residence time,
The upward rate of pulling is 4cm/min, and the naturals 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.
Step（6）Temperature is 700~800 DEG C during described vacuum evaporating coating machine plated film, and institute's metal-coated membrane thickness is 0.1
~0.3mm, silver acetate liquid quality fraction are 20%, and immersion coarsening time is 3~4h, and baking oven set temperature is dry for 80~90 DEG C
The dry time is 2~3h.
The beneficial effects of the invention are as follows：
（1）The aqueous solution of silver nitrate solution, sodium citrate is mixed to join in sodium borohydride solution by the present invention, is stirred to react
To silver-colored crystal seed liquid, polyvinylpyrrolidone, L-type ascorbic acid, cetyl trimethylammonium bromide and the brilliant solution of silver are mixed, and
Deionized water dilution is added in, obtains reproducibility dispersion liquid, using DMF as solvent, addition 4,4 '-diaminodiphenyl ether and equal benzene four
Formic anhydride is stirred to react to obtain polyamic acid colloidal sol, by reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol by certain
Mass ratio mixes, and obtains mixed glue solution, silver nitrate solution is gradually added dropwise into mixed glue solution, and polyamides Asia is obtained by being stirred to react
Amine precursor sol by czochralski method to glass substrate plated film, is torn to obtain load Ag films after film curing, finally be steamed with vacuum
It sends out coating machine and plates one layer of aluminium film to carrying Ag films, obtain metallized film, automatic go back is dried to obtain after metallized film is roughened
The capacitor metalized film of prototype, at work, temperature slowly increases the capacitor metalized film of the present invention, is glued between resin matrix
Tying power reduces, and the Brownian movement of conductive nano particle makes it assemble mutually, conductive cluster is caused gradually to increase, and forms conductive mesh
Network, improves the conductivity of metallized film, wherein the silver salt adulterated can be restored, is covered in resin matrix surface,
The conductivity of metal film is improved, the nano graphite powder adulterated in resin matrix expands when heated, can be by highly conductive silver powder ion
It is connected in series, improves the electrical efficiency of resin matrix, be improved the carrying current capacity of metallized film；
（2）The present invention can generate very strong machine because conducting particles uniformly disperses in polyimide resin matrix between them
Tool interlocking acts on, simultaneously as silver is a kind of blunt metal, without very strong interaction between polymer substrate, so metallization
Most of excellent properties such as high thermal stability that film will keep polyimide matrix, metallized film of the invention can be from gold
Categoryization, so-called " self-metallization " refer to that during being heat-treated to film the compound of internal silver is not plus any
In the case of reducing agent, by thermal induction effect and automatic reduction, a part of Particle diffusion therein to the surface of polymer, and
Certain aggregation occurs on the surface of polymer, it is nano level metal film on surface to form one layer of particle size, is formed in this way
Metal film is uniformly fine and close, and the capacitor stability being made of it is strong, conductive silver powder particle and nanometer stone in metallized film
Ink powder is discontinuous phase, and polyimide resin matrix is continuous phase, and the discontinuous phase molecule of electric conductivity can drop in continuous phase
The thermalization shrinking percentage of low metal film, nano graphite powder thermal expansion character can be such that metallized film expands at work again, from
And metallized film be heated occur miniature deformation when, can automatic reduction be original form and thickness, have a extensive future.
Specific embodiment
By the silver nitrate solution that 20~25mL mass fractions are 25% and the citric acid three that 30~40mL mass fractions are 20%
The aqueous solution of sodium is fitted into single port bottle, starts to stir, then into single port bottle with the rotating speed of 600~700r/min with magnetic stirring apparatus
The sodium borohydride solution that 2~3mL mass fractions are 10% is added in, is stirred to react 2~3min, 2~3h is stood, obtains silver-colored crystal seed liquid；
0.8~1.2g polyvinylpyrrolidones, 2~3gL type ascorbic acids, 1.0~1.5g cetyl trimethylammonium bromides are dissolved in
In deionized water and above-mentioned silver-colored crystal seed liquid is added in, deionized water is continuously added and is diluted to 100~120mL, obtain reproducibility dispersion
Liquid；100~120mLDMF is taken to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, controls water-bath pot temperature
It is 35~40 DEG C to spend, and starts magnetic stirring apparatus, is stirred with the rotating speed of 500~550r/min, 5~7g4 of addition into beaker, 4 '-
