TWI306868B - Redispersible latex comprising a polythiophene - Google Patents

Description

Ϊ 306868 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an aqueous latex dispersion of a polymer or copolymer comprising a polyanion disk comprising a polyanion disk, a thin or substituted porphin; It can be redispersed or soluble. Λ [Prior Art] • Preparation of polythiophenes and their dispersions for antistatic coatings has been described in the literature 'Handb〇〇k 10 of Organic Conductive Molecules and Polymers' (Handb〇〇k 10 of Organic Conductive Molecules and Polymers) , HS Nalwa, ed., L Wiley & Sons, 1997. Polythiophene has an electrically conductive property that can be controlled by the degree of doping. • FR-A-887976 discloses a method for preparing a conductive polymer based on polyporphin, which is a chemical polymerization reaction of a thiophene in a reaction medium comprising an iron salt, an alkyl group and 15 water. φ US-P-5254648 discloses a method for preparing an electrically conductive doped polythiophene. The method comprises: an unsubstituted porphin, an iron salt which is effective as a dopant and acts as an initiator for the polymerization reaction. And an anhydrous alkyl salt is added to the reaction medium, an alkyl halide, which is present in an amount of less than 0.04 liter per 2 gram of thiophene, and water, wherein the amount of water introduced is in the range of 0.009 of the alkyl halide Between 900% by weight, and wherein the water and anhydrous iron salts are present in a molar ratio ranging between 0.01 and 6. WO-A-9925753 describes a process for the preparation of polyaniline, polythiophene and polypyrrole. 13〇6868 EP-A0440957 Revealed in the presence of the arm position, the structure of the formula (1)

Independent of each other means hydrogen or Cl_4-alkyl, or together form a substituted Ci_4-alkyl residue. 15

EP-A-0686662 discloses a mixture comprising a and B, wherein A) has a repeating structural unit of the formula (I), a neutral polybenzazole, -rH

