DE4211459A1 - Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formation - Google Patents
Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formationInfo
- Publication number
- DE4211459A1 DE4211459A1 DE19924211459 DE4211459A DE4211459A1 DE 4211459 A1 DE4211459 A1 DE 4211459A1 DE 19924211459 DE19924211459 DE 19924211459 DE 4211459 A DE4211459 A DE 4211459A DE 4211459 A1 DE4211459 A1 DE 4211459A1
- Authority
- DE
- Germany
- Prior art keywords
- thiophene
- soln
- solution
- prodn
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
- G03C1/89—Macromolecular substances therefor
Abstract
Description
Die Erfindung betrifft die Herstellung permanenter Anti statikschichten auf Polythiophenbasis für fotografische Materialien.The invention relates to the production of permanent anti Polythiophene based static films for photographic Materials.
Polythiophene und deren Verwendung zur antistatischen Beschichtung von Kunststoff-Formteilen und Filmfolien auf Basis Cellulosetriacetat, Polyethylenterephthalat oder Polycarbonat, die als Unterlagen für fotografische Filmmaterialien verwendet werden, sind aus EP-A 340 512 und EP 440 957 bekannt.Polythiophene and their use for antistatic Coating of plastic moldings and film foils based on cellulose triacetate, polyethylene terephthalate or polycarbonate, which is used as documentation for photographic Film materials are used are EP-A 340 512 and EP 440 957.
In der letztgenannten Anmeldung wird besonders die Her stellung der zur antistatischen Beschichtung fotogra fischer Filmunterlagen verwendeten Polythiophene be schrieben.In the latter application, the Her Position of the antistatic coating fotogra fischer film documents used polythiophene be wrote.
Sie erfolgt in wäßriger Lösung durch oxidative Polymeri sation des Thiophens z. B. mit Kaliumperoxodisulfat in Gegenwart eines polymeren Anions wie Polystyrolsulfon säure, das gleichzeitig als Schutzkolloid für die ent stehende kolloidale Lösung fungiert, und gegebenenfalls in Gegenwart von einigen ppm Eisen-III-sulfat als Kata lysator.It is carried out in aqueous solution by oxidative Polymeri sation of thiophene z. B. with potassium peroxodisulfate in Presence of a polymeric anion such as polystyrene sulfone acid, which simultaneously acts as a protective colloid for the ent standing colloidal solution, and optionally in the presence of a few ppm of ferric sulfate as a kata lyst.
Diese oxidative Polymerisation wird gemäß EP 440 957 üblicherweise mit einem Unterschuß an Oxidationsmittel (z. B. Kaliumpersulfat) bezogen auf das monomere Thiophen (z. B. Ethylendioxythiophen = EDT) durchgeführt, um aus wäßriger oder wäßrig-organischer Lösung gut antragbare, klare Schichten zu erhalten. Eine Erhöhung der Per sulfatmenge führt zu Filtrationsproblemen und leicht trüben Schichten (Dendritenbildung). Weiterhin stören kleine, dunkel erscheinende Tröpfchen. Die Naßhaftung der Deckschicht ist unzureichend.This oxidative polymerization is described in EP 440 957 usually with a deficiency of oxidizing agent (eg, potassium persulfate) based on the monomeric thiophene (For example, ethylenedioxythiophene = EDT) is carried out to aqueous or aqueous-organic solution readily applicable, to get clear layers. An increase in per Sulfate amount leads to filtration problems and easily cloudy layers (dendrite formation). Continue to disturb small, dark droplets. The wet grip the topcoat is insufficient.
Da aus ökonomischen Gründen und zur Erzielung höherer Leitfähigkeit, bzw. wesentlich dünnerer und damit weniger gefärbter Schichten - bei gleicher Leitfähig keit - das eingesetzte monomere EDT möglichst quantitativ oxidiert werden sollte, ist eine Erhöhung der Kaliumpersulfatmenge und zwar maximal auf die theoretisch benötigte Menge (1,13 mol/mol EDT) erforder lich. Aufgabe der Erfindung ist, die Erhöhung der Per sulfatmenge so zu gestalten, daß die genannten Nachteile vermieden oder wenigstens verringert werden können.Because of economic reasons and to achieve higher Conductivity, or much thinner and thus less colored layers - with the same conductivity ability - the monomeric EDT used as far as possible should be oxidized quantitatively is an increase the amount of potassium persulfate and that maximum on the theoretically required amount (1.13 mol / mol EDT) required Lich. The object of the invention is to increase the Per to make the amount of sulfate so that the disadvantages mentioned avoided or at least reduced.
