EP0362141A2 - Electrically conductive support and polymer films, and process for manufacturing the same - Google Patents

Abstract

Electrically conductive networks of crystal needles are formed on a substrate by optionally substituted tetrathio-, tetraseleno- or tetratelluronaphthalenes or -tetracenes with electron acceptors, especially with halogen-containing organic compounds. Said needle networks can be coated electrolytically with metals, and/or be delaminated from the substrate with polymers in the form of films which are electrically conductive on one side.

Description

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.

J.C. Stark et al. describe in Organometallics, 3, pp. 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 3,510,072, 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 are insulated in the polymer matrix or the layer on a substrate has many contact points which increase the resistance.

• a) einer Verbindung der Formel I oder Ia oder Mischungen davon als Donor
  
  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
  
  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 H ein Kation bedeutet, und R¹⁰ H oder der um die NH₂-Gruppe verminderte Rest eines primären Amins ist, und
• b) einem Elektronenacceptor 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

• a) a compound of formula I or Ia or mixtures thereof as a donor
  
  wherein 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
  
  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 is -COR⁹ and R⁸ is H or -COR⁹, or R⁵ and R⁶ are H. and R⁷ and R⁸ together represent -CO-O-CO or -CO-NR¹⁰-CO-, wherein R⁹ represents halogen, -OH, -NH₂, or the rest of an alcohol, primary or secondary amine, or -OM, where H is a cation and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and
• b) an electron acceptor is coated.

worin R¹⁵ und R¹⁶ je Phenylthio, 4-Methyl- oder 4-Methoxyphenylthio oder 4-Pyridylthio oder worin R¹⁵ und R¹⁶ zusammen

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, oder Te darstellt, können z.B. wie nachfolgend beschrieben hergestellt werden: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. The new compounds of formulas II or IIa

wherein 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:

a) Tetramethylated tetracenes

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. 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 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)]. 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-methyltetracenes

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) tetrafluorotetracenes

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) naphthalenes

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 are obtained.

e) Dimethyl and dichlorotetracenes

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 the formulas I, Ia, II and IIa, X preferably represents S or Se. R⁹ is especially chlorine as halogen.

In the rest -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 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. 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-hydroxyethoxy, γ-hydroxypropoxy, δ-hydroxybutoxy and ω-hydroxyhexoxy.

The electron acceptor can be, for example, elemental halogen (Cl₂, Br₂, I₂) or preferably a halogen-containing organic compound which optionally cleaves halogen with the supply of energy and a batch with a compound of the formula I and / or Ia (donor) -Transfer complex (donor) (halogen) _x forms, where 0.3> x <0.9. Preferably 0.3> x <0.8 and especially x = 0.5 for halogen equal to Cl and Br and x equal to 0.76 for halogen equal to 1. 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-, 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. The halogen-containing compound is particularly preferably perchlorinated C₃-C₅-alkanes, C₃-C Alk-alkenes or organic compounds with trichloromethyl groups.

Examples of 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, perchlorocyclopentadiene, perchlorobutadiene, dichloroacetaldehyde diethylacetal, 1,4-dichloro-2-butene, 1,3-dichloro-2-butene, 3,4-dichloro-1-butene, tetrachlorocyclopropene, 1,3-dichloroacetone, 2, 3,5,6-tetrachloro-p-xylene, 1,4-bis (trichloromethyl) benzene, 1,3-dibromopropane, 1,6-dibromohexane, 3-chloropropionate, 3-chlorotoluene, 2-chloropropionate, 2-chloroacrylonitrile , Ethyl trichloroacetate, tris (trichloromethyl) triazine, 1,2,3-trichloropropane, 1,1,2-trichloroethane, butyl chloroformate, Trich lorethylene, 2,3-dichloromaleic anhydride, 1,12-dibromo dodecane, α, α'-dibromo-p-xylene, α, α'-dichloro-o-xylene, phenacyl chloride or bromide, 1,10-dibromo decane, α, α '-Dichloro-p-xylene, α, α'-dibromo-m-xylene, iodoacetonitrile, 2,3-dichloro-5,6-dicyanobenzoquinone, 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.

, SbF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$

, AsF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$

und PF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{@6}}$

. Beispiele für Kationen sind solche von Uebergangsmetallen oder seltenen Erdmetallen [Fe(III), Co(III), Ce(IV)] oder Nichtmetallkationen wie z.B. NO^⊖. Beispiele sind NOBF₄, FeCl₃ oder Co(PF₆)₃.Other suitable electron acceptors are, for example, O₂ or salts of oxidatively active cations with non-nucleophilic anions, such as halogen (F ^⊖ , Cl ^⊖ ), BF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{4th}}$

, SbF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$

, AsF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$

and PF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{@ 6}}$

. Examples of 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.

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.

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, Hi 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.

