CN1158349A - Conductive polyaniline doped with camphorsulfonic acid - Google Patents
Conductive polyaniline doped with camphorsulfonic acid Download PDFInfo
- Publication number
- CN1158349A CN1158349A CN96114325A CN96114325A CN1158349A CN 1158349 A CN1158349 A CN 1158349A CN 96114325 A CN96114325 A CN 96114325A CN 96114325 A CN96114325 A CN 96114325A CN 1158349 A CN1158349 A CN 1158349A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- film
- camphorsulfonic acid
- coating composition
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 43
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 title claims description 20
- 239000008199 coating composition Substances 0.000 claims abstract description 12
- -1 aromatic hydroxy compound Chemical class 0.000 claims abstract description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 10
- 229940100630 metacresol Drugs 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229920000775 emeraldine polymer Polymers 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000216843 Ursus arctos horribilis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
Abstract
The present invention discloses an coating composition contains polyaniline, camphor sulphonic acid and an aromatic hydroxy compound; a conductive film produced by coating composition; an shield for electronic equipment has coating composition with a conductive film.
Description
The present invention relates to a kind of layer/polyaniline conductive film that is doped with camphorsulfonic acid and be used to prepare the coating composition of the conducting film that electromagnetic shielding uses.
As everyone knows, the hertzian wave that is produced by various electronics/electrical equipment can disturb miscellaneous equipment, and when people were subjected to electromagnetic wave radiation for a long time, they were harmful to the health of human body.This phenomenon is referred to as electromagnetic interference (EMI).Over past ten years, people have carried out deep research to attempt to find the method (EMI shielding) that prevents hertzian wave and escape from source device.
Conventional EMI screen method comprises to be sealed source device with metal cap or the plastic lousing that comprises electro-conductive material, said electro-conductive material for example can be the carbon black, graphite, iron, stainless steel, silver, copper, nickel, lead of powder, fabric, screen cloth, grizzly bar or flocculus form etc.But because weight and expense aspect, it is unpractical adopting metal cap.And being its physical properties, the problem that comprises the plastic lousing of conductive filler material can degenerate; Because need complicated production process, expense also can increase.When the electroconductive stuffing skewness, often be unsafty for the shielding effect of EMI.
Recently people are making great efforts to develop electric conductive polymer such as polypyrrole, polyacetylene, polyaniline and Polythiophene always, and these polymkeric substance are a class type material, and its industrial use is extensive, comprise can be used for the EMI shielding.In these electric conductive polymers, polyaniline has extra high doping capacity.The structural formula of unadulterated low-molecular-weight aniline is referred to as the emeraldine base form of aniline usually as shown in the formula (I), or abbreviates " emeraldine base " (EB) [J.G.Masters et al., Syn.Met., 41,715 (1991)] as.
EB dissolves in the various polarity organic solvent, and this solution can be used for preparing unadulterated polyaniline film, on sheet glass, makes solvent evaporation as the solution casting that will contain EB again.The electric conductivity of this unadulterated film is lower, is 10
-9S/cm.But after mixing by for example film being immersed in the HCl aqueous solution and with proton, its electric conductivity has increased by 10 orders of magnitude, increases to about 5S/cm.Its reason has been to form the poly-semiquinone residue positively charged ion with following structural formula (II).
The open 92-348161 of Japan's special permission discloses a kind of electrically conductive polyaniline film, it is that wherein the structural formula of said polyaniline (III) is the reduced form structural formula with N-Methyl pyrrolidone (NMP) formulations prepared from solutions of pbz polymer amount polyaniline, tosic acid and a kind of oxygenant.This film can activate at elevated temperatures.
Particularly, be cast in nmp solution on the sheet glass and be heated to more than 100 ℃, wherein the generation of oxidisability doping subprocess makes the conducting film that forms have high physical strength.But the electric conductivity of the polyaniline film of being produced by this method is lower, is about 1S/cm or lower, and its surface resistivity then is 10
5Ω/mouth.
In order to develop the lighter novel EMI shielding material of weight, the inventor has carried out deep research, and unexpectedly find, when the process of the coating solution that is used for producing film in preparation is used the doping agent of particular combinations and solvent, mixed its electroconductibility phenomenal growth of film of emeraldine base has increased 1-2 the order of magnitude than the conduction value of previous report.
Therefore, an object of the present invention is to provide a kind of new coating solution, this solution is used in the coated membrane that forms the polyaniline of high conductivity on the cover of the electronics that is used for EMI shielding or device.
Another object of the present invention provides a kind of electronics of the coated membrane with effective EMI shielding or the cover of device.
According to one aspect of the present invention, provide a kind of coating composition that comprises polyaniline, camphorsulfonic acid and a kind of aromatic hydroxy compound.
