TWI306109B - Redispersible latex comprising a polythiophene - Google Patents

Description

A7 1306109 _B7____ V. INSTRUCTIONS (1) Scope of the Invention The present invention relates to a redispersible or obtainable by lyophilizing an aqueous latex dispersion comprising a polymer or a copolymer of a polyanion and a substituted or unsubstituted thiophene. Soluble product. 5 BACKGROUND OF THE INVENTION The preparation of polythiophenes and dispersions thereof for use in antistatic coatings has been described in the literature, for example, "Handbook of Organic Conductive Molecules and Polymers,", edited by HS Nalwa, J. Wiley & Sons, 1997. Polythiophene has a conductivity of 10 which can be controlled by the degree of doping. FR-A-88 7976 discloses a method for preparing a conductive polymer based on polythiophene. By a chemical polymerization of thiophene in a reaction medium comprising an iron salt, an alkyl complex, and water. US-P-5 254 648 discloses a method of preparing a conductive, doped polythiophene, 15 which comprises: Substituted thiophene, an iron salt which is effective as a dopant and acts as an initiator for the polymerization reaction, and is added to the reaction medium as an anhydrous iron salt, an alkyl i-form which is present in an amount per gram. Thiophene is less than 0.04 liters, and water, wherein water is introduced in an amount between 0.009 and 900% by weight of the alkyl halide, and wherein the water and anhydrous iron salt are present in a range of 20 to 0.01 and 6 molar ratios. WO-A-99 25 753 describes a process for the preparation of polyaniline, polythiophene and polypyrrole. EP-A 0 440 957 discloses a dispersion of polythiophenes consisting of structural units of formula (I) in the presence of polyanions: the paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- order--------- line (please read the notes on the back and fill out this page) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing 1306109 A7 Patent Application (No. 90117385, ROC Patent Apuin. No. 90117385) Corrected Chinese Manual without Replacement (5) Amended Pages of the Chinese Specification — Enci. (V 5, invention description (2 (Submitted on Febraa ^ f, 2007) R - 0, 〇 - - κ Ί where R1 and R2 independently of each other means hydrogen or (: 丨-enalkyl, or together constitute a substitution Ci-t alkylene residue. EP-A-0 686 662 discloses a mixture comprising A and B, wherein A) has a repeating structural unit of the formula (I), a neutral polythiophene, 10 15 R-oxime,

0——R Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 20 25 where R1 and R2 are independent of each other to represent hydrogen or Ci-4-alkyl, or together represent a substituted <:丨_4-alkylene group a residue, preferably an alkyl-substituted methylene group, optionally a CU2-alkyl or phenyl substituted 1,2-extended ethyl residue or a 1,2-cyclohexene residue, B) an organic compound containing a di- or polyhydroxyl and/or carboxyl group or a decylamine or an indoleamine group; and a conductive coating prepared therefrom, which is adjusted to increase its electrical resistance, preferably up to 300 ohms / square. EP-A 1 081 549 discloses a coating composition comprising a conductive polymer comprising a substituted or unsubstituted thiophene, a film-forming binder and an organic solvent medium; the medium having a water content of less than 37% by weight. The percentage by weight of poly(3,4-extended ethylenedioxythiophene) in the coating solution is 0.1%. -4-

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 90298A-connection (P.4,5,l 1-13,24,25) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1306109 V DESCRIPTION OF THE INVENTION (3) 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, ketones, naphthenes, aromatic rings, Esters, glycol ethers, and mixtures thereof; the medium has a water content of less than 12 weight percent. An example of the ECP of 0.02 to 0.18% by weight of the coating solution is 0.02 to 0.18%. EP-A 1 081 548 discloses a coating composition comprising a conductive polymer of a substituted or unsubstituted thiophene and an organic solvent medium; the medium having a water content of less than 12% by weight. The weight percentage of poly(3,4-extended ethylenedioxythiophene) in the coating dispersion is 0.02 to 0.1%. In a large-scale process for preparing an aqueous latex 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, etc. Caused by production factors. It should be noted that this fractional dispersion is often referred to as a solution due to the extremely small particle size (20 to 50 nm) of its polythiophene/polyanionic latex, even in the patent text. The transportation of such a dilute dispersion is expensive and cumbersome in view of the large volume and weight accompanying it. Cool and dry has been developed to preserve and increase the transportability of perishable organic matter (such as food 20, seasonings, spices, blood products and pharmaceutical formulations) in space navigation, exploration and military activities. Since the 1960s, it has been used in more than 400 foods ranging from meat to fruits and vegetables. This background is reflected in the lyophilization (or freeze-drying treatment) given by TA Jennings and H. Duan, 1995, Journal of Non-Enteral Science and Technology, Vol. 49, No. 6, pp. 272-25 282. In the definition, it is “a method of stabilization, in which the substance is first frozen, then sublimated, and then desorbed to reduce the amount of solvent to the non-paper scale applicable to China National Standard (CNS) A4 specification (210). X 297 mm)