Wherein R1 and r2 independently of each other represent hydrogen or Ci_4-alkyl, or together represent a Ci_4_alkyl residue which is optionally substituted, preferably a methylene group which is optionally substituted by an alkyl group, optionally by Ci_i2_ a 1,2-extended ethyl residue or a 1,2-cyclohexene residue substituted with a phenyl group, and B) a di- or poly-based and/or a suspending group or a guanamine or an indoleamine The organic compound of the group; and the conductive coating prepared therefrom are adjusted to increase its electrical resistance, preferably up to 300 ohms. EP-A1081549 discloses a coating composition comprising an octagonal or unsubstituted thiophene a conductive polymer, a film-forming binder, and a solution of an organic ~% medium; the medium having a water content of less than 37% by weight ☆ the weight percentage of the sword (3,4-ethylenedioxythiophene) in the coating solution is ^ 20 1306868 is an example of it. EP-A1081546 discloses a coating composition comprising an electrically conductive polymer (ECP) and an organic solvent medium, wherein the solvent is selected from the group consisting of alcohols, _, naphthenes, aromatic rings, esters, glycol ethers. And mixtures thereof; the medium has a water content of less than 12 weight percent. The weight percentage of ECP in the coating solution is 0.02 to 0.18% as an example. EP-A 10 871 548 discloses a coating composition comprising a conductive polymer of substituted or unsubstituted porphin and an organic solvent medium; the medium having a water content of less than 12% by weight. The weight percentage of poly(3,4_ethylenedioxythiophene) in the coating dispersion is 0.02 to 0.1% as an example. 15 In a large-scale process for preparing a latex aqueous dispersion comprising a polymer or a copolymer of a polyanion and a substituted or unsubstituted thiophene, the solids content is limited to only a small percentage due to, for example, ultrafiltration requirements, dispersion viscosity. Caused by production factors. It should be noted that such dispersions are often referred to as solutions due to the extremely small particle size (2 Å to 50 nm) of their polycarbo/polyanionic latex, even in the patent text. The transport of such dilute dispersions is both expensive and cumbersome to maintain and preserve perishable organic substances (such as foods, seasonings, flavors, blood products, and pharmaceutical formulations) from the standpoint of the large volume and weight involved. The method of transporting in space navigation, exploration, and military activities. Since the 196s, it has been treated with more than 400 foods, from meat to fruits and vegetables. This background is reflected in the TA (1) such as !10^ and 11 gamma (10) in 1995, Journal of Non-Enteral Science and Technology, Vol. 49, No. 6, pp. 272-282. Xindong 20 1306868 Drying treatment) is defined as a method of stabilization, in which the substance is first frozen, then sublimated, and then desorbed to reduce the amount of solvent to no longer maintain biological activity or chemical reaction. Numerical value 5 [Invention] One item of the present invention is to provide a highly concentrated latex of substituted or unsubstituted polythiophene. I Another aspect of the invention provides a method of making an antistatic or electrically conductive layer. Still another aspect of the present invention provides a coating solution or dispersion of a latex which is obtained from a highly concentrated dispersion latex of polythiophene. - Another aspect of the present invention is to provide a highly concentrated dispersion, liquid latex printing ink from polythiophene. Other objects and advantages of the present invention will become more apparent from the following description. 15 ° • The invention is directed to a latex dispersion or solution comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene to obtain a concentration. Product efforts are provided by conventional techniques for providing a solid or film, such as a composition for evaporating an aqueous dispersion or 20 precipitation, which has been shown to require considerable time for redispersion if redispersible in water or an organic solvent. And investment in thermal and/or mechanical energy. Surprisingly, it has been found that if lyophilization (a non-practical concentration technique) is applied to a latex-containing aqueous dispersion comprising a copolymer of a polyanion and a substituted or unsubstituted thiophene or a 1306868 polymer, a sponge can be produced. Shape or fluffy end 'which can be quickly redispersed or dissolved in water or organic solvent without consuming heat and/or mechanical energy' to obtain a coating dispersion or solution (additional / as he knows) Will leave a thick part. The resulting coating dispersion or solution can be applied to any object, such as a carrier. 4 Mamming provides a redispersible or soluble product which can be obtained by substituting or unsubstituted exemplified polymers or a total of (10): latex: JC. The method of the present invention provides a method for producing an antistatic or conductive layer or pattern, which comprises the steps of: re-dispersing or diluting the above product by adding water or an organic solvent to obtain a solution or dispersion; H brother adds other ingredients to the solution or dispersion; and 15 she uses 5 liters of night or dispersion to an object. 15 (d) The present invention also provides a coating solution or dispersion which comprises the above redispersible or soluble product. The invention also provides the use of the above coating solution or dispersion' for the preparation of an antistatic or electrically conductive layer. According to the present invention there is also provided a printing ink comprising the above-described re-dispersible or soluble product. The invention also provides the use of the above printing ink for the preparation of an antistatic or electrically conductive layer. Preferred embodiments of the invention are disclosed in the detailed description of the invention. 1306868 DETAILED DESCRIPTION OF THE INVENTION Definitions According to the present invention, lyophilization is a freeze-drying process in which a substance is first frozen and then reduced in amount of solvent (typically water), first by sublimation for 5 (= one drying procedure) and then via Desorption (== secondary drying procedure) until the shelf temperature becomes equal to the atmospheric temperature in the lyophilizer. This lyophilization method is achieved by the ability of a solid substance such as ice to sublimate under the correct conditions (direct change to I without gas). The term "dry product" according to the invention means that the contact is perceived to be dry 10 and is not accompanied by a pronounced liquid phase. The term "printing ink" according to the invention means an ink which can be applied to the printing method, for example for elastic relief printing, lithography, lithographic printing, offset printing, ink jet printing, (silk) screen printing. According to the invention, the term layer means a continuous coating. According to the invention, the term "pattern" means a discontinuous coating. _ The term "aqueous" as used herein shall be understood to mean a dispersion in which the liquid phase consists of water or a water/solvent mixture, provided that the water content is higher than the solvent content by volume. The rate is generally expressed by the surface resistivity Rs (unit Ω; often recorded as Ω / 2 〇 square). Alternatively, the conductivity can be expressed by the volume resistivity Rv = Rs'd, where d is the layer thickness and the volume conductivity kv = l /Rv [unit: west (door y cm) or surface conductivity ks = l / Rs [unit: west (door) · square]. According to the invention, the term "conductivity" means having less than 1 〇 6 The surface resistivity of the square. The 106iV square is typically considered to be a surface resistivity value that distinguishes between conductive materials -10- 1306868 and ♦ several electrostatic materials. Antistatic materials typically have a range of 1〇6 i 1〇11〇/ The surface resistivity in the square, / is not suitable; |乍 is the electrode. Bayan conductivity enhancement refers to a procedure in which a high-boiling liquid such as a mono- or polyhydroxyl and/or carboxyl group or a guanamine or an indoleamine group is contained. The organic compound of the group is contacted, and then heated at a high temperature, as the case may be. Preferably, the relationship is between 100 and 250 ° C, preferably between 1 and 90 seconds, resulting in an increase in conductivity, or an aprotic compound (such as ν·曱基_四氲) In the case of 0 ketones, a temperature lower than 100 〇C can be used. This conductivity enhancement can be seen in the polythiophene and can occur during or after the preparation of the layer. N-Mercapto-tetrahydropyrrolidone and diethylene glycol, as disclosed in EP-A 686 662 and EP-A 1003179. Lyophilization According to the present invention, it is provided that a polyanion can be substituted via lyophilization and substituted Or a redispersible or soluble product obtained by substituting an aqueous latex dispersion of a polymer or copolymer of thiophene. The first step in lyophilizing the product is to convert it to a frozen state. During the freezing process, Preferably, the solvent (water) is crystallized. The formation of ice crystals causes the solute to separate from the solvent. The ice crystals are then removed by sublimation under vacuum. Although sublimation or a drying process removes most of the water from the frozen substrate, But relative to the lyophilized product, it is still possible More than 5% by weight/weight of water is in the filter cake. The residual water is then removed by desorption. According to the present invention, it has been found that the water content of the lyophilized product has a strong influence on its redispersibility. The product is Southern hygroscopic. For example, the weight of PEDOT/PSS obtained by drying 1306868 1.2% by weight aqueous dispersion is increased by 16 to 23% at room temperature, whereas in a dryer the increase is only 8%. According to the present invention, the product which is lyophilized at room temperature typically has a water content of 15 to 20% by weight. In a vacuum drying cabinet at 110 ° C in a drying cabinet at room temperature 5, further drying has been frozen. The product of the dry product results in a more difficult product to be dispersed. According to a first embodiment of the redispersible or soluble product obtainable by lyophilization according to the present invention, the redispersible or soluble product is dried. Sponge-like plush powder, concentrated dispersion or paste. By completely lyophilizing the aqueous dispersion, a concentrated dispersion or paste can be obtained instead of a powder. It can be a redispersible or soluble product of a powder, a concentrated dispersion or a paste. It can be added by adding water, an organic solvent or a mixture of water/solvent, as the case may be, using other ingredients such as surfactants and dispersants. Dissolve or redisperse. According to a second specific embodiment of the redispersible or soluble product obtainable via lyophilization according to the invention, the concentrated dispersion or paste has a solids content of up to 10% by weight. According to a third specific embodiment of the redispersible or soluble product obtainable via lyophilization according to the invention, the concentrated dispersion or paste has a solids content of more than 20% by weight. 2〇 According to a fourth specific embodiment of the redispersible or soluble product obtainable via lyophilization according to the invention, the concentrated dispersion or paste has a solids content of more than 50% by weight. A concentrated dispersion in an organic solvent such as diethylene glycol or N-mercapto-tetrahydropyrrolidone, which can be obtained by containing an organic solvent and an aqueous polythiophene/polyanion-12-1306868: a liquid or a liquid The mixture is obtained by displacing/dispersing the dispersion in the solvent. The organic dispersion/paste can be redispersed in a powder-like manner, and any polymer or copolymer of (4) m ^ substituted or unsubstituted thiophene can be obtained according to the lyophilization obtainable according to the present invention. A fifth specific embodiment of the redispersible or soluble product, wherein the substituted thiophene is substituted at least one of the 3 or 4 position by a substituent selected from the group consisting of alkoxy groups, substituted The alkoxy group, the alkyl group, the substituted alkyl group, the aryl group and the substituted aryl group, or the 3- to 4-position system are bonded to an optionally substituted oxy-exetyloxy group. According to a sixth embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the substituted 11 phene polymerization system is represented by the formula (I). ^___〇 〇 R2 15

