WO2002074841A1 - Substrats a surfaces conductrices - Google Patents

Substrats a surfaces conductrices Download PDF

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Publication number
WO2002074841A1
WO2002074841A1 PCT/SG2001/000063 SG0100063W WO02074841A1 WO 2002074841 A1 WO2002074841 A1 WO 2002074841A1 SG 0100063 W SG0100063 W SG 0100063W WO 02074841 A1 WO02074841 A1 WO 02074841A1
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WO
WIPO (PCT)
Prior art keywords
substrate
monomer
oxidant
performance modifier
conductive
Prior art date
Application number
PCT/SG2001/000063
Other languages
English (en)
Inventor
Hailin Ge
Original Assignee
Hw Electrochem Technology Pte Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hw Electrochem Technology Pte Ltd filed Critical Hw Electrochem Technology Pte Ltd
Priority to PCT/SG2001/000063 priority Critical patent/WO2002074841A1/fr
Publication of WO2002074841A1 publication Critical patent/WO2002074841A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam

Definitions

  • This invention relates to imparting conductivity to at least the surface of a non-conductive substrate and, in particular, a natural or synthetic plastics material.
  • One conventional form of conductive foam material consists of a plastics material into which have been incorporated small conductive metal or carbon particles.
  • Another process involves forming a thin metal plating onto the surface of the polymer, e.g. placing the plastics material into a metal ion solution such as divalent copper with a reducing agent such that the copper becomes reduced and deposited on the polymer surface.
  • a metal ion solution such as divalent copper with a reducing agent such that the copper becomes reduced and deposited on the polymer surface.
  • electroless plating whilst providing conducting surface to the polymer, in many ways have a number of disadvantages.
  • One preferred manner of providing a polymer with a conducting surface is to polymerise a cyclic monomer, such as pyrrole, on the surface of a base polymer and react it with an oxidant such as ferric trichloride or ammonium persulphate to form an intrinsically conductive polymer such as polypyrrole, which renders the resulting polymeric surface conducting.
  • a cyclic monomer such as pyrrole
  • an oxidant such as ferric trichloride or ammonium persulphate
  • U.S. Patent No. 4 604 247 is an example of this method of forming an intrinsically electrically conductive polymer.
  • Intrinsically electrically conductive polymers such as this can be used to coat a non-conducting substrate in various ways.
  • a solution of the monomer can be coated onto the substrate polymer and then the thus coated substrate immersed in a solution of the oxidant.
  • the monomer may, itself, diffuse into the oxidant solution and so this is liable to render the process non- economic.
  • Another possible procedure is to polymerise the polymer by means of the oxidant and then to dissolve the resulting polymer in a solvent which is sprayed onto the surface of the substrate to render the surface conductive following evaporation of the solvent.
  • the resulting polymer e.g. polypyrrole
  • a further process involves applying the oxidant to the substrate and then exposing that to a vapour or a solution of the monomer so as to cause polymerisation and formation of the conductive surface film.
  • a disadvantage, however, of this procedure is that the oxidants are generally inorganic materials and so there are considerable difficulties in maintaining the oxidant on what is a generally a hydrophobic polymer and so adhesion of the resulting conductive surface polymeric layer is a problem.
  • an object of the present invention to provide an improved procedure for producing a conductive surface coating on non-conductive substrates.
  • a process for the formation of surface conductivity on a substrate comprising treating the substrate with a mixture of a monomer and an oxidant before substantial reaction between them occurs, and allowing the monomer and oxidant to react in contact with and on the surface of the substrate to give the substrate an intrinsically conductive polymeric surface.
  • the oxidant be mixed with the monomer prior to significant polymerisation of the monomer and that the polymerisation and implantation proceed in the presence of the reducing oxidant.
  • This can be achieved, for example, by mixing the two components in solution and then immediately applying the solution to the surface of the substrate and allowing the monomer to polymerise on the substrate and the oxidant to reduce.
  • the two can be mixed and then spayed or coated onto the substrate.
  • the substrate can be dipped into the mixed solution or a surface layer of the solution applied to the substrate.
  • the two components namely the monomer and the oxidant, can be sprayed onto the surface of the substrate either simultaneously or by spraying one immediately after the other and before there is any opportunity for significant polymerisation of the monomer to occur.
  • a performance modifier may be added to the mixture of oxidant and monomer prior to significant polymerisation.
  • a performance modifier will be chosen so as to provide the conductive polymer layer with various properties.
  • Such a performance modifier can, for example, be a solvent which helps the monomer, oligomer and the resulting polymer to diffuse into the structure of the substrate. Examples of such solvents are an alcohol, ketone, THF, DMSO, NMP or methylene chloride.
  • the performance modifier can also be a material which provides counter ions such as p-toluene sulphonate, dodecyl sulphate or dodecyl sulphonate, or a reaction speed controller such as an acid, e.g. sulphuric acid.
  • polymerisation occurs in stages, usually from the monomer to an oligomer and then to the polymer with increasing molecular weight.
  • polymerisation occurs on the surface of the substrate with assistance of the performance modifier which is preferably present.
  • the oxidant becomes reduced and the reduction product is usually left on the surface of the substrate and can then be eliminated by rinsing at the end of the reaction.
  • the intrinsically conductive polymer becomes integrated or implanted either chemically and/or physically into the surface layer of the substrate.
  • the intrinsically conductive polymer which is formed by the polymerisation is able to adhere well to the substrate and this is not in any way blocked or hindered by any previous deposition on the surface of the substrate. Also by polymerising the monomer in situ on the surface of the substrate one does not form a separate polymer layer which then needs to be adhered to the substrate.