A7 1306109 __B7___ V. OBJECT DESCRIPTION OF THE INVENTION (4) Maintaining the value of biological activity or chemical reaction". OBJECT OF THE INVENTION One item of the present invention is to provide a southern concentrated latex of substituted or unsubstituted polybenzazole. Another aspect is to provide a method of making an antistatic or conductive layer. Yet another aspect of the present invention is to provide a latex coating solution or dispersion that is derived from a highly concentrated dispersion latex of polythiophene. Another aspect of the present invention is to provide a printing ink made from a highly concentrated dispersion 10 of polythiophene. Other objects and advantages of the present invention will become more apparent from the following description. Efforts to obtain a concentrated product by a latex dispersion or solution of a polymer or copolymer of a substituted or unsubstituted thiophene, using a conventional technique to provide a solid or film, such as a composition obtained by evaporating an aqueous dispersion or precipitation, It has been confirmed that if it can be redispersed in water or an organic solvent, redispersion requires considerable time and heat and/or mechanical energy. Surprisingly, it has been found that lyophilization (a non-practical concentration technique) 20 can be applied to an aqueous latex dispersion comprising a copolymer or polymer of a polyanion and a substituted or unsubstituted thiophene. A sponge-like or fleece-like powder that can be quickly redispersed or dissolved in water or an organic solvent without consuming heat and/or mechanical energy to obtain a coating dispersion or solution (add other ingredients as appropriate) without leaving The lower part of the paper. The obtained paint dispersion paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- order--------- line ^^ (Please read the note on the back and then fill out this page.) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1306109 V. INSTRUCTIONS (Liquid or solution can be applied to any object, such as a carrier on the carrier) The polymer or copolymer of the ketone is coated with 5 kinds of antistatic or conductive layer or pattern (4) butterfly product, to obtain other components to the solution Or in the dispersion 10 _ application The solution or the dispersion is applied to an object. The bonding line may be a coating solution or a dispersion, which comprises the above-mentioned coating solution or dispersion, and is prepared for antistatic or 15 printing inks. The above redispersible or t-invention also provides the above printing ink for preparing an antistatic or conductive layer. The preferred embodiment of the invention is disclosed in the detailed description of the invention. Definitions According to the invention '; The drying method, in which the substance then reduces the amount of solvent (generally water), first by sublimation as a human drying procedure), and then via desorption (= secondary drying procedure, the paper scale is turned over to China (CNS) A4 X 297) 1306109 A7, invention description ( ) ' until the shelf temperature becomes equal to the green atmospheric temperature. This payment is achieved by the ability of the body material, such as ice, to sublimate under the right conditions (direct conversion to a 瑕* body without passing through the liquid phase). According to the "dry product" of the present invention, the term "drying" means that the contact is dry and does not accompany the apparent liquid phase. According to the invention, "printing ink," - means that it can be applied to the printing side: Ρ η, for example, for elastic letterpress printing, lithography, lithographic dry glue ρ brush, inkjet printing, (wire) mesh Printing. According to the invention, the term layer means a continuous coating. According to the invention, the term "pattern" means a discontinuous coating. The "aqueous"-word used in the text should be understood to define a dispersion, or a composition of hydrates, on the condition that the water content is in the solvent content by volume. 15 20 employees in the bureaucratic correction of the resistivity of the ancient layer is generally based on the surface resistivity Rs (unit Ω; often recorded as Ω / , conductivity can be represented by volume resistance material ... η layer thickness 'volume conductivity kv = l / Rv [ Unit: West (door) / cm] or surface conductivity ks = 1 / Rs [unit: West (door) · square]. According to the present invention, "guide" " - word system means having a lower than heart / square ^面^率. The square is typically considered to be a distinguishable surface resistivity of conductive materials and antistatic materials. The antistatic material typically has a surface resistivity of from 1 to 1 G Ω / square. It is not suitable as an electrode. The second conductivity is a procedure in which a high-boiling liquid such as an organic compound containing a soil and/or a slow-acting or a chelating amine or an indoleamine group is used. This paper size applies to the _ home standard (CNS) A4 specifications (2) Q x 297

I 消1306109 V. Description of the invention (A7 B7, touch: depending on the situation and then heating at high temperature) is better in the case of Qing and 2, the best in the period of 4 90 seconds' and the increase in conductivity ^ Aprotic compounds (such as N-methyl-tetrazole): In the brothers, temperatures below 峨 can be used. This conductivity enhancement is seen in poly-phenophenes and can occur during or after the preparation of the layer. For this reason, the special liquid is N_methyl_tetrahydropyrrolidone and diethylene glycol, which are not in EP-A 6 662 and EP-A I 〇〇3 m. 3 Freeze-drying < The invention provides a redispersible or soluble product obtainable by (iv) drying an aqueous dispersion of a latex comprising a polymer or copolymer of a substituted anion disk with a substituted or unsubstituted porphin. The first step is to convert it into a cold roll. f. Cold rolling, preferably the solvent (4) is crystallized. The formation of ice crystals will separate the solute from the solvent, and then sublimate under vacuum. = 15 ^ crystal. Although sublimation or a drying process removes most of the water from the cold substrate, it is relative to freeze-dried It is still possible that more than 彡% by weight/weight of water is in the cake. The residual water is then removed by desorption. The invention has found that the water content of the lyophilized product is redispersible. Has a strong effect. The product is highly hygroscopic. For example, by the weight of pED〇T/pss obtained in drying 1.2% by weight of the aqueous dispersion, the weight is increased by 16 to 23% at room temperature, however in the dryer The weight increase is only 8%. The product of the present invention i is lyophilized at room temperature, typically having 15 to 2% by weight of water containing cerium. At 110 ° C in a vacuum drying cabinet and in a drying oven In the process of drying the lyophilized product, it will result in a product that is more difficult to disperse. Please order 10 { - 9 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public Chu) 1306109 15 A7, the invention (8) t according to the first embodiment of the redispersible or soluble product obtainable according to the present invention; the redispersible or soluble product, the sponge-free hairy powder, Concentrating the dispersion or paste. By incompletely, the aqueous dispersion can be Obtaining a concentrated dispersion or paste instead of a powder. A redispersible or soluble product of a B powder, a concentrated dispersion or a paste, ^ 'V = water, an organic agent or a mixture of water/solvent, optionally using other Ingredients such as surfactants and dispersing agents, which are dissolved or redispersed. In accordance with a second embodiment of the redispersible or soluble material obtainable via lyophilization according to the present invention, the concentrated dispersion or paste Having a solids content of more than 10% by weight. A, according to a third embodiment of a redispersible or viscous product obtainable by lyophilization according to the invention, the concentrated dispersion or paste has ^ It has a solid content of 20% by weight. According to a fourth embodiment of the redispersible or soluble product obtainable via lyophilization according to the invention, the concentrated dispersion or paste has a solids content of 5% by weight. a concentrated dispersion in an organic solvent such as diethylene glycol or N-mercapto-tetrahydropyrrolidone, which can be frozen by allowing a mixture of organic solvent and aqueous polythiophene/polyanion = dispersion or solution It is obtained by drying a dispersion of a polythiophene/polyanion in an organic solvent. This concentrated dispersion or paste can be diluted or redispersed in a powder-like manner to achieve any desired concentration. The polymer or copolymer of substituted or unsubstituted thiophene is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) according to the redispersible or soluble -10 - private paper scale obtainable by lyophilization according to the present invention. ) --------Book ---------^9 — ΓPlease read the notes on the back and then fill out this page} Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1306109 V. Invention Description (9) A fifth specific embodiment of the product, wherein the substituted thiophene is substituted at least one of the 3- or 4-positions with a substituent selected from the group consisting of alkoxy groups, substituted alkanes An oxy group, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, or a 3- to 4-position system is bonded to a 5-substituted oxy-alkylene-oxy group. According to a sixth embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the substituted thiophene polymerization system is represented by formula (I):

Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing 1306109 A7 B7 V. Description of Inventions 10 15 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 20 25, (3,4-Exo-Ethyl D-Ben), (3,4 _Exetylene dioxy porphin) derivative, (3,4-propanedioxythiophene), (34_extended propoxy dioxythiophene) Ho, (3,4_ stretching methoxy π stopper Phenyl) and (3,4_butylenedioxythiophene) derivatives and copolymers formed therewith. According to an eighth embodiment of the redispersible or storable product obtainable via lyophilization according to the present invention, the substituted porphin polymerization or copolymer is (3,4-di-oxygen π-plug a polymer or copolymer of phenoxy) wherein the two alkoxy groups together represent a substituent selected from the group consisting of an alkyl group, an alkoxy group, an alkoxyalkyl group, a carboxyl group, a alkyl sulfonate group, and a carboxy ester. A substituted oxy-sub-alkyl-oxy bridge. According to a ninth embodiment of the redispersible or storable product obtainable via lyophilization according to the present invention, the substituted D-said polymer is poly(3,4-dioxaoxy porphin) Wherein the two methoxy groups together represent an optionally substituted oxy-alkylidene-oxy bridge group which is an alkyl group of 1,2-extended ethyl, optionally substituted by an alkyl group, 1,2-extended ethyl, propyl or 1,2-extended cyclohexyl groups are optionally precipitated by a C1-12 alkyl or phenyl group. Such polymerization systems are disclosed in the Handbook of Oligo- and Polybenzazoles, edited by D. Fichou, Wiley-VCH, Weinheim (1999); L. Groenendaal et al., Advanced Materials (Volume 12, pp. 481-494). 2000); LJ Kloeppner et al., Polymer Preprints, Vol. 40(2), p. 792 (I"9); P. Schottland et al., Synthetic Metals, Vol. 101, No. 7. -8 (1999); and DMWelsh et al., Polymer Preprint, Vol. 38(2), p. 320 (1997). This kind of polythiophene and its polyanion and substituted thiophene _ -12- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1306109 V. Invention description (11) or copolymerization The preparation of aqueous dispersions is described in EP-A-440 957 and the corresponding US-P-5 300 575. Basically, the preparation of polythiophene is carried out in the presence of a polymeric polyanionic compound by oxygenation of 3,4-dialkoxythiophene or 3,4-alkylenedioxythiophene according to formula (II). Reaction to proceed: R1 - 0 0 - R2

(II) 10 wherein R1 and R2 are both as defined in formula (1). An aqueous dispersion of a polymer or copolymer of a substituted or unsubstituted thiophene. The Department of Economic Affairs, Intellectual Property Office, Employees' Consumer Cooperative, prints a stable aqueous dispersion of a polymer or copolymer of substituted or unsubstituted thiophene. Thiophene, for example, corresponding to formula (II), polybasic acid and oxidizing agent 15 are dissolved in water, optionally containing an organic solvent, optionally containing a comonomer, and then stirred at 0 ° C to 10 ° C The solution or emulsion is obtained until the polymerization is completed. The polymer or copolymer of substituted or unsubstituted thiophene formed by oxidative polymerization has a positive charge, and the position and number of such positive charges cannot be reliably determined, and thus the substituted or unsubstituted thiophene The general formula of the polymer or copolymer repeating unit is not indicated. Suitable oxidizing agents are those which are typically used in the oxidative polymerization of aromatic monomers such as pyrrole, thiophene and aniline. Preferred oxidizing agents are iron (III) salts, such as FeCl3, Fe(Cl?4)3, and iron (III) salts of organic acids and inorganic acids containing organic residues, or combinations thereof. Other suitable oxidizing agents are H2 〇2, K2Cr2 〇7, metal or perchlorate, metal perborate, potassium permanganate and copper salts such as copper tetrafluoroborate. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1306109 A7 B7 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (I2) Air or oxygen can also be used as an oxidant. Theoretically, 2 to 25 equivalents of oxidant per mole of oxidizing agent is required for its oxidative polymerization (J. Polym. Sci. Part A, Polymer Chemistry, Vol. No., p. i287, 1988). However, in practice, the oxidizing agent is used in an excess amount, for example, more than α1炱2 equivalent per mole of thiophene. The polyanion can be disclosed in ΕΡ-Α 44〇957 via a polyanion of a redispersible or soluble product obtained by lyophilization according to the present invention, and can be prepared from a polybasic acid or a salt of a corresponding polybasic acid such as an alkali metal salt. Add to. According to an eleventh embodiment of the <re-dispersion or soluble product obtainable via lyophilization according to the invention, the polyanion is a carboxylic acid polymer such as poly(acrylic acid), poly(f-acrylic acid) and poly( Maleic acid) or a polymeric sulfonic acid, such as an anion of poly(styrenesulfonic acid) or poly(vinylsulfonic acid). These polycarboxylic acids and polysulfonic acids may also be copolymers of vinyl carboxylic acid and vinyl sulfonic acid with other polymerizable monomers such as acrylates, methacrylates and styrene. According to an eleventh embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the polyanion is an anion of poly(styrenesulfonate) or a copolymer thereof with styrene. These polyanions which form polybasic acids preferably have a molecular weight of between 1000 and 2 χ 106, more preferably between 2000 and 5 χ 105. Such polybasic acids or their alkali metal salts are commercially available and can be prepared according to known methods, for example in

Houben-Weyl, Methoden der Organische Chemie, Bd. E20 Makromolekulare Stoffe, Teil 2, (1987), p. 1141, e Coating solution or dispersion-14 - ------------ #t------ (Please read the notes on the back and fill out this page) Order --- >(:ύ-Λ. r-? rfer〇丄γρι rei λ** Heap ✓Door·NTr* \ λ i _te on *> JK. ί -

