TWI330652B - Water dispersible polyanilines made with polymeric acid colloids for electronics applications - Google Patents

Description

Technical Field of the Invention The present invention relates to an aqueous dispersion of an aniline conductive polymer obtained by synthesizing a conductive polymer in the presence of a polyacid colloid. [Prior Art] Conductive polymers have been used in many organic electronic devices, including the development of electroluminescent (EL) devices for use in luminescent displays. With regard to EL devices, such as organic light-emitting diodes (OLEDs) containing conductive polymers, such devices are generally provided with the following configurations: Anode/buffer layer/EL polymer/cathode anodes are generally capable of injecting holes Semiconductive EL polymers such as other indium oxide/tin (ITO) filled π-energy band materials. The anode is optionally loaded on a glass or plastic substrate. The EL polymer is typically a conjugated semiconductive polymer such as poly(p-phenylacetylene) or polyfluorene. The cathode is typically any material (e.g., Ca or Ba) that is capable of injecting electrons into other empty π*-bands of the semiconductive EL polymer. The buffer layer is typically a conductive polymer and can help the hole be injected into the EL polymer layer from the anode. This buffer layer is also referred to as a hole injection layer, a hole transfer layer, or a portion that can be depicted as a double layer anode. Typical conductive polymers used as buffer layers include polyaniline (PANI) and polydioxythiophene such as poly(3,4-ethylenedioxythiophene) (PEDT). These materials can be prepared by polymerizing the corresponding monomer in the presence of a water-soluble polyacid such as poly(styrenesulfonic acid) (PSS) in an aqueous solution. The aqueous conductive polymer dispersion obtained by synthesizing the water-soluble polysulfonic acid has an undesirably low pH. A low pH may cause a decrease in the stress life of the EL device including the buffer layer and cause corrosion inside the device. Therefore, there is a need for a composition and a buffer layer which are preferably made of O:\88\88436.DOC -6-133252. - Conductive polyaniline is generally obtained by oxidative polymerization of an aniline or a substituted aniline monomer in an aqueous solution using an oxidizing agent such as persulfate (APS), sodium persulfate or potassium persulfate. The aqueous solution contains a water-soluble polyacid such as poly(2-propenylamine-2-mercapto-1-propanesulfonic acid) (nPAAMPSA"), PSS and the like. Generally, a sufficient amount of acid is present to form an acid/base salt with the basic intermediate oxidation state polyaniline, wherein the formation of the acid/base salt renders the polyaniline conductive. Thus, for example, basic intermediate oxidation state polyaniline (PANI) generally forms a conductive-electric PANI/PAAMPSA with PAAMPSA. Aqueous polyaniline dispersions are commercially available from Ormecon Chemie GmbH and Co. KG (Ammersbeck, Germany). It is known as the D 1005 W LED. This polyamine is prepared from aniline and water-soluble/poly(styrenesulfonic acid). The dry film obtained from the D 1005 W LED can be easily redispersed in water. The water became acidic and the pH of 2.5% (w/w) was in the range 1. The film obtained about 24.0% (w/w) moisture under ambient conditions. The dry film obtained from the laboratory batch aqueous dispersion of polyaniline/poly(2-propenylamine-2-mercapto-1-propanesulfonic acid) is also easily redispersed in water. This polyaniline is prepared from aniline and water-soluble PAAMPSA. Conductive polymers also have utility as electrodes for electronic devices, such as thin film field effect transistors. In such a transistor, an organic semiconductive film is present between the source and the drain. For use in electrode applications, the conductive polymer and the liquid that disperses or dissolves the conductive polymer must be compatible with the semiconductive polymer and the solvent of the semiconductive polymer to avoid redissolution of the conductive polymer or semiconductive polymer. The conductivity of the electrode made of conductive polymer should be greater than 10 S/cm (its

O:\88\88436.DOC 1330652 where s is the reciprocal of ohms). However, the conductive polyaniline k made of polyacid has a conductivity ranging from 〜1〇·3 S/cm or less. In order to mention 1, a conductive additive can be added to the polymer. However, such J: has an adverse effect on the adhesion of conductive polyaniline. Therefore, it is a preferred conductive polyaniline with good processability and high conductivity. < SUMMARY OF THE INVENTION In one embodiment of the invention, a composition comprising an aqueous dispersion of polyaniline and a colloid to form a polyacid is provided. The composition of the present invention is used as a buffer layer in an organic electronic device such as an organic light-emitting diode (OLED). The composition of the present invention can also be used in applications such as the immersion, source or gate of thin film field effect transistors, etc., and the conductive plugs such as metal nanowires or carbon according to another The present invention provides an organic electronic device comprising a slow-laying layer of the composition of the present invention, comprising an electroluminescent device, according to another embodiment of the present invention. Provided is a process for producing an aqueous dispersion of polyaniline and at least one body to form a polyacid comprising the steps of forming an under-aniline monomer in any order, colloid forming a combination of a polyacid and an oxidizing agent, provided that the aniline monomer is added At least one part of the oxidant is present, and a part of the colloid is formed to form a polyacid. [Embodiment] The present invention provides an aqueous dispersion containing a polyamine and a colloid to form a polyacid == compound. As used herein, 'dispersion, The term is equivalent to a continuous liquid medium containing tiny particles ~ float. According to the invention, "continuous medium" is generally a body of water such as water. As used herein, the term "aqueous" is equivalent to mostly water.

The liquid of O:\88\S8436.DOC j33〇652, in a specific embodiment, at least about 4% by weight of the liquid is water. As used herein, "colloid""" is a small particle suspended in a continuous medium. The particle has a particle size of nanometer size. As used herein, "colloidal formation" - the word corresponds to a substance that forms fine particles when dispersed in an aqueous solution, that is, a colloid is formed. "Polyacids are not water soluble." As used herein, "including" includes "including" and "including" Words such as ",", "," or "any change" are intended to cover an inclusive possession. For example, 'a program, method, object, or device containing a series of components is not necessarily limited to these 7L pieces' and includes other A statement or a component that is inherent to the program, method, article, or device. In addition, unless stated to the contrary, " or" is either inclusive or inclusive. For example, any of the following cases may be full; 1 condition A or B: A is true (or exists) u is not true (or not), A is not true (or does not exist) and 8 is true (or exists) Both performance and performance 8 are true (or both). And use is used to describe the elements and components of the present invention. This is done merely to facilitate and provide the general concepts of the invention. This description should be interpreted as a package of three or at least one, and the singular also includes the plural meaning unless it is expressly intended. It has been found that when the aniline monomer is chemically polymerized in the presence of a colloid-forming polyacid, an aqueous dispersion of a conductive poly(stupylamine) can be obtained. Furthermore, it has been found that the use of poly I produces a composition having excellent electrical properties in which the polyacid is insoluble in the preparation of an aqueous dispersion of poly(stupylamine). An advantage of these aqueous dispersions is that the electrically conductive fine particles are stable in the aqueous medium and do not form a separate phase over a long period of time before use. And, once they dry out

O:\88\884J6.DOC •9- 1330652 Membranes are generally not redispersed. - The composition according to the invention comprises a continuous aqueous phase having a polyaniline and a colloid forming polyacid dispersed therein. The polyaniline to be used in the examples of the present invention is derived from a strepamine monomer having the following formula I:

In Formula I: η is an integer from 0 to 4; m is an integer from 1 to 5, provided n + m = 5; and R1 is independently selected such that each occurrence is the same or different, and is selected From alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkenyl, alkylthio, aryloxy, alkylsulfanyl, alkaryl, aralkyl, amine, alkylamine , dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkanesulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, chelating, a cyano group or an alkyl group substituted with one or more acid, sulphuric acid, functional groups, nitro 'cyano or epoxy groups; or any two R1 groups formed together to form 3, 4, 5, 6 or 7 An extended or extended base chain of a member or a alicyclic ring, which ring optionally contains one or more divalent nitrogen, sulfur or oxygen atoms. The polymerized material comprises aniline monomer units, and each aniline monomer unit has a structural formula selected from the following formula II and formula III.