Wherein the η system is greater than 1, and the R1 and r2 groups each independently represent hydrogen or, as the case may be, a substituted Ci-4 alkyl group, or together represent a substituted alkylene ring alkyl ring as an optionally substituted cycloalkane a base, preferably an ethylidene group, optionally substituted by a graft group, optionally substituted by a cl-12 alkyl group or a phenyl group, an extended ethyl group, a 1,3-propyl group or a 1,2-extension Cyclohexyl. According to a seventh embodiment of the redispersible or soluble rc-130-1306868 product obtainable via lyophilization according to the present invention, the polymer or copolymer of the substituted thiophene is (3,4-di) a polymer or copolymer of alkoxythiophene, wherein the two alkoxy groups together represent an optionally substituted oxy-alkylene-oxy bridge group selected from the group consisting of (3,4-methyleneoxy) a base σ septene), a (3, 'anthracene dioxythiophene) derivative, a (3,4-ethylenedioxythiophene), a (3,4-ethylenedioxythiophene) derivative, 3,4-propenyloxythiophene), (3,4-extended propylenedioxythiophene) derivative, (3,^-butylenedioxythiophene), and (3,4-butyleneoxy-- Thiophene derivatives and copolymers formed therewith. According to an eighth specific embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the polymer or copolymer of the substituted thiophene is a polymerization of (3,4-dioxaoxyphene) Or a copolymer wherein the two alkoxy groups together represent an oxy group substituted with a substituent selected from the group consisting of an alkyl group, an alkoxy group, an alkoxyalkyl group, a carboxyl group, an alkyl sulfonate group, and a carboxy ester. _ 焼 基 * base-oxy bridge. According to nine specific embodiments of the redispersible or soluble product obtainable by the bundle according to the present invention, the substituted α-phenophene polymer is poly(3,4-dialkoxythiophene), wherein The two alkoxy groups together represent an optionally substituted oxy-sub-alkyl-oxy bridge group which is a 1,2-extended ethyl group, optionally substituted by an alkyl group, optionally via C1. -12 alkyl or phenyl substituted 1,2-extended ethyl, 1,3-propenyl or 1,2-extended cyclohexyl. Such polymerization systems are disclosed in the Handbook of Oligo- and Polythiophenes, edited by D. Fichou, Wiley-VCH, Weinheim (1999); L. Groenendaal et al., Advanced MAterials, Vol. 12, pp. 481-494 (2) 〇〇〇); LJ Kloeppner et al., Polymer Preprints, Vol. 40(2) -14- 1306868, p. 792 (l"9), P. Schottland et al.

Metals), Vol. 101, pp. 7-8 (1999); and d. M. Welsh et al., Polymer Preprint, Vol. 38(2), p. 320 (1997). The preparation of such poly-σ-phenophenes and aqueous dispersions containing such polymers or copolymers of polyanions and substituted porphins is described in Ερ_α·440957 and the corresponding US-P-5300575. Basically, the preparation of polythiophene is carried out in the presence of a polymeric polyanionic compound by oxidative polymerization of 3,4-dialkyloxythiophene or 3,4-alkylenedioxythiophene according to formula (π). get on:

Wherein Rl and r2 are as defined by the formula (丨). A stable aqueous dispersion of a polymer or copolymer that has been substituted or not substituted. 厶 = = a stable water of a polymer or copolymer of 2 or unsubstituted thiophene

For the oxidative polymerization of aromatic monomers such as ΐίbilo, σ phenophene and -15-1306868 aniline. Preferred oxidizing agents are iron (m) salts such as FeCl3, Fe(Cl?4)3 and an organic acid containing a cerium residue and an iron of a mineral acid or a combination thereof. Other suitable oxidizing agents are H2〇2, K2Cr2〇7, gold test f or money persulfate, metal over-micro-salt, over- (four) unloading and copper salts such as tetra-acid copper. Air or oxygen can also be used as an oxidant. In theory, each oxidizing agent is required for its oxidative polymerization.

10

, l98〇/m SCi PartA, P〇lymerChemistry, Vol. 26, p. 1287. However, in practice, the oxidizing agent is used in an excess amount, for example, 0.1 to 2 equivalents per mole of thiophene. Polyanion: The redispersible or soluble or ionizable material obtained from the drying of the present invention is disclosed in ΕΡ_Α 440957 and is added from a polybasic acid salt such as an alkali metal salt. Sexually produced by the present invention, which is redispersible or soluble, such as ten specific examples, the polyanion is a carboxylic acid polymer, (7) poly(t-propenyl) and bismuth diacid) Or to agglomerate an anion such as poly(stupyl sulfonic acid) or poly(vinyl sulfonic acid).寻 几 几 酸 酸 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ π π π π π π According to the tenth embodiment of the redispersible or soluble acid obtained by lyophilization according to the present invention, the polyanion is an anion of poly(phenyl eti. 5 and stupid (four). a polyanion of open/infrared acid, preferably having a molecular weight of 1000