  • the products made according to the invention have a wide variety of uses. They can, for example, be used in the packaging for microchips, circuit boards and other electronic components where a conductive layer is required to ensure that there cannot be static charges which would damage the component. They can also be used to make a Faraday cage to minimise electric field interference by making a container, and earthing the conductive layers to provide and overall screen in which electronic equipment is placed. Other uses for such materials include conductive flooring for electronic component production plants where, again, electrostatic discharges need to be avoided, wafer storage and shipping, personal electrostatic protection devices, work stations in semiconductor or electronic factories, conductive paint, cable shielding material, and in the formation of conductive textiles.
  • Particularly attractive monomers for producing the intrinsically conductive polymer layer are those which form polypyrrole, polyaniline and their analogues.
  • Mol. Cryst. Liq. Cryst., 1982, Vol. 83, pp. 253-264 "Preparation and Characterization of Neutral and Oxidized Polypyrrole Films", G.B. Street, T.C. Clarke, M. Krounbi, K. Kanazawa, V. Lee, P. Pfluger, J.C. Scott and G.
  • polypyrrole see “Aqueous Chemistry and Electrochemistry of Polyacetylene and 'Polyaniline': Application to Rechargeable Batteries", pp.248 and 249," A. J. Karwczyk, R.J.Mammone, S.L. Mu, N.L. D. Somaasiri and W. Wu (polyaniline). These polymers exhibit good environmental stability and are potentially inexpensive to produce. Suitable monomers, therefore, are for example: pyrrole and its derivatives, aniline and its derivatives and thiophene and its derivatives.
  • Examples of derivatives of pyrrole and aniline are N-methylpyrrole, 3-methylpyrrole, 3,5-dimethylpyrrole, 2,2'-bippyrrole, N- methylaniline, 2-methylaniline, 3-methylaniline and N-phenyl-1 ,4- diaminobenzene.
  • the oxidant is used with the monomer to form an intrinsically conductive polymer layer.
  • Such oxidants include chemical compounds that can be reduced by monomers.
  • Such materials are exemplified by, but not limited to, FeCI 3 ⁇ Fe 2 (SO 4 ) 3 , (NH 4 ) 2 S 2 O 8 , Na 2 S 2 O 8 , K 2 Cr 2 O 7, HNO 3, HCIO 4 , H 2 O 2 , quinone, K 3 (Fe(CN) 6 ), H 3 PO 4 ,12MoO 3 , H 3 PO 4 12WO 3 , CrO 3 , (NH 4 )Ce(NO 3 ) 6 , Ce(SO 4 ) 2 , CuCI 2 , and AgNO 3 .
  • Particularly preferred compounds are FeCI 3 , ferric sulphate, persulphates such as ammonium persulphate and sodium persulphate, dichromates, nitric acid, perchloric acid, peroxides, and quinone.
  • Particularly preferred are ferric chloride and ammonium persulphate.
  • the substrate which is given the intrinsically conductive surface layer according to the invention can be chosen from a very wide range of materials.
  • substrates which can be used include polyurethane, polyvinyl chloride, acrylics, polystyrene, polypropylene, polyethylene, acrylonitrile- butadiene-styrene, nylon, polycarbonate, polyesters, polyethersulphone, polyphenylene sulphide, acetals, alkyds, polysulphone, cellulose, epoxies, cotton and wood.
  • the most preferred substrates are, however, natural or synthetic plastics materials.
  • the monomer and oxidant be mixed in solution in a suitable solvent such as water or alcohol.
  • a suitable solvent such as water or alcohol.
  • the concentration of the oxidant be from 0.001 M to saturated and more preferably from 0.01 to 1.0M.
  • the concentration of the monomer is preferably from 0.01 to 20% by volume and more preferably from 0.1 to 2.0% by volume. If the performance modifier is present this is preferably present from 0.01 % to 80% by volume. This performance modifier can, in some circumstances be the solvent for both the oxidant and monomer,
  • the reaction time to produce the conductive polymeric surface film on the substrate can vary over a wide range, e.g. from 3 seconds to 48 hours. Preferably, however, the reaction conditions are chosen so that the reaction is complete within a time of 1 minute to 12 hours.
  • the reaction temperature can vary widely from -40 to 100°C. More preferably it is from -10 to 40 °C, and room temperature is most preferred.
  • reagent A 54ml of 0.25M FeCI 3 was prepared as reagent A (oxidant). 60ml 1 % pyrrole was used as reagent B (monomer). 6ml of isopropanol was used as reagent C (performance modifier). The reagents A, B, and C were mixed to form a reaction solution. Immediately, a 7cm x 7cm x 1 cm polyurethane foam was dipped in the solution. The foam was pressed to allow the solution to diffuse into the pores. The mixture was allowed to react for 30 minutes. The foam was then taken out of the solution and squeezed to release remaining solution. The thus treated foam was submerged in water a few times to remove the residuals which could include reduced oxidant, excess polymer, unevaporated solvent and performance modifier.
  • Example 2 The resulting foam was dark brown to black in colour.
  • the surface conductivity was 2.9 x 10 4 ⁇ /square and static decay time was less than 0.01s.
  • reagent A oxidant
  • reagent B monomer
  • Reagents A and B were mixed to form a reaction solution.
  • a piece of 9cm x 15cm x 1cm polyurethane foam was dipped into the solution, and pressed allow the solution to diffuse into the pores. Reaction was allowed to continue for 2h.
  • the foam was squeezed to release the solution and then submerged in water a few times to remove residuals. The resulting foam was green in colour.
  • the surface resistivity was 8.5 x 10 4 ⁇ /square and static decay time was 0.2s.
  • reagent A 0.5m FeCI 3 in ethanol was used as reagent A (oxidant). 0.75% pyrrole in methanol was used as reagent B (monomer). Tetrahydrofuran was used as reagent C (performance enhancer). 10 Parts of reagent A, 7 parts by volume of reagent B and 3 parts of reagent C were mixed to form a reaction solution. 1.5ml of this solution was sprayed onto a 100mm x 100mm x 0.2mm PVC film and allowed to react for 5 minutes. The film was rinsed to remove residuals. The resulting film was transparent.
  • No implanted intrinsically conductive surface polymer layer was stripped.
  • the surface resistively was 5.4 x 10 3 ⁇ /square and static decay time was less than 0.01 s.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé relatif à l'établissement d'une conductivité de surface sur un substrat, qui consiste à traiter le substrat avec le mélange suivant: monomère, oxydant, et de préférence modificateur pouvant être un solvant qui facilite la diffusion du monomère, de l'oligomère et du polymère résultant dans la structure du substrat, avant le déclenchement d'une réaction sensible entre eux. Ensuite, le monomère et l'oxydant réagissent au contact de la surface du substrat et sur celle-ci, conférant au substrat une surface polymère à conductivité intrinsèque. Par exemple, le monomère utilisé pour l'établissement de la couche polymère à conductivité intrinsèque peut être pyrrole, aniline ou thiophène, et le substrat est de préférence en matériau polymère naturel ou synthétique. La surface du substrat traité présente une conductivité comprise entre 1 et 1011 Φ/carré et de préférence encore entre 10?2 et 108¿ Φ/carré.
PCT/SG2001/000063 2001-03-16 2001-03-16 Substrats a surfaces conductrices WO2002074841A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/SG2001/000063 WO2002074841A1 (fr) 2001-03-16 2001-03-16 Substrats a surfaces conductrices

