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EP0362141B1 - Electrically conductive support and polymer films, and process for manufacturing the same - Google Patents

Electrically conductive support and polymer films, and process for manufacturing the same 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)
French (fr)
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EP0362141A2 (en
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)

Description

Die Erfindung betrifft ein Trägermaterial aus einem Substrat, das -auf mindestens einer Oberfläche mit einem Nadelnetzwerk aus Kristallnadeln eines Charge-Transfer-Komplexes (CT-Komplex) aus einem Tetrathio-, Tetraseleno- oder Tetratelluronaphthalin oder -tetracen und einem Halogen beschichtet ist; Polymerfilme, in denen ein solches Nadelnetzwerk in einer Oberfläche eingebettet ist; Verfahren zur Herstellung dieser Materialien und deren Verwendung als elektrische Leiter.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.

J.C. Stark et al. beschreiben in Organometallics, 3, 5. 732 - 735 (1984), peri-dichalkogenierte Polyacene, von denen bestimmte Salze eine hohe elektrische Leitfähigkeit besitzen. In US-PS 4 384 025, US-PS 4 522 754, DE-OS 3 510 092, DE-OS 3 635 124 und EP-A-0 153 905 sind solche Halogenide beschrieben. Diese Halogenide weisen im allgemeinen einen Schmelzpunkt über 300°C auf. Ferner sind sie in organischen Lösungsmitteln praktisch unlöslich. Wegen dieser Eigenschaften können die Halogenide nur in Form von Pulvern in Polymere eingearbeitet oder auf Substrate aufgebracht werden. Solche Polymerzusammensetzungen bzw. beschichteten Substrate weisen nur eine geringe elektrische Leitfähigkeit auf, da die leitenden Teilchen in der Polymermatrix isoliert sind bzw. die Schicht auf einem Substrat viele Kontaktstellen aufweist, die den Widerstand erhöhen.J.C. Stark et al. describe in Organometallics, 3, 5. 732-735 (1984), peri-dichalogenated polyacenes, of which certain salts have a high electrical conductivity. Such halides are described in US Pat. No. 4,384,025, US Pat. No. 4,522,754, DE-OS 3,510,092, DE-OS 3,635,124 and EP-A-0 153 905. These halides generally have a melting point above 300 ° C. Furthermore, they are practically insoluble in organic solvents. Because of these properties, the halides can only be incorporated into polymers in the form of powders or applied to substrates. Such polymer compositions or coated substrates have only a low electrical conductivity, since the conductive particles in the polymer matrix are insulated or the layer on a substrate has many contact points which increase the resistance.

Ein Gegenstand der Erfindung ist ein Trägermaterial, das auf mindestens einer der Oberflächen eines Substrats mit einem Nadelnetzwerk eines CT-Komplexes (Donor)(Halogen)x, worin x 0,3 < x < 0,9 ist, und

  • a) Donor eine Verbindung der Formel I oder Ia oder Mischungen davon darstellt,
    Figure imgb0001
     worin X für S, Se oder Te steht, R¹, R², R³ und R⁴ unabhängig voneinander ein Wasserstoffatom oder Cl bedeuten oder R¹ und R² sowie R³ und R⁴ zusammen je
    Figure imgb0002
     oder R¹, R², R³ und R⁴ je Phenylthio, 4-Methyl- oder 4-Methoxyphenylthio oder 4-Pyridylthio darstellen, R⁵, R⁶ , R⁷ und R⁸ unabhängig voneinander H oder F bedeuten, R⁵ für CH₃ und R⁶ , R⁷ und R⁸ für H oder R⁵, R⁶ , R⁷ und R⁸ für CH₃ stehen, R⁵ und R⁶ für CH₃ oder Cl und R⁷ und R⁸ für H stehen oder R⁵ und R⁶ für H, R⁷ für -COR⁹ und R⁸ für H oder -COR⁹, oder R⁵ und R⁶ für H und R⁷ und R⁸ zusammen für -CO-O-CO oder -CO-NR¹⁰-CO- stehen, worin R⁹ Halogen, -OH, -NH₂, oder den Rest eines Alkohols, primären oder sekundären Amins darstellt, oder -OM ist, wobei M ein Kation bedeutet, und R¹⁰ H oder der um die NH₂-Gruppe verminderte Rest eines primären Amins ist, und
  • b) Halogen für Cl, Br oder I steht, beschichtet ist.
An object of the invention is a carrier material which on at least one of the surfaces of a substrate with a needle network of a CT complex (donor) (halogen) x , wherein x is 0.3 <x <0.9, and
  • a) donor represents a compound of formula I or Ia or mixtures thereof,
    Figure imgb0001
     where X is S, Se or Te, R¹, R², R³ and R⁴ independently represent a hydrogen atom or Cl or R¹ and R² and R³ and R⁴ together each
    Figure imgb0002
     or R¹, R², R³ and R⁴ each represent phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R⁵, R⁶, R⁷ and R⁸ independently of one another are H or F, R⁵ for CH₃ and R⁶, R⁷ and R⁸ for H or R⁵, R⁶, R⁷ and R⁸ are CH₃, R⁵ and R⁶ are CH₃ or Cl and R⁷ and R⁸ are H or R⁵ and R⁶ are H, R⁷ for -COR⁹ and R⁸ for H or -COR⁹, or R⁵ and R⁶ for H and R⁷ and R⁸ together represent -CO-O-CO or -CO-NR¹⁰-CO-, in which R⁹ represents halogen, -OH, -NH₂, or the remainder of an alcohol, primary or secondary amine, or is -OM, where M is a cation, and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and
  • b) halogen is Cl, Br or I, is coated.

Einige Verbindungen der Komponente a) und ihre Herstellung sind in den zuvor erwähnten Publikationen beschrieben. Bevorzugte Verbindungen der Komponente a) sind Tetrathiotetracen, Tetraselenotetracen, 2-Fluor- oder 2,3-Difluortetraselenotetracen. Bevorzugte Mischungen sind solche aus Verbindungen der Formeln I und Ia, wobei die Verbindung der Formel I besonders 2,3,6,7-Tetrathiophenyl-tetrathionaphthalin ist. Besonders bevorzugt stellt Komponente a) Tetraselenotetracen dar.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.

Die neuen Verbindungen der Formeln II oder IIa

Figure imgb0003

worin R¹⁵ und R¹⁶ je Phenylthio, 4-Methyl- oder 4-Methoxyphenylthio oder 4-Pyridylthio oder worin R¹⁵ und R¹⁶ zusammen
Figure imgb0004
bedeuten, R¹¹ für -CH₃ und R¹², R¹³ und R¹⁴ für H, R¹¹ und R¹² für Cl oder CH₃ und R¹³ und R¹⁴ für H stehen oder R¹¹, R¹², R¹³ und R¹⁴ für -CH₃ oder F stehen, und X S, Se oder Te darstellt, können z.B. wie nachfolgend beschrieben hergestellt werden:The new compounds of formulas II or IIa
Figure imgb0003
wherein R¹⁵ and R¹⁶ each phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio or wherein R¹⁵ and R¹⁶ together
Figure imgb0004
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:

a) Tetramethylierte Tetracenea) Tetramethylated tetracenes

Man setzt die bekannten Ausgangsverbindungen 4,5-Dimethylphthalsäureanhydrid und 2,3-Dimethyl-6,7-dihydroxynaphthalin in Gegenwart von B₂O₃ zu 2,3,8,9-Tetramethyl-5,12-dihydroxy-6,11-dioxo-tetracen (A) um. Diese Reaktion und die weitere Chlorierung und Reduktion zum in 5,6,11,12-Stellung tetrachlorierten Produkt sind in der DE-OS 3635124 beschrieben. Die Umsetzung mit Na₂X₂ führt zum entsprechenden tetrachalkogenierten Tetracen. In einer Variante kann das 2,3,8,9-Tetramethyl-5,5,6,11,12,12-hexachlordihydrotetracen (das bei der Chlorierung mit PCl₅/POCl₃ erhalten wird) mit 1 Val Na₂Se₂ und 2 Val Na₂Se direkt zum entsprechenden Tetraselenotetracen umgesetzt werden. Die Verbindung A kann auch mit Dimethylsulfat zum 5,12-Dimethoxyderivat alkyliert werden [vgl. Chem. Pharm. Bull. 20(4), 827 (1972)]. Die Umsetzung dieses Derivates mit P₄S₁₀ in Tetrahydrofuran, die nachfolgene Oxidation mit Br₂ und anschliessende Reduktion mit TiCl₃ führt zum 2,3,8,9-Tetramethyl-5,6,11,12-tetrathiotetracen.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. In a variant, 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)]. The implementation of this derivative with P₄S₁₀ in tetrahydrofuran, the subsequent oxidation with Br₂ and subsequent reduction with TiCl₃ leads to 2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene.

