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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
  • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
  • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints

Definitions

• the present invention relates to mixtures of conductive organic polymers and reaction products of polyfunctional organosilanes, conductive organic-inorganic hybrid materials thereof and their use for coating surfaces.
• Glass moldings and plastic moldings are made by rubbing or applying charges, e.g. Electron radiation in television picture tubes, electrostatically charged. These charges then lead to a rapid dusting of the molded parts due to dust attraction, which is undesirable in practice. There is therefore a need to protect these molded parts against electrostatic charging. This protection is e.g. achievable by coating the molded parts with an antistatic coating.
• antistatic materials are understood to mean those with surface resistances between 50 k ⁇ / D and 100 M ⁇ / D. With surface resistances ⁇ 50 k ⁇ / D one speaks of conductive materials.
• the surface resistance must be less than 3 k ⁇ / D for effective radiation shielding.
• these coatings must also have sufficient mechanical strength and adhesion.
• the layers In the case of glass as a carrier in particular, the layers must be sufficiently scratch-resistant in order to avoid damage to the coating and thus loss of the antistatic or conductive effect when cleaning the coated surfaces.
• Scratch-resistant coatings based on hydrolyzed siloxanes are known from EP-A 17 187. However, these are not compatible with preparations of polythiophene salts.
• WO 96/05606 describes coatings containing poly-3,4-ethylenedioxythiophene on screens.
• layers of SiO 2 or TiO 2 are applied to them via a sol-gel process, starting, for example, from metal alkoxides.
• Another disadvantage of this method is that conductive coatings with the required scratch resistance are only obtained if the conductive layer is provided with at least one scratch-resistant cover layer. For corresponding coatings with anti-reflective properties, the successive application of up to four different layers is necessary. This is extremely complex technically. With each additional layer, there is a growing risk that the entire layer composite has a defect.
• the object of the present invention was therefore to provide mixtures which, when applied to suitable substrates, give conductive coatings with good adhesion after removal of the solvents, with improved scratch resistance and transmission of visible light.
• the present invention therefore relates to mixtures comprising:
• polythiophenes as described in DE-OS 42 11 459, EP-A 339 340 and EP-A 440 957 are preferably used as component A). They contain polythiophene salts of the type polythiophene m + An 1 " " , in which the polythiophene cation contains polythiophene m + positively charged or uncharged units of the formula (I),
• C ⁇ -C2o-alkyl, -CH 2 -OH or C 6 -C 1 aryl groups substituted C ⁇ -C is 4 alkylene radical.
• the number of units in the polythiophene cation can be between 5 and 100.
• An TM " stands for a polyanion.
• polyanions examples include the anions of polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acids, polymaleic acids, and also anions of polymeric sulfonic acids such as polystyrene sulfonic acids and polyvinylsulfonic acids.
• polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acids, polymaleic acids
• polymeric sulfonic acids such as polystyrene sulfonic acids and polyvinylsulfonic acids.
• These polycarboxylic acids and polysulfonic acids can also be copolymers of vinyl carboxylic acids and methyl sulfonic acids with other polymerizable monomers such as acrylic acid esters and styrene.
• the average molecular weight M w of the polymeric acids from which the polyanions which can be used according to the invention are derived is 1,000 to 2,000,000, preferably 2,000 to 500,000.
• the polymeric acids or their alkali metal salts are commercially available or can be prepared by known processes, as described, for example, in Houben- Weyl: "Methods of Organic Chemistry", Volume E20, "Macromolecular Substances", Part 2, p.1141ff. are described.
• the mixtures according to the invention contain reaction products of polyfunctional organosilanes as component B).
• Polyfunctional organosilanes in the sense of the invention are those which contain at least 2, preferably at least 3, silicon atoms per molecule, each of which has 1 to 3 alkoxy or hydroxyl groups and are linked via at least one Si-C bond to a structural unit connecting two silicon atoms are.
• connecting structural units in the sense of the invention can be linear or branched C to CIO alkylene chains, C5 to CIO cycloalkylene radicals, aromatic radicals such as phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals.
• aromatic radicals such as phenyl, naphthyl or biphenyl
• the aliphatic and aromatic radicals can also contain heteroatoms such as Si, N, O, S or F.
• Chain, ring or cage-shaped siloxanes, for example silsesquioxanes, may also be mentioned as linking structural units.
• linking structural units examples include X denoting Si atoms which have 1 to 3 hydrolyzable and / or condensation-crosslinking groups and with Y corresponding Si atoms which are bonded to the linking structural unit via an alkylene chain ; n stands for a number 1 to 10, m for a number 1 to 6:
• R is an organic radical, for example alkyl, cycloalkyl, aryl or alkenyl.
• R is an organic radical, for example alkyl, cycloalkyl, aryl or alkenyl.