Es wurde nun gefunden, daß man diese Aufgabe dadurch lösen kann, daß man die mit erhöhter Persulfatmenge hergestellten Reaktionslösungen (auch Stammlösungen genannt) vor ihrem Einsatz als Gieß- bzw. Antragslösung einem Entsalzungsprozeß unterwirft, der den anorgani schen Salzgehalt um 60%, bevorzugt 70%, bezogen auf das eingesetzte Kaliumpersulfat, reduziert. It has now been found that one accomplishes this task can solve that one with increased Persulfatmenge prepared reaction solutions (also stock solutions called) before their use as a casting or application solution subjected to a desalination process, the anorgani salt content by 60%, preferably 70%, based on the potassium persulfate used, reduced.
Für die aus wäßrig-organischer Lösung angetragenen Schichten ergeben sich vor allem hohe ökonomische und qualitative Vorteile dadurch, daß die entsalzten Stamm lösungen im Gegensatz zu den nicht entsalzten mit we sentlich geringerer Schichtdicke (Faktor 6) - bei glei cher Leitfähigkeit und Permanenz - aufgetragen werden können und dadurch zusätzlich fast völlig farblos sind (Farbdichte <0,01).For those submitted from aqueous-organic solution Layers arise above all high economic and qualitative advantages in that the desalted strain solutions unlike the not desalted with we significantly lower layer thickness (factor 6) - with sliding conductivity and permanence can and therefore are almost completely colorless (Color density <0.01).
Außerdem zeigen diese Schichten in Verbindung mit einer Deckschicht eine gute Haftung auf der unsubstituierten Triacetat-Unterlage, was bei dickeren Schichten nicht der Fall ist.In addition, these layers in conjunction with a Topcoat good adhesion on the unsubstituted Triacetate underlay, which is not the case with thicker layers the case is.
Prinzipiell eignen sich zur Entsalzung die bekannten Verfahren wie Dialyse, Elektrodialyse, Ultrafiltration oder Behandlung mit basischen und/oder sauren Ionenaus tauschern.In principle, the known salts are suitable for desalting Procedures such as dialysis, electrodialysis, ultrafiltration or treatment with basic and / or acidic ions exchangers.
Um eine zu starke Verdünnung der Reaktions- bzw. Stamm lösung zu vermeiden und Gelierungseffekten vorzubeugen, zieht man die Ionenaustauschermethode oder Elektro dialyse vor.Too much dilution of the reaction or strain avoid solution and prevent gelation effects, one pulls the ion exchange method or electro dialysis before.
Die erfindungsgemäßen Vorteile der Entsalzung zeigen die nachstehenden Beispiele.The benefits of desalination according to the invention show the following examples.
In die Lösung von 20 g Polystyrolsulfonsäure (Mn≈40 000); 5,6 g 3,4-Ethylendioxy-thiophen; 2,7 g Kaliumperoxodisulfat (= 10 mmol) und 25 mg Eisen-III- sulfat in 972 ml vollentsalztem Wasser wird 24 Stunden bei Raumtemperatur unter Rühren Luft durchgeleitet. Die blaue Lösung wird anschließend durch ein Filtertuch fil triert und hat einen Feststoffgehalt von 2,1 Gew.-%. (Stammlösung 1)In the solution of 20 g of polystyrene sulfonic acid (Mn≈40,000); 5.6 g of 3,4-ethylenedioxythiophene; 2.7 g Potassium peroxodisulfate (= 10 mmol) and 25 mg iron-III Sulfate in 972 ml of deionized water is used 24 hours at room temperature with stirring air passed. The blue solution is then filtered through a filter cloth trated and has a solids content of 2.1 wt .-%. (Stock solution 1)
Eine Lösung von 20 g Polystyrolsulfonsäure (Mn≈40 000); 5,6 g 3,4-Ethylendioxythiophen; 8,1 g Kaliumperoxodisulfat (30 mmol) und 50 mg Eisen-III- sulfat (Fe-Gehalt 22 Gew.-%) in 966 ml vollentsalztem Wasser wird bei Raumtemperatur 24 Stunden gerührt. Man erhält eine blaugefärbte wäßrige Lösung des 3,4-Poly ethylendioxythiophens mit einem Feststoffgehalt von 3,2 Gew.-%.A solution of 20 g of polystyrenesulfonic acid (Mn≈40,000); 5.6 g of 3,4-ethylenedioxythiophene; 8.1 g Potassium peroxodisulfate (30 mmol) and 50 mg iron-III sulfate (Fe content 22 wt .-%) in 966 ml of deionized Water is stirred at room temperature for 24 hours. you receives a blue-colored aqueous solution of 3,4-poly ethylenedioxythiophene having a solids content of 3.2% by weight.