b) 2-Methyltetraceneb) 2-methyltetracenes

Entsprechend der Vorschrift in Chem. Ber. 64, 1713 (1931) wird 2-Methyl-5,12,dioxo-dihydrotetracen erhalten. Die Reduktion mit Zn in alkalischer Lösung führt zum 2-Methyl-5,12-tetrahydrotetracen, das mit Chloranil zum 2-Methyltetracen dehydriert werden kann. Die Umsetzung mit S (siehe US-PS 3 723 417) ergibt das 2-Methyl-5,6,11,12-tetrathiotetracen. Man kann auch wie in a) beschrieben das 2-Methyl-5,6,11,12-tetrachlortetracen herstellen und mit Na₂X₂ umsetzen.According to the regulation in Chem. Ber. 64, 1713 (1931) 2-methyl-5,12, dioxodihydrotetracene is obtained. The reduction with Zn in alkaline solution leads to 2-methyl-5,12-tetrahydrotetracene, which can be dehydrated with chloranil to 2-methyltetracene. The reaction with S (see US Pat. No. 3,723,417) gives the 2-methyl-5,6,11,12-tetrathiotetracene. You can also as described in a) produce the 2-methyl-5,6,11,12-tetrachlorotetracene and react with Na₂X₂.

c) Tetrafluortetracenec) tetrafluorotetracenes

Gemäss der Vorschrift in Chem. Ber 31, 1159 und 1272 (1898) wird durch Kondensation von 2,3-Difluorphthalsäureanhydrid mit Bernsteinsäure und anschliessende Behandlung des Kondensationsproduktes mit Natriumethylat in Ethanol 2,3,8,9-Tetrafluor-5,12-dihydroxy-6,12-dioxo-tetracen (B) erhalten. Die weitere Umsetzung mit PCl₅ und anschliessend mit SnCl₂/CH₃COOH zum 2,3,8,9-Tetrafluor-5,6,11,12-tetrachlortetracen erfolgt analog der Vorschrift in Zhuv. Org. Khim. 15(2), 391 (1979). Die Umsetzung mit Na₂X₂ ergibt die entsprechenden 2,3,8,9-Tetrafluortetrachalkogentetracene. Die Reduktion von Verbindung B mit Al in Cyclohexanol führt zum 2,3,8,9-Tetrafluortetracen, das mit Schwefel [siehe Bull. Soc. Chim. 15, 27 (1948)] zum 2,3,8,9-Tetrafluor-5,6,11,12-tetrathiotetracen reagiert.According to the instructions in Chem. Ber 31, 1159 and 1272 (1898), 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). The reaction with Na₂X₂ gives the corresponding 2,3,8,9-tetrafluorotetrachalkogen tetracenes. The reduction of compound B with Al in cyclohexanol leads to 2,3,8,9-tetrafluorotetracene, which is mixed with sulfur [see Bull. Soc. Chim. 15, 27 (1948)] to 2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene.

d) Naphthalined) naphthalenes

Ausgehend von bekannten (siehe US-PS 3 769 276) 2,3,6,7-Tetrachlortetrachalkogennaphthalinen können durch die Umsetzung mit den Kaliumsalzen von Thiophenol, 4-Methylthiophenol, 4-Methoxythiophenol, 4-Mercaptopyridin, 1,2-Benzodithiol bzw. Pyrazin-2,3-dithiol die entsprechenden 2,3,6,7-substituierten Tetrachalkogennaphthaline erhalten werden.Starting from known (see US Pat. No. 3,769,276) 2,3,6,7-tetrachlorotetrachalkogen naphthalenes, the reaction with the potassium salts of thiophenol, 4-methylthiophenol, 4-methoxythiophenol, 4-mercaptopyridine, 1,2-benzodithiol or Pyrazine-2,3-dithiol the corresponding 2,3,6,7-substituted tetrachalkogen naphthalenes can be obtained.

e) Dimethyl- und Dichlortetracenee) Dimethyl and dichlorotetracenes

Man verfährt analog wie unter a) beschrieben, setzt aber als Ausgangsverbindungen 4,5-Dimethyl- bzw. 4,5-Dichlorphthalsäureanhydrid mit 6,7-Dihydroxynaphthalin um und chloriert mit PCl₅/POCl₃.The procedure is analogous to that described under a), but the starting compounds are 4,5-dimethyl- or 4,5-dichlorophthalic anhydride with 6,7-dihydroxynaphthalene and chlorinated with PCl₅ / POCl₃.

In den Formeln I, Ia, II und IIa stellt X bevorzugt S oder Se dar. R⁹ ist als Halogen besonders Chlor. In dem Rest -OM kann M ein Metall- oder Ammoniumkation sein. Als Metallkation kommen insbesondere solche der Alkali- und Erdalkalimetalle in Frage, z.B. Li⊕, Na⊕, K⊕, Mg2⊕, Ca2⊕, Sr2⊕ und Ba2⊕. Ferner sind Zn2⊕ und Cd2⊕ geeignet. Als Ammoniumkationen kommen z.B. NH₄⊕ und primäres, sekundäres, tertiäres oder quaternäres Ammonium in Frage, udie vorzugsweise C₁-C₁₂-Alkyl-, Cyclohexyl-, Cyclopentyl-, Phenyl- oder Benzylgruppen enthalten können. Die Ammoniumkationen können sich auch von 5- oder 6-gliedrigen heterocyclischen Aminen ableiten, z.B. Piperidin, Pyrrol und Morpholin.In the formulas I, Ia, II and IIa, X preferably represents S or Se. R⁹ is especially chlorine as halogen. In the remainder -OM, 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. Examples of 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.

Bei R⁹ als Rest eines Alkoholes handelt es sich bevorzugt um C₁-C₆-Alkoxy oder C₂-C₆-Hydroxyalkoxy, Benzyloxy, Phenoxy, Cyclopentyloxy oder Cyclohexyloxy.R⁹ as the residue of an alcohol is preferably C₁-C₆-alkoxy or C₂-C₆-hydroxyalkoxy, benzyloxy, phenoxy, cyclopentyloxy or cyclohexyloxy.

R⁹ als Rest eines primären oder sekundären Amins leitet sich bevorzugt von Alkylaminen mit einer bzw. 2 C₁-C₆-Alkylgruppen ab.
R¹⁰ stellt bevorzugt H, C₁-C₁₈-Alkyl, Phenyl oder Benzyl dar.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 enthält als Alkyl bevorzugt 1 bis 12 und besonders 1 bis 6 C-Atome. Beispiele für Alkyl, das linear oder verzweigt sein kann, sind: Methyl, Ethyl, n- oder i-Propyl, n-, i- oder t-Butyl, Pentyl, Hexyl, 2-Ethylhexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl und Dodecyl. Beispiele für Alkoxy und Hydroxyalkoxy sind: Methoxy, Ethoxy, Propoxy, Butoxy, Pentoxy, Hexoxy, β-Hydroxyetboxy, γ-Hydroxypropoxy, δ-Hydroxybutoxy und ω-Hydroxyhexoxy.R¹⁰ preferably contains 1 to 12 and especially 1 to 6 carbon atoms as alkyl. Examples of 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. Examples of alkoxy and hydroxyalkoxy are: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, β-hydroxyetboxy, γ-hydroxypropoxy, δ-hydroxybutoxy and ω-hydroxyhexoxy.