爱公97 X Iu fv Pity 0- Λ / 〇ζ J ί I 1306109 Δ7 ι\ι B7 V. Description of invention (I3) (Please read the note on the back and fill out this page) The coating solution or dispersion is based on The invention obtains a redispersible or soluble product which may be a powder, paste or concentrated dispersion which may be aqueous via lyophilization of a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene Obtained from the dispersion. 5 According to a first embodiment of the coating solution or dispersion liquid of the present invention, the coating solution or dispersion further comprises water or an organic solvent. According to a second 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 the coating solution or At least 2% by weight of the 10 dispersions. According to a third 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 the coating solution or At least 5% by weight of the dispersion. According to a fourth specific 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 the coating At least 10% by weight of the solution or dispersion. The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative prints a fifth specific embodiment of the coating solution or dispersion according to the present invention, the 20 coating solution or dispersion having a polymer or copolymer comprising a polyanion and a substituted or unsubstituted thiophene The latex of the composition 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 dispersion. According to the sixth embodiment of the coating solution or dispersion of the present invention, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1306109 V. Invention Description (Μ 10 15 Ministry of Economy Intellectual Property Bureau employee consumption cooperative printed 1 material 1 volume = dispersion has a latex containing wheat anion and substituted or unsubstituted 2 body or copolymer, the concentration of which is the coating solution or 6 points of weight = % by weight, and the water content is less than the seventh embodiment of the coating solution or dispersion: the coating solution or dispersion, which can be used to prepare an antistatic or conductive layer. The solution or dispersion may contain other ingredients, such as a hardener, such as = oxy money, such as 3 glycidyloxypropyl-tertyloxy alcohol, as described in EP_A! Covered on a glass substrate; one or two interface active agents, spacer particles; adhesion promoter, light agent or IR-absorbent. Printing ink: a printing ink is obtained according to the present invention, which includes Powder three paste or concentrated dispersion a redispersible or soluble product obtainable via an aqueous latex dispersion of a bead s♦ anion with a polymer or copolymer of substituted or unsubstituted porphin. According to a first embodiment of the printing ink of the present invention, Further comprising water or an organic solvent. According to a second embodiment of the printing ink according to the invention, the printing ink has a latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted porphin, the concentration of which is the printing At least 2% by weight of the ink. According to a third embodiment of the printing ink of the present invention, the printing ink has a latex comprising a polyanion and a polymer or copolymer of substituted or unsubstituted (d) at a concentration of the printing ink At least 5% by weight. ί 297 mm) 1306109 A7 Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printing 5, Invention Description (1S) According to the fourth embodiment of the printing ink of the present invention, the printing ink has I The tempering of a polymer or copolymer of a polyanion and a substituted or unsubstituted porphin having a wavelength of at least the weight of the printing ink %. According to a fifth (4) embodiment of the printing ink according to the present invention, the printing ink has a latex of a polymer or a mixture of a substituted or unsubstituted thiophene at a concentration of at least 1 of the printing ink. % by weight and the water content is less than U% by weight of the printing ink. According to a sixth embodiment of the printing ink of the present invention, the printing ink has a latex comprising a polymer or a mixture of a polyanion and a substituted or unsubstituted porphin at a concentration of at least 5% 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 - or a plurality of binders; a hard agent, such as Epoxy 6, such as 3 glycidyl lactyl trimethoxy sulphur as described in ΕΡ·Α564911 t Suitable for coating one or more surfactants on the glass substrate 15; one or more dispersing agents, spacer particles; ^ occupying an accelerator, a UV-filter or an IR-absorbing agent. Suitable polymer binders are described in EP-A564 911. - The lithographic inks have a viscosity of from about 15 Baska·second to 35 Baska. sec depending on the ink formulation, dry handling mechanism, printing press and printing speed. Gravure 2 〇 printing and flexographic printing inks vary widely, but the typical viscosity of embossed inks is about 15 millipascals per second. The code for the screen printing ink (four) is H s. seconds. The inkjet ink depends on the type of ink method, the nozzle configuration, the printing speed, the ink drying mechanism, and the desired printing quality, and the viscosity varies from about 2 Mabasca seconds to 2 〇bass. Hot melt inkjet ink at room temperature -^^ 裂 订 ------- (Please read the back of the precautions and then fill out this page)

This "I Zhang scale applies Chinese National Standard (CNS) A4 specifications (210 X 297 public)