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Application Number Priority Date Filing Date Title
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WO2002074841A1 true WO2002074841A1 (fr) 2002-09-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004071151A2 (fr) * 2003-02-12 2004-08-26 Gesellschaft Fuer Biotechnologische Forschung Mbh (Gbf) Article en plastique moule electro-conducteur
CN114249916A (zh) * 2022-01-12 2022-03-29 华尔科技集团股份有限公司 一种高分子复合薄膜以及采用该薄膜的静电产生器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4604427A (en) * 1984-12-24 1986-08-05 W. R. Grace & Co. Method of forming electrically conductive polymer blends
JPS63213518A (ja) * 1987-03-02 1988-09-06 Sumitomo Chem Co Ltd 導電性材料の製造方法
US5035926A (en) * 1988-04-22 1991-07-30 Bayer Aktiengesellschaft Method of imparting antistatic properties to a substrate by coating the substrate with a novel polythiophene
US5683744A (en) * 1993-04-30 1997-11-04 Commissariat A L'energie Atomique Process for the preparation of a porous material layer covered with an electronically conductive polymer and the product obtained by this process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4604427A (en) * 1984-12-24 1986-08-05 W. R. Grace & Co. Method of forming electrically conductive polymer blends
JPS63213518A (ja) * 1987-03-02 1988-09-06 Sumitomo Chem Co Ltd 導電性材料の製造方法
US5035926A (en) * 1988-04-22 1991-07-30 Bayer Aktiengesellschaft Method of imparting antistatic properties to a substrate by coating the substrate with a novel polythiophene
US5683744A (en) * 1993-04-30 1997-11-04 Commissariat A L'energie Atomique Process for the preparation of a porous material layer covered with an electronically conductive polymer and the product obtained by this process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004071151A2 (fr) * 2003-02-12 2004-08-26 Gesellschaft Fuer Biotechnologische Forschung Mbh (Gbf) Article en plastique moule electro-conducteur
WO2004071151A3 (fr) * 2003-02-12 2004-10-28 Biotechnolog Forschung Gmbh Article en plastique moule electro-conducteur
CN114249916A (zh) * 2022-01-12 2022-03-29 华尔科技集团股份有限公司 一种高分子复合薄膜以及采用该薄膜的静电产生器

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