Das Halogen wird mit einer halogenhaltigen organischen Verbindung eingeführt, welche unter Zufuhr von Energie Halogen abspaltet und mit einer Verbindung der Formel I und/oder Ia (Donor) einen Charge-Transferkomplex (Donor)(Halogen)x bildet, wobei 0,3 ≦x< 0,9 ist. Bevorzugt ist 0,3 ≦x< 0,8 und besonders x gleich 0,5 für Halogen gleich Cl und Br und x gleich 0,76 für Halogen gleich I. Bei der Energie kann es sich z.B. um thermische Energie oder Strahlungsenergie handeln.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. Preferably 0.3 ≦ x <0.8 and especially x equals 0.5 for halogen equal to Cl and Br and x equals 0.76 for halogen equal to I. The energy can be, for example, thermal energy or radiation energy.

Thermische Energie bedeutet zum Beispiel eine Temperatur von Raumtemperatur bis 300°C, insbesondere 50 bis 250°C, und ganz besonders 80 - 170°C.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.

Bei der halogen-, besonders Cl-, Br- oder I-haltigen organischen Verbindung kann es sich um eine halogenierte, gesättigte oder ungesättigte, aliphatische, cycloaliphatische, aliphatisch-heterocyclische, aromatische oder heteroaromatische organische Verbindung handeln, die durch -CN, HO-, =O, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, -CO-C₁-C₄-Alkyl, -COOC₁-C₄-Alkyl substituiert sein kann. Die Halogenverbindungen können einzeln oder in Gemischen eingesetzt werden. Die organische Verbindung ist bevorzugt chloriert, bromiert und/oder iodiert. Die Verbindungen können einfach halogeniert sein, wie z.B. N-bromierte oder N-chlorierte Dicarbonsäureimide. C-halogenierte Verbindungen weisen zweckmässig einen höheren Halogenierungsgrad auf; bevorzugt sind diese Verbindungen zu mindestens 80 % C-halogeniert, besonders C-bromiert und/oder C-chloriert. Verbindungen, deren Halogenatome durch elektronenziehende Gruppen aktiviert sind, sind besonders günstig. Besonders bevorzugt handelt es sich bei der balogenhaltigen Verbindung um perchlorierte C₃-C₅-Alkane, C₃-C₅-Alkene oder organische Verbindungen mit Trichlormethylgruppen.The halogen-containing, especially Cl-, Br- or I-containing organic compound can be a halogenated, saturated or unsaturated, aliphatic, cycloaliphatic, aliphatic-heterocyclic, aromatic or heteroaromatic organic compound which is represented by -CN, HO- , = O, C₁-C₄-alkyl, C₁-C₄-alkoxy, -CO-C₁-C₄-alkyl, -COOC₁-C₄-alkyl can be substituted. 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. N-brominated or N-chlorinated dicarboximides. 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.

Beispiele für halogenierte organische Verbindungen sind Tetrabrommethan, Bromoform, Trichlorbrommethan, Hexachlorpropen, Hexachlorcyclopropan, Hexachlorcyclopentadien, Hexachlorethan, Octachlorpropan, n-Octachlorbutan, n-Decachlorbutan, Tetrabromethan, Hexabromethan, Tetrabrom-o-benzochinon, 2,4,4,6-Tetrabrom-2,5-cyclohexadienon, Hexabrombenzol, Chloranil, Hexachloraceton, 1,4,5,6,7,7-Hexachlor-5-norbornen-2,3-dicarbonsäure, 1,2,5,6,9,10-Hexabromcyclododecan, Tetrachlorethylen, Perchlorcyclopentadien, Perchlorbutadien, Dichloracetaldehyd-diethylacetal, 1,4-Dichlor-2-buten, 1,3-Dichlor-2-buten, 3,4-Dichlor-1-buten, Tetrachlorcyclopropen, 1,3-Dichloraceton, 1,4-Bis(trichlormethyl)-benzol, 1,3-Dibrompropan, 1,6-Dibromhexan, 3-Chlorpropionsäureethylester, 2-Chlorpropionsäuremethylester, 2-Chloracrylnitril, Trichloressigsäureethylester, Tris-(trichlormethyl)-triazin, 1,2,3-Trichlorpropan, 1,1,2-Trichlorethan, Chlorameisensäurebutylester, Trichlorethylen, 2,3-Dichlormaleinsäureanhydrid, 1,12-Dibromdodecan, α,α′-Dibrom-p-xylol, α,α′-Dichlor-o-xylol, Phenacylchlorid oder -bromid, 1,10-Dibromdecan, α,α′-Dichlor-p-xylol, α,α′-Dibrom-m-xylol, Iodacetonitril, 2,3-Dichlor-5,6-dicyanobenzochinon, 2,3-Dichlorpropionsäuremethylester, 1-Brom-2-chlorethan, 1-Brom-2-chlorpropan, Chlorameisensäure-2-bromethylester, Iodessigsäureethylester, N-Chlor-, N-Brom- oder N-Iodsuccinimid oder -phthalsäureimid, oder Mischungen aus zwei oder mehreren dieser halogenierten Verbindungen.Examples of 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, Tetrachlorethylene, perchlorocyclopentadiene, perchlorobutadiene, dichloroacetaldehyde diethylacetal, 1,4-dichloro-2-butene, 1,3-dichloro-2-butene, 3,4-dichloro-1-butene, tetrachlorocyclopropene, 1,3-dichloroacetone, 1, 4-bis (trichloromethyl) benzene, 1,3-dibromopropane, 1,6-dibromohexane, 3-chloropropionic acid ethyl ester, 2-chloropropionic acid methyl ester, 2-chloroacrylonitrile, trichloroacetic acid ethyl ester, tris (trichloromethyl) triazine, 1,2,3-trichloropropane , 1,1,2-trichloroethane, butyl chloroformate, trichlorethylene, 2,3-dichloromaleic anhydride d, 1,12-dibromododecane, α, α′-dibromo-p-xylene, α, α′-dichloro-o-xylene, phenacyl chloride or bromide, 1,10-dibromodecane, α, α′-dichloro-p- xylene, α, α′-dibromo-m-xylene, iodoacetonitrile, 2,3-dichloro-5,6-dicyanobenzoquinone, methyl 2,3-dichloropropionate, 1-bromo-2-chloroethane, 1-bromo-2-chloropropane, 2-bromoethyl chloroformate, ethyl iodoacetate, N-chloro, N-bromo or N-iodosuccinimide or phthalimide, or mixtures of two or more of these halogenated compounds.

Als Substrate können unterschiedliche feste Materialien Verwendung finden, z.B. Metalle, Glas, Keramik, Papier und Polymere. Bevorzugt wird Glas als Substrat verwendet. Handelt es sich bei dem Substrat um ein quellbares Polymer, so kann das Nadelnetzwerk teilweise in der Oberfläche eingebettet sein.Different solid materials can be used as 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.

Das Nadelnetzwerk kann ferner mit einem Metall beschichtet sein, z.B. einem Halbedel- oder Edelmetall. Beispiele für Metalle sind Cu, Ag, Au, Pt, Ir, Co, Ni und Cr.The needle network may also be coated with a metal, e.g. a semi-precious or precious metal. Examples of metals are Cu, Ag, Au, Pt, Ir, Co, Ni and Cr.

Auf dem Nadelnetzwerk kann eine Schutzschicht aufgebracht sein, besonders Schutzschichten aus linearen, verzweigten oder strukturell vernetzten Polymeren, z.B. Duroplaste, Thermoplaste oder Elastomere.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.