5 4 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1306109 V. The invention description (丨6) is solid, and when its viscosity is 4〇bass. seconds, it is normally tied at about 150°C. print. The opaque printing ink can be obtained by additionally incorporating a pigment such as LEVacryl@a_SF (a black pigment obtained from BAYER) which is held in a weight sufficient to impart opacity in the thickness of the applied layer. The printing ink layer exhibits superior adhesion to the phosphor layer, the polyacrylate auxiliary layer, the polycarbonate bismuth layer and the polyester layer such as poly(ethylene terephthalate) layer, and its visual transmittance is > 75% The bottom has a surface resistance of $1 〇〇〇 Ω / square, where 285% can be obtained. Binder According to a twelfth embodiment of the redispersible or soluble product obtainable via lyophilization according to the invention, the product further comprises a binder. According to a thirteenth embodiment of the redispersible or soluble product of the present invention, the product further comprises a binder having a glass transition temperature of greater than 251. According to an eighth embodiment of the coating solution or dispersion of the present invention, the coating solution or dispersion further comprises a binder or a thickener. According to a seventh embodiment of the printing ink of the present invention, the printing ink further comprises a binder or a thickener. Adhesives suitable for use in the present invention are described in U.S. Pat. No. 5, 641, 911, incorporated herein by reference, and incorporated herein by reference, in the the the the the the the the the the the Homopolymer and copolymer of acrylic acid and polymer latex. Suitable thickeners are polyacrylates and polysaccharides. Preferred polyacrylate thickeners are acrylic high molecular weight homopolymers and copolymers crosslinked with polyalkenyl polyethers, - - 18 - paper size iiiTiiii^-NS) A4 size (2) 〇i 297 mm ------Install--------Book--------- (Please read the note on the back and fill in the truth) 1306109 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative A7 B7 V. INSTRUCTIONS (Π) For example, CARBOPOL® resin of BF Goodrich, which is particularly good with CARBOPOL® ETD-2623. Preferred polysaccharide thickeners include cellulose, cellulose derivatives such as chitosan cellulose, guar gum and Xanthan gum, among which Sanxian gum is particularly good as purchased from the United States. Hercules' BIOSAN® S and 5 are available from Kelzan® T of the Kelco division of Merck, USA. Particularly preferred binders and thickeners for use in redispersible or soluble products, coating solutions, coating dispersions or printing inks according to the invention are: POLYVIOLT M WX4820 = Poly(vinyl alcohol) available from WACKER CHEMIE > 10 CARBOPOLtmETD2623 = Acrylic copolymer crosslinked with polyalkenyl polyether. Available from BF Goodrich; CERIDUSTTM 130 = Polyethylene from HOECHST; JONREZT M SM700 = Resin based on Johnson Polymer based on rosin; J〇NREZTM SM705 =. from Johnson p〇iymer rosin-based resin; JONREZTM SM729 = gambling from j〇hnS〇np〇iymer rosin-based resin; KLUCELTMH= from Hercules Propyl cellulose; 20 NE〇CRYLT M BT24 = soluble acrylic copolymer from Zenica resin. Preferred water-soluble binders include poly(vinyl alcohol), a copolymer of a homopolymer and a copolymer of hydroxyethyl methacrylate and a copolymer of 2-phosphonic acid oxy), and a 2-methyl group. a copolymer of 2-(2-phosphonooxy)ethyl acrylate. _ - 19 - This paper size applies to China National Standard (CNS) A4 specification (21〇X 297 public) --------Book ---------^9— (Please read first Precautions on the back side of this page) 1306109 ( ' A7 B7 V. INSTRUCTION DESCRIPTION (I8) The preferred polymer latex is selected from the group consisting of styrene, acrylate, methacrylate and diene (eg different A homopolymer or copolymer of pentadiene and butadiene. The preferred polymer latex for use in the redispersible or soluble product, coating solution, coating dispersion or printing ink according to the invention is: 5 Latex 01 = Poly(methacrylate methacrylate) latex with a particle size of 90 nm, available in 20% by weight aqueous dispersion; Latex 02 = 26.5 mol% terephthalic acid, 20 mol% isophthalic acid, 3.5 The copolyester latex obtained by mol% sulfonate isophthalic acid and 50 mol% ethylene glycol can be obtained by 20% by weight aqueous dispersion 10; latex 03 = vinylidene chloride, decyl methacrylate, sub Tertyl succinic acid (88/10/2) terpolymer, can be obtained in 30% by weight aqueous dispersion; latex 04 = 80% ethyl acrylate Copolymer with 2% methacrylic acid, available in 27% by weight aqueous dispersion; 15 latex 05 = 49% copolymer of decyl methacrylate, 49% butadiene and 2% methylene succinic acid, It can be obtained in 30% by weight aqueous dispersion, latex 06 = poly(ethyl acrylate), which can be obtained in 30% by weight aqueous dispersion. Latex 03, Latex 04, Latex 05 and Latex 06 all have a glass turnover of less than 25 ° C. The adhesive can be treated with a hardener such as an epoxy group, such as 3-glycidoxypropyltrimethoxydecane as described in EP-A 564 911, which is especially suitable for coating. Overlay on glass substrate. Surfactant _-20 -_ This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) * I * ---------Book---- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Clothing 1306109 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Β7 Β7 V. Invention Description (19) According to the basis The fourteenth of the redispersible soluble product obtained by lyophilization of the present invention In an embodiment, the product further comprises a surfactant. According to a ninth embodiment of the coating solution or dispersion of the invention, the coating solution or dispersion further comprises a surfactant. 5 The eighth printing ink according to the invention In a specific embodiment, the printing ink further comprises a surfactant. Preferred are anionic and nonionic surfactants for use in the redispersible or soluble product, coating solution, dispersion or according to the present invention or Suitable surfactants for printing inks are: 10 surfactant Nr〇l=perfluoro-octanoic acid ammonium salt, which can be obtained in 30% solution; surfactant Nr 〇2 = MARLONtm A365, from HULS to sodium alkylbenzene sulfonate 65% concentrate supply; surfactant Nr 〇3 = AKYPOTMOP80, from CHEMY with octyl-phenyl-oxy-polyethylene glycol (E08) acetic acid 60% concentrate for 15; surfactant Nr 04 = ARKOPALT M N060 (formerly HOSTAPALT MW), a nonyl phenyl polyethylene glycol from HOECHST; a surfactant Nr 〇 5 = ZONYLTMFSO 100, a block copolymer of polyethylene glycol and polytetrafluoroethylene, which has The following structure: 20 F(CF2 cf2 )y ch2 ch2 〇(ch2 ch2 0)xh , where x = 0 to about 15, and y = 1 to about 7, purchased from DUPONT, supplied as a 5% by weight solution; surfactant Nr 06 = HOSTAPALtmB, sodium phenyl-polyethylene glycol (EO 7-8) sodium sulfate from HOECHST, 50% concentrated _ - 21 - This paper scale applies to China National Standard (CNS) A4 specification (21 〇χ 297 mm) --------Book --------- (Please read the notes on the back and fill out this page) 1306109 A7

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Clothes, Liquid Supply; Surfactant Nr〇7 = ARKOPONtmt, an n-methyl-N-2-linoleic acid ethyl-oleylamine from HOECHST Sodium salt, supplied as 40% concentrate; 5 Surfactant Nr 08 = MERSOLATMH76, purchased from BAYER's fifteen base sodium, supplied as 76% concentrate; Surfactant Nr09= SURFINOLTM485, purchased from Air Products Alkyl acetylene glycol surfactant. Conductivity Enhancer 10 According to a fifteenth embodiment of the redispersible or soluble product obtainable via lyophilization according to the present invention, the product further comprises a conductive agent.曰

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. X 15 According to a ninth embodiment of the printing ink of the present invention, the coating solution or dispersion further comprises a conductivity enhancer. The appropriate conductivity enhancer is a linear, branched or cyclic aliphatic c2_2G hydrocarbon, or an optionally substituted aromatic tetrahydrocarbon, or an anthracene or a pyrene, the compound comprising at least two hydroxyl groups or at least one _c〇x* _c〇NYz group wherein X represents _0H, and ¥ and 2 independently of each other represent an alkyl group; or a heterocyclic compound containing at least one indoleamine group. An organic compound for use in a redispersible or soluble product, coating solution, coating dispersion or printing ink according to the invention, examples of which are, for example, N-methyl-2-tetrahydropyrrolidone, 2-tetrahydropyrrole Ketone, bismuth ______* 22 - paper ruler & Talk China National Standard (CNS) A4 specification (2) G χ 公 公 ) ) -------- set --------- Line win (please read the notes on the back and fill out this page) 1306109 A7 B7

