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EP0362141B1 - Support électriquement conducteur et films polymères et leur procédé de fabrication - Google Patents

Support électriquement conducteur et films polymères et leur procédé de fabrication Download PDF

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Publication number
EP0362141B1
EP0362141B1 EP19890810718 EP89810718A EP0362141B1 EP 0362141 B1 EP0362141 B1 EP 0362141B1 EP 19890810718 EP19890810718 EP 19890810718 EP 89810718 A EP89810718 A EP 89810718A EP 0362141 B1 EP0362141 B1 EP 0362141B1
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Prior art keywords
halogen
support material
material according
compound
und
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EP19890810718
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German (de)
English (en)
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EP0362141A2 (fr
EP0362141A3 (en
Inventor
Jürgen Dr. Finter
Bruno Dr. Hilti
Carl W. Dr. Mayer
Ernst Minder
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Novartis AG
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Ciba Geigy AG
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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
    • H01B1/121—Charge-transfer complexes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the invention relates to a carrier material made of a substrate which is coated on at least one surface with a needle network of crystal needles of a charge transfer complex (CT complex) made of a tetrathio-, tetraseleno- or tetratelluronaphthalene or -tetracen and a halogen; Polymer films in which such a needle network is embedded in a surface; Process for the production of these materials and their use as electrical conductors.
  • CT complex charge transfer complex
  • component a) Some compounds of component a) and their preparation are described in the publications mentioned above.
  • Preferred compounds of component a) are tetrathiotetracene, tetraselenotetracene, 2-fluoro- or 2,3-difluorotetraselenotetracene.
  • Preferred mixtures are those of compounds of the formulas I and Ia, the compound of the formula I being in particular 2,3,6,7-tetrathiophenyl-tetrathionaphthalene.
  • Component a) is particularly preferably tetraselenotetracene.
  • R15 and R16 each phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio or wherein R15 and R16 together mean, R11 is -CH3 and R12, R13 and R14 are H, R11 and R12 are Cl or CH3 and R13 and R14 are H or R11, R12, R13 and R14 are -CH3 or F, and XS, Se or Te can be produced as described below, for example:
  • the known starting compounds are 4,5-dimethylphthalic anhydride and 2,3-dimethyl-6,7-dihydroxynaphthalene in the presence of B2O3 to 2,3,8,9-tetramethyl-5,12-dihydroxy-6,11-dioxo-tetracene (A) um.
  • This reaction and the further chlorination and reduction to the tetrachlorinated product in the 5,6,11,12-position are described in DE-OS 3635124.
  • the reaction with Na2X2 leads to the corresponding tetrachalogenated tetracene.
  • the 2,3,8,9-tetramethyl-5,5,6,11,12,12-hexachlorodihydrotetracene (which is obtained in the chlorination with PCl5 / POCl3) with 1 Val Na2Se2 and 2 Val Na2Se directly to corresponding tetraselenotetracene are implemented.
  • the compound A can also be alkylated with dimethyl sulfate to give the 5,12-dimethoxy derivative [cf. Chem. Pharm. Bull. 20 (4), 827 (1972)].
  • 2,3,8,9-tetrafluoro-5,12-dihydroxy is obtained by condensing 2,3-difluorophthalic anhydride with succinic acid and then treating the condensation product with sodium ethylate in ethanol -6,12-dioxo-tetracene (B) obtained.
  • the further reaction with PCl5 and then with SnCl2 / CH3COOH to 2,3,8,9-tetrafluoro-5,6,11,12-tetrachlorotetracene is carried out analogously to the instructions in Zhuv. Org. Khim. 15 (2), 391 (1979).
  • X preferably represents S or Se.
  • R9 is especially chlorine as halogen.
  • M can be a metal or ammonium cation. Suitable metal cations are, in particular, those of the alkali and alkaline earth metals, for example Li ⁇ , Na ⁇ , K ⁇ , Mg 2 ⁇ , Ca 2 ⁇ , Sr 2 ⁇ and Ba 2 ⁇ . Zn 2 ⁇ and Cd 2 ⁇ are also suitable.