Beispiele für Polymere sind:Examples of polymers are:

  • 1. Polymere von Mono- und Diolefinen, beispielsweise Polypropylen, Polyisobutylen, Polybuten-1, Polymethylpenten-1, Polyisopren oder Polybutadien sowie Polymerisate von Cycloolefinen wie z.B. von Cyclopenten oder Norbornen; ferner Polyethylen, z.B. Polyethylen hoher Dichte (HDPE), Polyethylen niederer Dichte (LDPE), lineares Polyethylen niederer Dichte (LLDPE).1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, and polymers of cycloolefins such as, for example, cyclopentene or norbornene; also polyethylene, for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).
  • 2. Mischungen der unter 1) genannten Polymeren, z.B. Mischungen von Polypropylen mit Polyisobutylen, Polypropylen mit Polyethylen (z.B. PP/HDPE, PP/LDPE) und Mischungen verschiedener Polyethylentypen (z.B. LDPE/HDPE).2. Mixtures of the polymers mentioned under 1), e.g. Mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).
  • 3. Copolymere von Mono- und Diolefinen untereinander oder mit anderen Vinylmonomeren, wie z.B. Ethylen-Propylen-Copolymere, Propylen-Buten-1-Copolymere, Propylen-Isobutylen-Copolymere, Ethylen-Buten-1-Copolymere, Ethylen-Hexen-Copolymere, Ethylen-Methylpenten-Copolymere, Ethylen-Hepten-Copolymere, Ethylen-Octen-Copolymere, Propylen-Butadien-Copolymere, Isobutylen-Isopren-Copolymere, Ethylen-Alkylacrylat-Copolymere, Ethylen-Alkylmethacrylat-Copolymere, Ethylen-Vinylacetat-Copolymere, sowie Terpolymere von Ethylen mit Propylen und einem Dien, wie Hexadien, Dicyclopentadien oder Ethylidennorbornen; ferner Mischungen solcher Copolymere untereinander und mit unter 1) genannten Polymeren, z.B. Polypropylen/Ethylen-Propylen-Copolymere, LDPE/Ethylen-Vinylacetat-Copolymere, LDPE/Ethylen-Acrylsäureester-Copolymere, LLDPE/Ethylen-Vinylacetat-Copolymere und LLDPE/Ethylen-Acrylsäureester-Copolymere.3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as e.g. Ethylene-propylene copolymers, propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene Copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers, and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with one another and with polymers mentioned under 1), e.g. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid ester copolymers, LLDPE / ethylene-vinyl acetate copolymers and LLDPE / ethylene-acrylic acid ester copolymers.
  • 4. Polystyrol, Poly-(p-methylstyrol), Poly-(α-methylstyrol).4. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).
  • 5. Copolymere von Styrol oder α-Methylstyrol mit Dienen oder Acrylderivaten, wie z.B. Styrol-Butadien, Styrol-Acrylnitril, Styrol-Alkylmethacrylat Styrol-Butadien-Alkylacrylat Styrol-Maleinsäureanhydrid, Styrol-Acrylnitril-Methylacrylat; Mischungen von hoher Schlagzähigkeit aus Styrol-Copolymeren und einem anderen Polymer, wie z.B. einem Polyacrylat, einem Dien-Polymeren oder einem Ethylen-Propylen-Dien-Terpolymeren; sowie Block-Copolymere des Styrols, wie z.B. Styrol-Butadien-Styrol, Styrol-Isopren-Styrol, Styrol-Ethylen/Butylen-Styrol, Styrol-Ethylen/Propylen-Styrol oder Styrol-4-Vinylpyridin-Styrol.5. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, e.g. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate styrene-butadiene-alkyl acrylate styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength from styrene copolymers and another polymer, e.g. a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, e.g. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene, styrene-ethylene / propylene-styrene or styrene-4-vinylpyridine-styrene.
  • 6. Pfropfcopolymere von Styrol oder α-Methylstyrol, wie z.B. Styrol auf Polybutadien, Styrol auf Polybutadien-Styrol- oder Polybutadien-Acrylnitril-Copolymere, Styrol und Acrylnitril (bzw. Methacrylnitril) auf Polybutadien; Styrol, Acrylnitril und Methylmethacrylat auf Polybutadien; Styrol und Maleinsäureanhydrid auf Polybutadien; Styrol, Acrylnitril und Maleinsäureanhydrid oder Maleinsäureimid auf Polybutadien; Styrol und Maleinsäureimid auf Polybutadien, Styrol und Alkylacrylate bzw. Alkylmethacrylate auf Polybutadien, Styrol und Acrylnitril auf Ethylen-Propylen-Dien-Terpolymeren, Styrol und Acrylnitril auf Polyalkylacrylaten oder Polyalkylmethacrylaten, Styrol und Acrylnitril auf Acrylat-Butadien-Copolymeren, sowie deren Mischungen mit den unter 5) genannten Copolymeren, wie sie z.B. als sogenannte ABS-, MBS-, ASA- oder AES-Polymere bekannt sind.6. graft copolymers of styrene or α-methylstyrene, such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and Maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the 5 below ) mentioned copolymers, as are known, for example, as so-called ABS, MBS, ASA or AES polymers.
  • 7. Halogenhaltige Polymere, wie z.B. Polychloropren, Chlorkautschuk, chloriertes oder chlorsulfoniertes Polyethylen, Epichlorhydrinhomo- und -copolymere, insbesondere Polymere aus halogenhaltigen Vinylverbindungen, wie z.B. Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylfluorid, Polyvinylidenfluorid; sowie deren Copolymere, wie Vinylchlorid-Vinylidenchlorid, Vinylchlorid-Vinylacetat oder Vinylidenchlorid-Vinylacetat.7. Halogen-containing polymers such as e.g. Polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers from halogen-containing vinyl compounds, such as e.g. Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
  • 8. Polymere, die sich von Derivaten α,β-ungesättigter Säuren ableiten, wie Polyacrylate, Polymethacrylate und Polyacrylnitrile.8. Polymers derived from derivatives of α, β-unsaturated acids, such as polyacrylates, polymethacrylates and polyacrylonitriles.
  • 9. Copolymere der unter 8) genannten Monomeren untereinander oder mit anderen ungesättigten Monomeren, wie z.B. Acrylnitril-Butadien-Copolymere, Acrylnitril-Alkylacrylat-Copolymere, Acrylnitril-Alkoxyalkylacrylat-Copolymere, Acrylnitril-Vinylhalogenid-Copolymere, Acrylnitril-Alkylmethacrylat-Butadien-Terpolymere oder Alkylmethacrylat-4-Vinylpyridin-Copolymere.9. Copolymers of the monomers mentioned under 8) with one another or with other unsaturated monomers, such as e.g. Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers, acrylonitrile-alkyl methacrylate-butadiene terpolymers or alkyl methacrylate-4-vinylpyridine copolymers.
  • 10. Polymere, die sich von Acylderivaten oder Acetalen ungesättigter Alkohole ableiten, wie Polyvinylacetat, -stearat, -benzoat, -maleat, Polyvinylbutyral, Polyallylphthalat; sowie deren Copolymere mit in Punkt 1 genannten Olefinen.10. Polymers derived from acyl derivatives or acetals of unsaturated alcohols, such as polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate; and their copolymers with olefins mentioned in point 1.
  • 11. Homo- und Copolymere von cyclischen Ethern, wie Polyalkylenglykole, Polyethylenoxyd, Polypropylenoxyd oder Polybutylenglykol.11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or polybutylene glycol.
  • 12. Polyacetale, wie Polyoxymethylen, sowie solche Polyoxymethylene, die Comonomere, wie z.B. Ethylenoxid, enthalten; Polyacetale, die mit termoplastischen Polyurethanen, Acrylaten oder MBS modifiziert sind.12. Polyacetals, such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, such as, for example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • 13. Polyphenylenoxide und -sulfide und deren Mischungen mit Styrolpolymeren.13. Polyphenylene oxides and sulfides and their mixtures with styrene polymers.
  • 14. Polyurethane, die sich von Polyethern, Polyestern und Polybutadienen mit endständigen Hydroxylgruppen einerseits und aliphatischen oder aromatischen Polyisocyanaten andererseits ableiten, sowie deren Vorprodukte.14. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their precursors.
  • 15. Polyharnstoffe, Polyimide und Polybenzimidazole. Unter den Polyimiden sind besonders lösliche Polyimide bevorzugt wie sie z.B. in DE-AS 1962588, EP-A-132221, EP-A-134752, EP-A-162017, EP-A-181837 und EP-A-182745 beschrieben sind.15. Polyureas, polyimides and polybenzimidazoles. Among the polyimides, particularly soluble polyimides are preferred, such as those e.g. in DE-AS 1962588, EP-A-132221, EP-A-134752, EP-A-162017, EP-A-181837 and EP-A-182745.
  • 16. Polycarbonate, Polyester, z.B. Polyalkylenterephthalate, und Polyestercarbonate.16. Polycarbonates, polyester, e.g. Polyalkylene terephthalates, and polyester carbonates.
  • 17. Polysulfone, Polyethersulfone und Polyetherketone.17. Polysulfones, polyether sulfones and polyether ketones.
  • 18. Polyvinylcarbazol.18. Polyvinyl carbazole.
  • 19. Vernetzte Acrylharze, die sich von substituierten Acrylsäureestern ableiten, wie z B. von Epoxyacrylaten, Urethan-acrylaten oder Polyester-acrylaten, z.B. Ester von Polyolen wie Glykolen, Trimethylolpropan, Pentaerythrit oder Polyepoxiden.19. Crosslinked acrylic resins derived from substituted acrylic esters, such as epoxy acrylates, urethane acrylates or polyester acrylates, e.g. Esters of polyols such as glycols, trimethylolpropane, pentaerythritol or polyepoxides.
  • 20. Vernetzte Epoxidharze, die sich von Polyepoxiden ableiten, z.B. von Bis-glycidylethern oder von cycloaliphatischen Diepoxiden. Sie können z B. mit Anhydriden, thermisch unter Verwendung von Härtungsbeschleunigern oder durch Einwirkung von UV-Strahlung vernetzt sein.20. Crosslinked epoxy resins derived from polyepoxides, e.g. of bis-glycidyl ethers or of cycloaliphatic diepoxides. For example, they can be crosslinked with anhydrides, thermally using hardening accelerators or by the action of UV radiation.
  • 21. Polymerhomolog chemisch abgewandelte Derivate von Cellulose, wie Celluloseacetate, -propionate und -butyrate, bzw. die Celluloseether, wie Methylcellulose.21. Polymer homologue of chemically modified derivatives of cellulose, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose.
  • 22. Mischungen (Polyblends) der vorgenannten Polymeren, wie z.B. PP/EPDM, PVC/EVA, PVC/ABS, PVC/MBS/ PC/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/thermoplastisches PUR, PC/thermoplastisches PUR, POM/Acrylat, POM/MBS, PPO/HIPS.22. Mixtures (polyblends) of the aforementioned polymers, such as e.g. PP / EPDM, PVC / EVA, PVC / ABS, PVC / MBS / PC / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS.
  • 23. Mit Schwefel vernetzte (vulkanisierte) Produkte aus Doppelbindungen enthaltenden Polymeren wie z.B. Naturkautschuk, Synthesekautschuk, Butadien- bzw. Isoprenpolymerisate oder -copolymerisate.23. Sulfur crosslinked (vulcanized) products from polymers containing double bonds, such as Natural rubber, synthetic rubber, butadiene or isoprene polymers or copolymers.
  • 24. Polyaddukte aus Epoxidverbindungen mit zwei Epoxidgruppen und Diolen, disekundären Diaminen, primären Aminen oder Dicarbonsäuren, z.B. solche aus Bisphenol-A-Diglycidylether und Bisphenol-A.24. Polyadducts of epoxy compounds with two epoxy groups and diols, secondary diamines, primary amines or dicarboxylic acids, e.g. those from bisphenol A diglycidyl ether and bisphenol A.