500 ml der PEDT/PSS-Lösung 2 werden mit 250 ml Wasser verdünnt. Nach Zugabe von 40 g schwach basischem Ionen austauscher und 40 g stark saurem Ionenaustauscher wird die Lösung 8 Stunden bei Raumtemperatur gerührt. Danach wird der Ionenaustauscher abfiltriert, und man erhält eine entsalzte PEDT/PSS-Lösung mit einem Feststoffgehalt von 1,6 Gew.-%. Die Lösung enthält nur noch 0,4 g Kaliumionen/l und 5 mg Sulfationen/l, d. h. die Kalium ionenmenge wird durch den Ionenaustauscher um 74% und die Sulfationenmenge um 99% reduziert (Stammlösung 2).500 ml of PEDT / PSS solution 2 are mixed with 250 ml of water diluted. After addition of 40 g of weakly basic ion exchanger and 40 g of strongly acidic ion exchanger the solution stirred for 8 hours at room temperature. After that the ion exchanger is filtered off, and obtained a desalted PEDT / PSS solution with a solids content of 1.6% by weight. The solution contains only 0.4 g Potassium ions / l and 5 mg sulfate ions / l, d. H. the potassium Amount of ion is by the ion exchanger by 74% and the sulfate ion amount is reduced by 99% (stock solution 2).
In der nachstehenden Reihenfolge versetzt man die unter schiedlichen Mengen der nicht entsalzten Stammlösung 1 nacheinander mit Wasser, Methanol und Aceton in den unten angegebenen Mengen. Die so erhaltenen Lösungen werden durch ein übliches Faltenfilter filtriert und dann aus einer Tauchschale über eine Anspülwalze im Gegenlauf auf eine unsubstituierte Cellulosetriacetat unterlage aufgebracht und bei 60 bis 70°C getrocknet.In the following order you put the under different amounts of non-desalted stock solution 1 successively with water, methanol and acetone in the below indicated quantities. The solutions thus obtained are filtered through a standard pleated filter and then from a dip bowl via a Anspülwalze in Run on an unsubstituted cellulose triacetate applied pad and dried at 60 to 70 ° C.
In gleicher Weise und Zugabefolge stellt man aus der Stammlösung 2 die Antragslösungen 4 und 5 her und zwar nach folgenden Rezepten:In the same way and in addition one poses from the Stock solution 2 the application solutions 4 and 5 ago and that according to the following recipes:
und trägt dieselben unter den gleichen Antragsbedin gungen jeweils auf eine Triacetat-Unterlage auf.and carries them under the same application condition each on a triacetate pad.
Alle 5 Antistatikschichten werden anschließend noch mit einer Deckschicht überschichtet, indem man unter gleichen Antragsbedingungen eine Lösung der folgenden Zusammensetzung aufbringt:All 5 antistatic layers are then still with a top layer overcoated by under same application conditions a solution of the following Composition applies:
Wie man aus Tabelle 1 ersieht, benötigt man mit der An tragslösung 1, die eine nicht entsalzte Polythiophen lösung, hergestellt unter Verwendung einer geringen Per sulfatmenge enthält, einen wesentlich höheren Fest stoffauftrag (4-6,5fach), um die gleiche Oberflächen leitfähigkeit und Permanenz zu erreichen, die man mit Polythiophenlösungen erhält, die mit einer größeren Persulfatmenge hergestellt und die entsalzt wurden. (Antragslösungen 4 und 5). Bei gleichem Feststoffan trag wie bei den Antragslösungen 4 und 5, sinken Ober flächenleitfähigkeit und Permanenz stark ab (Antrags lösung 2 und insbesondere Antragslösung 3).As can be seen from Table 1, you need to use the on Solution 1, which is a non-desalted polythiophene solution prepared using a low per- contains a much higher solids Fabric application (4-6.5 times) to the same surfaces to achieve conductivity and permanence, one with Polythiophene solutions obtained with a larger Persulfate produced and desalted. (Application solutions 4 and 5). At the same Feststoffan As with application solutions 4 and 5, Ober sink area conductivity and permanence (application solution 2 and in particular application solution 3).