5 15 ketone, N, tendon '-tetramethylurea', urethane, dimethylformamide and cake decyl acetamide. Preferred examples are sugars or sugar derivatives, preferably = glucose, fructose and lactose, or di- or polyhydric alcohols, #=2, cut alcohol, mannitol, mannose, galactose, caloside, gluconic acid glycol, Or tris(ethylene glycol), caffeic trimethyl alcohol-propane, U-propylene glycol 1,5,pentanediol, glycerol, butyl glycerol, hexane triol, or aromatic di- or Polyols such as resorcinol. Particularly preferred conductivity enhancers for use in coating solutions or dispersions or printing inks according to the present invention are: N-methyl-tetrahydropyrrolidone and diethylene glycol. A suitable carrier for use in the method of the present invention is a polymeric film such as poly(p-benzoene & L-single-poly(ethylene naphthalate), polystyrene, polyethersulfone, polycarbonate, Polyacrylates, polyamines, polyimines, cellulose triacetate, polyolefins, polychloroethylenes, etc. Inorganic substrates, such as oxides, glass, polymeric film tempered glass, Glass / plastic laminate. ---------- (Please read the note on the back and fill out this page) nn --Book --------------- Ministry of Economic Affairs Intellectual Property Bureau staff consumption Cooperative printing

Industrial Applicability According to the present invention, a redispersible or soluble product obtainable by lyophilizing an aqueous latex dispersion containing a polymer or a copolymer of a polyanion and a substituted or unsubstituted thiophene can be used for various application tissues. The dispersion or liquid mixture, printing ink and coating layer obtained therefrom can be used to manufacture electrodes which can be used in various electronic or semiconductor devices. #About the preferred application of the conductive layer made of dispersion, is a photovoltaic cell, an electroluminescent device, such as an organic or inorganic light-emitting diode, and I________ - 23 - The paper scale is suitable for 1^^ (CNS) A^72iQ x 297 public) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1306109, : 5, invention description (22) display, such as LCD. The conductive layer comprising the polythiophene produced in accordance with the present invention has a resistivity which is sufficiently low to act as an electrode in a device (e.g., a solar cell) that will draw or generate a small current. However, devices that can draw higher currents, such as LEDs, may require electrodes in which the organic conductive layer is combined with another layer having a preferred conductivity, such as an ITO layer. Other embodiments are disclosed in EP-A 10 134 413 and EP-A 0 554 588. 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 embodiment. The ingredients used in the examples but not mentioned above are summarized below: ECCOCOAT^^CC-2 = Conductive Polymers from Emerson & Cumming Specialty Polymers Z6040 = 3 from Dow Corning - Glycidyloxy 15-propyl propyl dimethoxy chop. Preparation of an example polythiophene dispersion The poly(3,4-exoethylenedioxythiophene) [PEDOT] and an aqueous dispersion of polystyrene sulfonate [PSS] as a polyanion according to EP-20 A 1 079397 Prepared by the method described. The dispersion thus obtained had a solid content of 1.15 wt%, and the weight ratio average particle size was measured by a Chemical Process Specialists (CPS) DCP 20000 disc centrifugation method using an aqueous solution of 8% sucrose, which was about 50 nm, wherein the main peak was About 25 nm. Table 1 lists the particle size distribution characteristics of several representative 25 PEDOT/PSS dispersions. -24- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm)

1306109 V. INSTRUCTIONS (23) Table 1: Average particle size by weight [nm] Main peak maximum [nm] Main peak half width [nm] 90% by weight of particles have a size smaller than the following [nm] 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

5 Separation of PEDOT/PSS by evaporation from polythiophene dispersion Preliminary evaporation experiment using I.2% aqueous dispersion of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid HPEDOT/PSS) It has been shown that simple evaporation of a liquid 10 present in a latex solution or dispersion of a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene provides a solid which is not easily redispersed by the addition of water or Film. The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed a specific 1.1% aqueous dispersion of 100 grams of PEDOT/PSS and a surfactant containing the solid amount shown in Table 2, Nr. 01, 02, 03, 04 or 05 The aqueous solution or latex 01, latex 02, latex 03 or 15 aqueous dispersion of latex 06 or solid poly(vinyl alcohol) is mixed to produce a mixture of samples II to IX. Sample I is the same 1.1 grams of PEDOT/PSS. % Aqueous dispersion. -25- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1306109 A7 B7 V. Description of invention (24) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Table 2: Sample [g] I II III IV V VI VII VIII IX X XI 1.1% aqueous PEDOT/PSS 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 - - 朦乳 01 - - - - - - 1.1 Latex 02 - - - - - - 1.1 Latex 03 - - - - - - 1 1 Latex 04 - - - - - - 1 1 POLYVIOLTM WX48 / 20 — 1.1 Sample I-IX is attached to a drying cabinet and evaporated at 11 (rc for 24 hours to produce sample Ι-A to KA. Sample!_A is The pED〇_ obtained by evaporating the sample was found to have a bet specific surface area of 0.5 m 2 /g. (Please read the precautions on the back and fill out this page) -Installation. ----Book - -26 - A7 1306109 __BT^__ V. Description of invention (25) Study PEDOT/ obtained by evaporating samples I to IX Redispersion of PSS-samples Ι-A to IX-A in water. Very little expansion was observed after 8 hours of contact with water, but in the case of the sample Π-A, a moderate amount of expansion was observed. The redispersion of the 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 10 minutes, followed by treatment with Ultra-TurraxTM for 10 minutes. Pass the GAULIN homogenizer twice at 400 bar and pass the MICROFLUIDIZERtm once. The redispersed evaporated PEDOT/PSS dispersion is mixed with N-methyl-tetrahydropyrone, Zonyl FSO 100, Z6040, latex 03, and coated on a secondary PEDOT/PSS 10 carrier to produce the table. Layer composition in 3.垚3 : PEDOT/PSS 28·9 mg/m 2 Zonyl FSO 100 8 mg/m 2 Z6040 1〇〇mg/m 2 Latex 03 100 mg/m 2 N-methyltetrahydroindanone [2 ml/m 2]* * theoretically exists, but evaporates during the drying process, thereby producing conductivity enhancement 15 which exhibits a surface resistivity of 18 Ω / square, which is equivalent to the use of the original PEDOT/PSS-dispersion with the same composition The surface resistivity of the 1700 Ω / square of the coating of the liquid. These experiments show that it is possible to redisperse after evaporation, but only under the measurable energy and time.