(Η)πι-1 0:\88\$8436. OOC -10- 1330652

Wherein η, m and R1 are as defined above. The colloid-forming polyacid to be used in the examples of the present invention is insoluble in water and forms a colloid when dispersed in an aqueous medium. The molecular weight of the polyacid is generally in the range of from about 10,000 to about 4,000,000. In a particular embodiment, the molecular weight of the polyacid is from about 100,000 to about 2,000,000. The particle size of the colloid is generally in the range of from 2 nanometers (nm) to about 140 nanometers. In one embodiment, the colloidal particles are The diameter is from 2 nanometers to about 30 nanometers. Any polyacid which forms a colloid when dispersed in water is suitable for use in the examples of the present invention. In a specific embodiment, the colloid-forming polyacid is a polysulfonic acid. Acceptable polyacids include polyphosphoric acid, polycarboxylic acids, and polyacrylic acids and mixtures thereof, including mixtures containing polysulfonic acids. In another embodiment, the polysulfonic acid is fluorinated. In another embodiment The colloid-forming polysulfonic acid is perfluorinated. In another embodiment, the colloid-forming polysulfonic acid is a perfluoroalkylalkyl acid. In another embodiment, the colloid-forming polyacid is a highly fluorine-containing compound. A sulfonic acid polymer ("FSA polymer";" is highly fluorinated, meaning that at least about 50% of the total number of halogen and hydrogen atoms in the polymer is a fluorine atom, and in one embodiment is At least about 75 baht /., at In another embodiment, it is at least about 90%. In another embodiment, the polymer is perfluorinated. The term "sulfonated functional group" is equivalent to a salt of a sulfonic acid group or a sulfonic acid group. In one and O:\S8V88436.DOC • 11 - 1330652 body examples are alkali metal or ammonium salts. The functional groups may be represented by the formula _S〇3X, wherein X is a carbon 'also known as counterion 11 . X may be Η, Li, Na, K or N(Rt)(R2)(R3)(R4), and R2, 尺3 and r4 may be the same or different, in one embodiment Η, CH3 or (:2仏. In one embodiment, X is Η, in this case, the polymer may be either "acidic or multivalent, as represented by ions such as Ca++ and Α1+++. The skilled artisan clearly understands that in the case of multivalent counterions, generally expressed as +, the number of sulfonated functional groups per counterion will be equal to the valence "n". In one embodiment, the FSA polymer comprises The polymer backbone and the recycle side chain are attached to the backbone, wherein the side chain carries a cation exchange group. The polymer comprises two or more a homopolymer or copolymer. The copolymer is typically a non-functional monomer and a second monomer bearing a cation exchange group or a precursor thereof, such as a sulfonium fluoride group which can then be hydrolyzed to a sulfonate functional group. A copolymer formed of a first fluorinated vinyl monomer together with a fluorinated vinyl monomer having a sulphur gas base 〇s 2F) may be used. The first monomer available may be tetrafluoroethylene (TFE). , hexafluoropropylene, fluorinated ethylene, vaporized vinylene, - ethylene ethylene, chaotic three said ethylene, total gas (burning ethylene base (4) and combinations thereof. Penalty is the preferred first monomer. In another - In a specific embodiment, the second monomer that can be used comprises a fluorinated ethylene having a precursor acid group or a side chain precursor which can provide a polymer, if necessary, an additional monomer, including acetamidine, In the propylene and r-CH=CH2 polymers, wherein ... to a carbon atom of the total smelting base, the polymer may be in the phase of the messy copolymer type in this phase, that is, by the relative concentration of the comonomer May be ma ' ma ', hold 疋 ' to make monomer units along the polymer

0\88\884) 6.D0C, 12-1330652, the knife cloth is made according to the polymerization of its relative concentration and relative reactivity =,,, and polymer. It is also possible to use a copolymer which is less chaotic by changing the relative brightness of the monomers during the polymerization. Polymers of the so-called block copolymer type can also be used, as disclosed in the European Patent Application No. 1 026 152 A1. In a specific embodiment, the FSA polymer used in the present invention comprises a high and oxidized carbon backbone comprising these perfluorinated carbon backbones and a side chain of the formula: (0-CF2CFRf)a-〇-CF2CFR, fS03X: wherein Rf And 11> are independently selected from F, C1 or a fully gasified yard with from 1 to 1 carbon atom, a = 0, 1 or 2, and X is Η 'Li, Na, K or 111) 2) (113) (114), and the rulers 2, 113 and 114 are the same or different, in one embodiment Η, CH3 or C2H5. In another embodiment, 'X is Η. As stated above, X can also be multivalent. In a specific embodiment, the FSA polymer comprises, for example, the polymers disclosed in U.S. Patent No. 3,282,875 and U.S. Patent Nos. 4,358,545 and 4,94,525. Examples of FSA polymers include a perfluorocarbon backbone and side chains of the formula

-0-CF2CF(CF3)-0-CF2CF2S03X wherein X is as defined above. This type of FS A polymer is disclosed in U.S. Patent No. 3,282,875 and may be based on tetrafluoroethylene (butyl) and perfluorinated vinyl ether CF2=CF-0-CF2CF(CF3)-0-CF2CF2S02F, Fluorine (3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF) copolymerization, followed by hydrolysis of the sulfonyl fluoride group to a sulfonate group, which is converted into a It needs to be prepared in an ionic state. Examples of preferred polymer types have side chains -o-cf2cf2so3x, wherein X is as defined above, in U.S. Patent Nos. 4,358,545 and 4,940,525. The polymer can be copolymerized with tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF2 = CF-0-CF2CF2S02F, perfluoro(3-ox-4-pentenesulfonyl fluoride) (P〇PF), followed by copolymerization. Hydrolysis and further ion exchange if necessary. In a specific embodiment, the FSA polymer used in the present invention has an ion exchange ratio of less than about 33. In this application, "ion exchange ratio" or "IXR" is defined as the number of carbon atoms relative to the cation exchange group in the polymer backbone. For a particular application, the IXR can be varied, if necessary, to less than about 33. For most polymers, the IXR is from about 3 to about 33, and in one embodiment from about 8 to about 23. The cation exchange capacity of a polymer is often expressed in terms of equivalent (EW). For the purposes of this application, equivalent (EW) is defined as the weight of the acid polymer required to neutralize one equivalent of sodium hydroxide. In the case of a sulfonated polymer having a perfluorocarbon backbone and a side chain of -o-cf2cf(cf3)-o-cf2-cf2-so3h (or a salt thereof), the corresponding IXR is from about 8 to about 23 The equivalent range is from about 750 EW to about 1500 EW. The relationship between the IXR and the equivalent of the polymer can be expressed by the following formula: 50 IXR + 344 = EW. The sulfonated polymer disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525, such as a polymer having a side chain of -0-CF2CF2S03H (or a salt thereof), use the same IXR range, but a monomer having a cation exchange group. The unit has a lower molecular weight, so the equivalent is slightly lower. For a preferred IXR range of from about 8 to about 23, the corresponding equivalent weight ranges from about 575 EW to about 1325 EW. The relationship between the IXR and the equivalent of this polymer can be explained by the following formula: 50 IXR + 178 = EW. O:\88\88436.DOC -14· 1330652 F S A polymer can be made into a steroidal aqueous dispersion. They may also be in the form of dispersions which are soluble in other media, examples of which include, but are not limited to, alcohols, water-soluble I1, such as tetrahydrofuran, mixtures of water-soluble oximes, and oximes thereof. An acid type polymer can be used when the dispersion is produced. U.S. Patent Nos. 4,433, 〇 82, 6,150, 426 and WO 03/006537 disclose methods of making aqueous alcohol dispersions. After the dispersion is prepared, the concentration and dispersion of the liquid composition can be adjusted by methods known in the art. The colloid-forming polyacid' includes an aqueous dispersion of the FSA polymer having a particle size as small as possible and as small as possible Ew as long as a stable colloid can be formed. The colloid forms a polyacid, and the aqueous dispersion comprising the F S A polymer can be purchased from commercial a 1 such as Naficm® dispersion available from β·L du Pont de Nemours and the company (Warington, Dy.). According to the present invention, a stable aqueous dispersion is obtained by synthesizing a conductive polyaniline in the presence of an aqueous colloid-forming phthalic acid dispersion, thereby forming an aqueous dispersion obtained by synthesizing a conductive polyaniline and a colloidal polyacid. The conductive polyaniline used in this X-month is generally used in the formation of oxidizing agents in aqueous colloidal polyacid syrups, such as ammonium persulfate (Aps), sodium persulfate, potassium persulfate and the like, by aniline or The aqueous dispersion obtained by oxidative polymerization of a substituted aniline monomer comprises at least a sufficient amount of a suitable colloid to form a poly-I to form an acid/base salt with a basic intermediate oxidation state polyaniline, wherein the formation of the acid/base salt causes polymerization Stupid amines are electrically conductive. The method for producing polyaniline and at least one colloid to form a water-repellent H-knives in a specific embodiment comprises combining the water, the aniline monomer, the colloid-forming polyacid and the oxidizing agent to form a reaction mixture in any order, conditions. When at least one of the aniline monomer and the oxidizing agent is added to the coffee V88436.doc -15· 1330652, at least a part of the colloid forming polyacid is present. In a specific embodiment, the method for producing a polyaniline and at least one colloid to form an aqueous dispersion of a polyacid comprises: (a) providing a colloid to form an aqueous dispersion of a polyacid; (b) an oxidizing agent and the step (a) The dispersion is combined; and (c) the aniline monomer is combined with the dispersion of step (b). In another embodiment, the aniline monomer is combined with the colloid-forming aqueous dispersion of the polyacid prior to the addition of the oxidizing agent. The step (b) of combining with an oxidizing agent is then carried out. In another embodiment, a mixture of water and aniline is formed wherein the concentration of aniline is generally in the range of from about 0.5% by weight to about 2,000% by weight. This aniline mixture is added to the body to form an aqueous dispersion of the polyacid, which is then combined with an oxidizing agent. In another embodiment, the aqueous polymeric dispersion can comprise a polymeric surfactant such as ferric sulfate, ferric chloride, and the like. The catalyst is added at the last step. In another embodiment, the catalyst is added with an oxidant. In one embodiment, the polymerization is carried out in the presence of a water miscible co-dispersion. Examples of suitable co-dispersion liquids include, but are not limited to, ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitrile 'sulfoxides, guanamines, and combinations thereof. In a specific embodiment, the co-dispersion is an alcohol. In a specific embodiment, the co-dispersion liquid is selected from the group consisting of n-propanol 'isopropanol, third butanol, decyl alcohol-methyl ethanoamine, dimethyl aryl amine, N-mercapto ru ratio ρ Ketones and mixtures thereof. O:\88\88436.DOC -16· 1330652 In a particular embodiment, the amount of co-dispersion should be less than about 6% by volume. In a particular embodiment, the amount of co-dispersion is between about 2 Torr and 5 Torr. The use of the co-dispersion in the polymerization significantly reduces the particle size and improves the filterability of the dispersion. Moreover, the buffer material obtained by this procedure shows a large viscosity, and the film made of these dispersions is of high quality. The co-dispersion can be added to the reaction mixture at any point in the process, prior to the addition of the oxidizing agent or aniline monomer, whatever is added last. In a specific embodiment, the co-dispersion is added before the aniline monomer and the colloid form a polyacid and finally the oxidant is added. In a particular embodiment, the co-dispersion is added prior to the addition of the aniline monomer and finally the oxidant is added. In a particular embodiment, the polymerization is carried out in the presence of a eu-acid wherein the co-acid is a Bronsted acid. The acid may be a mineral acid such as HCl, sulfuric acid and the like, or an organic acid such as acetic acid. Alternatively, the acid may be water/glutenic acid such as poly(p-ethyl benzoic acid), poly(2. acrylamide, 2 fluorenyl), or the like, or the above The dicolloid forms an acid. A variety of acid compositions can be used. The co-acid can be added to the reaction mixture at any point in the process, prior to the addition of the oxidizing agent or the strepamine monomer. In a specific embodiment, the co-acid is added prior to the formation of the polyacid by the strepamine monomer and the colloid and is followed by the addition of an oxidizing agent. In a particular embodiment, the co-acid is added prior to the addition of the aniline monomer, followed by the addition of a colloid to form a polyacid and finally the addition of an oxidizing agent. In a particular embodiment, the polymerization is carried out in the presence of a co-dispersion and a co-acid. A device having a buffer layer exhibits high efficiency, low operating voltage, low leakage, and long life, wherein the buffer layer is composed of an alcohol co-dispersant and