Between -16- 1306868 and 2xl06, preferably between 2000 and 5xl〇5. Such polybasic acids or alkali metal salts thereof are commercially available and can be obtained according to known methods, for example, in Houben-Weyl, Methoden der Organische Chemie, Bd. E20 Makromolekulare Stoffe, Teil 2, (1987), 1141 The coating solution or dispersion according to the present invention is obtained according to the present invention and comprises a redispersible or soluble product which may be a powder, or a concentrated residue, and the pot may be substituted or not It is obtained by substituting an aqueous latex dispersion of a 2 or a copolymer. R σ according to the coating solution or dispersion of the present invention, the coating solution or dispersion further comprises water or organic _ body, 15 20 pieces of the coating solution or dispersion of the invention, the second specific 5 hai paint shout Or the dispersion has a latex comprising a polymer or copolymer of a ionic ion and a second-generation thiophene, which is at least 2% by weight of the sputum dispersion.尺',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The latex is scented at least 5% by weight of the dispersion. X is a side coating solution. According to the coating solution or dispersion of the present invention, the coating solution or dispersion has a polyanion red, a polymer or a material of the phenotype, and the heart = generation Or not at least 1% by weight of the monodisperse. ^^ is the coating solution side. 17-1306868. According to a fifth embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion has a polymer or copolymer comprising a polyanion and a substituted or unsubstituted thiophene. The latex of the material has a concentration of at least 1% by weight of the coating solution or dispersion, and the water content is less than 12% by weight of the coating solution or the dispersion. According to a sixth embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion has a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene at a concentration of At least 1% by weight of the coating solution or dispersion, and the water content is less than 6% by weight of the coating solution or dispersion. According to a seventh embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion can be used to prepare an antistatic or electrically conductive layer. The coating solution or dispersion may comprise other ingredients, such as a hardener such as an epoxy decane, such as 3-glycidyloxy 15 propyl-triethoxy-decane as described in EP-A 564 911, which is especially Suitable for coating on glass substrates; _ one or more surfactants; spacer particles; adhesion promoters, UV-filters or IR-absorbers. Printing Ink A printing ink obtained according to the invention comprising a redispersible or soluble product which may be a powder 2 powder, a paste or a concentrated dispersion which may comprise a polyanion via a lyophilization and a substituted or unsubstituted Obtained as an aqueous latex dispersion of a polymer or copolymer of thiophene. According to a first embodiment of the printing ink of the present invention, it further comprises water or an organic solvent. -18- 1306868 According to a second embodiment of the printing ink of the present invention, the printing ink has a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene at a concentration of at least 2 of the printing ink weight%. According to a third embodiment of the printing ink of the present invention, the printing ink 5 ink has a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene at a concentration of at least 5% by weight of the printing ink. . According to a fourth embodiment of the printing ink of the present invention, the printing ink> ink has a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene at a concentration of at least 10 by weight of the printing ink. %. According to a fifth embodiment of the printing ink of the present invention, the printing ink has a polymer comprising a polyanion and a polymer or a copolymer of a substituted or unsubstituted thiophene at a concentration of at least 1% by weight of the printing ink. And the water content is less than 12% by weight of the printing ink. According to a sixth embodiment of the printing ink of the present invention, the printing ink 15 has a latex comprising a polymer or a copolymer of a polyanion and a substituted or unsubstituted thiophene at a concentration of at least 1 by weight of the printing ink. %, and the water content is less than 6% by weight of the printing ink. The printing ink may comprise other ingredients, such as one or more binders; a hardener such as an epoxy crumb, such as 3-condensed 20 glyceryloxypropyltrimethoxydecane as described in EP-A 564 911, which is particularly suitable For coating on a glass substrate; one or more surfactants; one or more dispersing agents; spacer particles; adhesion promoters, UV-filters or IR-absorbers. Suitable polymeric binders are described in EP-A 564,911. The lithographic inks have a viscosity of from about 15 Bass. seconds to 35 Bass. seconds depending on the ink formulation, drying mechanism, printing press and printing speed 1306868. Gravure printing and flexographic printing inks vary widely', but the typical viscosity of imprinted inks is about 15 millipascals per second. The typical viscosity of screen printing inks is about 2 Baska. seconds. The inkjet inks are determined by the type of ink jet method, the nozzle configuration, the printing speed, the ink drying mechanism, and the desired printing quality, and the viscosity varies from about 2 millipascals per second to 20 millipascals per second. The hot melt inkjet ink is solid at room temperature, and when its viscosity is 4 〇bass. seconds, _' is normally printed at about 150 °C. The opaque printing ink can be obtained by additionally incorporating a pigment such as ίο LEVACRYL® A-SF (a black pigment obtained from BAYER) which is incorporated by weight sufficient to impart opacity in the thickness of the applied layer «印刷. The printing ink layer exhibits superior adhesion to the phosphor layer, the polyacrylate auxiliary layer, the polycarbonate and the polyester such as poly(ethylene terephthalate) layer, and its visual transmittance is >75 The surface has a surface resistance of $10000/square, where B can obtain 285%. The binder is according to twelve specific embodiments of the redispersible or soluble product obtainable via lyophilization according to the invention, the product further comprising a binder 20 ° according to the invention, a redispersible or soluble product of the thirteenth In a specific embodiment, the product further comprises a binder having a glass transition temperature higher than 25 ° C. According to the eighth embodiment of the coating solution or dispersion of the present invention, -20- 1306868 the coating solution or dispersion further comprises a binder Or a thickener. (4) A seventh specific embodiment of the printing ink of the present invention, the printing oil 1 further comprising a binder or an augmenting agent. The adhesives suitable for use in the present invention are described in the gripping side, 5 and are referred to herein by reference to 'and include water-soluble complexes such as poly(ethylene), propylene@夂, water-soluble homopolymers and copolymers. And methyl propylene polymers, as well as polymer latexes. Appropriate / ~, • Suitable thickeners are polyacrylic acid vinegar and polysaccharides. Preferably, the polyacrylic acid thickener is a high molecular weight homopolymer of propionic acid crosslinked with a polyene ether ether, such as B. F. Goodrich's CARBOPOL positive resin, of which CAHBOPOL ETD-2623 is particularly preferred. Preferred polysaccharide thickeners include cellulose, cellulose derivatives such as carboxymethyl cellulose, vermiculite, guar gum and Xanthangum, of which trisin is particularly preferred, such as from the United States.