Außerdem erlauben die entsalzten Polythiophenlösungen eine starke Verringerung des Wassergehaltes in der An tragslösung, was die Ablösung der Antistatikschicht im Entwicklungsprozeß (pH 12; 38°C) vermeidet.In addition, the desalted polythiophene solutions allow a strong reduction in water content in the on solution, what the replacement of the antistatic layer in Development process (pH 12, 38 ° C) avoids.
Bei Verwendung von PET-Unterlagen werden zur Herstellung Dendriten-freier PEDT/PSS-Schichten die folgenden Lösun gen eingesetzt:When using PET substrates are used for manufacturing Dendrite-free PEDT / PSS layers the following solution used:
Eine Lösung von 20 g Polystyrolsulfonsäure (Mn=40 000); 5,6 g 3,4-Ethylendioxythiophen; 5,4 g Kaliumperoxydisul fat und 100 mg Eisen-III-sulfat (9 aq.) werden in voll entsalztem Wasser zu 1 l Lösung gelöst. Diese wird bei Raumtemperatur 24 Stunden gerührt. Man erhält eine blaugefärbte wäßrige Lösung des 3,4-Polyethylendi oxythiophens mit einem Feststoffgehalt von 3 Gew.-%.A solution of 20 g of polystyrenesulfonic acid (Mn = 40,000); 5.6 g of 3,4-ethylenedioxythiophene; 5.4 g of potassium peroxydisul fat and 100 mg ferric sulfate (9 aq.) are in full demineralized water to 1 l solution. This is added Room temperature stirred for 24 hours. You get one blue-colored aqueous solution of 3,4-Polyethylendi oxythiophene with a solids content of 3 wt .-%.
Eine Lösung von 20 g Polystyrolsulfonsäure (Mn=40 000); 5,6 g 3,4-Ethylendioxythiophen; 8,1 g Kaliumperoxydisul fat und 100 mg Eisen-III-sulfat (9 aq.) werden in voll entsalztem Wasser zu 1 l Lösung gelöst. Diese wird bei Raumtemperatur 24 Stunden gerührt. Man erhält eine blaugefärbte wäßrige Lösung des 3,4-Polyethylendi oxythiophens mit einem Feststoffgehalt von 3,4 Gew.-%. A solution of 20 g of polystyrenesulfonic acid (Mn = 40,000); 5.6 g of 3,4-ethylenedioxythiophene; 8.1 g of potassium peroxydisul fat and 100 mg ferric sulfate (9 aq.) are in full demineralized water to 1 l solution. This is added Room temperature stirred for 24 hours. You get one blue-colored aqueous solution of 3,4-Polyethylendi oxythiophene having a solids content of 3.4% by weight.
500 ml der obigen PEDT/PSS-4-Lösung werden mit 250 ml Wasser verdünnt. Nach Zugabe von 40 g schwach basischem Ionenaustauscher und 40 g stark saurem Ionenaustauscher wird die Lösung 8 Stunden bei Raumtemperatur gerührt. Danach wird der Ionenaustauscher abfiltriert und man erhält eine entsalzte PEDT/PSS-Lösung mit einem Fest stoffgehalt von 1,4 Gew.-%. Die Lösung enthält nur noch 0,15 g Kaliumionen pro Liter. Das heißt, die Kaliumionen werden durch den Ionenaustauscher um 88% reduziert.500 ml of the above PEDT / PSS-4 solution are mixed with 250 ml Diluted with water. After addition of 40 g of weakly basic Ion exchanger and 40 g of strongly acidic ion exchanger the solution is stirred for 8 hours at room temperature. Thereafter, the ion exchanger is filtered off and you gets a desalted PEDT / PSS solution with a feast content of 1.4 wt .-%. The solution only contains 0.15 g of potassium ions per liter. That is, the potassium ions are reduced by the ion exchanger by 88%.