O:\88\88436.DOC •17· 1330652 Polyaniline/Nafi〇n8 obtained by polymerization in the presence of a co-acid. In the method of producing polyaniline and at least one colloid to form an aqueous dispersion of polyacid, the molar ratio of oxidant to aniline monomer is in the range of Q·丨 to 2〇, in a specific implementation column Is 5. The molar ratio of the colloid forming polyacid to the aniline monomer is generally in the range of 〇 2 to 5. The total solids content is generally in the range of from about U by weight to about 6% by weight, and in one embodiment from about 2% to about 4.5%. The reaction temperature is generally in the range from about generation to thief, and in a particular embodiment about 2 〇〇c to hunger. The molar ratio of the co-acid to the aniline leather is about G.G5 to 4. The addition time of the oxidant affects the particle size and viscosity. Therefore, the particle diameter can be lowered due to the decrease in the addition speed. Similarly, the viscosity is increased by the decrease in the rate of addition. The reaction time is generally in the range of up to about 30 hours. The aqueous dispersion of polyaniline and polyacid colloid thus synthesized generally has an extremely low pH. It has been found that the pH can be adjusted to generally between about 1 and about 8. There is no adverse effect on the nature of the device, and it is often desirable to have a near neutrality, since acidity may cause rot. It has been found that ρΗβ can be formed by known techniques such as ion exchange or titration with an aqueous solution. A stable dispersion of polyaniline and fluorinated polyacid colloids. Polyaniline and other colloids form an aqueous dispersion of polyacids which can be similarly treated to adjust pH. In a specific embodiment, after completion of the polymerization, The t-dispersion obtained by synthesizing is contacted with at least one ion-exchange resin under conditions suitable for removing decomposition species, side reaction products and unreacted monomers and adjusting conditions, thus producing a stable aqueous dispersion having a desired pH. A dendrimer embodiment, the aqueous dispersion thus synthesized is in the order of O:\g8\88436.DOC -18-13330652 an ion exchange resin and a second ion exchange Replacing the resin. The aqueous dispersion thus synthesized can be treated with the first and second ion exchange resins at the same time, or it can be treated one by one, and then treated with another. Ion exchange is a reversible chemical reaction in which the fluid The fixed solid particles are insoluble in the fluid medium, such as the ion system in aqueous dispersion and the similar charge ion exchange coupled to the fixed solid particles. The ion exchange resin "-word system is equivalent to all such Substance. The polymer support supported by the ion parent group is insoluble in the resin. The sub-exchange resin can be divided into a cation (tetra) agent or an anion exchanger. The cation exchanger has a positive charge exchangeable mobile ion, generally a proton. Or a metal ion such as a nano ion. The anion exchanger has an exchangeable negatively charged ion, typically a hydroxide ion. In a specific embodiment, the first ion exchange resin is a cation\acid exchange resin which may be proton or Metal ions, generally sodium ions! The first ion parent resin is a basic, anion exchange resin. Acidic, cationic, including proton exchange resin and m, anion exchange tree, are used in the examples of the present invention. In a specific embodiment, the acid cation cationic parent resin is a mineral acid, a cation exchange resin, such as κι Cationic parent resin. The acid cation parent resin to be used in the examples of the present invention includes, for example, a sulfonated styrene-divinylbenzene copolymer, a sourized parent-linked ethylene polymer, and a phenol-formaldehyde-sulfonic acid. Resin, stupid-furfural _ oleic acid resin and mixtures thereof. In another embodiment, the acidic, cation exchange resin is an organic acid, a cation exchange resin such as carboxylic acid, propylene or scales & Ion exchange resin. Also, different cations can be used.