  • ammonium cations are NH4 ⁇ and primary, secondary, tertiary or quaternary ammonium, which can preferably contain C1-C12-alkyl, cyclohexyl, cyclopentyl, phenyl or benzyl groups.
  • the ammonium cations can also be derived from 5- or 6-membered heterocyclic amines, for example piperidine, pyrrole and morpholine.
  • R9 as the residue of an alcohol is preferably C1-C6-alkoxy or C2-C6-hydroxyalkoxy, benzyloxy, phenoxy, cyclopentyloxy or cyclohexyloxy.
  • R9 as the residue of a primary or secondary amine is preferably derived from alkylamines with one or 2 C1-C6 alkyl groups.
  • R10 preferably represents H, C1-C18 alkyl, phenyl or benzyl.
  • R10 preferably contains 1 to 12 and especially 1 to 6 carbon atoms as alkyl.
  • alkyl which can be linear or branched are: methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, Undecyl and dodecyl.
  • alkoxy and hydroxyalkoxy are: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, ⁇ -hydroxyetboxy, ⁇ -hydroxypropoxy, ⁇ -hydroxybutoxy and ⁇ -hydroxyhexoxy.
  • the halogen is introduced with a halogen-containing organic compound which splits off halogen with the supply of energy and forms a charge transfer complex (donor) (halogen) x with a compound of the formula I and / or Ia (donor), where 0.3 ⁇ x ⁇ 0.9.
  • a charge transfer complex donor
  • halogen halogen
  • a compound of the formula I and / or Ia donor
  • x 0.5 for halogen equal to Cl and Br
  • x equals 0.76 for halogen equal to I.
  • the energy can be, for example, thermal energy or radiation energy.
  • Thermal energy means, for example, a temperature from room temperature to 300 ° C, in particular 50 to 250 ° C, and very particularly 80 - 170 ° C.
  • the halogen compounds can be used individually or in mixtures.
  • the organic compound is preferably chlorinated, brominated and / or iodinated.
  • the compounds can be simply halogenated, e.g.
  • C-halogenated compounds expediently have a higher degree of halogenation; these compounds are preferably at least 80% C-halogenated, especially C-brominated and / or C-chlorinated.
  • Compounds whose halogen atoms are activated by electron-withdrawing groups are particularly favorable. It is particularly preferred that the compound containing halogen contains perchlorinated C3-C5-alkanes, C3-C Alk-alkenes or organic compounds with trichloromethyl groups.
  • halogenated organic compounds are tetrabromomethane, bromoform, trichlorobromomethane, hexachloropropene, hexachlorocyclopropane, hexachlorocyclopentadiene, hexachloroethane, octachloropropane, n-octachlorobutane, n-decachlorobutane, tetrabromethane, hexabromethane, tetrinomo-2,4-tetrabromo- o-2,4-tetrabromo- 2,5-cyclohexadienone, hexabromobenzene, chloranil, hexachloroacetone, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, 1,2,5,6,9,10-hexabromocyclododecane, Tet
  • substrates e.g. Metals, glass, ceramics, paper and polymers. Glass is preferably used as the substrate. If the substrate is a swellable polymer, the needle network can be partially embedded in the surface.
  • the needle network may also be coated with a metal, e.g. a semi-precious or precious metal.
  • a metal e.g. a semi-precious or precious metal.
  • metals are Cu, Ag, Au, Pt, Ir, Co, Ni and Cr.
  • a protective layer can be applied to the needle network, especially protective layers made of linear, branched or structurally cross-linked polymers, e.g. Thermosets, thermoplastics or elastomers.
  • polymers examples are:
  • thermoplastic polymers are polyvinyl alcohol, polyolefins, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylates, polymethacrylates, polycarbonates, aromatic polysulfones, aromatic polyethers, aromatic polyether sulfones, polyimides and polyvinyl carbazole.
  • the polymers can additionally contain auxiliaries required for processing and use, e.g. Plasticizers, leveling agents, mold release agents, fillers, flame retardants, antioxidants and light stabilizers, stabilizers, dyes, pigments and conductive salts.
  • auxiliaries required for processing and use, e.g. Plasticizers, leveling agents, mold release agents, fillers, flame retardants, antioxidants and light stabilizers, stabilizers, dyes, pigments and conductive salts.
  • the protective layer can also consist of photocrosslinked polymer systems.