Hercules' BIOSAN®s and Kelzan8T from the Kgc〇 is division of Merck, USA. φ Specially preferred binders and thickeners for use in redispersible or soluble products, coating solutions, coating dispersions or printing inks according to the invention are: POLYVIOLTMWX482® = poly(ethylene glycol) available from WACKERCHEMIE; C ARBOPOLTMETD2623 = acrylic copolymer crosslinked with polyalkenyl polyether, 2 〇 from BF Goodrich; CERIDUSTTM 130 = polyethylene wax from HOECHST; JONREZTMs M700 = rosin-based resin from Johnson Polymer; JONREzTMs M705 JohnsonPolymer resin based on rosin; JONREZTM SM729 = rosin-based resin from JohnsonPolymer; -21 · 1306868 KLUCELTMH = hydroxypropyl cellulose available from Hercules; NEOCRYLTM BT24 = soluble acryl from Zenica resin Acid copolymer. Preferred water-soluble ageing agents include poly(7) scales, homopolymers and copolymers of methyl (tetra) acid with ethyl esters, and copolymers of 2-acrylic acid (2-phosphonic acid) ethyl ester, and 2 - This polymer of methyl-2-acrylic acid (2-phosphonic acid) ethyl ester. The best polymer latex is a monomer selected from the group consisting of styrene, (iv) _, methacrylic acid vinegar and di- (such as isoprene and butyl diene). According to the material, it can be subdivided into a special polymer glue for coating solution, paint dispersion or printing ink. Emulsifying poly(methyl acrylate) latex with a particle size of 90 nm. , can be obtained in 20% by weight aqueous dispersion; latex 02 = 26.5 mol% terephthalic acid, 2 %%% stupid 15 3.5 mol% 赖 基间笨二? Acid and 5 () Moco Ethyl Alcohol: Copolymerized Rotor' can be 2G wt% aqueous fraction of latex 03 = vinylidene chloride, mercapto acrylate vinegar, methylene (Ob/2/2) terpolymer , can be 30 weight; ^ ^ ^ ^ acid latex 0 and 80% ethyl acrylate and 20% methyl edenoic acid and take I wait, with 27% by weight of aqueous dispersion;;, difficult, latex. 49% mercapto acrylate acid, 49% butyl diamide and copolymer of dipic acid 'can be 3 〇 wt% water = butyl latex 06, acrylic acid vinegar), can be 30% by weight aqueous -22- 20 1306868 Latex 03, Latex 04, Latex 05 and Latex 〇6 all have glass transition temperatures below 25t. Such binders may be treated with a hardener such as an epoxy decane, such as 3-glycidoxypropyltrimethyl & sylvestre as described in EP-A 564 911, which is especially suitable for coating on glass On the substrate. Surfactant According to a fourteenth embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the product further comprises an interfacial activator. According to a ninth embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion further comprises a surfactant. According to an eighth embodiment of the printing ink of the present invention, the printing ink is inked into a surfactant. Preferred are anionic and nonionic surfactants. Suitable surfactants for use in the redispersible or soluble product, coating solution, coating dispersion or printing ink according to the invention are: surfactant Nr01 = perfluoro-octanoic acid ammonium salt, obtainable in 30% solution; interfacial activity Nr02=MARLONTMA365, supplied by HULS as a 65% concentrate of sodium alkylbenzene sulfonate; surfactant Nr03=AKYPOTMOP80, by CHEMY with octyl-phenyl-oxy-polyethylene glycol (Ε08) acetic acid 60 % concentrate supply; interface/tongue agent Nr〇4=ARKOPALTMN〇6〇 (formerly hOSTAPAlTMw), mercaptophenyl polyethylene glycol from HOECHST; .... (-3 -23- 1306868 interfacial activity Agent Nr05=ZONYLTMFS0100, a block copolymer of polyethylene glycol and polytetramethylene having the following structure: F(CF2CF2)yCH2CH2〇(CH2CH20)xH, wherein x=0 to about 15, and y=l to about 7, purchased from 5 DUPONT, supplied as a 5% by weight solution; surfactant Nr06=HOSTAPALTMB, sodium phenyl-polyethylene glycol (E07-8) sodium sulfate from HOECHST, 50 > % Concentrate supply; surfactant Nr07=ARKOPONTMT, a 10 N-mercapto-N-2-linyl ethyl ester from HOECHST Base salt of basal amine, supplied as 40% concentrate; surfactant Nr08=MERSOLATMH76, purchased from BAYER 15. Sodium sulfonate, supplied as 76% concentrate; Surfactant Nr09=SURFINOLTM485, purchased from AirProducts 15 ethoxylated ethyl bromide surfactant. | Conductivity enhancer According to the fifteenth embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the product further comprises Conductivity Enhancer. According to a tenth embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion further comprises a conductivity enhancer. According to a ninth embodiment of the printing ink of the present invention, The coating solution or dispersion further comprises a conductivity enhancer. Suitable conductivity enhancers are linear, branched or cyclic aliphatic C2-20 -24-1306868 hydrocarbons, or optionally substituted aromatic C6-14 hydrocarbons, Or a piper or furan, the organic compound comprising at least two hydroxyl groups or at least one -COX or -CONYZ group, wherein X represents -OH, and Y and Z independently of each other represent a hydrazine or an alkyl group; or a heterocyclic compound of an intrinsic amine group. 5 An organic compound for use in a redispersible or soluble product, a coating solution, a coating dispersion or a printing ink according to the present invention, an example of which is, for example, an anthracene-fluorenyl group. -2-tetrahydro 0 fluorenone, 2-tetrahydro alpha pirone, 1,3-dioxyl | -2-imidazolidinone, hydrazine, hydrazine, hydrazine, Ν'-tetradecylurea, A Guanamine, dimethyl decylamine and hydrazine, hydrazine-dimethylacetamide. Preferred examples are sugars or sugar derivatives such as aleus latopraose, sucrose, glucose, fructose and lactose, or di- or polyhydric alcohols such as sterol, xylitol, mannitol, mannose, galactose , flower sucrose, gluconic acid, ethylene glycol, di- or tri(ethylene glycol), 1,1,1-tridecyl alcohol-propane, 1,3-propanediol, 1,5-pentanediol 1,2,3-propanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, or an aromatic di- or polyhydric alcohol, such as resorcinol. 15 Particularly preferred conductivity enhancers for use in the coating solution or dispersion or printing ink g according to the invention are: fluorenyl-mercapto-tetrapyrrolidone and diethylene glycol. Suitable carriers for use in the process of the invention are polymeric films such as poly(ethylene terephthalate), poly(ethylene naphthalate), polystyrene, poly 20 ether sulfone, polycarbonate, poly. Acrylate, polyamide, polyimine, cellulose triacetate, polyolefin, polyvinyl chloride, and the like. Inorganic substrates such as tantalum, ceramics, oxides, glass, polymeric film tempered glass, and glass/plastic laminates can also be used. -25- Industrial Conn According to the present invention, it can be obtained from a bundle of a latex-containing aqueous dispersion containing a polyanion and a substituted or non-W or = Γ copolymer, which can be used in various applications. . The fractions obtained from the night or bath, printing oil black g, m A and coating can be used to make electrodes that can be used in various electronic or semiconductor devices.

l 较佳 For the preferred application of the conductive layer made of Knife Liquid, it is a photovoltaic cell, an electroluminescent device such as an organic or money LED, and a display, such as a flat panel display, such as an LCD. 15