109 ml der Polythiophen-Stammlösung PEDT/PSS3 werden mit Wasser auf bis 1 l verdünnt. Die erhaltene Lösung wird durch ein Seitz-3500-Filter filtriert.109 ml of the polythiophene stock solution PEDT / PSS3 diluted with water to 1 liter. The resulting solution is filtered through a Seitz 3500 filter.
Auf eine Polyethylen-terephthalat-Unterlage (PET), die mit einer Haftschicht aus einem Terpolymerlatex aus Vi nylidenchlorid/Methacrylat/Itaconsäure und kolloidaler Kieselsäure mit einer Oberfläche von 100 m2/g versehen ist, bringt man die Antragslösung mit einem Naßauftrag von 25,6 ml/m2 und einer Gießgeschwindigkeit von 10 m/min auf und trocknet bei 120°C zu einer Trocken schichtdicke von 64 mg/m2.On a polyethylene terephthalate support (PET), which is provided with an adhesive layer of a terpolymer latex of Vi nylidenchlorid / methacrylate / itaconic acid and colloidal silica having a surface area of 100 m 2 / g, bringing the application solution with a wet coverage of 25, 6 ml / m 2 and a casting speed of 10 m / min and dried at 120 ° C to a dry film thickness of 64 mg / m 2 .
Die Antistatikschicht wird mit einer Deckschicht von 0,5 g/m2 Polymethylmethacrylat (PMMA) aus einem Lösungs mittelgemisch von Aceton/Methoxypropanol 80/20 über schichtet. Der Naßauftrag betrug 19 ml/m2, die Gießge schwindigkeit 10 m/min und die Trockentemperatur 110°C. The antistatic layer is overcoated with a top layer of 0.5 g / m 2 polymethylmethacrylate (PMMA) from a solvent mixture of acetone / methoxypropanol 80/20. The wet application was 19 ml / m 2 , the casting speed 10 m / min and the drying temperature 110 ° C.
44 ml der Polythiophen-Stammlösung PEDT/PSS4 werden mit Wasser und EtOH (10%) verdünnt. Sodann wird gemäß Tab. 2 die Antraglösung mit Wasser so verdünnt, daß man die in Tab. 2 aufgeführten Trockenfilmdicken erhält.44 ml of the polythiophene stock solution PEDT / PSS4 diluted with water and EtOH (10%). Then according to Tab. 2 the application solution with water so diluted that one receives the dry film thicknesses listed in Tab.
Auf eine Polyethylen-terephthalat-Unterlage (PET), die mit einer Haftschicht aus einem Terpolymerlatex aus Vi nylidenchlorid/Methacrylat/Itaconsäure und kolloidaler Kieselsäure mit einer Oberfläche von 100 m2/g versehen ist, bringt man die verdünnten Antragslösungen gemäß Tab. 2 auf.On a polyethylene terephthalate support (PET), which is provided with an adhesive layer of a terpolymer latex from Vi nylidenchlorid / methacrylate / itaconic acid and colloidal silica having a surface area of 100 m 2 / g, bringing the diluted application solutions according to Tab ,
Die so erhaltenen Antistatikschichten werden wiederum mit einer Deckschicht von 0,5 g/m2 PMMA überschichtet.The antistatic layers thus obtained are in turn overcoated with a top layer of 0.5 g / m 2 PMMA.