O:\SSV88436.DOC 1330652 The father changed the resin mixture. In another embodiment, the anionic, anion exchange resin is a tertiary amine anion exchange resin. The tertiary amine anion exchange resin to be used in the examples of the present invention includes, for example, a tertiary aminated styrene-divinylbenzene copolymer, a secondary aminated crosslinked stupid ethylene polymer, and a tertiary aminated phenol-formaldehyde resin. , a secondary aminated benzene-furfural resin and mixtures thereof. In another embodiment, the basic, anion exchange resin is a quaternary amine anion exchange resin or a mixture of these with other exchange resins. -r The first and second ion exchange resins may be contacted simultaneously or sequentially with the aqueous dispersion thus synthesized. For example, in one embodiment, the two resins may be simultaneously added to the aqueous dispersion of the conductive polymer thus synthesized and kept in contact with the dispersion at least about! Hours, such as about 2 hours to about an hour. The ion exchange resin is then removed from the dispersion by filtration. The size of the filter is selected such that relatively large ion exchange resin particles are removed and smaller dispersion particles are passed through. Without wishing to be bound by theory, it is believed that the ion exchange resin terminates the polymerization and effectively removes ionic and nonionic impurities and most of the unreacted monomers from the aqueous dispersion obtained by this synthesis. In addition, the anionic, anion exchange and/or acidic, cation exchange resins make the acid site more alkaline, resulting in a dispersion? ]9[Improved. Typically, about 1 to 5 grams of ion exchange resin is used per gram of polystyrene/polyacrylate system. In many instances, the positive ion exchange resin can be used to adjust the anode to the desired value. In some instances, an aqueous solution such as sodium hydroxide, oxynitride, tetramethylammonium hydroxide or the like can be adjusted to adjust the pH. In one embodiment, a mixture of water, an alcohol co-dispersant, and an inorganic co-acid O:\88\88436.DOC • 20· 1330652 is initially charged to the reaction vessel. An aniline monomer and an aqueous dispersion of a gasified polysulfonic acid colloid and an oxidizing agent are sequentially added thereto. The oxidizing agent is added slowly and dropwise to prevent local formation of high ion concentration regions where the acid colloid is unstable. The mixture is stirred and the reaction is allowed to proceed at a controlled temperature. Upon completion of the polymerization, the reaction mixture is treated with a strong acid cation resin and stirred and filtered, then treated with a basic anion resin and stirred and filtered. Different order of addition can be used as discussed above. In another embodiment, a more conductive dispersion can be formed by the addition of a highly conductive additive to the aqueous dispersion of polyaniline and colloid to form a polyacid. Since a relatively high pH dispersion can be formed, the conductive additive, particularly the metal additive, is not attacked by the acid of the dispersion. Moreover, since the polyacid is a colloidal property having a surface mainly containing an acid group, the conductive polyaniline is formed on the surface of the colloid. Because of this unique structure, only a low weight percentage of highly conductive additives is required to achieve the percolation limit. Examples of suitable conductive additives include, but are not limited to, metal particles and nanoparticles, nanowires, carbon nanotubes, graphite fibers or particles, carbon particles, and combinations thereof. In another embodiment of the invention, a buffer layer cast from an aqueous dispersion comprising a polyaniline and a colloid to form a polyacid is provided. In a specific embodiment, the buffer layer is cast from an aqueous dispersion comprising a colloid to form a polysulfonic acid. In a specific embodiment, the buffer layer is cast from an aqueous dispersion comprising a polyamidamine and a fluorinated polyacid colloid. In another embodiment, the fluorinated polyacid colloid is a fluorinated polysulfonic acid colloid. In another embodiment, the buffer layer is cast from an aqueous dispersion comprising a polystyrene and a full I ethylene sulfonic acid colloid. 0\S6V88436.DOC -21 - 1330652 The dry film of pro-aniline and polyacid colloid, such as fluorinated polysulfonic acid colloid, is generally not redispersible in water. Thus the buffer layer can be painted into multiple thin layers. Moreover, the 'buffer layer' can be covered by a layer of different water-soluble or water-dispersible materials. Further, in a specific embodiment, a buffer layer comprising a polyaniline and a colloid to form a polyacid and blending an aqueous dispersion of other water-soluble or water-dispersible materials is provided. Depending on the final application of the composition of the present invention, examples of types of materials that can be added include, but are not limited to, polymer 'carbon nanotubes _, Nai: line' dyes, coating auxiliaries, organic and inorganic conductive inks and Pastes, charge transfer materials, parent binders, and combinations thereof. Other water soluble or water administrable materials can be simple molecules or polymers. Examples of suitable polymers include, but are not limited to, conductive polymers such as poly p-phene, polyaniline, polyamine, polyfluorene, polyacetylene, and combinations thereof. In another embodiment of the invention, there is provided an electronic device having at least one electroactive layer (typically a semiconductive conjugated polymer) disposed between two electrical contact layers, wherein at least one of the device layers comprises a buffer layer of the invention . A specific embodiment of the present invention is a device of the type shown in Figure i, and a device having an anode layer 11, a buffer layer 12, an electroluminescent layer 13 and a cathode layer bo. . Adjacent to the cathode layer 15 is an electron injecting/transporting layer 140 " between the buffer layer 120 and the cathode layer 5 (or electron injecting/transporting layer 14) is the electroluminescent layer 130. The device can include a support or substrate (not shown) that can abut anode layer 110 or cathode layer 150. Most often the support abuts the anode layer 11〇. The support can be flexible or rigid, organic or inorganic. Generally, glass or flex organic

0: V88VS9436.tX) C -22- 1330652 The film can be used as a branch. The anode layer 11G is an electrode which can be injected into the cavity more efficiently than the cathode 15 废. The anode may comprise a material comprising a metal, a mixed metal, an alloy, a metal oxide or a mixed oxide. Suitable materials include Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), pi; ^b Groups 4, 5 and 6 elements and Group 8.1 过渡 transition metals & Oxide. If the anode m is permeable to light, a mixed oxide of elements of Groups 12, 13 and 14 such as indium tin telluride may be used. As used herein, a mixed oxide, sheet language is equivalent to an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Part of the anode layer 11 〇 material is not limited. Specific examples include, but are not limited to, indium tin oxide ("IT〇"), oxidized chain tin 'gold, silver, copper, and nickel. The anode may also comprise an organic material such as polyaniline, poly phenanthrene or poly(tetra). Thorough use of the IUPAC naming system, which groups the population of the periodic table from left to right as 1]8 (CRC Handbook of Chemistry and Physics, the second, the anode layer can be chemically vapor deposited or rotated. Forming. Chemical vapor deposition can be performed by plasma assisted chemical gas (• column (10)” or metal organic chemical vapor deposition (" coffee VD.) Physical vapor deposition can include all types of sputtering, including ion beam reading. And t-beam and thermal resistance evaporation. Special types of physical vapor deposition include _ controlled sputtering and induced coupling plasma physical vapor deposition (,, lMp " ^

Techniques are well known in the art of semiconducting manufacturing. - The anode layer 110 can be patterned during the lithography operation. This pattern can be changed. These layers may be formed by applying a pattern mask or a resist to the first-wound composite barrier structure. Or 'coat these layers into a monolithic layer Z

O:\88\8S436.DOC •23· 1330652 Product) Use, for example, the pattern resist layer and the chemical or dry name engraving technology. Patterning programs well known in the art can also be used. When the electronic device is located within the array, the anode layer <RTIgt;forms substantially parallel strips, and the length of the strip extends substantially in the same direction. The buffer layer 120 is typically rinsed onto the substrate using a variety of techniques well known to those skilled in the art. Typical materials include, for example, solution casting, droplet washing, curtain washing, spin coating, screen printing, ink jet printing, and the like. Alternatively, the buffer layer can be patterned using a number of deposition processes, such as ink jet printing. The electroluminescent iridium layer 130 is typically a conjugated polymer such as poly(p-phenylacetylene), abbreviated as PPV or polyfluorene. The specific material selected can be used to determine the potential used during operation or other factors in the application. The EL layer 130 comprising an electroluminescent organic material can be applied by solution by any conventional technique, including spin coating, casting, and printing. Depending on the nature of the material, the EL organic material can be directly coated by a vapor deposition process. In another embodiment, the el polymer is coated and then typically converted to a polymer by heat or other applied energy source such as visible light or UV radiation. Layer 140 may be selected to aid electron injection/transfer and may also serve as a confinement layer to prevent the layer interface from terminating the reaction. More specifically, if layers 13 and 15 are otherwise in direct contact, layer 140 promotes electron mobility and reduces the likelihood of termination of the reaction. Examples of materials for the optional layer 140 include, but are not limited to, metal chelating oxinoid compounds (such as Alq3 or the like); morphine matrix compounds (such as 2,9-dimethyl-4,7-diphenyl _ ;ι,1〇_phenoline ("DDpAI,)' 4 7 diphenyl q phenanthroline ("DPA") or analogue); azole compound (such as 2_(4_biphenyl(1)-tert-butylbenzene) Base)-1,3,4-oxadiazole ("PBD" or the like), 3·(4_biphenyl O:\88\8W36.DOC •24- 丄 652 native-5-(4 a third butyl succinyl (,, taz" or the like, or a mixture of other compounds or any one or more thereof. Alternatively, a layer of ruthenium inorganic material is selected and contains Ba0, LiF, Li2 ruthenium or the like. The cathode layer 15G is an electrode particularly effective for injecting electrons or negatively charged carriers. The cathode layer 15G may be any metal or non-metal having a lower working function than the first electrical contact layer (in the column, the anode layer 11G). The term "lower working function" used in this article refers to a material whose working function is not greater than about 4. "ν. The "higher working function" used in this article is intended to mean that the working function is at least 4 The material of the cathode layer of the shot material may be selected from the group 1 metal (such as u, Na, K, Rb, cS), the group 2 metal (such as Mg, Ca, Ba or the like), the group Metals, lanthanides (such as Ce, Sm, Eu or the like) and (iv) (such as Th, ^ analogs). Materials such as aluminum, indium, bismuth and combinations thereof may also be used. The cathode layer (9) material is not limited Examples include, but are not limited to, ruthenium, lithium, osmium, planer, ruthenium, osmium, iridium, magnesium, osmium, and alloys and compositions thereof. Cathode layer 150 is typically formed by a chemical or physical vapor deposition process. Typically, the cathode layer will Patterned as discussed above with respect to the anode layer 11. If the device is placed in an array, the cathode layer 15 can be patterned into substantially parallel strips 'where the length of the strips of the cathode layer extend substantially in the same direction And substantially perpendicular to the length of the strip of the anode layer. The electronic component called the pixel is formed on the father and the point (when the array is viewed from a plane or a plan view, the strip of the anode layer intersects the strip of the cathode layer) In other embodiments, additional layers may be present in the organic electronic device For example, a layer between the buffer layer 120 and the EL layer 130 (not shown) can help