  • Photocrosslinkable systems are e.g. by G.E. Green et al. in J. Macro, Sci.-Revs. Macro. Chem. C21 (2), 187-273 (1981-82).
  • the protective layer can be applied by generally customary coating methods for curable mixtures or polymer solutions, e.g. Brushing, pouring or knife coating, if necessary removing solvents and subsequent thermal and / or radiation-induced curing.
  • Suitable solvents for the polymers mentioned are, for example, polar, aprotic or protic solvents, which can be used alone or in mixtures of at least two solvents.
  • Examples are: water, alkanols such as methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, diols such as ethylene glycol, propylene glycol and diethylene glycol, ethers such as dibutyl ether, tetrahydrofuran, dioxane, dimethylethylene glycol, dimethyldiethylene glycol, diethyldiethylene glycol, dimethyltriethylene glycol, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-1-dichloroethane, 1,1 1,2,2-tetrachloroethane, carboxylic acid esters and lactones such as ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl a
  • the composition additionally contains an inert solvent, e.g. polar, aprotic solvents as previously mentioned.
  • the preferred solvent is dimethylformamide.
  • Component a) is preferably present in an amount of 0.001 to 5% by weight, particularly 0.01 to 2% by weight and in particular 0.01 to 1% by weight, based on component b) and optionally one inert solvents.
  • Component b) is included in the excess. It can also serve as a solvent.
  • the excess when using a solvent can e.g. are twenty times and preferably ten times the amount, based on component a).
  • Another object of the invention is a process for the preparation of the carrier material according to the invention, in which a composition according to the invention is applied to a substrate, the halogen-containing compound is allowed to act on the compound of the formula I and / or Ia and the halogen-containing compound is removed.
  • the energy is preferably supplied by thermal energy, e.g. by heating from room temperature to 300 ° C, preferably 50 to 250 ° C and especially 80 to 170 ° C, optionally in vacuo.
  • Component b) is contained in excess in the composition used according to the invention.
  • the carrier material according to the invention has a high electrical conductivity and is outstandingly suitable for use as an electrical conductor.
  • the carrier material can be converted into highly conductive materials by means of metallization, e.g. switches the carrier material in an electrolysis bath as a cathode and electrolyzes.
  • Suitable polymers are the aforementioned polymers, including the preferences.
  • the needle network is coated with a metal.
  • the polymer films can be produced by coating a carrier material according to the invention with a polymer film and then detaching the polymer film from the substrate.
  • Glass is particularly suitable as a substrate.
  • the polymer films according to the invention can be laminated to multilayer layers with several electrically conductive layers.
  • Support materials according to the invention coated with photocrosslinkable polymers can also be irradiated in a known manner under an image mask and then developed, the CT complexes formed in the developed areas being removed mechanically, for example by wiping, if appropriate. In this way, conductor structures can be created.
  • Electrodes In addition to the production of antistatic and electrically conductive coatings and polymer films for electrostatic shielding, a preferred area of application is the use as electrodes which, depending on the polymer used, can be transparent.
  • compositions and polymer films containing a CT complex according to the invention are distinguished by high chemical stability and temperature resistance and low migration of the CT complexes. Furthermore, surprisingly high conductivities are achieved, which can be up to 25% of the conductivity of the pure CT complexes. Under the manufacturing conditions, the CT complexes surprisingly form a network (needle felt) made of electrically conductive crystal needles.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Claims (18)