The conductive layer of the polybenzazole prepared according to the present invention has a resistivity which is low in order to serve as an electrode in a device (e.g., solar power) which can absorb or generate a small current. However, a device that can draw a higher current, such as LED, may require an electrode of an organic conductive layer and a layer having a better conductivity such as an ITO layer. Other specific embodiments are disclosed in ep_a1〇13413 and EP-A0554588. While the invention will be described in conjunction with the preferred embodiments of the present invention, it is understood that the invention is not limited to the specific embodiments. The components used in the examples but not mentioned above are summarized below: ECCOCOAtTMcc_2 = Conductive Polymers from Emerson & Cumming Special Polymers Company Z6040 = 3-Glycidoxypropyl Group from DowComing Trimethoxy decane. 1... 3 -26- 20 1306868 [Embodiment] Preparation of polythiophene dispersion poly(3,4-ethylenedioxythiophene)[PED0T] and polystyrene sulfonate [PSS] as polyanion The aqueous dispersion was prepared according to the method described in Ep_A1〇79397. The dispersion thus obtained had a solid content of 115% by weight' and the weight ratio average particle size was measured by Chemicai Pr〇cess Specij|sts DCP 20000 disc centrifugation using an aqueous solution of 8% sucrose, and the main peak was about 50 nm. At about 25 nm. Table 1 lists the particle size distribution characteristics of several representative PEDOT/PSS dispersions. Table 1: Weight ratio average particle size [nm 1 main peak maximum [nm] Main peak half width [nm] 90% by weight of particles have a size smaller than the following "nm 1 47 25 35 58 46 25 33 58 53 25 32 70 53 22 29 90 54 23 30 90 48 25 29 63 50 23 24 70 47 25 26 58

Separation of PEDOT/PSS 15 from the polythiophene dispersion by evaporation A preliminary evaporation experiment using a 1.2% aqueous dispersion of poly(3,4-ethylenedioxythiophene y poly(styrenesulfonic acid) [PEDOT/PSS], It has been shown that simple evaporation of a liquid present in a latex solution or dispersion comprising a polyanion and a polymer or copolymer of substituted or unsubstituted phage -27-1306868 provides a re-dispersion that is not easily re-dispersed by the addition of water. Solid or film. 100 g of a specific 1.1% aqueous dispersion of PEDOT/PSS and an aqueous solution or latex 01, latex 02 containing the solid amount of surfactant Nr. 01, 02, 03, 04 or 05 shown in Table 2. An aqueous dispersion of Latex 03 or Latex 06 or a solid poly(vinyl alcohol) was mixed to produce a mixture of Samples II to IX. Sample I was the same 1.1% aqueous dispersion of 100 grams of PEDOT/PSS.

Table 2: 10 samples [g] I II Ill IV V VI VII VIII IX X XI 1.1% aqueous pmxnypss dispersion 100 100 100 100 100 100 100 100 100 100 100 Surfactant Nr 01 - 0.59 - - Surfactant Nr 02 - - 0.59 - - - - - - - - Surfactant Nr 03 - - - 0.59 - - - - - - - Surfactant Nr 04 - - - - 0.59 - 0.02 - - - Surfactant Nr 05 - - - - ~ 0.59 - - - - - Surfactant Nr 06 - - - Surfactant Nr 07 0,09 - Surfactant Nr 08 0.02 - - -28 - 1306868 Latex 01 Latex 02 Latex 03 Latex 04 ---- POLYVIOLTM WX48/20 u — - - - - - - 1.1 - - - 1.1 - - - - - η - - 1.1 The sample ι-ιχ is attached to a dry bridge and produces samples Ι-A to Ιχ_Α at u. In the next 24 hours, the A 5 style 1-A was used to test the PEDOT/PSS through the tomb, and it was found that the study by the sample I was based on the specific surface area of the steam card/gram. The Ι-A to ΙΧ-Α obtained in 4 samples I to IX were subdivided into OT/PSS in the water. The test showed little expansion, but I was transferred to I;/, after 8 hours, the condition of rr spicy pure Π·Α Medium, observed

10 Re-dispersion of sample Ι-A to a blue-black dispersion can be carried out by contacting 1.5 liters of deionized water at room temperature for a period of 48 hours, and then treating the mixture with Ultra-TurraxTM for 1 minute. Then pass the GAULIN homogenizer twice and pass the MICHOFLUIDIZErTM twice at 4 bar. The redispersed evaporated PED〇T/PSS dispersion is mixed with N-methyl-tetrahydropyrrolidone, Zonyl FSO100, Z6040, latex 03, and coated on a secondary pED〇T/PSS carrier to produce the table. Layer composition in 3. -29- 15 l3〇6868 Z6040

PEDOT/PSS Zonyl F SO 100 杳./来2

10

15 latex 03___ N-methyltetrahydro t? than sigh g | 100 m夯 / come 2 ------------ [2 ml / half 2 -I*, exist on, but ^ the same The square surface resistivity, which corresponds to the i7 〇〇 Ω / square < surface resistivity of the layer coated with the original PED 〇 T / Pss_ dispersion. These experiments have shown that it is possible to redistribute after evaporation with considerable energy and time. , but only by the separation of pED〇T/pSS ^ from the polythiophene dispersion by freezing, the melt-blown solution or dispersion of the latex or the dispersion containing the polyanion and the substituted or unsubstituted thiophene Phase separation is caused, but separation by centrifugation or filtration is not possible. Despite the fact that macroscopic PEDOT/PSSA macropolymers are formed upon thawing, treatment of the thawed dispersion in a microfluidizer bed at 400 bar produces a dispersion which is as described above. When the same layer composition was applied, it exhibited '1700 Ω/square surface resistivity' which corresponds to a surface resistivity of 1700 Q/square using a layer coated with the original PED〇T/PSS-dispersion having the same composition. This freezing experiment showed that freezing itself did not separate the solid PEDOT/PSS. -30- 20 Ϊ306868

The addition of a non-solvent by precipitating PEDOT/PSS from an aqueous dispersion by adding a non-solvent does not cause precipitation of PEDOT/PSS into a form that can be separated by centrifugation or centrifugation. Freeze-drying of polythiophene dispersions The PED0T/PSS dispersions of formulas I to XI were dried under high vacuum (〇·7 mbar) in a CHRISTBETA 2-16 rack dryer until all

10 The water is evaporated (ie, until the shelf temperature is equal to room temperature), and dry powders I-B to XI-B are obtained. Two bET measurements were performed on the sample IB powder to obtain a BET specific surface area of 3 and 6 m 2 /g, which is assumed to be a density of 1 〇 6 g/m 3 (density of water)' which means an average particle size of 1.0 to 2.0 μm. . I present a lyophilized powder of I-B containing 79 2% by weight of pED〇T/pss, and 13.0% by weight can be at 2〇〇.移除Water removed during drying, and 7 8 f% of water cannot be removed when dried at 200 °C. 15