Diaminodiphenyl ether stirs 10~15min, adds 6~8g pyromellitic dianhydrides, be stirred to react 3~4h, obtain polyamic acid
Colloidal sol；Above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol for 2 ︰, 1 ︰ 7 are mixed in mass ratio, obtain epoxy glue
Mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel by liquid, by the silver nitrate solution that mass fraction is 30%
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, metal film of aluminizing to load Ag films, 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
The aqueous solution of the silver nitrate solution that 20mL mass fractions are 25% and the trisodium citrate that 30mL mass fractions are 20% is filled
Enter in single port bottle, start to stir with the rotating speed of 600r/min with magnetic stirring apparatus, then add in 2mL mass fractions into single port bottle and be
10% sodium borohydride solution is stirred to react 2min, stands 2h, obtains silver-colored crystal seed liquid；By 0.8g polyvinylpyrrolidones, 2gL types
Ascorbic acid, 1.0g cetyl trimethylammonium bromides are dissolved in deionized water and add in above-mentioned silver-colored crystal seed liquid, continuously add
Ionized water is diluted to 100mL, obtains reproducibility dispersion liquid；100mLDMF is taken to be put into beaker, beaker is moved into and is stirred with magnetic force
In the water-bath for mixing device, control water-bath pot temperature is 35 DEG C, starts magnetic stirring apparatus, is stirred with the rotating speed of 500r/min, to burning
5g4 is added in cup, 4 '-diaminodiphenyl ether stirs 10min, adds 6g pyromellitic dianhydrides, be stirred to react 3h, gathered
Amide acid-sol；Above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol for 2 ︰, 1 ︰ 7 are mixed in mass ratio, obtained
Mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel by mixed glue solution, by the nitric acid that mass fraction is 30%
Silver-colored solution is fitted into dropping funel, and silver nitrate solution is added dropwise with the drop rate of 4mL/min, after being added dropwise, reacts 30min,
Obtain polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and stops 10min, with 4cm/
The rate of min lifts upwards, and natural drying 20min, which is placed in baking oven, is heated to 80 DEG C, isothermal holding 30min, by glass
The cured film of glass substrate surface is torn, and obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine, is heated to 700
DEG C, Ag films will be carried and be put into vacuum chamber, metal film of aluminizing to load Ag films, control institute metal-coated membrane thickness is 0.1mm, is obtained
Metallized film is put into the silver acetate solution that mass fraction is 20% by metallized film, impregnates roughening 3h, obtains roughening film,
Film will be roughened to be put into the baking oven that set temperature is 80 DEG C, dry 2h obtains the capacitor metalized film of automatic reduction type.
Example 2
The aqueous solution of the silver nitrate solution that 22mL mass fractions are 25% and the trisodium citrate that 35mL mass fractions are 20% is filled
Enter in single port bottle, start to stir with the rotating speed of 650r/min with magnetic stirring apparatus, then add in 2mL mass fractions into single port bottle and be
10% sodium borohydride solution is stirred to react 2min, stands 2.5h, obtains silver-colored crystal seed liquid；By 1.0g polyvinylpyrrolidones, 2gL
Type ascorbic acid, 1.2g cetyl trimethylammonium bromides are dissolved in deionized water and add in above-mentioned silver-colored crystal seed liquid, continuously add
Deionized water is diluted to 110mL, obtains reproducibility dispersion liquid；110mLDMF is taken to be put into beaker, beaker is moved into magnetic force
In the water-bath of blender, control water-bath pot temperature is 37 DEG C, starts magnetic stirring apparatus, is stirred with the rotating speed of 520r/min, to
6g4 is added in beaker, 4 '-diaminodiphenyl ether stirs 12min, adds 7g pyromellitic dianhydrides, be stirred to react 3.5h, obtain
To polyamic acid colloidal sol；Above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol are mixed in mass ratio for 2 ︰, 1 ︰ 7,
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
32min obtains polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and stops 12min,
It is lifted upwards with the rate of 4cm/min, natural drying 22min, which is placed in baking oven, is heated to 85 DEG C, isothermal holding
35min tears the cured film of glass substrate surface, obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine, is heated
750 DEG C are warming up to, Ag films will be carried and be put into vacuum chamber, aluminized metal film to carrying Ag films, control institute metal-coated membrane thickness is
0.2mm obtains metallized film, metallized film is put into the silver acetate solution that mass fraction is 20%, impregnates roughening
3.5h obtains roughening film, will be roughened film and is put into the baking oven that set temperature is 85 DEG C, dry 2.5h obtains automatic reduction type electricity
Canister metals film.