O:\88\88436.DOC •25· 1330652 Positive charge transfer, with gaps to match the layers, as a protective layer or the like, an additional layer between the 'el layer m and the cathode layer 150 (not shown to help the negative charge) Passing the 'band gaps' with the layers in between, as a protective layer or the like. The layers known in the art can be used. Moreover, any of the above layers 2 is made of two or more layers, some or all of the inorganic anode layers are vacant, buffered. The layer 120, the EL layer 130, and the cathode layer 15 can be subjected to surface treatment to increase the charge carrier transfer efficiency. The material selection of each component layer can be made by the purpose and manufacturing cost of the device providing high device efficiency, manufacturing complexity or The balance between other possible factors may be determined. The different layers may have any suitable thickness. The inorganic anode layer is typically no greater than approximately 500 nanometers, such as near-center (four) micrometers; the buffer layer (3) is typically μ approximately 250 nanometers, eg, approximately 5 〇 2 〇〇 nanometer; the anal layer 13 〇 is usually no more than nearly 1 _ nanometer, for example, nearly 5 nanometers; the optional layer (10) is usually no more than nearly 1 〇〇 nanometer, for example, nearly 2 〇 8 〇 nanometer; cathode 15〇 is usually no more than approximately 1 GG nm, such as near (four) nanometers. If the anode (10) or cathode 150 must penetrate at least some of the light 'this layer thickness should not exceed nearly (10) nanometer. Depending on the application of the electronic device, the anal layer 13〇 can be a light-emitting layer activated by a signal (such as in a light-emitting diode) or a material layer (such as a krypton) or a voltaic cell that responds to radiant energy and generates a signal with or without an applied voltage. Examples of the electronic device are selected from the group consisting of a photoconductive battery, a photoresistor, a photoelectric switch, a biosensor, a 弁雷尤电 sa body, an optoelectronic official, and a photovoltaic cell. After reading this patent specification, a person skilled in the art will be able to select a suitable one. The material luminescent material for its specific application can be dispersed in the substrate of another material with or without additives or formed separately. The layer of bismuth 13 〇 generally has a range of nearly nanometers.

O:\88\88436.DOC •26- The thickness of Hawthorn 652. In the organic light-emitting diode (1) LED, electrons and holes are injected into the iris layer 13 from the cathode/anode layer, respectively, to form negative and positively charged ions in the polymer. These polar ions migrate under the influence of the applied electric field, forming a polar ionic exciton with the opposite electrothermal species, followed by radiation recombination. A sufficient potential difference between the anode and the cathode can be applied in the device, typically below. Volt, in many cases, is no greater than approximately 5 volts. The actual potential difference visual device depends on the application in the larger electronic components. In many embodiments, the anode layer 11 is biased to a positive voltage, and the cathode layer 15 is substantially at ground potential or zero volt during operation of the electronic device. A battery or other power source can be electrically connected to the electronics as part of the circuit, but is not illustrated in Figure 1. It has been found that an OLED having a buffer layer having a long life, wherein the buffer layer is formed of an aqueous dispersion (IV) comprising polyaniline and a colloid to form a polyacid. The buffer layer may be cast from an aqueous dispersion of polyaniline and a fluorinated polysulfonic acid colloid. In one embodiment, the aqueous dispersion is a dispersion having a pH adjusted to about 3.5 or greater. The use of lower acid or pH neutral materials significantly reduces the etching of the IT layer during device fabrication, resulting in a very low ratio and "ion concentration diffused into the LED polymer layer. Because of the suspected In and Sn ions, the operating lifetime is reduced. It is an important benefit. Lower acidity also reduces corrosion of metal components (such as electrical contact pads) on the display during manufacturing and during long-term storage. PANI/PSS A residues will interact with residual moisture, releasing acid to the display causing slow corrosion.

O:\88\88436.DOC -27· 1330652 The buffer layer of the present invention has a low moisture absorption, so that the device manufacturing process contains less water. This lower moisture content also gives the device a better operating life and less corrosion. The equipment used to disperse the PA PA SSA must be specially designed to fall into the strong acidity of the state. For example, it has been found that a chrome-plated slot die coating head for coating job/PSSA on an ITO substrate is rotted by the acidity of PANI/PSSA. This makes the head unable to make S because the coated crucible is contaminated by the chromium particles. Moreover, the manufacture of 〇LED displays is of interest to certain inkjet printheads. He is used to distribute the buffer layer and the luminescent polymer layer in the intensive position on the display. These print heads contain a nickel mesh filter as an internal trap for the ink particles. These nickel filters are decomposed by acidic pANI/PSSA and rendered unusable. These corrosion problems will not occur with the aqueous PANI dispersion of the present invention which has been reduced in acidity. Furthermore, it has been found that certain luminescent polymers are sensitive to acidic conditions and that their contact with an acidic buffer layer will reduce their ability to luminesce. It is preferred to form the buffer layer using the aqueous PANI dispersion of the present invention because it is less acidic or neutral. If each luminescent material requires a different cathode material to optimize its performance, it would be complicated to make a full color or partial color display using two or more different luminescent materials. The display device is composed of multiple illuminating pixels. A colorful device has at least two different types of pixels that emit different colors of light (sometimes equivalent to sub-pixels). The sub-pixels are composed of different luminescent materials. It is highly desirable to have a single cathode material that provides good device performance for all light emitters. This reduces the complexity of device fabrication. It is foreseen that the ordinary cathode can be used in the buffer layer which is made of the aqueous PANI dispersion of the present invention and which maintains good device performance in each color. O:\S8\8S436.DOC-28, 1330652. The cathode can be made of any of the materials discussed above and can be coated with a more inert metal such as aluminum. Other organic electronic devices obtainable from one or more layers of aqueous dispersions comprising polyaniline and at least one colloid to form a polyacid include (1) devices that convert electrical energy into light (eg, luminescence: polar body, luminescence: polar display or two) Polar laser)' (2M device for measuring the signal of electronic program (such as photodetector (such as photoconductive battery varistor, photoelectric switch, photoelectric crystal, photocell), claw detection benefit), (3) will A device for converting radiation into electrical energy) and (4) a device (eg, a transistor or a diode) comprising - or a plurality of electronic components, wherein the electronic component comprises one or more organic semiconducting layers. The buffer layer may be additionally covered by an aqueous solution or a layer of a conductive polymer coated with a solvent. Conductive polymers can help charge transfer as well as improve coating properties. Examples of suitable conductive polymers include, but are limited to, polyaniline, polythiophene, polythiophene-polyacid colloids, such as those disclosed in the application Dup〇nt No. ρΕ嶋 or polythiophene/poly Stupid vinyl sulfonic acid, polypyrrole, polyacetylene and combinations thereof. Providing a thin film field effect transistor comprising polyaniline and colloid in another embodiment of the invention is an electrode for thin film field effect formation of polysulfonic acid. The transistor is used as an electrode, and the conductive polymer and the liquid for dispersing or dissolving the conductive polymer must be compatible with the solvent of the semiconductive polymer and the semiconductive polymer to avoid redissolution of the conductive polymer or the semiconductive polymer. The thin film field effect transistor electrode made of a conductive polymer should have a conductivity greater than 1 〇 s/cm. However, conductive polymers made of water-soluble polyacids only provide conductivity in the range of ~heart/cm or lower. Thus, in a specific embodiment O: \88\S84J6.DOC -29- 2 = 2: stupamine and fluorinated colloid form a polyacid and combine conductivity - ^ ' no, rice noodles, carbon nanotubes or the like Things. In another and body = in:! The pole contains polyaniline and steroids to form a full-air ethylene sulphuric acid I-causing agent such as a metal nanowire 'carbon nanotube tube or the like. The composition of the present invention can be used as a gate, a gate or a source in a thin film field effect transistor, and the other embodiment of the present invention is a thin film field effect transistor shown in Fig. 2. In this brother's month, the ''an electric polymer or dielectric oxide film 21 has a gate 220 on one side and a drain 23 on the other side and a source 24 (eight). The organic semiconductive film 25 is deposited on the bungee. Between the sources. The lunar water slurry containing metal nanowire or carbon nanotube tube can be ideally used for gate, drain and source applications because it is in solution film deposition with organic matrix dielectric polymer. And compatibility of semiconductive polymers. Since the conductive composition of the present invention, such as PANI and colloidal perfluoroethylenesulfonic acid, is present as a colloidal dispersion, the percentage of conductive filler required to achieve a high conductivity percolation limit is lower (relative to the inclusion of a water-soluble polyacid) Composition). In another embodiment of the invention, there is provided a method of making an aqueous dispersion of polyaniline comprising polymerizing a strepamine monomer in the presence of a polysulfonic acid colloid. In another embodiment, the colloid-forming polyacid is a carboxylic acid, propylene k, humiliation, phosphoric acid or the like or a combination thereof. In a specific embodiment of the method of the invention, the polyaniline is a polyaniline and the colloid-forming polyacid is fluorinated. In another embodiment of the method of the invention, 'polyaniline is an unsubstituted polyaniline, and the colloid-forming polyacid is perfluorinated. In another embodiment, the colloid-forming acid is polyvinylsulfonic acid. In another embodiment having O:\88\88436.DOC •30·, the polyvinyl sulfonic acid is perfluorinated. The polymerization is carried out in the presence of water. In another embodiment, the polymerization of the perfluoroethylene-containing acid is carried out as described above with an additional acid. The resulting reaction mixture can be treated with an ion exchange resin to remove reaction by-products and to obtain a desired pHA dispersion. In another embodiment, the pH can be further adjusted with an ion exchanger or an aqueous test solution. The invention will now be described in more detail by reference to the following non-limiting examples. EXAMPLES - Comparative Example 1 This comparative example illustrates the high moisture absorbance and redispersibility of dry solids prepared by Ormecon Corporation's D 005 W OLD. It also illustrates the acidity of the water that is in contact with the dry film. D 1005 W LEDs from Ormecon Chemie GmbH and company KG (Ammersbeck, Germany) are aqueous polyaniline dispersions. The polyaniline polymer is prepared by polymerization of a stilbene amine and a water-soluble poly(styrenesulfonic acid). Approximately 15 ml of the aqueous dispersion was dried with a flowing nitrogen stream. 〇_〇 5 g of dry polymer film was mixed with 45 g of deionized water having a pH of 7. The pH was measured with a piece of Color pHast® indicator strip (EM Science 'pH 0-14 range, catalog number 9590). The color of the wet indicator strip is compared to the color table to read the pH. Once the polymer film is in contact with deionized water, the water turns dark green and is soon completely dispersed in the water. The pH of the water is about 1 'which is very acidic. Under ambient conditions (~25 °C / 50% RH), the dry film also absorbed about 24% moisture. This example illustrates that a polyamine which is formed by a water-soluble polyacid is easily dispersed in water to form a low pH dispersion. It also absorbs a lot of water. All results show that the acid is highly mobile and has a high O:\S8\88436.DOC -31 - 1330652 tends to migrate to adjacent polymer layers, such as photopolymer layers, which impair its function. Comparative Example 2 This comparative example illustrates the redispersibility of a dry solid obtained from an aqueous PANI/PAAMPS A dispersion in which the dispersed polyaniline was produced using aniline and water-soluble PAAMPSA. It also illustrates the acidity of the aqueous dispersion. 60.65 g (43.90 nm acid monomer unit) aqueous PAAMPSA solution (Aldrich, catalog number 19,197-3, lot number 07623 EO, Mw~2 million, 15% solids in water) was introduced into the jacket 500 ml three neck In the flask, 33 5.07 grams of deionized water was added. The flask was equipped with a stirring paddle driven by a pneumatic overhead stirrer and a small tube for adding ammonium persulfate. Place the small tube into the glass pipette with the top removed and insert the pipette into the No. 29 septum so that the end of the tube extends out of the pipette at approximately 1/2" above the reaction mixture. The circulation of the 22 °C fluid was maintained using a thermocouple having an inlet for monitoring the temperature of the polymerization liquid in the jacketed flask. After the stirring of the PAAMPS A/water mixture was started, freshly distilled aniline (4.0 ml, 43_9 mmol) was pipetted into the flask. Stir the mixture _ mixture for nearly 1 hour. With continuous stirring, ammonium persulfate (4.01 g, 17.572 mmol, purity 99.999 + % from Aldrich) was placed in a scintillation vial and the mass was mixed with 16.38 grams of deionized water. This mixture was placed in a Norm-Ject 30 ml syringe and attached to the tube of the flask using a 17 gauge syringe needle. The syringe was attached to a high pressure pump of a programmed Harvard apparatus 44 to add ammonium persulfate (APS) over 30 minutes. The temperature of the mixture was about 23 ° C during the addition of APS. One minute after the start of APS addition, the reaction mixture turned blue and began to darken. After the addition of the APS solution was completed, the reaction was continued for 24 hours with continuous stirring. O:\88\88436.DOC -32· 1330652 After 24 hours, pour the reaction mixture into a 4 liter plastic Naigen 8 beaker and start mixing. Pour acetone (2 liters) into a 4 liter beaker. in. The acetone mixture was continuously stirred for 3 minutes. Once the agitation was stopped, the mixture was allowed to stand in two layers, and most of the reddish-yellow liquid phase was poured out, leaving the residual mouth product and then moving it to the Erlenmeyer flask. The flask was placed in a manner that was mixed with a knife. In addition, 430 ml of fresh acetone was quickly added to the beaker. This disturbed for 15 minutes. This caused a muddy, which was allowed to stand for about 3 minutes before being filtered through a Buchner funnel containing a 54-gauge paper. The mother liquor was clarified as a colorless one and 43 g of fresh _ quick added to the product. This stirring for nearly 90 minutes 'with a piece of Whatman No. 54 filter paper