20 Samples I_B4 to XI_B_I ' with U weight % were produced by contact with deionized water for 8 hours to study the PEDOT/PSS-samples into the evening. From all of these samples, it can be observed that visually complete the two-two I without the need to consume mechanical energy or heat energy. However, in the case of the sample ΙΠ-Β (make == Nr. 02), large cohesive polymers can be seen. And the sample of the rtr彡 material. All "consumption (4) energy or heat energy, the particle size distribution of the small foxes 1 and v, together with the particle size distribution of the starting material 1 - is shown in Table 4. c S ) -31 - 1306868

Table 4 :

These granularity metrics show that in jvh, v there are & into η 八 &... and VI_B-I: there are several kings of redistribution, in the case of coffee, there is a substantial re-policy, and in In the case of II-BI, there is some slight cohesion. 4 These experiments contain 4 dry PED() T/PSS redispersion of interface recording agent, polymer or water-soluble polymer, as compared with the evaporated FEDOT/PSS-sample. It is easy to be astonished, and the benefits + geese use mechanical energy or heat. ",, money, water-based paint dispersion XH-B-I, χιι_Β-Π and I_B_m damage lyophilized powder (sample XII_B) is obtained from the above as specified

• W PEDOT/PSS (Sample XH) dispersion, which is redispersed by adding deionized water to obtain the following samples with different solid contents:

15 1306868 A coating dispersion of the above sample was then prepared. The composition of all coating dispersions containing equal amounts of polythiophene is shown in Table 5. Table 5: Sample XIII XIV XV XVI Sample XII [g] 21.74 - - - Sample XII-BI [g] - 21.74 - - Sample ΧΠ-Β-ΙΙ [g] - - 10.87 - Sample XII-B -III [g] - - - 7.24 Latex 〇 3 [g] 0.83 0.830.83 0.83 ZONYLT M FSO 100 (5 wt% surfactant purchased from DuPont) [g] 0.40 0.40 0.40 0.40 N-decyl tetrahydro σ Pirolozone [g] 5.00 5.00 5.00 5.00 Ζ6040 [g] 0.25 0.25 0.25 0.25 deionized water [g] 71.78 71.78 82.65 86.28 (*)Comparatively, the polythiophene dispersion before lyophilization has samples XIII, XIV, XV and Preparation of Conductive Layer of XVI and Measurement of Conductivity Using a coating blade (50 micron wet coating thickness), the aqueous coating dispersions of samples XIII, XIV, 10 XV and XVI were applied to the auxiliary polyethylene terephthalate. The diester film was supported on a carrier and dried at 40 ° C. The auxiliary carrier of the coated conductive layer was cut to obtain a strip having a length of 27.5 - 33 - 1306868 a knife and a width of 35 mm. The conductive polymer ecc〇c〇atcc 2 electrode is applied at a distance of 1 () centimeters above the width of the strip. The resistivity is determined by applying a fixed potential between the electrodes in the following manner, measuring the current flowing through the circuit in picoamperes = EITHLEY485, and calculating the surface resistivity from the potential and current 'in Q/square, considering the interelectrode The geometry of the area. The results are shown in Table 6. Table 6 Surface resistivity of the tantalum layer Sample PEDOT/PSS Surface resistivity of the sample [iy square] XIII XII(*) 1200 XIV XII-BI 1200 XV _ XII-B-TT 1550 XVI ΧΠ-Β4ΙΙ 1575 ΠComparative, The polythiophene dispersion before lyophilization 10 The results of Table 6 show that all of the samples exhibited comparable surface resistivities within experimental error. The polythiophene dispersion can thus be lyophilized and redispersed to different concentrations without affecting the conductive properties of the layer to which it is applied.

® lyophilized PEDOT/PSSA with further drying Ι-C

15 Preparation of aqueous coating dispersion ICI The lyophilized powder of the polythiophene dispersion sample IB was further dried in a vacuum drying cabinet for 12 hours to produce a sample 1-〇 after adding 2 liters of deionized water, the further dried lyophilized The powder did not redisperse immediately as in sample IB and ΧΠ-Β. It was allowed to wet with 2 liters of deionized water at room temperature over a period of 48 hours. The mixture was then subjected to Ultra-TurraxTM treatment for a minute, then passed through a GAULIN homogenizer twice at 400 bar and once through -34- 1306868 MICROFLUIDIZERTM, after which a blue-black dispersion was obtained. Next, a coating dispersion of the above sample was prepared. The composition of this coating dispersion is shown in Table 7 〇 5 10

Table 7: Sample ICI Polythiophene Dispersion [g] 7.24 Latex 03 "g] 0.83 ZONYLTM FS0100 (5 wt% surfactant purchased from DuPont) [g] 0.40 N-methyltetrapyrrolidone [g 1 5.00 Preparation of the screen printing ink of sample XVII to ΧΧΙΠ by adding different solvents, as the case may be accompanied by CARBOPOlTM ETD2623 're-dispersion of the end of the phenol dispersion, followed by Ultra-TURRAXTM pre-dispersion and extended ball milling (continuation See Table 8) for the time to obtain the composition of the composition shown in Table 8 t. Table 8:

PEDOT/ PSSA [% by weight] 1.19

Solvent medium [% by weight]

Diethylene glycol / carbitol acetate 98.5 4/1 XVIII XIX 48 48 1.58 1.58 0.42 0.42 ethylene glycol Ν-methyl-tetrahydro 96.0 96.0

1306868 The characteristics of the dispersions XVII to XXIII obtained by the redispersion procedure are shown in Table 9. Table 9 * Sample dispersion characteristics XVII Viscous and raw fluff XVIII Extremely thick dispersion XIX Very thick dispersion XX Extremely thick dispersion XXII Strong raw villi XXIII Uniform flow dispersion Sample XXIII Complex viscosity η* AR1000 conical flat type Ji Shishi Shi, at 25. (: and 1〇, 1 and 〇.1 Hertz are measured at the frequency, and respectively, Baska·second, 5000 Baska·second and 40, 〇〇〇baska. Second. Screen printing system using sample XXIII was carried out on a P59 screen on an auxiliary poly(ethylene dicarboxylate) support. The surface resistivity was measured in the manner disclosed for the coatings of samples xm, χιν, XV and XVI, and with MACBETHTM The optical density measured by a Τ128 densitometer via a visible filter is shown in the table. -36· 1306868 Table 10: Mesh for surface resistivity optical density of screen printing [Ω/square] [visible filter Mirror 1 ΧΧΠΙ P59 370 0.11 Preparation of lithographic dry printing inks for samples XXIV to XXVII 5