2. Separation of PEDOT/PSS by freezing from polythiophene dispersions Polymers or copolymers containing polyanions and substituted or unsubstituted thiophenes -27 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) -------- Order — (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives, M 1306109 A7 B7 V. INSTRUCTIONS (26) Thawing of the frozen solution or dispersion of the latex causes phase separation, but separation by centrifugation or filtration is impossible. Despite the fact that macroscopic PEDOT/PSSA macromolecules are formed during thawing, treatment of the thawed dispersion 5 with a microfluidizer bed unit at 4 Torr produces a dispersion which is as above When the same layer composition is applied, it exhibits a surface resistivity of 1700 Ω/square, which is equivalent to a surface resistance of 1700 Ω / square using a layer coated with the original PEDOT/PSS-dispersion having the same composition. rate. This freezing experiment showed that freezing itself did not separate the solid PEDOT/PSS.

Precipitation of PEDOT/PSS by addition of a non-solvent from an aqueous dispersion to add a non-solvent does not result in precipitation of PEDOT/PSS into a form that can be separated by filtration or centrifugation. Lyophilization of Polythiophene Dispersion 15 The PEDOT/PSS dispersions of Samples 1 through XI were lyophilized in a high vacuum (0.7 mbar) in a CHRIST BETA 2-16 shelf lyophilizer until all water was After evaporation (meaning that the shelf temperature is equal to room temperature), dry powder workers _ B to XI-B are obtained. Two BET measurements were made with sample IB powder to give a 2 〇 BET specific surface area of 3 and 6 m 2 /g, which is assumed to be a density of 106 g/m 3 (density of water), which means an average particle size of 1.0 to 2.0 μm. . The lyophilized powder of Samples I-B was found to contain 712% by weight of PEDOT/PSS, 13.0% by weight of water which was removed when dried at 200 ° C, and 7.8 % by weight of water which could not be removed at 2 ° C. -28 - This paper size applies to China National Standard (CNS) A4 specification (21〇 X 297 mil) (Please read the note on the back and fill out this page) 1. * ▼ Install! I----- s'. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1306109 A7 B7 V. Invention description (π ^ contact with deionized water for 8 hours to produce u weight Jiaqing SS ° work, IBI to ] 'Research on the pED〇T/pss sample and then redisperse two°. From all these samples, visually complete redispersible 4 mechanical energy or thermal energy can be observed, but in the sample ΙΠ Β (using interface activity) In the case of the agent, it is seen that the large cohesive polymer and the sample are obtained from the intestines. All of them are obtained without consuming mechanical energy or heat, Β I ΙΙΙ-Β-Ι, iv-bj and V_B· The particle size distribution 'is shown together with the particle size distribution of the starting material I. Table 4: Average weight ratio of the sample to the weight [nm] Peak maximum [nm] Peak half width [millimeter] Micron] 90% by weight of particles

I 54

IBI 68 95 57 These granularity metrics show complete redistribution in the case of 乂, 〗, and VI_BI, with substantially complete redispersion in the case of IBI, and slightly in the case of II-BI Sticky. 15 These experiments thus confirmed the redispersion of lyophilized PEDOT/PSS materials containing surfactants, polymer latexes or water-soluble polymers, as compared to the Evaporated PEDOT/PSS-samples, surprisingly Easy without the need to apply mechanical or thermal energy. Preparation of Waterborne Coating Dispersion XII-BI, ΧΙΙ-Β-Π and I B-ΠΙ-29 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1306109 B7 V. Description of invention ( 28) (Please read the notes on the back and fill out this page.) The lyophilized powder (Sample XII-B) is obtained from the specific 1.1% by weight of PEDOT/PSS (Sample XII) dispersion as described above and added by Ionized water to redisperse it to obtain the following samples with different solid contents: Sample solid content (% by weight) Viscosity at 25 ° C [Mbas-By·second] XII-BI 1.15 96 XII-B- II 2.30 762 XII-B-III 3.45 6612 5 The 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 XII-B-II [g] - - 10.87 - Sample XII-B- III [g] - - - 7.24 Latex 03 [g] 0.83 0.830.83 0.83 ZONYLTMFSO 100 (5 wt% surfactant purchased from DuPont) [g] 0.40 0.40 0.40 0.40 N-methyltetrahydroσ-pyrrolidone [克] 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 (*)Comparative, before the bed dry polythiophene dispersion liquid Ministry of Intelligence Intellectual Property Bureau employee consumption cooperative print 10 Preparation and Conductivity Measurement of Conductive Layers of Samples XIII, XIV, XV and XVI

Samples XIII, XIV, XV -30 - The paper size is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) using a coating blade (50 micron wet coating thickness). 1306109 A7 B7 V. Description of the invention The aqueous coating dispersion of (29) and XVI was applied to an auxiliary polyethylene terephthalate film carrier and dried at 40 ° C. (Please read the precautions on the back and fill out this page.) Cut the auxiliary carrier of the coated conductive layer to obtain a strip having a length of 27.5 cm and a width of 35 mm. The conductive polymer ECCOCOAT CC-2 electrode 5 was applied over a distance of 10 cm above the width of the strip. The resistivity is measured in the following manner, a fixed potential is applied between the electrodes, the current flowing through the circuit is measured by a picoamperometer KEITHLEY 485, and the surface resistivity is calculated from the potential and the current, expressed in Ω/square, considering the inter-electrode region Geometric shape. The results are shown in Table 6. 10 Table 6: Surface resistivity of conductive layer Sample PEDOT/PSS Surface resistivity of sample [Ω / square] XIII ΧΙΙ (*) 1200 XIV ΧΙΙ-Β-Ι 1200 XV ΧΙΙ-Β-ΙΙ 1550 XVI ΧΙΙ-Β- ΙΙΙ 1575 (*) Comparison, the results of Table 6 after the drying of the poly-sigma thiophene dispersion showed that all the samples exhibited comparable surface resistivity within the experimental error. The polythiophene dispersion can thus be lyophilized and redispersed to a concentration that does not affect the conductive properties of the layer to which it is applied. Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