The slurry was allowed to stand for about 4 hours before the Buckner funnel was filtered. At the same time, the pale green solid product was collected on the filter paper and the filtrate was extremely pale green. The filter cake has fine particles and some large size particles +. The funnel and its contents were placed in a vacuum oven (~20 inches of mercury, ambient temperature) for about 2 days. The yield is u93 grams. 〇.3 1 gram of PANI/PAAMPSA powder prepared from above was mixed with 2 〇 38 g of deionized water. This polymer powder disperses very quickly in water to form 1.5/. (Heavy 1 / reset) dispersion. 15 grams of the dispersion was mixed with 3 grams of deionized water to test the pH using one of the above Color pHast® indicator strips. The pH of the dispersion was 3. This example shows that polyaniline prepared by water-soluble polyacid can be easily dispersed in water to form a low pH dispersion. The results show that the acid is highly mobile and highly prone to migrate to adjacent polymer layers, such as photopolymer layers, which impair its function. Example 10: \88\88436.0 (X: -33· 1330652) This example illustrates aqueous PANI/ Preparation of a Nafion® dispersion in which the dispersed polyaniline is made from aniline and Nafion®, a colloidal perfluoroethylene sulfonic acid. This example also illustrates the non-dispersibility of dry solids prepared from aqueous PANI/Nafion® dispersions. Low water analysis. This also indicates the neutrality of the water in contact with the dry film. The present invention utilizes Nafion® polymer dispersion prepared according to the method described in U.S. Patent No. 6,150,426, issued Nov. 21, 2000. The Nafion® polymer dispersion sample contained 12.0% (w/w) perfluoroethylenelithic acid solids in water, and the Nafion® polymer had 1 〇50 g/mole acid monomer unit. 191.63 g ( 21.90 millimoles of Nafion 8 monomer unit) Nafion® polymer dispersion and 206.32 grams of deionized water were poured into a 5 cc three-necked flask equipped with a pneumatic agitator driven paddle And sulfur Small tube for ammonium. Place the small tube into the glass pipette with the top removed. Pass this through the No. 29 diaphragm and extend the tube out of the pipette at approximately 1 / 2 " above the reaction mixture. The thermocouple has its own The inlet of the temperature of the polymerization liquid in the jacketed flask was monitored to recycle 20. The helium fluid was then started. The Nafion®/water mixture was then stirred. Then the aniline was distilled off by pipetting 2 ml (21 9 mmol). 1 hour. With stirring, 2 〇 2 g (8.852 mmol) of persulfate (Jing from Aldrich, purity 99.999 + 0/.) was placed in a scintillation counter bottle. Then the group was 8 丨Mix 6 grams of deionized water. Then inhale into a N〇rm-ject 3 〇 ml syringe and hook it into the tube with a 17 gauge syringe needle. This syringe is hooked on the Harvard equipment 44 high pressure pump. The pressure pump was established by adding ammonium persulfate (Aps) in 3 minutes, but the actual addition time was 28 minutes. During the polymerization, the temperature system was about O:\88\88436 DOC -34- 1330652 20 °C ° The reaction mixture is very easy to foam and within minutes of adding ApS2 It is blue. The polymerization is very dark in color within 1 hour and shows very uniform. The polymerization is allowed to proceed for about 25 hours and the entire polymerization liquid content is poured into a 1 liter Erlenmeyer flask. It is dark green, the color of the conductive polyaniline expected. The liquid is kept undisturbed for about 44 hours. It is surprisingly found that the polymerization liquid does not split into two phases' means that the clear liquid layer is at the top and the green precipitate is at the bottom. This result clearly shows that a stable polyaniline/Nafi〇n8 aqueous dispersion g has been prepared and the liquid is then pumped through a Buchnei bucket containing two pieces of Whatman No. 54 filter paper. When the filtrate began to pass, it was dark green and the color became light due to the shielding of the filter paper. Filtration becomes extremely slow, so the filter paper must be replaced several times. The collected filter cake was redispersed in 4 mL of deionized water while still wet. Filtration was accomplished in the same manner and the filter cake was redispersed in 300 mL of deionized water while still wet. A portion of the 300 ml PANI/Nafion* dispersion was allowed to stand undisturbed for 1 week. Again, the dispersion did not separate into a clear liquid phase, although some green precipitates were at the bottom. Hey. A portion of the dispersion was dried by flowing nitrogen to form a solid film to measure the percentage of solids. It was found to be 3.2%. The dry film is then ground into a fine powder which is very dark green. TGA showed that the dry powder only absorbed 1.7% moisture when equilibrated at 25t/50% RH. 〇·1255g PANI/Nafion® powder is mixed with 4_877 gram of ion, neutral water and shaken. The PANI/Nafi〇n® polymer powder remains intact without fading the water. The pH of the water remains neutral when tested on a piece of pHast® litmus paper. This result clearly shows that the polyacid remains in the polymer, even if it is in contact with water O:\88\88436.DOC •35·1330652 to keep the water neutral. Example 2 This example illustrates the preparation of an aqueous PANI/Nafi〇n8 dispersion and the effect of resin treatment on the stability of the dispersion and pH. This example also illustrates the non-dispersibility and low moisture absorption of dry solids prepared from aqueous PANI/Nafi〇n® dispersions. It also indicates that the water in contact with the dry film is neutral. In the present examples, SE 10072 Nafion® is used to polymerize with aniline. Nafion® is commercially available from Dup〇nt Heart Nem〇urs & In contrast to Nafion® having a colloidal size ranging from 2 to 3 nanometers as disclosed in U.S. Patent No. 6,150,426, issued on Nov. 21, 2000, to the present invention, SE 1〇〇72fNafi〇 The colloidal size of n8 is in the range of 40 nm to 140 nm. The polymerization procedure described in the examples of the present invention was followed to produce PANI/Nafion®. The SE i〇〇72 Nafion 8 colloidal dispersion used in this example contained 11.2% (w/w) perfluoroethylene sulfonic acid colloid in water. Nafion® polymers have an acid monomer unit of about 920 grams per mole. 97 29 g (11.84 mmol of Nafion® monomer unit) of Nafi〇n 8 dispersion and 296.15 g of deionized water were poured into a jacketed 500 ml three-necked flask. Then start stirring the Nafion®/water mixture while 2 (rc fluid is continuously circulated through the jacketed flask. Then 1.079 ml (11.84 mmol) of the distilled aniline is pipetted into the flask and allowed to stir for 1 hour. Time. A total of 1.08 g (4.733⁄4 mol) persulfate (purchased from Aldrich, purity 99.999 + %) was placed in a scintillation vial. The pellet was then mixed with 4.38 grams of deionized water. The ammonium persulfate solution was added to the reaction mixture in minutes. Polymerization O:\88\88436.DOC -36-13330652 The temperature was about 20 4 ° C during the reaction. The reaction mixture was highly foamable. It is very dark green in color and shows unevenness. Place the droplet polymer on the microscope sheet 'once dry out to form a very thick film. 7 t for about 24.5 hours. Pour the polymerization liquid from the reactor into two In a plastic bottle, one part is 184 g; the other is 203 g. 184 g is allowed to stand overnight. It is divided into two layers. The upper layer is a clear liquid, but the bottom layer is a dark green precipitate. 203 g of a part of the polymerization liquid and 769克D〇wex(g)55〇A mixed, 7.94 grams of Dowex® 66 was added to the reaction flask for 2 hours. D〇wex® 550A is a quaternary amine anion exchange resin and D〇wex8 is a tertiary amine ion exchange resin (D〇w of Michigan) Chemical company). Before use, wash the resin repeatedly with deionization until the water cleaning solution has no color or odor. Then the resin treated slurry is pre-filtered through gauze to the 丨 liter beaker. The second filtration is 5 〇〇. The mesh stainless steel was completed. The filtrate was stable and passed through a 0.45 micron dp filter (Whatman 25 cm gdX, catalog number: 6992-2504). The pH of the filtered dispersion was measured using a 63s pH meter purchased from Jenco Electronics. It was found to be 7.4. Resin treatment obviously makes the PANI/Nafion® polymerization liquid into a stable dispersion. It should also be understood that depending on the amount of the ion exchange resin used and the resin treatment time, the pH of the polymerization liquid can be changed from ~ 1.5 Adjusted to any below neutral ipH. The pH of a liquid typically derived from the polymerization of 1 mole of aniline / 1 mole of Nafi〇n® / 0.4 moles of ammonium persulfate is 1.5. Dry a small portion with flowing nitrogen Resin PANI/Nafi(10)8 was treated until the stem was fixed. Then it was continuously equilibrated at room temperature to absorb water. O:\S8\88436DOC -37- 1330652 The water absorbance was measured to be 3.6%. The dry solids were no longer