Eine bevorzugte Gruppe von thermoplastischen Polymeren sind Polyvinylalkohol, Polyolefine, Polystyrol, Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylidenfluorid, Polyacrylate, Polymethacrylate, Polycarbonate, aromatische Polysulfone, aromatische Polyether, aromatische Polyethersulfone, Polyimide und Polyvinylcarbazol.A preferred group of 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.

Die Polymeren können zusätzlich für die Verarbeitung und Anwendung benötigte Hilfsmittel enthalten, z.B. Weichmacher, Verlaufmittel, Formtrennmittel, Füllstoffe, Flammschutzmittel, Antioxidantien und Lichtschutzmittel, Stabilisatoren, Farbstoffe, Pigmente und Leitsalze.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.

Die Schutzschicht kann auch aus photovernetzten Polymersystemen bestehen. Photovernetzbare Systeme sind z.B. von G.E. Green et al. im J. Macro, Sci.-Revs. Macro. Chem. C21(2), 187-273 (1981-82) beschrieben.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).

Die Schutzschicht kann nach allgemein üblichen Beschichtungsverfahren für härtbare Mischungen bzw. Polymerlösungen aufgebracht werden, z.B. Streichen, Giessen oder Rakeln, gegebenenfalls Entfernung von Lösungsmitteln und anschliessende thermische und/oder strahlungsinduzierte Härtung.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.

Geeignete Lösungsmittel für die genannten Polymeren sind z.B. polare, aprotische oder protische Lösungsmittel, die alleine oder in Mischungen aus mindestens zwei Lösungsmitteln verwendet werden können. Beispiele sind: Wasser, Alkanole wie Methanol, Ethanol, Propanol, Butanol, Ethylen glykolmonomethylether, Diole wie Ethylenglykol, Propylenglykol und Diethylenglykol, Ether wie Dibutylether, Tetrahydrofuran, Dioxan, Dimethylethylenglykol, Dimethyldiethylenglykol, Diethyldiethylenglykol, Dimethyltriethylenglykol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, 1,2-Dichlorethan, 1,1,1,-Trichlorethan, 1,1,2,2-Tetrachlorethan, Carbonsäureester und Lactone wie Essigsäureethylester, Propionsäuremethylester, Benzoesäureethylester, 2-Methoxyethylacetat, γ-Butyrolacton, δ-Valerolacton und Pivalolacton, Carbonsäureamide und Lactame wie N-Methylformamid, N,N-Dimethylformamid, N,N-Diethylformamid, N,N-Dimethylacetamid, N,N-Diethylacetamid, γ-Butyrolactam, ε-Capro-lactam, N-Methylpyrrolidon, N-Acetylpyrrolidon, N-Methylcaprolactam, Tetramethylharnstoff, Hexamethylphosphorsäuretriamid, Sulfoxide wie Dimethylsulfoxid, Sulfone wie Dimethylsulfon, Diethylsulfon, Trimethylensulfon, Tetramethylensulfon, N-Methylpyrrolidin, N-Methylpiperidin, N-Methylmorpholin, substituierte Benzole wie Benzonitril, Chlorbenzol, o-Dichlorbenzol, 1,2,4-Trichlorbenzol, Nitrobenzol, Toluol und Xylol.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 acetate, γ-butyrolactone, δ-valerolactone and pivalolactone, carboxamides and lactams such as N-methylformamide, N, N, dimethylformamide, Diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, γ-butyrolactam, ε-capro-lactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam, tetramethylurea, hexamethylphosphoric acid triamide, sulfoxides, such as dimone sulfonethyl sulfonate, Trimethylene sulfone, tetramethylene sulfone, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine , substituted benzenes such as benzonitrile, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene and xylene.