Examples of polymers are:

• 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene as well as polymers of cycloolefins such as cyclopentene or norbornene; also polyethylene, for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).
• 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. 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. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).
• 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. 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, and mixtures thereof with the 5 below ) called copolymers, as they are known, for example, as so-called ABS, MBS, ASA or AES polymers.
• 7. Halogen-containing polymers such as e.g. Polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers of 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. Polymers derived from derivatives of α, β-unsaturated acids, such as polyacrylates, polymethacrylates and polyacrylonitriles.
• 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. 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. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or polybutylene glycol.
• 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. Polyphenylene oxides and sulfides and their mixtures with styrene polymers.
• 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. 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. Polycarbonates, polyester, e.g. Polyalkylene terephthalates, and polyester carbonates.
• 17. Polysulfones, polyether sulfones and polyether ketones.
• 18. Polyvinyl carbazole.
• 19. Crosslinked acrylic resins derived from substituted acrylic acid esters such as epoxy acrylates, urethane acrylates or polyester acrylates, e.g. Esters of polyols such as glycols, trimethylolpropane, pentaerythritol or polyepoxides.
• 20. Crosslinked epoxy resins derived from polyepoxides, e.g. of bis-glycidyl ethers or of cycloaliphatic diepoxides. They can be crosslinked, for example, with anhydrides, thermally using hardening accelerators or by the action of UV radiation.
• 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. 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. Sulfur crosslinked (vulcanized) products from polymers containing double bonds, such as Natural rubber, synthetic rubber, butadiene or isoprene polymers or copolymers.
• 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.

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.

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.

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 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-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam, tetramethylurea, hexamethylphosphoric acid triamide, sulfoxides, such as dimethyldimethylsulfonate, sulfoxides, such as dimethyldimethylsulfonate, Tetramethylene sulfone, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, substituted benzenes such as benzonitrile, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene and xylene.

• a) eine Verbindung der Formel I oder Ia oder Mischungen davon,
  
  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
  
  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 -C0R⁹, 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 -0M 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.

Another object of the invention is a composition containing

• a) a compound of the formula I or Ia or mixtures thereof,
  
  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
  
  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 R⁸ for H or R⁵ and R⁶ for H, R⁷ for -COR⁹ and R⁸ for H or -C0R⁹, or R⁵ and R⁶ for H and R⁷ and R⁸ together for -CO -O-CO or -CO-NR¹⁰-CO-, where R⁹ is halogen, -OH, -NH₂, or the rest of an alcohol, primary or secondary amine, or -0M, where M is a cation, and R¹⁰ 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 a preferred embodiment 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, in particular 0.01 to 2% by weight and in particular 0.01 to 1% by weight, based on component b) and optionally an inert one Solvent.

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.

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 preferably present in excess in the composition according to the invention.

If the electron acceptor is a gas (e.g. O₂, halogens), 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. If 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.

It is also possible to detach the polymer as a film from the material coated with a polymer according to the invention. This gives one-sided electrically conductive polymer films, which can also be used as electrical conductors.

• a) einer Verbindung der Formel I oder Ia oder Mischungen davon als Donor
  
  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
  
  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 -C0R⁹ 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) einem Elektronenacceptor eingebettet ist.

Another object of the invention is a polymer film, characterized in that a needle network of a CT complex is formed in a surface of the film

• a) a compound of formula I or Ia or mixtures thereof as a donor
  
  wherein 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
  
  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 stand for CH₃, R⁵ and R⁶ for CH₃ or Cl and R⁷ and R⁸ for H or R⁵ and R⁶ for H, R⁷ for -COR⁹ and R⁸ for H or -C0R⁹ 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 remainder of an alcohol, primary or secondary amine, or -OM, where M is a cation, and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and
• b) an electron acceptor is embedded.

Suitable polymers are the aforementioned polymers, including the preferences. In a preferred embodiment, 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 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.

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.

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.

The following examples explain the inventions in more detail. The specific resistance is determined using the four-point method.

Example 1 :

1.6 mg 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 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. Table 1: polymer solvent Polymer concentration (w / w) Evaporation temperature (° C) Poly (bisphenol A carbonate) Methylene chloride 10% 50 Poly (vinyl alcohol) water 5% 80 Poly (bisphenol A carbonate) Methylene chloride 14% 50 Polyethylene Xylene 5% 80 Poly (imide) ¹⁾ DMF 15% 100 Poly (vinyl carbazole) Nitrobenzene 5% 120 Poly (vinyl cinnamate) THF 10% 80 ¹⁾ polyimide from benzophenonetetracarboxylic acid dianhydride, diaminodurol and 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane ( M _w = 40,000)

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 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 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 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 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 in 7.5 g of nitrobenzene at 150 ° C. 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 the solvent has evaporated, an electrically conductive needle network remains in all cases.