• polyfunctional organosilanes are compounds of the general formula (IT)
• R 3 alkyl or aryl
• R can also be hydrogen.
• R 7 can also be hydrogen.
• polyfunctional organosilanes are compounds of the general formula (V)
• polyfunctional organosilanes according to the invention are also silanols such as Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 4 and cyclo- [OSiMe ((CH 2 ) 2 Si (OH) Me 2 )] 4 , or alkoxides such as cyclo- [OSiMe ((CH 2 ) 2 Si (OEt) 2 Me)] 4 and cyclo- [OSiMe ((CH 2 ) 2 Si (OMe) Me 2 )] 4 .
• silanols such as Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 4 and cyclo- [OSiMe ((CH 2 ) 2 Si (OH) Me 2 )] 4
• alkoxides such as cyclo- [OSiMe ((CH 2 ) 2 Si (OEt) 2 Me)] 4 and cyclo- [OSiMe ((CH 2 ) 2 Si (OMe) Me 2 )]
• the mixtures according to the invention can contain, as component C), reaction products of alkoxides of the elements B, Al, Si, Sn, Ti, Zr.
• the alkoxides which can be used in the preparation of the mixtures according to the invention preferably correspond to the general formula M (OR) y , where y assumes the value 3 if M represents boron or aluminum and y has the value 4 if M is silicon, tin, titanium or zirconium is.
• Examples of alkoxides which can be added in the production of the mixtures according to the invention in order to improve the scratch resistance of coatings produced therefrom are Si (OEt), Al (O'Pr) 3 or Zr (O'Pr) 4 , Si (OEt) 4 is preferred.
• the refractive index of the conductive, organic-inorganic hybrid material produced from the mixtures according to the invention can be increased by adding titanium alkoxides, for example Ti (O ! Pr) 4 or Ti (O "Bu) 4.
• titanium alkoxides for example Ti (O ! Pr) 4 or Ti (O "Bu) 4.
• Condensation products formed, for example by reaction with the solvent, polyfunctional organosilanes, polythiophene preparations, catalysts or by self-condensation.
• these can be reacted with water before they are reacted with the polyfunctional organosilanes.
• These solvolysis and condensation products form component C) of the mixtures according to the invention.
• the polyfunctional organosilanes are reacted with water in the presence of a catalyst, preferably in a solvent, for example an alcohol, and optionally in the presence of metal alkoxides.
• a catalyst preferably in a solvent, for example an alcohol, and optionally in the presence of metal alkoxides.
• Inorganic or organic acids are used as catalysts, for example formic acid.
• the solvolysis and condensation products of the polyfunctional organosilanes form component B) of the mixtures according to the invention.
• the mixtures according to the invention can contain as component D) metal oxides or metal oxide hydroxides of the elements B, Al, In, Si, Sn, Ti or Zr.
• Mixed metal oxides eg indium tin oxides (ITO)
• ITO indium tin oxides
• particles with primary particle sizes in the range from 1 to 50 nm are preferably used.
• the best way to incorporate them into the mixtures according to the invention is to add the particles as a dispersion in a solvent, such as water or alcohols.
• a solvent such as water or alcohols.
• An example of this is a dispersion of SiO 2 (primary particle size approx. 9 nm) in isopropanol.
• the conductivity of the amorphous organic-inorganic hybrid materials that can be produced from the mixtures according to the invention can be further improved.
• the mixtures according to the invention are prepared from the reactive solutions obtained by reacting polyfunctional organosilanes or their mixtures with alkoxides, metal oxides or metal oxide hydroxides by adding preparations of polythiophenes with stirring.
• the reactive solutions obtained by reacting polyfunctional organosilanes or their mixtures with alkoxides, metal oxides or metal oxide hydroxides by adding preparations of polythiophenes with stirring.
• Components preferably diluted with solvents that are at least partially water-miscible, since the polythiophene preparation can generally only be prepared as a dilute, aqueous solution and with which in the reactive solution usually only gives homogeneous mixtures in a narrow range.
• the corresponding monomers for example 3,4-ethylenedioxythiophene, to the reactive solution and to polymerize them, for example in the presence of iron sulfonate.
• Preparations can be diluted, e.g. Alcohols such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, ethylene glycol or glycerol, ketones such as acetone or methyl ethyl ketone and amides such as N, N-dimethylformarnide or N-methylpyrrolidone. Mixtures of two or more solvents can also be used.
• Alcohols such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, ethylene glycol or glycerol, ketones such as acetone or methyl ethyl ketone and amides such as N, N-dimethylformarnide or N-methylpyrrolidone.
• Mixtures of two or more solvents can also be used.
• the proportion of polythiophene salts in the mixtures according to the invention is preferably 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the sum of components A), B) and C).