Aus der nachstehenden Tab. 3 ist ersichtlich, daß durch die Entsalzung der Stammlösung die Schichten frei von störenden Dendriten werden, und daß auch noch sehr dünne entsalzte Schichten gleich hohe Leitfähigkeit wie die dickere nicht entsalzte Schicht besitzen. From the following Table 3 it can be seen that desalting the stock solution free the layers disturbing dendrites are, and that also very thin Desalted layers have the same high conductivity as the have thicker non-desalted coating.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924211459 DE4211459A1 (en) | 1992-04-06 | 1992-04-06 | Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924211459 DE4211459A1 (en) | 1992-04-06 | 1992-04-06 | Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formation |
Publications (1)
Publication Number | Publication Date |
---|---|
DE4211459A1 true DE4211459A1 (en) | 1993-10-07 |
Family
ID=6456168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19924211459 Withdrawn DE4211459A1 (en) | 1992-04-06 | 1992-04-06 | Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formation |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE4211459A1 (en) |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5766515A (en) * | 1994-05-06 | 1998-06-16 | Bayer Aktiengessellschaft | Conductive coatings |
US5792558A (en) * | 1995-10-02 | 1998-08-11 | Bayer Aktiengesellschaft | Process for the electrostatic lacquering of non-conductive surfaces |
WO1999034371A1 (en) * | 1997-12-23 | 1999-07-08 | Bayer Aktiengesellschaft | Screen printing paste for producing electrically conductive coatings |
US5998014A (en) * | 1996-07-11 | 1999-12-07 | Bayer Aktiengesellschaft | Flexible, deep-drawing, electrically conductive films |
DE19830176A1 (en) * | 1998-07-06 | 2000-01-13 | Worwag Lack Farbenfabrik Gmbh | Temporary protection of plastic objects against electrostatic charging |
US6084040A (en) * | 1996-08-19 | 2000-07-04 | Bayer Ag | Scratch-resistant conductive coatings |
EP1081549A1 (en) * | 1999-08-30 | 2001-03-07 | Eastman Kodak Company | Coating composition containing polythiophene, film-forming binder, and solvent mixture |
EP1081546A1 (en) * | 1999-08-30 | 2001-03-07 | Eastman Kodak Company | Coating composition containing electrically-conductive polymer and solvent mixture |
US6201051B1 (en) | 1996-12-04 | 2001-03-13 | Bayer Aktiengesellschaft | Conducting organic-inorganic hybrid materials |
US6287713B1 (en) | 1998-07-04 | 2001-09-11 | Bayer Aktiengesellschaft | Electroluminescent assemblies containing boron chelates |
US6316130B1 (en) | 1998-07-04 | 2001-11-13 | Bayer Aktiengesellschaft | Electroluminescent assemblies using azomethine-metal complexes |
US6368731B2 (en) | 1998-07-04 | 2002-04-09 | Bayer Aktiengesellschaft | Electroluminescent assemblies using boron chelates of 8-aminoquinoline derivatives |
US6376105B1 (en) | 1996-07-05 | 2002-04-23 | Bayer Aktiengesellschaft | Electroluminescent arrangements |
US6503643B1 (en) | 1998-09-02 | 2003-01-07 | Bayer Aktiengesellschaft | Electro-luminescent arrangements with thiophene carboxylate metal complexes |
US6534200B1 (en) | 1998-09-02 | 2003-03-18 | Bayer Aktiengesellshaft | Electroluminescent systems with polynulcear metal complexes |
WO2003048229A1 (en) * | 2001-12-04 | 2003-06-12 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
WO2003048228A1 (en) * | 2001-12-04 | 2003-06-12 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US6652976B2 (en) | 2000-07-05 | 2003-11-25 | Bayer Aktiengesellschaft | Conductive, highly abrasion-resistant coatings, a process for their production and their use |
US6692662B2 (en) | 2001-02-16 | 2004-02-17 | Elecon, Inc. | Compositions produced by solvent exchange methods and uses thereof |
US6743241B2 (en) | 2002-03-01 | 2004-06-01 | Intellimed Surgical Solutions Llc | Laparoscopic port site fascial closure device |
US6890584B2 (en) | 2000-06-28 | 2005-05-10 | Agfa-Gevaert | Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene |
US7104458B2 (en) | 2002-07-18 | 2006-09-12 | Agfa Photo Gmbh | Identity card |
US7122130B2 (en) | 2001-12-04 | 2006-10-17 | Agfa Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7337973B2 (en) | 2002-07-18 | 2008-03-04 | Opco Gmbh | Identity card |
US7836884B2 (en) | 2004-07-06 | 2010-11-23 | Wright Vivian A | Face and tracheostomy nebulizing mask |