Example 8:

In an analogous manner, conductive needle networks are made from 2,3-difluorotetraselenotetracene with tribromomethane and hexachloropropene with nitrobenzene as a 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 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 (20)

1. Support material that is made on at least one of the surfaces of a substrate with a needle network of a CT complex a) a compound of formula I or Ia or mixtures thereof as a donor

wherein 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

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 are -C0R⁹ and R⁸ are H or -COR⁹, or R⁵ and R⁶ are H and R⁷ and R⁸ together stand for -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 -0M, where H denotes a cation, and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and b) an electron acceptor is coated. 2. Support material according to claim 1, characterized in that component a) is tetrathiotetracene, tetraselenotetracene, 2-fluoro- or 2,3-difluorotetraselenotetracene. 3. Support material according to claim 1, characterized in that the electron acceptor b) is a halogen-containing organic compound which cleaves halogen with the supply of energy. 4. Support material according to claim 3, characterized in that the halogen-containing compound is a halogenated, saturated or unsaturated, aliphatic, cycloaliphatic, aliphatic-heterocyclic, aromatic or heteroaromatic organic compound. 5. Support material according to claim 4, characterized in that the organic compound is chlorinated, brominated and / or iodinated. 6. Support material according to claim 3, characterized in that the halogen-containing compound is perchlorinated C₃-C₅ alkanes, C₃-C₅ alkenes or organic compounds with trichloromethyl groups. 7. Support material according to claim 3, characterized in that the halogen-containing organic compound is tetrabromomethane, bromoform, trichlorobromomethane, hexachloropropene, hexachlorocyclopropane, hexachlorocyclopentadiene, hexachloroethane, octachloropropane, n-octachlorobutane, n-decachlorobutane, tetrabromomethane -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, tetrachlorethylene, perchlorocyclopentadiene, perchlorobutadiene, dichloroacetaldehyde diethylacetal, 1,4-dichloro-2-butene, 1,3-dichloro-2-butene, 3,4-dichloro-1 -butene, tetrachlorocyclopropene, 1,3-dichloroacetone, 2,3,5,6-tetrachloro-p-xylene, 1,4-bis (trichloromethyl) benzene, 1,3-dibromopropane, 1,6-dibromohexane, 3- Chloropropionic acid ethyl ester, 3-chlorotoluene, 2-chloropropionic acid methyl ester, 2-chloroacrylonitrile, trichloroacetic acid ethyl ester, tris (trichloromethyl) triazine, 1,2,3-T richlorpropane, 1,1,2-trichloroethane, butyl chloroformate, trichlorethylene, 2,3-dichloromaleic anhydride, 1,12-dibromo dodecane, 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, 2,3-dichloropropionic acid methyl ester , 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. 8. Support material according to claim 1, characterized in that the substrate consists of glass. 9. Carrier material according to claim 1, characterized in that the needle network is coated with a metal. 10. Carrier material according to claim 1, characterized in that a protective layer is applied to the needle network. 11. Carrier material according to claim 1, characterized in that the substrate is a swellable polymer, in which the needle network is partially embedded in the surface. 12. Composition containing a) a compound of the formula I or Ia or mixtures thereof,

wherein 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

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 is -COR⁹ and R⁸ is H or -COR⁹, or R⁵ and R⁶ are H. and R⁷ and R⁸ together represent -CO-O-CO or -CO-NR¹⁰-CO-, wherein R⁹ represents halogen, -OH, -NH₂, or the rest of an alcohol, primary or secondary amine, or -OM, where M is a cation and R¹⁰ 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. 13. The composition according to claim 12, characterized in that it additionally contains an inert solvent. 14. The composition according to claim 13, characterized in that component a) is contained in an amount of 0.001-5% by weight, based on component b) and optionally an inert solvent. 15. A process for the production of a carrier material according to claim 1, characterized in that a composition according to claim 12 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. 16. The method according to claim 15, characterized in that the composition is heated to 50 to 250 ° C after application. 17. Polymer film, characterized in that in a surface of the film a needle network of a CT complex a) a compound of formula I or Ia or mixtures thereof as a donor

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

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, R⁵ and R⁶ for CH₃ or Cl and R⁷ and R⁸ for H or R⁵ and R⁶ for H, R⁷ for -C0R⁹ and R⁸ for H or -C0R⁹, 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 -OH, where H is a cation, and R¹⁰ is H or the residue of a primary amine reduced by the NH₂ group, and b) an electron acceptor is embedded. 18. Polymer film according to claim 17, characterized in that the needle network is coated with a metal. 19. A method for producing a polymer film according to claim 17, characterized in that a carrier material according to claim 1 is coated with a polymer film and then the polymer film is detached from the substrate. 20. Use of a carrier material according to claim 1 or a polymer film according to claim 17 as an electrical conductor.