dispersed. In water, the pH of the water contacted with the solid was measured by a type 63 ρ from Jenco Electronics. Example 3 This example illustrates the preparation and device properties of a high pH aqueous PANI/Nafion® dispersion. In the present invention, SE 10072 Nafion® is used to polymerize with aniline. Nafion® is commercially available from Ej Dup〇nt Heart Nem〇urs & In contrast to Nafion®, which has a colloidal size in the range of 2 to 30 nm, as described in U.S. Patent No. 6,150,426, issued to the present invention, which is incorporated herein by reference in its entirety, the Nafion® in SE 10072 The colloidal size is in the range of 40 nm to 140 nm. The polymerization procedure described in the examples of the present invention was followed to produce PANI/Nafion®. The SE 1〇〇72 Nafi〇n® colloidal dispersion used in this example contained 11.20/. (Weight/weight) perfluoroethylene sulfonic acid colloid in water. Nafion® polymers have an acid monomer unit of about 920 grams per mole. 1946 grams (23.69 millimoles of Nafion® monomer units) of Nafion® dispersion and 602.28 grams of deionized water were poured into a jacketed 1 liter three-necked flask. The mixture of Nafion 8 /water was then stirred while the 2 liters of fluid were continuously circulated through the jacketed flask. Then 2.159 ml (23.69 mmol) of the distilled aniline was pipetted into the flask via a pipette. Let this stir for 1 hour. With stirring, 2 j 8 g (9.5533⁄4 mol) of ammonium persulfate (purchased from Aldrich, purity 99.999 ten 0/〇) was placed in a scintillation counter bottle. The mass was then mixed with 8.74 grams of deionized water. The persulfate solution was added to the reaction mixture over 30 minutes. During the polymerization, the temperature was about 20.4 °C. The reaction mixture is extremely foamy. In 1 hour O:\88\88436 DOC •38-1330652, the polymerization has turned into a very dark green color, showing a very uniform color. The polymerization was allowed to proceed for about 24 hours. 18·82 g of 〇_@@〇8 and 14 88 g of D〇wex® 66 were added to the reaction flask and stirring was continued for 4 hours. D〇wex® 550A is a quaternary amine anion exchange resin and D〇wex 866 is a tertiary amine ion exchange resin (D〇w Chemical Company, Michigan). For use, the resin is repeatedly washed with deionization until the water wash has no color or odor. The resin treated slurry is then pre-filtered through gauze into a 丨 liter beaker. The second filtration was done via 5 inch mesh stainless steel. The yield is 670 670.80 g. Approximately 30 ml of the dispersion sample prepared above was filtered through a 微米 45 micron ferrule filter (Whatman 25 cm GDX, catalog number: 6992-2504). The pH of the filtered dispersion was measured by a model of Model 61 from Jenco Electronics and found to be 7.4. For luminescence measurement, an aqueous PANI/Nafion® having a pH of 7.2 was spin-coated on an ιτο/glass substrate at a rotation speed of 800 rpm to form a thickness of 1 〇〇〇. The ITO/glass substrate coated with PANI/Nafion® was dried in nitrogen at 9 ° C for 30 minutes. The ultra-yellow emitter (ρΓ)γΐ31) is then applied to the top surface of the Pani/Nafion® layer, wherein the ultra-yellow emitter is a poly(substituted-present acetylene) (Covi on, Inc., Frankfurt, Germany). The thickness of the electroluminescent (el) layer is approximately 70 nm. The thickness of all films was measured with a TEnc® R 500 surface profiler. For the cathode, and the A1 layer was deposited on the top surface of the EL layer under a vacuum of 1 χ 1 〇 - 6 Torr. The final thickness of the layer B a is 30 angstroms; the thickness of the ruthenium layer is 3000 angstroms. The test of device performance is as follows. Measurement of current versus voltage, luminescence intensity versus voltage with 236 source-measurement unit (Keithley) and S37 illuminance meter 0\88\SWJ6.DOC -39· 1330652 (UDT Sensor) with calibrated 矽photodiode - Variation and efficiency The illuminating device shows an operating voltage of 3 65 volts, a luminous efficiency of 7.2 Cd/A at 2 〇〇 candle/m2 (Cd: candlelight; a: ampere example 4 at room temperature 'will be 92.00 g DI water and 92.00 g of 99.7% n-propanol were placed directly into a 500 ml double-layer reaction vessel. Next, 3.58 ml (43.59 mmol) of 37 wt./〇HCl and 1.988 ml (21.80 mmol) were used. The aniline (steamed) was added to the reactor via a dropper. The mixture was stirred overhead with a U-shaped stir bar set at 5 〇〇 RpM. After 5 minutes, 91.98 g (10.90 mmol) was slowly added via a glass funnel. The Nafi〇n® (DE-1020, 10.9〇/〇 solid, 920EW) has been dispersed in the water of the 微米·3 micron profile filter. The mixture is homogenized for 5 minutes. The pump is injected with high pressure for 1 hour.丨99 g (8 72 mmol) is dissolved in 20 g of DI water ammonium persulfate (99.99+%) After 8 minutes, the solution turned pale blue-green. The solution turned dark blue before turning to very dark green. After the APS was started, the mixture was stirred for 90 minutes and - 7.00 g of Amberlyst-15 (Pennsylvania Rohm and Haas) ion exchange resin (already washed several times with a mixture of 32% n-propanol (dissolved in DI water) and dried under nitrogen) and started mixing overnight at 200 RPM. The next morning, the mixture was filtered through a stainless steel mesh and with Amberjet 4400 (〇H) (Rohm and Haas, Philadelphia, PA) Anion exchange resin was stirred (already washed several times with a mixture of 32% n-propanol (dissolved in DI water) and dried under nitrogen) until the pH changed from 0.9 to 4.4. Again The resin was filtered off. Prior to use, the dispersion was filtered through a 45 micron Millipore Millex-HV syringe filter with a Pvdf membrane. Yield: Nearly 3 grams of dispersion with 4% n-propanol / 68% DI water 4% Solid: O:\88\88436.00C -40- 1330652 A film having a thickness of 1600 RPM was applied by spin coating on a glass of U51 angstrom. The conductivity was i 36x1 〇 -5 s / cm. As described in Example 3. a device made in general. The device has the following Performance provided. Where /2 is the time at which the brightness is half of the initial brightness at the indicated temperature: _ turbidity / square meter voltage and efficiency: 3 45 volts and 98 candelas / amp; at -7 volts Leakage under: 2 microamperes; T"2 at 8 °C (initial brightness: 412 candelas per square meter): 97 hours. Example 5 88.11 g of 99.7 was added at room temperature. /. N-propanol and 88.11 g of 1) 1 water were placed in a 5 〇〇 ml double-layer reaction vessel. Next, 0167 ml (2 〇 millimolar) 37% by weight of HC1 and 0.901 ml (9-9 mM) of aniline were added. (Distilled) was added to the reactor via a dropper. The mixture was stirred overhead with a 500 RP MiU-shaped stir bar. After 5 minutes, slowly add 3 g (11.90 mmol) via a glass funnel to the water dispersing Nafi〇n® (DE-1020, 11.1% solids, 935 EW) through a 微米.3 micron profile filter. The mixture was allowed to homogenize for another 10 minutes. 2 82 g (12 4 mmol) of ammonium persulfate (99.99 +%) dissolved in 20 g of DI water was added dropwise to the reaction over 6 hours via a high pressure injection pump. After 7 minutes, the solution turned pale blue green. The solution gradually turns dark blue before turning the solution to very dark green. After the initial addition of APS, the mixture was stirred for 360 minutes and added with 7.5 0 g of 八!1^61' with 3 br 15 cation exchange resin (already 32 〇 / () n-propanol (dissolved in DI water) mixture washed several times and in nitrogen Dry down) and start the separator at 2 rpm. On the morning of 13⁄4, the mixture was passed through a steel mesh and cleaned with a mixture of A mberjet O:\88\88436.DOC -41 · 1330652 4400(OH) anion exchange resin (already 32% n-propanol (dissolved in 〇1 water)) Stir several times and under nitrogen) until pH*丨3 becomes 48. The resin was filtered off again. Prior to use, the dispersion was filtered through a 45 micron Millipore Millex-HV syringe filter with a pvDF septum. Yield: Nearly 27 grams of dispersion, 31% n-propanol / 69% DI water with 4% solids. The dispersion was spin-coated on the glass at 1000 RPM to form a film having a thickness of 2559 Å. The conductivity is 1.67x1 〇_6S/cm. A device was prepared as described in Example 3. The device has the following properties: · Voltage and efficiency at 600 candelas per square meter: 3 brothers volts and ι〇3 turbidity/amperes; leakage at -7 volts: 6 microamperes; T1/1 at 8 °C a (initial brightness: 49 〇 candle / square meter): hour. Although the present invention has been described in detail with reference to the particular preferred embodiments thereof, it is understood that modifications and variations are within the spirit and scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a cross-sectional view of an electronic device incorporating a buffer layer in accordance with the present invention. Figure 2 illustrates a cross-sectional view of a thin film field effect transistor comprising an electrode in accordance with the present invention. [Description of Symbols] 110 Anode Layer 120 Buffer Layer 130 Electroluminescent Layer 140 Electron Injection/Transfer Layer 150 Cathode Layer