According to another aspect of the present invention, provide a kind of electronics with covering with conducting film coating, said coating comprises the polyaniline that is doped with camphorsulfonic acid.
The accompanying drawing summary
Fig. 1 illustrative the measurement of shielding rate; With
Fig. 2 has shown the shielding rate of film of the present invention in 10-1000MHz.
The term that uses in this specification " polyaniline " refers to the polyaniline (structural formula I) of emeraldine base (EB) form, is commonly referred to as EB. Generally, the molecular weight of EB is lower, is 8,000-20, and 000, it dissolves in polar organic solvent, such as 1-METHYLPYRROLIDONE (NMP), chloroform, formic acid, phenolic compounds etc. The solution of this EB of containing can be used for preparing unadulterated polyaniline film.
The organic solution that comprises EB and organic sulfonic acid also can prepare under given conditions, and this solution can be directly used in the EB film that preparation is mixed. This method for preparing doping EB film is more simpler than the method for coming with another step unadulterated EB film is mixed, and unexpectedly finds, can give the electrical property of film wide region. For example, use camphor-10-sulfonic acid (CSA) as adulterant, when solvent was respectively chloroform, formic acid and metacresol, the conductance of the doping EB film that makes was respectively 0.5S/cm, 5S/cm and 190S/cm. On the other hand, use metacresol as solvent, when adulterant was respectively naphthalene sulfonic acids (NSA), DBSA (DBSA) and CSA, the conductance of film was respectively 0.6S/cm, 15S/cm and 190S/cm. From the angle of prior art, it is beat all on the whole that the above-mentioned conductance of observing changes, and this may be that this depends on used solvent and adulterant because formed the different crystal forms structure of doping EB.
The coating solution that can be used for preparing the high conductivity film of doped polyaniline of the present invention comprises at least three kinds of components: the polyaniline of (1) emeraldine base form; (2) the large alkanesulfonic acid that crowds on the space is such as camphor-10-sulfonic acid; (3) a kind of solvent that contains aromatic hydroxy compound is selected from phenol, cresols, xylenol and derivative thereof. The most preferred coating composition of the present invention comprises polyaniline, camphor-10-sulfonic acid and metacresol.
Coating composition of the present invention can be used for electronic equipment is carried out coated with effective shielding EMI with the surface of cover. In the present invention, preliminary treatment can be carried out so that conducting film adheres to better thereon in the surface of cover, as carrying out precoating with priming paint. In addition, the adhesiveness of conducting film of the present invention can be by using following coating composition or using other suitable method as known in the art to strengthen, said composition also comprises a kind of epoxy resin, its consumption is 10-50% (weight), in last composition total weight.
Following embodiment is used to be described more specifically the present invention, but is not limitation of the invention.
In embodiment and comparative example, according to measurement electromagnetic shielding rate as described below.Referring to Fig. 1, in the middle of electromagnetic wave generator (1) and detector (2), place sample (3), its shielding rate is:
Shielding rate (dB)=10log (P
1/ P
2) wherein, P
1Expression incident electromagnetic power, P
2The transmission power that expression is received by detector.
When the distance between electromagnetic wave source and sample during, use flanged coaxial radioparent tester to measure according to ASTM:D4935-89 greater than λ/2 π.Preparation embodiment: the preparation of polyaniline (emeraldine base)
The aniline of 20ml (about 0.22mol) is dissolved in the 1N hydrochloric acid soln of 300ml, is cooled to 0 ℃, in 2 minutes, stir and when keeping temperature to be 0 ℃ to wherein adding a kind of solution, this solution is the ammonium peroxydisulfate [(NH with 11.5g (about 0.05mol)
4)
2S
2O
8] be dissolved in and make in the 1N hydrochloric acid of 200ml.This mixture was converted into deep green after 5 minutes, continue to stir 90 minutes at 0 ℃.Leach the solid of separating out, colourless with the salt acid elution of 1N until filtrate, air drying 10 minutes.Obtain 50% protonated polyaniline powder.Protonated polyaniline powder is scattered in the 0.1NNH of 500ml
4Among the OH, using 1NNH
4When OH adjusting pH is 9, stirred 15 hours, leach the neutral polyaniline powder, use 0.1NNH
4OH solution washs, and thorough drying is 48 hours under 10 torrs, obtains the polyaniline that molecular weight is about 70,000 emeraldine base form.The polyaniline product that obtains is ground and stores with mortar and pestle.Embodiment 1: the adulterated polyaniline film of camphorsulfonic acid
To prepare 0.724g polyaniline powder that embodiment obtains and camphor-10-sulfonic acid of 0.927g (0.004mol) mixes fully with mortar and pestle.The powdered mixture that obtains is placed the solvent (meta-cresol, chloroform, formic acid) of 50g, stirred 10 minutes.Remove by filter undissolved solid, obtain containing the settled solution of polyaniline and camphorsulfonic acid.This solution is poured on the sheet glass of cleaning, in remaining on 60 ℃ normal reheating furnace dry 15 hours, the movable film of the polyaniline of the camphorsulfonic acid that obtained mixing (free-standing film).