  1. Matériau support qui est enduit sur au moins une des surfaces d'un substrat ayant un réseau aiguilleté d'un complexe TC (donneur)(halogène)x, dans lequel x est tel que 0,3 < x < 0,9, et
    a) "donneur" représente un composé de formule I ou Ia ou bien leurs mélanges,
    Figure imgb0018
     dans lesquelles X repésente S, Se ou Te, R¹, R², R³ et R⁴ signifient, indépendamment l'un de l'autre, un atome d'hydrogène ou Cl ou bien R¹ et R² ainsi que R³ et R⁴, chacun ensemble, représente
    Figure imgb0019
     ou R¹, R², R³ et R⁴ représentent chacun un phénylthio, un 4-méthyle ou un 4-méthoxyphénylthio ou un 4-pyridylthio, R⁵, R⁶, R⁷ et R⁸ signifient, indépendamment l'un de l'autre, H ou F, R⁵ représente CH₃ et R⁶, R⁷ et R⁸ représentent H ou bien R⁵, R⁶, R⁷ et R⁸ représentent CH₃, R⁵ et R⁶ représentent CH₃ ou Cl et R⁷ et R⁸ représentent H ou bien R⁵ et R⁶ représentent H, R⁷ eprésente -COR⁹ et R⁸ représente H ou -COR⁹, ou bien R⁵ et R⁶ représentent H et R⁷ et R⁸ représentent ensemble -CO-O-CO- ou -CO-NR¹⁰-CO-, dans lesquels R⁹ représente un halogène, -OH, -NH₂, ou le reste d'un alcool, d'une amine primaire ou secondaire, ou bien est -OM, M signifiant un cation, et R¹⁰ est H ou le reste d'une amine primaire réduit au groupe NH₂, et
    b) "halogène" représente Cl, Br ou I.
  2. Matériau support selon la revendication 1, caractérisé en ce qu'il s'agit, en ce qui concerne le composant a), du tétrathiotétracène, du tétrasélénotétracène, du 2-fluoro- ou 2,3-difluorotétrasélénotétracène.
  3. Matériau support selon la revendication 1, caractérisé en ce que le substrat est constitué en verre.
  4. Matériau support selon la revendication 1, caractérisé en ce que le réseau aiguilleté est enduit d'un métal.
  5. Matériau support selon la revendication 1, caractérisé en ce qu'une couche protectrice est déposée sur le réseau aiguilleté.
  6. Matériau support selon la revendication 1, caractérisé en ce que le substrat est un polymère gonflable, dans lequel on insère partiellement le réseau aiguilleté dans la surface.
  7. Procédé de préparation d'un matériau support selon la revendication 1, en déposant sur un substrat
    a) un composé de formule I ou Ia ou leurs mélanges, et
    b) un excès d'un composé organique halogéné, qui libère un halogène par apport d'énergie, caractérisé en ce qu'on laisse réagir ensuite par apport d'énergie le composé halogéné sur le composé de formule I et/ou Ia et on élimine le composé halogéné.
  8. Procédé selon la revendication 7, caractérisé en ce qu'on utilise en plus un solvant inerte.
  9. Procédé selon la revendication 7, caractérisé en ce que le composant a) est contenu dans une quantité allant de 0,001 à 5% en poids, par rapport au composé b) et éventuellement un solvant inerte.
  10. Procédé de préparation d'un matériau support selon la revendication 7, caractérisé en ce qu'il s'agit, en ce qui concerne le composé halogéné, d'un composé organique halogéné, saturé ou insaturé, aliphatique, cycloaliphatique, aliphatique-hétérocylique, aromatique ou hétéroaromatique.
  11. Procédé de préparation d'un matériau support selon la revendication 7, caractérisé en ce que le composé organique est chloré, bromé, et/ou iodé.
  12. Procédé de préparation d'un matériau support selon la revendication 7, caractérisé en ce qu'il s'agit, en ce qui concerne le composé halogéné, d'un alcane en C₃-C₅, d'un alcène en C₃-C₅ perchloré ou de composés organiques ayant des groupes trichlorométhyle.
  13. Procédé de préparation d'un matériau support selon la revendication 7, caractérisé en ce qu'il s'agit, en ce qui concerne le composé organique halogéné, des composés suivants : tétrabromométhane, bromoforme, trichlorobromométhane, hexachloropropène, hexachlorocyclopropane, hexachlorocyclopentadiène, hexachloroéthane, octachloropropane, n-octa-chlorobutane, n-décachlorobutane, tétrabromoéthane, hexabromoéthane, tétrabromo-o-benzoquinone, 2,4,4,6-tétrabromo-2,5-cyclohexadiènone, hexabromobenzène, chloranile, hexachloroacétone, acide 1,4,5,6,7,7-hexachloro-5-norbornène-2,3-dicarboxylique, 1,2,5,6,9,10-hexabromocyclodo décane, tétra-chloroéthylène, perchlorocyclopentadiène, perchloro-butadiène, dichloroacétaldéhyde-diéthylacétal, 