US7923475B2 (en) | 2001-01-26 | 2011-04-12 | H. C. Starck Gmbh | Electroluminescent arrangements |
US8062553B2 (en) | 2006-12-28 | 2011-11-22 | E. I. Du Pont De Nemours And Company | Compositions of polyaniline made with perfuoropolymeric acid which are heat-enhanced and electronic devices made therewith |
US8153029B2 (en) | 2006-12-28 | 2012-04-10 | E.I. Du Pont De Nemours And Company | Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof |
US8318046B2 (en) | 2002-09-24 | 2012-11-27 | E I Du Pont De Nemours And Company | Water dispersible polyanilines made with polymeric acid colloids for electronics applications |
US8409476B2 (en) | 2005-06-28 | 2013-04-02 | E I Du Pont De Nemours And Company | High work function transparent conductors |
US8491819B2 (en) | 2006-12-29 | 2013-07-23 | E I Du Pont De Nemours And Company | High work-function and high conductivity compositions of electrically conducting polymers |
US8765022B2 (en) | 2004-03-17 | 2014-07-01 | E I Du Pont De Nemours And Company | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
-
1992
- 1992-04-06 DE DE19924211459 patent/DE4211459A1/en not_active Withdrawn
Cited By (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6083635A (en) * | 1994-05-06 | 2000-07-04 | Bayer Ag | Conductive coatings |
US5766515A (en) * | 1994-05-06 | 1998-06-16 | Bayer Aktiengessellschaft | Conductive coatings |
US5792558A (en) * | 1995-10-02 | 1998-08-11 | Bayer Aktiengesellschaft | Process for the electrostatic lacquering of non-conductive surfaces |
US6376105B1 (en) | 1996-07-05 | 2002-04-23 | Bayer Aktiengesellschaft | Electroluminescent arrangements |
US5998014A (en) * | 1996-07-11 | 1999-12-07 | Bayer Aktiengesellschaft | Flexible, deep-drawing, electrically conductive films |
US6084040A (en) * | 1996-08-19 | 2000-07-04 | Bayer Ag | Scratch-resistant conductive coatings |
US6201051B1 (en) | 1996-12-04 | 2001-03-13 | Bayer Aktiengesellschaft | Conducting organic-inorganic hybrid materials |
WO1999034371A1 (en) * | 1997-12-23 | 1999-07-08 | Bayer Aktiengesellschaft | Screen printing paste for producing electrically conductive coatings |
US6287713B1 (en) | 1998-07-04 | 2001-09-11 | Bayer Aktiengesellschaft | Electroluminescent assemblies containing boron chelates |
US6316130B1 (en) | 1998-07-04 | 2001-11-13 | Bayer Aktiengesellschaft | Electroluminescent assemblies using azomethine-metal complexes |
US6368731B2 (en) | 1998-07-04 | 2002-04-09 | Bayer Aktiengesellschaft | Electroluminescent assemblies using boron chelates of 8-aminoquinoline derivatives |
DE19830176A1 (en) * | 1998-07-06 | 2000-01-13 | Worwag Lack Farbenfabrik Gmbh | Temporary protection of plastic objects against electrostatic charging |
US6503643B1 (en) | 1998-09-02 | 2003-01-07 | Bayer Aktiengesellschaft | Electro-luminescent arrangements with thiophene carboxylate metal complexes |
US6534200B1 (en) | 1998-09-02 | 2003-03-18 | Bayer Aktiengesellshaft | Electroluminescent systems with polynulcear metal complexes |
EP1081546A1 (en) * | 1999-08-30 | 2001-03-07 | Eastman Kodak Company | Coating composition containing electrically-conductive polymer and solvent mixture |
EP1081549A1 (en) * | 1999-08-30 | 2001-03-07 | Eastman Kodak Company | Coating composition containing polythiophene, film-forming binder, and solvent mixture |
US6429248B2 (en) | 1999-08-30 | 2002-08-06 | Eastman Kodak Company | Coating composition containing electrically-conductive polymer and solvent mixture |
US6890584B2 (en) | 2000-06-28 | 2005-05-10 | Agfa-Gevaert | Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene |
US6652976B2 (en) | 2000-07-05 | 2003-11-25 | Bayer Aktiengesellschaft | Conductive, highly abrasion-resistant coatings, a process for their production and their use |
US7923475B2 (en) | 2001-01-26 | 2011-04-12 | H. C. Starck Gmbh | Electroluminescent arrangements |
US6692662B2 (en) | 2001-02-16 | 2004-02-17 | Elecon, Inc. | Compositions produced by solvent exchange methods and uses thereof |
WO2003048229A1 (en) * | 2001-12-04 | 2003-06-12 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7108805B2 (en) | 2001-12-04 | 2006-09-19 | Agfa Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7122130B2 (en) | 2001-12-04 | 2006-10-17 | Agfa Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
EP1780232A1 (en) * | 2001-12-04 | 2007-05-02 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent. |