So the electric conductivity of the film of preparation depends on used solvent:
Solvent electric conductivity (S/cm)
Meta-cresol 190
Chloroform 0.5
As implied above, have extra high electric conductivity by meta-cresol as the polyaniline film of the doping camphorsulfonic acid of solvent preparation, its surface resistivity is also lower, is 2-5 Ω/.When using flanged coaxial radioparent tester to measure, as shown in Figure 2, obtain high shielding rate during for 10-1000MHz in frequency, be 38-41dB.These results all list in the table 1.Comparing embodiment 1: with the adulterated polyaniline film of Witco 1298 Soft Acid
Repeat the process of embodiment 1, just the Witco 1298 Soft Acid (DBSA) with 0.004mol replaces camphorsulfonic acid, obtains using meta-cresol as solvent, with the movable film of the adulterated polyaniline of Witco 1298 Soft Acid.The performance perameter of this film is listed in the table 1.Comparing embodiment 2: with the adulterated polyaniline film of naphthene sulfonic acid
Repeat the process of embodiment 1, just the naphthene sulfonic acid with 0.004mol replaces camphorsulfonic acid, obtains using meta-cresol as solvent, with the movable film of the adulterated polyaniline of naphthene sulfonic acid.The performance perameter of this film is listed in table 1.Comparing embodiment 3: with the adulterated polyaniline film of HCl
Repeat the process of embodiment 1, just the HCl with 0.004mol prepares the adulterated polyaniline film of HCl.The performance perameter of this film is listed in table 1.Reference example: the polyaniline film that comprises carbon black
Stir down, the 2g polyaniline powder that preparation embodiment is obtained adds among the 30mlNMP lentamente, then to the carbon black that wherein disperses to advance 1.5g.The mixture that forms is poured on the sheet glass of cleaning, carries out drying, obtain comprising the movable film of the polyaniline of carbon black as embodiment 2.The performance perameter of this film is listed in table 1.
The performance perameter of table 1. polyaniline conducting film
*. survey frequency is 10-1000Mhz from the result of table 1 as can be seen, and embodiment 1 adopts film of the present invention that meta-cresol does the solvent preparation to have more excellent performance perameter as electric conductor and EMI shielding material than other conducting film.
| Doping agent/additive | Electric conductivity | Surface resistivity | Shielding rate * | |
| ???S/cm | ??Ω/□ | ????dB | ||
| Embodiment 1 | ???CSA | ???190 | ???4 | ????38-41 |
| Comparing embodiment 1 | ???DBSA | ???15 | ???100 | ????22-26 |
| | ???NSA | ???0.6 | ???1000 | ????8-10 |
| | ???HCl | ???5 | ???150 | ????20-23 |
| Reference example | Carbon black | ???160 | ???40 | ????20-23 |
Invention has been described more than to adopt several specific embodiments, it may be noted that its various improvement of carrying out and change all to belong to protection scope of the present invention.
Claims (5)
1, a kind of coating composition comprises polyaniline, camphorsulfonic acid and a kind of aromatic hydroxy compound.
2, according to the coating composition of claim 1, wherein said aromatic hydroxy compound is a meta-cresol.
3, according to the coating composition of claim 2, further comprise a kind of Resins, epoxy.
4, a kind of conducting film comprises polyaniline and camphorsulfonic acid, and described film is to use claim 1,2 or 3 coating composition to make.