L〇 Samples XXIV to XXVII lithographic dry printing inks were prepared by ball milling for 20 hours with respect to the components shown in Table 11 for specific samples, and PEDOT/PSS was used; In the case of sample xxiv, the rosin is first dissolved in water by means of monoethanolamine, followed by the PEDOT/PSS powder of Donggan, followed by dissolution of other components prior to ball milling. In the case of the samples XXV to XXVII, the rosin was first dissolved in an isopropyl alcohol/water mixture by means of monoethanolamine, and subjected to a 20-hour ball mill after the addition of the other components. Table 11: Sample XXIV XXV XXVI XXVII Milling time [hours] 20 20 20 20 IB PEDOT/PSSA [g] 2.38 2.38 2.38 2.38 water [g] 76.72 91.16 91.16 91.16 isopropyl alcohol [g] 10.00 1.24 1.24 1.24 仰4 0H [g] 6.00 0.05 0.05 0.05 styrene-maleic anhydride resin [g] 0.73 0.73 0.73 0.73 -37- 1306868 1.44 JONREZT M SM700 [g] JONREZTMSM705 [g] 1.46 1.44 JONREZTMSM729 [g] monoethanolamine [g] 1.44 0.13 0.55 0.55 0.55 pH after dissolution NEOCRYLTMBT24 [g] 8.5 8.5 8.5 0.40 0.40 0.40 0.40 KLUCELT M Η [g] 0.63 0.63 0.63 0.63 butyl carbitol [g] 0.70 0.70 0.70

Surfactant Nr 9 [g] 0.50 0.50 0.25 0.50 0.70 0.25 0.50 Printing test 100 pieces of oil '1 recording test is carried out in ABDiek9_ line, which is equipped with a dry printing plate such as ± A ? M ^ PRESSTEKTM : Medium-sized AGFATM T474 Transparex sheet purchased from AGFA-GEVAERTN.V. Good print quality was obtained with samples XXIV to χχνπ, with the exception of sample XXVI giving extremely fine printing with no visible background image. The present invention may include any combination of features or features, or any generalized form, whether implicit or explicit, whether or not it relates to the presently claimed invention. In view of the foregoing description, it will be apparent to those skilled in the art that various modifications may be made within the scope of the invention. e····, -38 —

Claims (1)

&quot;1306868, ...complement i8,1. Apply for Patent Fanyuan: Patent Application No. 96104679 ROC Patnet Application No.96104679 Amendment to the scope of application for patent replacement of greed-attachment;) Amended Claims in Chinese - EncUTi, (Republic of China) Submitted on August 1, 9th) (Submitted on August 1? 2008) 5 10 15 A redispersible or soluble product obtainable by lyophilizing a dried product or paste comprising an aqueous dispersion of a polyanion and an unsubstituted or substituted thiophene copolymer latex, wherein the substituted thiophene is Substituted at least one of the 3- or 4-positions by a substituent selected from the group consisting of an alkoxy group, a substituted alkoxy group, an alkyl group, a substituted alkyl group, an aryl group, and a substituted group. An aryl group, or a 3- to 4-position linkage to a substituted oxy-alkylene-oxy group; and wherein the polyanion is an anion of a polymeric carboxylic acid or a polymeric sulfonic acid. 2. The product according to item 1 of the patent application, wherein the paste has a solid content of more than 10% by weight. 3. The product according to claim 1 wherein the polyanion is an anion of poly(styrene sulfonate) or an anion thereof in copolymer with styrene. 4. According to the product of the patent application, the aqueous dispersion further comprises a surfactant. 5. A method of producing an antistatic or conductive layer or pattern 'which includes the following 20 6. - or an organic solvent to redisperse or dilute according to the application, ^^ only <product' to obtain a solution or dispersion; Or disperse onto the object. Party:: The method of manufacturing antistatic or conductive layer or pattern in Item 5 of the target garden, wherein the ^^^β method further comprises the step of: adding the other ingredients to the arrow cutter on the application solution or dispersion to the object The solution or dispersion %058-invention manual-connected-39- 25 1306868 10 15 According to the method of claim 5, the support body. According to the method of claim 5, the liquid is a coating solution or dispersion. According to the method of claim 5, the liquid is a printing ink. 1 〇. According to the method of claim 5, 4 has a surface resistivity of less than 1〇6〇/square. U. According to the method of claim 5, the pattern has at least a square surface resistivity. An electrostatic layer or a coating solution or dispersion comprising the product of item 1. w According to the coating solution or dispersion of Section 12 of the Shenqing patent scope, it further contains water or an organic solvent. According to the coating solution or dispersion of claim 12, the gel comprising a copolymer of a polyanion and a substituted or unsubstituted porphin. , the concentration is at least $ 8. 9. 12. 13. 14. wherein the object is a solution in which the solution or dispersion of the solution or dispersion of the conductive layer or Figure 15. The coating solution or dispersion of claim 12, wherein the latex comprising a copolymer of a polyanion and a substituted or unsubstituted thiophene is at a concentration of % by weight of the coating solution or coating dispersion. ν 16. According to the coating solution or dispersion of Clause 12 of the patent application, the stepwise step comprises a binder or a thickener. 1306868 17. A coating solution or dispersion according to item 12 of the scope of the patent application contains a surfactant in one step. 18. According to the coating solution or basin of Article 17 of the patent application, the organic solvent is included in the step. Knife, month, and advance 19. A coating solution or dispersion containing the product according to item 4. Looking for a dry brother 2 . ·==: The coating solution or dispersion of item 19, which is a printing ink, ink, which contains 10 15 according to the scope of the patent application. Things. Block 22. According to the printing ink of No. 21 of the patent application, it is further scooped with human water or organic solvent. '匕3 23. The printing ink of claim 21, wherein the latex comprising a copolymer of a poly(ionic) ion and a substituted or unsubstituted 4 phen is at least 5 of the printing ink. weight%. 24. The printing ink according to claim 21, wherein the latex comprising a copolymer of poly f ions and a peak or unsubstituted phenanthrene is at a concentration of at least 10% by weight of the printing ink. /, 25. According to the printing ink of the &amp; page of the patent application, it further comprises a binder or a thickener. The printing ink according to claim 21, wherein the printing ink is a lithographic dry printing ink. ^Use the printing ink according to § § 21 of the patent scope / it is used to prepare an antistatic or conductive layer. -41 -