Für die Herstellung des Trägermaterials bereitet man eine Zusammensetzung, enthaltend

  • a) eine Verbindung der Formel I oder Ia oder Mischungen davon,
    Figure imgb0005
     worin X für S, Se oder Te steht, R¹, R², R³ und R⁴ unabhängig voneinander ein Wasserstoffatom oder Cl bedeuten oder R¹ und R² sowie R³ und R⁴ zusammen je
    Figure imgb0006
     oder R¹, R², R³ und R⁴ je Phenylthio, 4-Methyl- oder 4-Methoxyphenylthio oder 4-Pyridylthio darstellen, R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander H oder F bedeuten, R⁵ für CH₃ und R⁶, R⁷ und R⁸ für H oder R⁵, R⁶, R⁷ und R⁸ für CH₃ stehen, R⁵ und R⁶ für CH₃ oder Cl und R⁷ und R⁶ für H stehen oder R⁵ und R⁶ für H, R⁷ für -COR⁹ und R⁸ für H oder -COR⁹, oder R⁵ und R⁶ für H und R⁷ und R⁸ zusammen für -CO-O-CO oder -CO-NR¹⁰-CO- stehen, worin R⁹ Halogen, -OH, -NH₂, oder den Rest eines Alkohols, primären oder sekundären Amins darstellt, oder -OM ist, wobei M ein Kation bedeutet, und R¹⁰ H oder der um die NH₂-Gruppe verminderte Rest eines primären Amins ist, und
  • b) eine halogenhaltige, organische Verbindung, die unter Zufuhr von Energie Halogen abspaltet.
A composition containing is prepared for the production of the carrier material
  • a) a compound of the formula I or Ia or mixtures thereof,
    Figure imgb0005
     where X is S, Se or Te, R¹, R², R³ and R⁴ independently represent a hydrogen atom or Cl or R¹ and R² and R³ and R⁴ together each
    Figure imgb0006
     or R¹, R², R³ and R⁴ each represent phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R⁵, R⁶, R⁷ and R⁸ independently of one another are H or F, R⁵ for CH₃ and R⁶, R⁷ and R⁸ for H or R⁵, R⁶, R⁷ and R⁸ for CH₃ stand for R₃ and R⁶ for CH₃ or Cl and R⁷ and R⁶ for H or R⁵ and R⁶ for H, R⁷ for -COR⁹ and R⁸ for H or -COR⁹, or R⁵ and R⁶ for H and R⁷ and R⁸ together for -CO -O-CO or -CO-NR¹⁰-CO-, in which R⁹ is halogen, -OH, -NH₂, or the rest of an alcohol, primary or secondary amine, or -OM, where M is a cation, and R¹ R is H or the residue of a primary amine reduced by the NH₂ group, and
  • b) a halogen-containing, organic compound which splits off halogen with the supply of energy.

In einer bevorzugten Ausführungsform enthält die Zusammensetzung zusätzlich ein inertes Lösungsmittel, z.B. polare, aprotische Lösungsmittel, wie sie zuvor erwähnt wurden. Bevorzugtes Lösunbsmittel ist Dimethylformamid.In a preferred embodiment the composition additionally contains an inert solvent, e.g. polar, aprotic solvents as previously mentioned. The preferred solvent is dimethylformamide.

Die Komponente a) ist bevorzugt in einer Menge von 0,001 bis 5 Gew.-%, besonders 0,01 bis 2 Gew.-% und insbesondere 0,01 bis 1 Gew.-% enthalten, bezogen auf die Komponente b) und gegebenenfalls einem inerten Lösungsmittel.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.

Die Komponente b) ist im Ueberschuss enthalten. Sie kann gleichzeitig als Lösungsmittel dienen. Der Ueberschuss bei Mitverwendung eines Lösungsmittels kann z.B. die zwanzigfache und vorzugsweise zehnfache Menge betragen, bezogen auf die Komponente a).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).

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung des erfindungsgemässen Trägermaterials, bei dem man eine erfindungsgemässe Zusammensetzung auf ein Substrat aufbringt, darauf unter Energiezufuhr die halogenhaltige Verbindung auf die Verbindung der Formel I und/oder Ia einwirken lässt und die halogenhaltige Verbindung entfernt.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.

Das Aufbringen auf das Substrat kann z.B. durch Giessen erfolgen. Die Energiezufuhr erfolgt bevorzugt durch thermische Energie, z.B. durch Erwärmen von Raumtemperatur bis 300°C bevorzugt 50 bis 250°C und besonders 80 bis 170°C, gegebenenfalls im Vakuum. In der erfindungsgemäß eingesetzten Zusammensetzung ist die Komponente b) im Ueberschuss enthalten.Application to the substrate can e.g. done by casting. 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.

Das erfindungsgemässe Trägermaterial weist eine hohe elektrische Leitfähigkeit auf und eignet sich hervorragend zur Verwendung als elektrischer Leiter. Das Trägermaterial kann mittels Metallisierung in hochleitende Materialien übergeführt werden, indem man z.B. das Trägermaterial in einem Elektrolysebad als Kathode schaltet und elektrolysiert.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.

Es ist auch möglich, vom erfindungsgemässen mit einem Polymer beschichteten Material das Polymer als Film abzulösen. Hierbei erhält man einseitig elektrisch leitende Polymerfilme, die ebenfalls als elektrische Leiter verwendet werden können.It is also possible to detach the polymer as a film from the material coated according to the invention with a polymer. This gives one-sided electrically conductive polymer films, which can also be used as electrical conductors.

Ein weiterer Gegenstand der Erfindung ist ein Polymerfilm, dadurch gekennzeichnet, dass in einer Oberfläche des Films ein Nadelnetzwerk eines CT-Komplexes (Donor)(Halogen)x, worin x 0,3 < x < 0,9 ist, und

  • a) Donor eine Verbindung der Formel I oder Ia oder Mischungen davon darstellt,
    Figure imgb0007
     oder worin X für S, Se oder Te steht, R¹, R², R³ und R⁴ unabhängig voneinander ein Wasserstoffatom oder Cl bedeuten oder R¹ und R² sowie R³ und R⁴ zusammen je
    Figure imgb0008
     oder R¹, R², R³ und R⁴ je Phenylthio, 4-Methyl- oder 4-Methoxyphenylthio oder 4-Pyridylthio darstellen, R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander H oder F bedeuten, R⁵ für CH₃ und R⁶, R⁷ und R⁸ für H oder R⁵, R⁶, R⁷ und R⁸ für CH₃ stehen, R⁵ und R⁶ für CH₃ oder Cl und R⁷ und R⁸ für H stehen oder R⁵ und R⁶ für H, R⁷ für -COR⁹ und R⁸ für H oder -COR⁹, oder R⁵ und R⁶ für H und R⁷ und R⁸ zusammen für -CO-O-CO oder -CO-NR¹⁰-CO- stehen, worin R⁹ Halogen, -OH, -NH₂, oder den Rest eines Alkohols, primären oder sekundären Amins darstellt, oder -OM ist, wobei M ein Kation bedeutet, und R¹⁰ H oder der um die NH₂-Gruppe verminderte Rest eines primären Amins ist, und
  • b) Halogen für Cl, Br oder I steht, eingebettet ist.
Another object of the invention is a polymer film, characterized in that in a surface of the film a needle network of a CT complex (donor) (halogen) x , wherein x is 0.3 <x <0.9, and
  • a) donor represents a compound of formula I or Ia or mixtures thereof,
    Figure imgb0007
     or where X is S, Se or Te, R¹, R², R³ and R⁴ independently of one another represent a hydrogen atom or Cl or R¹ and R² and R³ and R⁴ together each
    Figure imgb0008
     or R¹, R², R³ and R⁴ each represent phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R⁵, R⁶, R⁷ and R⁸ independently of one another are H or F, R⁵ for CH₃ and R⁶, R⁷ and R⁸ for H or R⁵, R⁶, R⁷ and R⁸ are CH₃, R⁵ and R⁶ are CH₃ or Cl and R⁷ and R⁸ are H or R⁵ and R⁶ are H, R⁷ for -COR⁹ and R⁸ for H or -COR⁹, or R⁵ and R⁶ for H and R⁷ and R⁸ together represent -CO-O-CO or -CO-NR¹⁰-CO-, in which R⁹ represents halogen, -OH, -NH₂, or the remainder of an alcohol, primary or secondary amine, or is -OM, where M is a cation, and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and
  • b) halogen is Cl, Br or I, is embedded.

Als Polymere kommen die zuvor erwähnten Polymere in Frage, einschliesslich der Bevorzugungen. In einer bevorzugten Ausführungsform ist das Nadelnetzwerk mit einem Metall beschichtet.Suitable polymers are the aforementioned polymers, including the preferences. In a preferred embodiment, the needle network is coated with a metal.

Die Polymerfilme können hergestellt werden, indem man ein erfindungsgemässes Trägermaterial mit einem Polymerfilm beschichtet und darauf den Polymerfilm vom Substrat ablöst. Als Substrat ist besonders Glas geeignet.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.

Die erfindungsgemässen Polymerfilme können zu mehrlagigen Schichten mit mehreren elektrisch leitenden Ebenen laminiert werden.The polymer films according to the invention can be laminated to multilayer layers with several electrically conductive layers.

Mit photovernetzbaren Polymeren beschichtete erfindungsgemässe Trägermaterialien können auch in bekannter Weise unter einer Bildmaske bestrahlt und danach entwickelt werden, wobei in den entwickelten Bereichen die gebildeten CT-Komplexe gegebenenfalls mechanisch, z.B. mittels Abwischen, entfernt werden. Auf diese Weise können Leiterstrukturen erzeugt werden.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.

Ein bevorzugter Anwendungsbereich ist neben der Herstellung von antistatischen und elektrisch leitenden Beschichtungen und Polymerfilmen für die elektrostatische Abschirmung die Verwendung als Elektroden, die je nach verwendetem Polymer transparent sein können.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.

Die erfindungsgemässen, einen CT-Komplex enthaltenden Zusammensetzungen und Polymerfilme zeichnen sich durch eine hohe chemische Stabilität und Temperaturbeständigkeit und eine geringe Migration der CT-Komplexe aus. Ferner werden überraschend hohe Leitfähigkeiten erzielt, die bis zu 25 % der Leitfähigkeit der reinen CT-Komplexe betragen können. Die CT-Komplexe bilden unter den Herstellungsbedingungen überraschend ein Netzwerk (Nadelfilz) aus elektrisch leitenden Kristallnadeln.The 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.

Die nachfolgenden Beispiele erläutern die Erfindungen näher. Der spezifische Widerstand wird nach der Vierpunktmethode bestimmt.

  • Beispiel 1 : 1,6 mg Tetraselenotetracen werden in 10 ml D m/l bei 120°C gelöst. Dann gibt man 3,5 µl Perchlorpropen zu und giesst die Lösung auf eine vorgeheizte Glasplatte. Nach Abdampfen des Lösungsmittels bei Temperaturen zwischen 90 - 130°C verbleibt ein transparentes Nadelnetzwerk aus elektrisch leitenden Kristalliten. Der spezifische Widerstand beträgt 0,4 Ωcm.
  • Beispiel 2: Das Trägermaterial gemäss Beispiel 1 wird mit einer Lösung eines Polymers in einem Lösungsmittel überschichtet. Nach Abdampfen des Lösungsmittels und Ablösen von der Glasunterlage verbleibt ein einseitig elektrisch leitender Polymerfilm mit unveränderter Leitfähigkeit. Die Herstellungsbedingungen sind in Tabelle 1 angegeben.
    Figure imgb0009
  • Beispiel 3: Beispiel 1 wird mit einer Polyethylenterephthalatfolie anstelle der Glasunterlage wiederholt. Auch in diesem Fall wird ein transparentes Nadelnetzwerk aus elektrisch leitenden Kristalliten erhalten, das in der aufgequollenen Oberfläche der Folie gewachsen ist. Der spezifische Widerstand beträgt 3,2 Ωcm.
  • Beispiel 4: Beispiel 1 wird mit einer chrombedampften Glasunterlage wiederholt. Auch in diesem Fall wird ein Nadelnetzwerk aus elektrisch leitenden Kristalliten erhalten. Der spezifisch Widerstand des in einem Film aus Polyvinylalkohol übertragenen Nadelnetzwerks beträgt 0,4 Ωcm.
  • Beispiel 5: Ein Trägermaterial gemäss den Beispielen 1 und 3 wird als Kathode in einem handelsüblichen schwefelsauren Kupferelektrolysebad geschaltet. Auf dem Nadelnetzwerk scheidet sich Kupfer ab. Die spezifische Leitfähigkeit beträgt 0,08 Ωcm.
  • Beispiel 6: Ein Trägermaterial gemäss Beispiel 4 wird als Kathode in einem sauren Goldelektrolysebad geschaltet. Auf dem Nadelnetzwerk scheidet sich Gold ab, während der Chromträger nicht metallisiert wird. Das metallisierte Nadelnetzwerk wird mit einer 10 %igen Lösung von Polycarbonat in Methylenchlorid überschichtet. Nach Abdampfen des Lösungsmittels und Ablösen von der Unterlage verbleibt eine einseitig elektrisch leitende Polymerfolie. Ihr spezifischer Widerstand beträgt 10⁻² Ωcm, der spezifische Widerstand einer in identischer Weise hergestellten Folie ohne Vergoldung 0,4 Ωcm.
  • Beispiel 7: 1,65 mg 2-Fluortetraselenotetracen werden bei 150°C in 7,5g Nitrobenzol unter Rühren gelöst. Man versetzt die Lösung mit 2 ml Tribrommethan. Dann gibt man jeweils 1,5 ml dieser Lösung in thermostatisierte Petrischalen, die auf 130, 140, 150, 160 und 170°C thermostatisiert sind. Nach Abdampfen des Lösungsmittels verbleibt in allen Fällen ein elektrisch leitendes Nadelnetzwerk.
  • Beispiel 8: In analoger Weise werden leitende Nadelnetzwerke aus 2,3-Difluoro-tetraselenotetracen mit Tribrommethan sowie Hexachlorpropen mit Nitrobenzol als Lösungsmittel hergestellt.
  • Beispiel 9: Das Nadelnetzwerk gemäss Beispiel 7 wird mit einer Lösung von 10 g Poly(vinylcinnamat) und 0,5g Thioxanthon in 50 ml THF in 100 µm Nassfilmdicke beschichtet. Nach Abdampfen des Lösungsmittels wird der entstandene Film mit einer 5 kW Quecksilberhochdrucklampe durch eine Maske 30 s lang belichtet und mit THF entwickelt. Man erhält ein elektrisch leitendes Muster.
The following examples explain the inventions in more detail. The specific resistance is determined using the four-point method.
  • Example 1: 1.6 mg of tetraselenotetracene are dissolved in 10 ml D m / l at 120 ° C. Then add 3.5 µl perchloropropene and pour the solution onto a preheated glass plate. After evaporation of the solvent at temperatures between 90 - 130 ° C, a transparent needle network made of electrically conductive crystallites remains. The specific resistance is 0.4 Ωcm.
  • Example 2: The support material according to Example 1 is covered with a solution of a polymer in a solvent. After evaporation of the solvent and detachment from the glass base, a polymer film that is electrically conductive on one side remains with unchanged conductivity. The manufacturing conditions are given in Table 1.
    Figure imgb0009
  • Example 3: Example 1 is repeated with a polyethylene terephthalate film instead of the glass base. In this case too, a transparent needle network of electrically conductive crystallites is obtained, which has grown in the swollen surface of the film. The specific resistance is 3.2 Ωcm.
  • Example 4: Example 1 is repeated with a chromium-vapor-coated glass base. In this case too, a needle network of electrically conductive crystallites is obtained. The specific resistance of the needle network transferred in a film made of polyvinyl alcohol is 0.4 Ωcm.
  • Example 5: A support material according to Examples 1 and 3 is switched as the cathode in a commercially available sulfuric acid copper electrolysis bath. Copper deposits on the needle network. The specific conductivity is 0.08 Ωcm.
  • Example 6: A carrier material according to Example 4 is switched as the cathode in an acidic gold electrolysis bath. Gold is deposited on the needle network, while the chrome carrier is not metallized. The metallized needle network is covered with a 10% solution of polycarbonate in methylene chloride. After evaporation of the solvent and detachment from the base remains a one-sided electrically conductive polymer film. Their specific resistance is 10⁻² Ωcm, the specific resistance of a foil made in the same way without gold plating is 0.4 Ωcm.
  • Example 7: 1.65 mg of 2-fluorotetraselenotetracene are dissolved at 150 ° C. in 7.5 g of nitrobenzene with stirring. The solution is mixed with 2 ml of tribromomethane. Then 1.5 ml of this solution are placed in thermostated Petri dishes, which are thermostatted at 130, 140, 150, 160 and 170 ° C. After evaporation of the solvent, an electrically conductive needle network remains in all cases.
  • Example 8: In an analogous manner, conductive needle networks are produced from 2,3-difluorotetraselenotetracene with tribromomethane and hexachloropropene with nitrobenzene as the solvent.
  • Example 9: The needle network according to Example 7 is coated with a solution of 10 g poly (vinyl cinnamate) and 0.5 g thioxanthone in 50 ml THF in a 100 µm wet film thickness. After evaporation of the solvent, the resulting film is exposed to a 5 kW high-pressure mercury lamp through a mask for 30 s and developed with THF. An electrically conductive pattern is obtained.

Claims (18)

  1. A support material which is coated on at least one of the surfaces of a substrate with a needle network of a CT complex (donor)(halogen)x, in which 0.3 < x < 0.9, and
    a) donor is a compound of the formula I or Ia or mixtures thereof
    Figure imgb0014
     in which X is S, Se or Te, R¹, R², R³ and R⁴, independently of one another, are a hydrogen atom or Cl, or R¹ and R² and R³ and R⁴ together are each
    Figure imgb0015
     R¹, R², R³ and R⁴ are each phenylthio, 4-methyl or 4-methoxyphenylthio or 4-pyridylthio, R⁵, R⁶, R⁷ and R⁸, independently of one another, are H or F, R⁵ is CH₃, and R⁶, R⁷ and R⁸ are H, or R⁵, R⁶, R⁷ and R⁸ are CH₃, R⁵ and R⁶ are CH₃ or Cl, and R⁷ and R⁸ are H, or R⁵ and R⁶ are H, R⁷ is -COR⁹, and R⁸ is H or - COR⁹, or R⁵ and R⁶ are H, and R⁷ and R⁸ together are -CO-O-CO or -CO-NR¹⁰-CO- in which R⁹ is halogen, -OH, -NH₂, or the radical of an alcohol, primary or secondary amine, or is -OM in which M is a cation, and R¹⁰ is H or the radical of a primary amine minus the NH₂ group, and
    b) halogen is Cl, Br or I.
  2. A support material according to claim 1, wherein component a) is tetrathiotetracene, tetraselenotetracene, 2-fluoro- or 2,3-difluorotetraselenotetracene.
  3. A support material according to claim 1, wherein the substrate consists of glass.
  4. A support material according to claim 1, wherein the needle network is coated with a metal.
  5. A support material according to claim 1, wherein a protective layer has been applied to the needle network.
  6. A support material according to claim 1, wherein the substrate is a swellable polymer in which the needle network is partly embedded in the surface.
  7. A process for the preparation of a support material according to claim 1, where
    a) a compound of the formula I or Ia or mixtures thereof and
    b) an excess of a halogen-containing organic compound which eliminates halogen upon supply of energy are applied to a substrate, which comprises allowing the halogen-containing compound to act upon the compound of the formula I and/or Ia, while supplying energy, and removing the halogen-containing compound.
  8. A process according to claim 7, wherein an inert solvent is additionally used.
  9. A process according to claim 7, wherein the component a) is present in an amount of 0.001 - 5 % by weight, relative to component b) and, if appropriate, an inert solvent.
  10. A process for the preparation of a support material according to claim 7, wherein the halogen-containing compound is a halogenated, saturated or unsaturated, aliphatic, cycloaliphatic, aliphatic-heterocyclic, aromatic or heteroaromatic organic compound.
  11. A process for the preparation of a support material according to claim 7, wherein the organic compound is chlorinated, brominated and/or iodinated.
  12. A process for the preparation of a support material according to claim 7, wherein the halogen-containing compound comprises perchlorinated C₃-C₅alkanes, C₃-C₅alkenes or organic compounds which have trichloromethyl groups.
  13. A process for the preparation of a support material according to claim 7, wherein the halogen-containing organic compound is tetrabromomethane, bromoform, trichlorobromomethane, hexachloropropene, hexachlorocyclopropane, hexachlorocyclopentadiene, hexachloroethane, octachloropropane, n-octachlorobutane, n-decachlorobutane, tetrabromoethane, hexabromoethane, tetrabromo-o-benzoquinone, 2,4,4,6-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, tetrachloroethylene, perchlorocyclopentadiene, perchlorobutadiene, dichloroacetaldehyde diethyl acetal, 1,4-dichloro-2-butene, 1,3-dichloro-2-butene, 3,4-dichloro-1-butene, tetrachlorocyclopropene, 1,3-dichloroacetone, 1,4-bis(trichloromethyl)benzene, 1,3-dibromopropane, 1,6-dibromohexane, ethyl 3-chloropropionate, methyl 2-chloropropionate, 2-chloroacrylonitrile, ethyl trichloroacetate, tris(trichloromethyl)triazine, 1,2,3-trichloropropane, 1,1,2-trichloroethane, butyl chloroformate, trichloroethylene, 2,3-dichloromaleic anhydride, 1,12-dibromododecane, α,α′-dibromo-p-xylene, α,α′-dichloro-o-xylene, phenacyl chloride or phenacyl bromide, 1,10-dibromodecane, α,α′-dichloro-p-xylene,α,α′-dibromo-m-xylene, iodoacetonitrile, 2,3-dichloro-5,6-dicyanobenzoquinone, methyl 2,3-dichloropropionate, 1-bromo-2-chloroethane, 1-bromo-2-chloropropane, 2-bromoethyl chloroformate, ethyl iodoacetate, N-chloro-, N-bromo- or N-iodosuccinimide or -phthalimide, or mixtures thereof.
  14. A process according to claim 7, wherein the composition after the application is heated to 50 to 250°C.
  15. A polymer film wherein a needle network of a CT complex (donor)(halogen)x, in which 0.3 < x < 0.9 and
    a) donor is a compound of the formula I or Ia or mixtures thereof
    Figure imgb0016
     in which X is S, Se or Te, R¹, R², R³ and R⁴, independently of one another, are a hydrogen atom or Cl, or R¹ and R² and R³ and R⁴ together are each
    Figure imgb0017
     R¹, R², R³ and R⁴ are each phenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R⁵, R⁶, R⁷ and R⁸, independently of one another, are H or F, R⁵ is CH₃, and R⁶, R⁷ and R⁸ are H, or R⁵, R⁶, R⁷ and R⁸ are CH₃, R⁵ and R⁶ are CH₃ or Cl, and R⁷ and R⁸ are H, or R⁵ and R⁶ are H, R⁷ is -COR⁹, and R8 is H or -COR⁹, or R⁵ and R⁶ are H, and R⁷ and R⁸ together are -CO-O-CO or -CO-NR¹⁰-CO- in which R⁹ is halogen, -OH, -NH₂, or the radical of an alcohol, primary or secondary amine, or is -OM in which M is a cation, and R¹⁰ is H or the radical of a primary amine minus the NH₂ group, and
    b) halogen is Cl, Br or I, is embedded in one surface.
  16. A polymer film according to claim 15, wherein the needle network is coated with a metal.
  17. A process for the preparation of a polymer film according to claim 15, which comprises coating a support material according to claim 1 with a polymer film and then peeling off the polymer film from the substrate.
  18. Use of a support material according to claim 1 or of a polymer film according to claim 15 as electric conductor.
EP19890810718 1988-09-30 1989-09-21 Electrically conductive support and polymer films, and process for manufacturing the same Expired - Lifetime EP0362141B1 (en)

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