O:\88\88436.DOC -42· 1330652 210 Dielectric polymer; Dielectric oxide film 220 Gate 230 Tungsten 240 Source 250 Organic semiconductive film O.V88\88436.DOC -43 -

Claims (1)

1330652 Pickup, Patent Application Range: 1. A composition comprising an aqueous dispersion of polyaniline and at least one colloid to form a polyacid. 2. The composition according to claim 1, wherein the polyaniline has an aniline monomer unit, and the aniline monomer unit has a structural formula selected from the group consisting of: A this Wherein: η is an integer from 0 to 4; m is an integer from 1 to 5 'premise that n + m = 5; and R1 is independently selected such that each occurrence is the same or different and is selected from the group consisting of , alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylsulfanyl, alkaryl, aralkyl, amine, alkylamino, secondary Amine, aryl, sinter, oxyalkyl, sulfhydryl, arylthio, aryl, oxycarbonyl, carboxylic acid, halogen, cyano or One or more alkyl groups substituted with a repeating acid, a carboxylic acid, a halogen group, a nitro group, a cyano group or a cyclic lactyl group; or any two groups together form an O:\88\88436.DOC 1330652 to 4 5 6 or A 7-membered aromatic or alicyclic ring having an extended or extended base bond, which ring optionally contains one or more divalent nitrogen, sulfur or oxygen atoms. 3. The composition according to claim 1 or 2, wherein the colloid-forming polyacid is selected from the group consisting of polyacids, m η Κ ^ 竣 citric acid, and polyphosphoric acid or polyacrylic acid or a mixture thereof. 4. According to the scope of the patent application, the composition of the invention is in which the polyacid comprises perfluoroethylene-sintered acid β. 5. The aqueous dispersion of polyaniline and at least 趿ν colloid to form polyacid A liquid method comprising: (a) providing a homogeneous aqueous mixture of monohydrate and aniline; (b) providing an aqueous dispersion of the polyacid; (c) incorporating the aniline mixture into the colloid to form an aqueous dispersion of the polyacid And (d) incorporating the oxidizing agent and catalyst into the aqueous dispersion of step (c) in any order of addition. 6. The method of claim 5, wherein the method further comprises contacting the aqueous polyaniline dispersion with at least one ion exchange resin, wherein the ion exchange resin is a cation exchange resin, an anion exchange resin, or a mixture thereof. 7. The method of claim 5, wherein the method further comprises an oxidizing agent, a catalyst, a co-dispersing agent, (IV) or all of these additional force finishing aids. 8. The method according to claim 5, wherein the method further comprises: an oxidizing agent selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate or a combination thereof; O:\88\88436.DOC • 2- 1330652 A catalyst is selected from the group consisting of iron sulfate, iron carbide or a mixture thereof; a co-dispersant is selected from the group consisting of ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitriles, sub-sectors and combinations thereof And further comprising contacting the dispersion with an ion exchange resin, wherein the ion parent resin is selected from the group consisting of sulfonated styrene-divinylbenzene copolymer, sulfonic acid, sulfonated crosslinked styrene polymer, benzene-formaldehyde sulfonate Acid, citric acid, acrylic acid, phosphoric acid, tertiary amine, quaternary amine anion exchange resin, and mixtures thereof. 9. An organic electronic device comprising at least one organic layer, wherein the organic layer is made from a composition comprising an organic aqueous dispersion of polyaniline and at least one colloid to form a polyacid. 10. The device according to claim 9, wherein the device is a photo sensor, a photoelectric switch, a photoresistor, a photoelectric crystal, a photocell, a claw detector, a photovoltaic cell, a solar cell, a light emitting diode, Biosensor, LED display or diode laser. O:\88\88436.DOC