5, the cover used of a kind of electronics has the coating of the conducting film of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR52565/95 | 1995-12-20 | ||
| KR1019950052565A KR970058474A (en) | 1995-12-20 | 1995-12-20 | Electromagnetic shielding case |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1158349A true CN1158349A (en) | 1997-09-03 |
Family
ID=19441742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96114325A Pending CN1158349A (en) | 1995-12-20 | 1996-12-20 | Conductive polyaniline doped with camphorsulfonic acid |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH09183945A (en) |
| KR (1) | KR970058474A (en) |
| CN (1) | CN1158349A (en) |
| DE (1) | DE19653196A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803388A (en) * | 2009-06-12 | 2012-11-28 | 出光兴产株式会社 | Pi-conjugated polymer composition |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
| CN114133653A (en) * | 2021-12-08 | 2022-03-04 | 崔俊 | Anti-static EVA and preparation method thereof |
| CN115433511A (en) * | 2022-10-21 | 2022-12-06 | 吉林大学 | Blended aqueous polyurethane-based electromagnetic shielding coating and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU9637798A (en) * | 1997-11-07 | 1999-05-31 | Bicc Public Limited Company | Conductive polymer compositions |
| DE10038201A1 (en) * | 2000-08-04 | 2002-02-14 | Siemens Axiva Gmbh & Co Kg | New electrolytes for electrolytic capacitors and their use |
| KR20020082243A (en) * | 2001-04-19 | 2002-10-31 | 주식회사 두람하이테크 | Electromagnetic radiation shielding composition and preparing method thereof |
| KR20070004736A (en) * | 2004-03-18 | 2007-01-09 | 오르메콘 게엠베하. | A composition comprising a conductive polymer in colloidal form and carbon |
| EP1884354A4 (en) * | 2005-05-27 | 2008-08-06 | Idemitsu Kosan Co | Conductive polymer multilayer body |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69231312T3 (en) * | 1991-06-12 | 2003-12-11 | Dupont Displays Inc | APPLICABLE FORMS OF ELECTRICALLY CONDUCTIVE POLYANILINES AND CONDUCTIVE PRODUCTS PRODUCED THEREOF |
-
1995
- 1995-12-20 KR KR1019950052565A patent/KR970058474A/en not_active Application Discontinuation
-
1996
- 1996-12-19 JP JP8339753A patent/JPH09183945A/en active Pending
- 1996-12-19 DE DE19653196A patent/DE19653196A1/en not_active Ceased
- 1996-12-20 CN CN96114325A patent/CN1158349A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803388A (en) * | 2009-06-12 | 2012-11-28 | 出光兴产株式会社 | Pi-conjugated polymer composition |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
| CN103137848B (en) * | 2013-02-06 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Obtain the method for high-performance polyaniline base thermoelectric material |
| CN114133653A (en) * | 2021-12-08 | 2022-03-04 | 崔俊 | Anti-static EVA and preparation method thereof |
| CN115433511A (en) * | 2022-10-21 | 2022-12-06 | 吉林大学 | Blended aqueous polyurethane-based electromagnetic shielding coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19653196A1 (en) | 1997-06-26 |
| KR970058474A (en) | 1997-07-31 |
| JPH09183945A (en) | 1997-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Morphology of conductive, solution-processed blends of polyaniline and poly (methyl methacrylate) | |
| Hopkins et al. | Characterization of solution and solid state properties of undoped and doped polyanilines processed from hexafluoro-2-propanol | |
| KR101138295B1 (en) | Dispersions of intrinsically conductive polymers and processes for preparing them | |
| US4737557A (en) | 3-N-higher alkylthiophene polymer and composition thereof | |
| KR0160212B1 (en) | Electrically conductive pressure sensitive adhesives | |
| WO2010015468A1 (en) | Method for producing polythiophenes using hydrogen peroxide as an oxidizing agent | |
| EP0690457A2 (en) | Polyaniline-containing solution, articles coated therewith, and methods for the preparation of same | |
| US4803011A (en) | Electrically conducting films comprising at least one monomolecular layer of an organic charge transfer complex | |
| DE102010048032A1 (en) | Polythiophene-containing dispersions with a defined content of thiophene monomer | |
| EP2185661A1 (en) | Process for producing conducting polymers | |
| DE3544957A1 (en) | METHOD FOR PRODUCING AN ELECTRICALLY CONDUCTING COMPOSITE POLYMER MOLDED BODY | |
| DE102009048434A1 (en) | Conductive polymer composition, process for its preparation and solid electrolytic capacitor | |
| DD282020A5 (en) | CONDUCTIVE POLYMER COMPOSITIONS | |
| CN1158349A (en) | Conductive polyaniline doped with camphorsulfonic acid | |
| Wan et al. | Transparent and conducting coatings of polyaniline composites | |
| DE69828573T2 (en) | Transparent conductive polymers | |
| JP2001278975A (en) | Highly electric conductive polyaniline capable of melt processing or solution processing and production method of the same and blend of the same with pvc and eva | |
| DE60032744T2 (en) | AROMATIC AMINO DERIVATIVES, SOLUBLE CONDUCTIVE COMPOSITION, AND ELECTROLUMINESCENT DEVICE | |
| DE3105948A1 (en) | METHOD FOR THE PRODUCTION OF STABLE ELECTRICALLY CONDUCTIVE POLYMERIC SYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS | |
| DE10206294A1 (en) | Transparent polythiophene layers with high conductivity | |
| Wang et al. | Conducting Polyaniline Confined in Semi‐Interpenetrating Networks | |
| US7109258B1 (en) | Polymeric material with antistatic properties and method for obtaining it | |
| Kuwabata et al. | Electrical conductivity of polypyrrole films doped with carboxylate anions | |
| KR100548045B1 (en) | Conductive polymer film and method for preparing the same | |
| US6309694B1 (en) | Method for manufacturing a conductive polymer film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |