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 substrate 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 tetracene and an electron acceptor; 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 are XS, or Te , can be manufactured as described below:
• 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-6,12-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 be 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 LiO ⁇ , 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 may 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, ⁇ -hydroxyethoxy, ⁇ -hydroxypropoxy, ⁇ -hydroxybutoxy and ⁇ -hydroxyhexoxy.
• 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.
• the halogen-containing compound is particularly preferably 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, tetrabromomethane, hexabromethane, tetrabromo-2,4-tetrabromo- 2,4-hexachloro- 2,5-cyclohexadienone, hexabromobenzene, chloranil, hexachloroacetone, 1,4,5,6,7,7-hexachlor-5-norbornen-2,3-dicarboxylic acid, 1,2,5,6,9,10-hexabromocyclododecane, Tetrachlorethylene,
• Suitable electron acceptors are, for example, O2 or salts of oxidatively active cations with non-nucleophilic anions, such as halogen (F ⁇ , Cl ⁇ ), BF ⁇ 4th , SbF ⁇ 6 , AsF ⁇ 6 and PF ⁇ @ 6 .
• cations are those of transition metals or rare earth metals [Fe (III), Co (III), Ce (IV)] or non-metal cations such as NO ⁇ . Examples are NOBF4, FeCl3 or Co (PF6) 3.
• 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, Hi and Cr.
• 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
• Component b) is preferably present in excess, especially if it also serves as a solvent.
• the excess when using a solvent can e.g. amount to twenty times, preferably ten times and particularly five times, 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 preferably present in excess in the composition according to the invention.
• the heating is expediently carried out in an appropriate gas atmosphere and a solvent is also used for the compounds of the formula I and / or Ia.
• the electron acceptor is a salt of an oxidative cation
• the carrier material is expediently cleaned after the heat treatment, e.g. by washing with water.
• the carrier material according to the invention has a high electrical conductivity and is outstandingly suitable for use as an electrical conductor.
• the support material can be converted into highly conductive materials by means of metallization, for example by switching the support material in an electrolysis bath as the cathode and electrolysing it.
• 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 levels.
• Carrier 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 necessary. 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.
• the specific resistance is determined using the four-point method.
• tetraselenotetracene 1.6 mg are dissolved in 10 ml D m / l at 120 ° C. Then add 3.5 ⁇ l 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 ⁇ cm.
• the carrier 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.
• 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 ⁇ cm.
• 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 ⁇ cm.
• a carrier material according to Examples 1 and 3 is connected as a cathode in a commercially available sulfuric acid copper electrolysis bath. Copper deposits on the needle network.
• the specific conductivity is 0.08 ⁇ cm.
• 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 solution By means of and detachment from the base there remains a polymer film which is electrically conductive on one side. Their specific resistance is 10 ⁇ 2 ⁇ cm, the specific resistance of a foil made in the same way without gold plating is 0.4 ⁇ cm.
• conductive needle networks are made from 2,3-difluorotetraselenotetracene with tribromomethane and hexachloropropene with nitrobenzene as a solvent.
• 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 100 ⁇ m 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.

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

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• 1989
  • 1989-09-21 EP EP19890810718 patent/EP0362141B1/fr not_active Expired - Lifetime
  • 1989-09-21 DE DE58909496T patent/DE58909496D1/de not_active Expired - Fee Related
  • 1989-09-25 US US07/411,948 patent/US5096780A/en not_active Expired - Fee Related
  • 1989-09-29 JP JP1252522A patent/JPH02136233A/ja active Pending

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