US7223357B2 (en) | 2001-12-04 | 2007-05-29 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7048874B2 (en) | 2001-12-04 | 2006-05-23 | Agfa-Gevaert | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythionphene or thiophene copolymer |
WO2003048228A1 (en) * | 2001-12-04 | 2003-06-12 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7338621B2 (en) | 2001-12-04 | 2008-03-04 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
US7378039B2 (en) | 2001-12-04 | 2008-05-27 | Agfa-Gevaert | Aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
US6743241B2 (en) | 2002-03-01 | 2004-06-01 | Intellimed Surgical Solutions Llc | Laparoscopic port site fascial closure device |
US7337973B2 (en) | 2002-07-18 | 2008-03-04 | Opco Gmbh | Identity card |
US7104458B2 (en) | 2002-07-18 | 2006-09-12 | Agfa Photo Gmbh | Identity card |
US8318046B2 (en) | 2002-09-24 | 2012-11-27 | E I Du Pont De Nemours And Company | Water dispersible polyanilines made with polymeric acid colloids for electronics applications |
US8765022B2 (en) | 2004-03-17 | 2014-07-01 | E I Du Pont De Nemours And Company | Water dispersible polypyrroles made with polymeric acid colloids for electronics applications |
US7836884B2 (en) | 2004-07-06 | 2010-11-23 | Wright Vivian A | Face and tracheostomy nebulizing mask |
US8409476B2 (en) | 2005-06-28 | 2013-04-02 | E I Du Pont De Nemours And Company | High work function transparent conductors |
US8153029B2 (en) | 2006-12-28 | 2012-04-10 | E.I. Du Pont De Nemours And Company | Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof |
US8062553B2 (en) | 2006-12-28 | 2011-11-22 | E. I. Du Pont De Nemours And Company | Compositions of polyaniline made with perfuoropolymeric acid which are heat-enhanced and electronic devices made therewith |
US8491819B2 (en) | 2006-12-29 | 2013-07-23 | E I Du Pont De Nemours And Company | High work-function and high conductivity compositions of electrically conducting polymers |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE4211459A1 (en) | Antistatic permanent coating prodn. on photographic material with poly:thiophene - by oxidative polymerisation with at least stoichiometric amt. of peroxy acid salt and desalination for high yield avoiding haze by dendrite formation | |
EP0440957B1 (en) | New polythiophene dispersions, their preparation and their use | |
EP0129674B1 (en) | Polyester foil with an adhesive copolyester coating | |
DE3904544C2 (en) | ||
EP0394791B1 (en) | Photographic material having an antistatic layer | |
EP0564911B1 (en) | Antistatic plastic parts | |
DE2161434A1 (en) | ||
DE4334390C2 (en) | Process for making a processable, conductive, colloidal polymer | |
EP0254924A2 (en) | Drawing material | |
EP0322529B1 (en) | Polyester film with a copolyester coating acting as a metal adhesion mediator | |
DE1572119C3 (en) | ||
DE1572119B2 (en) | Aqueous adhesive layer dispersion | |
DE2750542A1 (en) | METHOD FOR PRODUCING POLYMERS CONTAINING FREE OR SALT-BASED AMINIC GROUPS AND QUATERNAUS AMMONIUM GROUPS, AND THE PRODUCTS OBTAINED THEREOF | |
DE2116299C3 (en) | Process for the preparation of aqueous solutions containing chromium (III) coordination complexes | |
EP0213231A1 (en) | Waterproof paper support for photographic layers | |
DE2326759C2 (en) | Waterproof photographic paper coated with thermoplastic resins | |
DE2423201A1 (en) | FILM CARRIER MATERIAL | |
DE1570305B1 (en) | PROCESS FOR MANUFACTURING MODIFIED PHENOLFORMALDE HYDRO RESINS AND THEIR USE FOR ANTISTATIC MESHING OF PLASTICS | |
DE1570305C (en) | Process for the production of modified phenol-formaldehyde resins and their use for rendering plastic antistatic | |
DE2150137A1 (en) | Process for producing a photographic material | |
CH622361A5 (en) | ||
DE2042833C3 (en) | Process for the production of an electrically conductive layer support for electrographic or electrophotographic recording materials | |
DE2844775B2 (en) | Process for the production of a photographic recording material | |
DE2008636C3 (en) | Process for the production of an electrically conductive layer | |
DE2239018A1 (en) | COATED MATERIALS |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
8110 | Request for examination paragraph 44 | ||
8125 | Change of the main classification |
Ipc: G03C 189 |
|
8139 | Disposal/non-payment of the annual fee |