1,4-dichloro-2-butène, 1,3-dichloro-2-butène, 3,4-dichloro-1-butène, tétrachlorocyclopropène, 1,3-dichloracétone, 1,4-bis-(tri-chlorométhyl)-benzène, 1,3-dibromopropane, 1,6-di-bromohexane, 3-chloropropionate d'éthyle, 2-chloropropionate de méthyle, 2-chloroacrylonitrile, trichloracétate d'éthyle, tris-(trichlorométhyl)-triazine, 1,2,3-trichloropropane, 1,1,2-trichloréthane, chloroformiate de butyle, trichloro-éthylène, anhydride de l'acide 2,3-dichloromaléïque, 1,12-dibromododécane, α,α′-dibromo-o-xylène, α,α′-dichloro-p-xylène, chlorure ou bromure de phénacyle, 1,10-dibromodécane, α,α′-dichloro-p-xylène, α,α′-dibromo-m-xylène, iodoacétonitrile, 2,3-dichloro-5,6-dicyanobenzoquinone, 2,3-dichloropropionate de méthyle, 1-bromo-2-chloroéthane, 1-bromo-2-chloropropane, chloroformiate de 2-bromoéthyle, iodo-acétate d'éthyle, N-chloro, N-bromo ou N-iodo-succinimide ou -phtalimide ou leurs mélanges.
  14. Procédé selon la revendication 7, caractérisé en ce qu'on chauffe la composition après le dépôt à une température comprise entre 50 et 250°C.
  15. Film de polymère, caractérisé en ce qu'on insère dans une surface du film un réseau aiguilleté d'un complexe TC (donneur) (halogène)x, dans lequel x est tel que 0,3 < x < 0,9, et
    a) "donneur" représente un composé de formule I ou Ia ou leurs mélanges,
    Figure imgb0020
     dans lesquelles X repésente S, Se ou Te, R¹, R², R³ et R⁴ signifient, indépendamment l'un de l'autre, un atome d'hydrogène ou Cl ou bien R¹ et R² ainsi que R³ et R⁴, représente chacun ensemble,
    Figure imgb0021
     ou R¹, R², R³ et R⁴ représentent chacun le phénylthio, le 4-méthyl- ou 4-méthoxyphénylthio ou le 4-pyridylthio, R⁵, R⁶, R⁷ et R⁸ signifient, indépendamment l'un de l'autre, H ou F, R⁵ représente CH₃ et R⁶, R⁷ et R⁸ représentent H ou bien R⁵, R⁶, R⁷ et R⁸ représentent CH₃, R⁵ et R⁶ représentent CH₃ ou Cl et R⁷ et R⁸ représentent H ou bien R⁵ et R⁶ représentent H, R⁷ représente -COR⁹ et R⁸ représente H ou -COR⁹, ou bien R⁵ et R⁶ représentent H et R⁷ et R⁸ représentent ensemble -CO-O-CO- ou -CO-NR¹⁰-CO-, dans lesquels R⁹ représente un halogène, -OH, -NH₂, ou le reste d'un alcool, d'une amine primaire ou secondaire, ou bien est -OM, M signifiant un cation, et R¹⁰ est H ou le reste d'une amine primaire réduit au groupe NH₂, et
    b) "halogène" représente Cl, Br ou I.
  16. Film de polymère selon la revendication 15, caractérisé en ce que le réseau aiguilleté est enduit avec un métal.
  17. Procédé de préparation d'un film de polymère selon la revendication 15, caractérisé en ce qu'on enduit le matériau support selon la revendication 1 avec un film en polymère et ensuite on sépare le film de polymère du substrat.
  18. Utilisation d'un matériau support selon la revendication 1 ou d'un film de polymère selon la revendication 15 en tant que conducteur électrique.
EP19890810718 1988-09-30 1989-09-21 Support électriquement conducteur et films polymères et leur procédé de fabrication Expired - Lifetime EP0362141B1 (fr)

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CH364788 1988-09-30

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EP0362141A3 EP0362141A3 (en) 1990-11-07
EP0362141B1 true EP0362141B1 (fr) 1995-11-15

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DE59202440D1 (de) * 1991-07-02 1995-07-13 Ciba Geigy Ag Verfahren zur Herstellung von elektrisch leitenden Schichten.
JP2002357843A (ja) * 2001-06-04 2002-12-13 Matsushita Electric Ind Co Ltd 液晶表示パネル
CN114536899B (zh) * 2022-01-13 2024-03-15 深圳市亿铭粤科技有限公司 多层纹理装饰结构制作方法及多层纹理装饰结构

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US4384025A (en) * 1975-09-19 1983-05-17 Ciba-Geigy Corporation Metallically conducting 5,6,11,12-tetrathiotetracene-iodine charge-transfer complex and processes for the production thereof
EP0285564A1 (fr) * 1987-04-03 1988-10-05 Ciba-Geigy Ag Polymères et matériaux à mouler antistatiques et conducteurs

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DE58909496D1 (de) 1995-12-21
JPH02136233A (ja) 1990-05-24
EP0362141A2 (fr) 1990-04-04
US5096780A (en) 1992-03-17
EP0362141A3 (en) 1990-11-07

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