Example 3
The aqueous solution of the silver nitrate solution that 25mL mass fractions are 25% and the trisodium citrate that 40mL mass fractions are 20% is filled
Enter in single port bottle, start to stir with the rotating speed of 700r/min with magnetic stirring apparatus, then add in 3mL mass fractions into single port bottle and be
10% sodium borohydride solution is stirred to react 3min, stands 3h, obtains silver-colored crystal seed liquid；By 1.2g polyvinylpyrrolidones, 3gL types
Ascorbic acid, 1.5g cetyl trimethylammonium bromides are dissolved in deionized water and add in above-mentioned silver-colored crystal seed liquid, continuously add
Ionized water is diluted to 120mL, obtains reproducibility dispersion liquid；120mLDMF is taken to be put into beaker, beaker is moved into and is stirred with magnetic force
In the water-bath for mixing device, control water-bath pot temperature is 40 DEG C, starts magnetic stirring apparatus, is stirred with the rotating speed of 550r/min, to burning
7g4 is added in cup, 4 '-diaminodiphenyl ether stirs 15min, adds 8g pyromellitic dianhydrides, be stirred to react 4h, gathered
Amide acid-sol；Above-mentioned reproducibility dispersion liquid, nano graphite powder, polyamic acid colloidal sol for 2 ︰, 1 ︰ 7 are mixed in mass ratio, obtained
Mixed glue solution is fitted into the four-hole boiling flask with blender and dropping funel by mixed glue solution, by the nitric acid that mass fraction is 30%
Silver-colored solution is fitted into dropping funel, and silver nitrate solution is added dropwise with the drop rate of 5mL/min, after being added dropwise, reacts 35min,
Obtain polyimide precursor colloidal sol；Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and stops 15min, with 4cm/
The rate of min lifts upwards, and natural drying 25min, which is placed in baking oven, is heated to 90 DEG C, isothermal holding 40min, by glass
The cured film of glass substrate surface is torn, and obtains carrying Ag films；Aluminum steel is put into vacuum evaporating coating machine, is heated to 800
DEG C, Ag films will be carried and be put into vacuum chamber, metal film of aluminizing to load Ag films, control institute metal-coated membrane thickness is 0.3mm, is obtained
Metallized film is put into the silver acetate solution that mass fraction is 20% by metallized film, impregnates roughening 4h, obtains roughening film,
Film will be roughened to be put into the baking oven that set temperature is 90 DEG C, dry 3h obtains the capacitor metalized film of automatic reduction type.
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 automatic
The capacitor metalized film of automatic reduction type in the capacitor metalized film of reduced form and comparative example carries out performance detection, detection
The results are shown in Table 1：
1st, test method：
Lateral shrinkage test is detected by 15585 standards of GB/T；
The test of longitudinal contraction rate is detected by 15585 standards of GB/T；
Transverse tensile strength test is detected by GBT228-2002 standards；
Longitudinal tensile strength test is detected by GBT228-2002 standards；
Minimum breakdown voltage test is detected by 3333 standards of GB/T.
1 capacitor metalized film performance measurement result of table
Shrinking percentage is low at high temperature for the capacitor metalized film of automatic reduction type produced by the present invention according to above-mentioned middle data,
Performance is stablized, i.e., high-temperature stability is preferable, and minimum breakdown voltage reaches 600V/um, can bear heavy current impact, conductive capability
By force, it 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 specifically preparation process is：
（1）The aqueous solution of 20~25mL silver nitrate solutions and 30~40mL trisodium citrates is fitted into single port bottle, is stirred with magnetic force
Device stirring is mixed, then 2~3mL sodium borohydride solutions are added in into single port bottle, is stirred to react, stands, obtains silver-colored crystal seed liquid；
（2）By 0.8~1.2g polyvinylpyrrolidones, 2~3g ascorbic acid, 1.0~1.5g cetyl trimethylammonium bromides
It is dissolved in deionized water and adds in above-mentioned silver-colored crystal seed liquid, continuously add deionized water dilution, obtain reproducibility dispersion liquid；
（3）100~120mLDMF is taken to be put into beaker, beaker is moved into the water-bath with magnetic stirring apparatus, starts magnetic force
Blender stirs, and 5~7g4,4 '-diaminodiphenyl ether are added in into beaker, and stirring adds 6~8g pyromellitic dianhydrides,
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, polyimide precursor colloidal sol is obtained by the reaction；
（5）Glass substrate is inserted perpendicularly into polyimide precursor colloidal sol and is stopped, is 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 carrying 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：
Step（1）The mass fraction of the silver nitrate solution is 25%, and the aqueous solution mass fraction of trisodium citrate is 20%, and magnetic force stirs
Device rotating speed is mixed as 600~700r/min, the mass fraction of sodium borohydride solution is 10%, is stirred to react the time as 2~3min, quiet
The time is put as 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：
Step（2）The ascorbic acid is L-type ascorbic acid, adds in deionized water silver-colored crystal seed liquid is diluted after volume 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：
Step（3）The control water-bath pot temperature be 35~40 DEG C, magnetic stirring apparatus rotating speed be 500~550r/min, mixing time
For 10~15min, the time is stirred to react as 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：
Step（4）The reproducibility dispersion liquid, nano graphite powder, the mixing of polyamic acid colloidal sol mass ratio be 2 ︰, 1 ︰ 7, 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：
Step（5）It is 10~15min that the glass substrate, 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：
Step（6）Temperature is 700~800 DEG C during described vacuum evaporating coating machine plated film, and institute's metal-coated membrane thickness is 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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