• the mixtures according to the invention contain solvent as component E). These serve to achieve a homogeneous mixture of the individual components.
• Water, inorganic acids such as hydrochloric acid, or organic solvents can be present as solvents in the mixtures according to the invention.
• Organic solvents can, for example, alcohols such as methanol, ethanol, isopropanol, n-butanol, sec-butanol,
• Ethylene glycol or glycerol ketones such as acetone or methyl ethyl ketone, amides such as N, N-dimethylformamide or N-methylpyrrolidone or organic acids such as formic acid.
• ketones such as acetone or methyl ethyl ketone
• amides such as N, N-dimethylformamide or N-methylpyrrolidone
• organic acids such as formic acid.
• Most of the mixtures according to the invention will contain a mixture of solvents, since the components required for the preparation of the mixtures according to the invention are mostly used in dissolved form.
• an organosilane of the formula Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] 4 is first prepared in the presence of tetraethylorthosilicate (1 mol: 4 mol) in ethanol with water and formic acid to prepare the mixtures according to the invention reacted; after a reaction time of one hour, the mixture is diluted with n-butanol and ethylene glycol and an aqueous solution of a preparation of poly-3,4-ethylenedioxythiophene / polystyrene sulfonic acid is added.
• inorganic-organic hybrid materials are obtained. These can be used, for example, as an antistatic or conductive surface coating.
• the mixtures according to the invention are applied to surfaces; after the evaporation of the solvents and the curing of the organic-inorganic hybrid material formed, conductive, scratch-resistant coatings are obtained.
• the coating of surfaces with the mixtures according to the invention can be carried out using common techniques, e.g. Spraying, knife coating, dipping, flooding or spinning (spin coating).
• the applied layer of inorganic-organic hybrid material will preferably have a thickness of 20 nm to 100 ⁇ m, particularly preferably a thickness of 100 nm to 10 ⁇ m.
• the conductivity of the layers is preferably 0.2 to 10 8 ⁇ / D, particularly preferably 100 to 10 8 ⁇ / D.
• the coatings are cured at temperatures from 15 ° C. to 250 ° C., preferably from 50 ° C. to 200 ° C., particularly preferably from 100 ° C. to 200 ° C.
• the mixtures according to the invention can be used, for example, to coat surfaces of moldings and films made from inorganic or organic materials, such as plastics.
• suitable plastics are those based on polyethylene, polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate,
• the mixtures according to the invention are particularly suitable for coating inorganic shaped articles made of materials such as glass or ceramic, for example materials containing aluminum oxide, silicon carbide or silicon nitride.
• the mixtures according to the invention are preferably used for the antistatic or conductive coating of cathode ray tubes made of glass.
• the polyfunctional organosilanes used for example Si [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] or ⁇ yc / o- [OSiMe ((CH 2 ) 2 Si (OEt) 2 Me)] 4 , were obtained by hydosilylation of Tetravinylsilane or cyc / o- [OSiMe (C 2 H 3 )] with HSiClMe 2 or HSiCl 2 Me and subsequent hydrolysis or alcoholysis. Further information can be found in DE-OS 196 03 242 and German patent application 196 03 241.5.
• the surface resistance was determined based on DEN EEC 93. Two 5 mm wide and 5 cm long conductive silver strips were applied to the sample surface at a distance of 5 cm. Unless otherwise stated, the conductive silver strips were cured by annealing at 160 ° C. for 15 minutes.
• the pencil hardness was determined based on ASTM D 3363.
• the coating was crack-free, transparent and homogeneous.
• the conductive silver strips were cured for 1 h at 160 ° C. All films were crack-free, transparent and homogeneous.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Physics & Mathematics (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Paints Or Removers (AREA)
• Silicon Polymers (AREA)
• Conductive Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Compositions Of Oxide Ceramics (AREA)

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• 1996
  • 1996-12-04 DE DE19650147A patent/DE19650147A1/de not_active Withdrawn
• 1997
  • 1997-11-24 JP JP52514198A patent/JP4499838B2/ja not_active Expired - Fee Related
  • 1997-11-24 EP EP97953695A patent/EP0979514B1/de not_active Expired - Lifetime
  • 1997-11-24 AT AT97953695T patent/ATE341084T1/de active
  • 1997-11-24 KR KR10-1999-7004897A patent/KR100516085B1/ko not_active Expired - Fee Related
  • 1997-11-24 CA CA002273302A patent/CA2273302C/en not_active Expired - Fee Related
  • 1997-11-24 AU AU57510/98A patent/AU5751098A/en not_active Abandoned
  • 1997-11-24 WO PCT/EP1997/006559 patent/WO1998025274A1/de not_active Ceased
  • 1997-11-24 DE DE59712737T patent/DE59712737D1/de not_active Expired - Lifetime

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