The aqueous coating dispersion ICI was prepared from the lyophilized PEDOT/PSSA with further drying ΐ-c so that the lyophilized powder of the polythiophene dispersion sample Ι-Β was further dried in a vacuum drying cabinet for 12 hours to produce a sample Ι-C. . After the addition of 2 liters of deionized water, the further dried lyophilized powder was not immediately dispersed as in the samples Ι-Β and ΧΙΙ-Β. Wet at 2 liters of deionized water at room temperature for 48 hours -31 - This paper scale applies to China National Standard (CNS) A4 specification (210 297 297 mm) 1306109 A7 __B7_ V. Invention (3Q). The mixture was then subjected to Ultra-TurraxTM treatment for 10 minutes, followed by two passes through a GAULIN homogenizer and one pass through MICROFLUIDIZERtm at 400 bar, 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 75. Table 7: Sample ICI Polythiophene Dispersion [g] 7.24 Latex 03 [g] 0.83 ZONYLTM FS0100 (5 wt% surfactant purchased from DuPont) 0.40 [g] N-mercaptotetrahydropyrrolidone [g] 5.00 Trial Preparation of screen printing inks of samples XVII to XXIII by re-dispersing the lyophilized powder from the polythiophene dispersion by adding different solvents, optionally with CARBOPOLtm ETD 2623, followed by Ultra-TURRAXtm pre-dispersion and extended ball milling (duration) See Table 8) to obtain samples XVII to XXIII having the compositions shown in Table 8. --------------------Book --------- (Please read the phonetic on the back? Please fill out this page again) Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 15 20 -32 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1306109 A7 B7 V. Invention Description (31) Table 8 : Sample ball milling time [hours] PEDOT / PSSA [% by weight] Water [% by weight] Solvent medium CARBOPO LETD 2623 [% by weight] [% by weight] XVII 24 1.19 0.31 Diethylene glycol / carbitol acetate 4" 98.5 XVIII 48 1.58 0.42 Diethylene glycol 96.0 2 XIX 48 1.58 0.42 N-Mercapto-tetrahydroindole π ketone 96.0 2 XX 48 1.58 0.42 Isopropanol 96.0 2 XXII 96 1.98 0.52 n-propanol 97.5 - XXIII 24 1.24 0.31 II Ethylene Glycol 98.45 - The characteristics of the dispersions XVII to XXIII obtained by the redispersion procedure are shown in Table 9 〇5 Table 9 ·· Sample dispersion characteristics XVII Adhesive copper and raw thieves XVIII Extremely thick dispersion XIX Thick dispersion XX Extremely thick dispersion XXII Strong raw villi XXIII Uniform flow dispersion sample XX The complex viscosity of III is 7? * measured by the AR1000 conical flat rheometer at 25 ° C and 10, 1 and 0.1 Hz, respectively, and 1000 Pascal seconds, 5000 Baska. seconds and 40,000 Baska. Seconds. 10 Screen printing uses sample XXIII to apply the Chinese National Standard (CNS) A4 specification (210 297 297 mm) in the auxiliary polyethylene terephthalate-33 - paper scale ------- --------Book --------- (Please read the note on the back and then fill out this page) 1306109 Δ7 Ά / Β7 5, invention description (32) on the carrier Ρ 59 screen version get on. The surface resistivity measured in the manner disclosed for the coating layers of samples XIII, XIV, XV and XVI, and the optical density measured by the visible filter on the MACBETHtm T924 densitometer are shown in Table 1 〇5 Table 10 ·· Samples for screen printing mesh surface resistivity [Ω/square] Optical density [visible filter] XXIII P59 370 0.11 Sample XXIV to XXVII lithographic dry offset printing ink preparation sample The lithographic dry printing inks of XXIV to XXVII were prepared by ball milling for 20 hours with the ingredients shown in Table 11 for the specific samples, and the PEDOT/PSS system 10 was used in the form of a lyophilized powder. In the case of the sample XXIV, the rosin was first dissolved in water by means of monoethanolamine, followed by lyophilized PEDOT/PSS powder, followed by dissolution of other components before ball milling. In the case of the samples XXV to XXVII, the rosin was first dissolved in the isopropyl alcohol/water mixture by means of monoethanolamine, and after the other components were added, it was subjected to a ball milling for 20 hours. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Agriculture - 34 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). Bureau employee consumption cooperative printing 1306109 C Δ7 A/ B7 V. Invention description (33) Table 11: Sample XXIV XXV XXVI XXVII Ball milling time [hours] 20 20 20 20 IB PEDOT/PSSA [g] 2.38 2.38 2.38 2.38 Water [克] 76.72 91.16 91.16 91.16 Isopropanol [g] 10.00 1.24 1.24 1.24 ΝΗ4ΟΗ [g] 6.00 0.05 0.05 0.05 styrene-maleic anhydride resin [g] 0.73 0.73 0.73 0.73 JONREZtmSM700 [g] - 1.44 - - JONREZtmSM705 [克] 1.46 - 1.44 - JONREZtmSM729 [g] » - - 1.44 monoethanolamine [g] 0.13 0.55 0.55 0.55 pH after dissolution - 8.5 8.5 8.5 NEOCRYLtmBT24 [g] 0.40 0.40 0.40 0.40 KLUCELTMH [g] 0.63 0.63 0.63 0.63 butyl card Alcohol [g] 0.70 0.70 0.70 0.70 CERIDUSTtm130 [g] 0.25 0.25 0.25 0.25 Surfactant Nr9 [g] 0.50 0.50 0.50 0.50 Printing test 100 tablets ink acceptance test in ABDick 9860 The PRESSTEKtm dry card printing plate with 8 gram/m2 lithographic press paper is mounted on the press machine, wherein each fifth sheet is an AGFAtmT474 Transparex sheet purchased from AGFA-GEVAERT NV. . Good print quality was obtained with samples XXIV to XXVII, with the exception of sample XXVI giving very fine prints with no visible image background. 10 The present invention may include any combination of features or features, whether implicit or explicit, or any generalized form thereof, whether or not it is -35 - - This paper scale applies to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) ------------ Clothing -------1-Book--------- (Please read the phonetic on the back? Fill in this page) 1306109 Γ Α7 __Β7 V. INSTRUCTIONS (34) The present invention as claimed. In view of the foregoing, it will be apparent that various modifications may be made within the scope of the present invention. -----------Install--------Book ------ (Please read the notes on the back and fill out this page) # 经济部知曰慧物局Employee consumption Co-operative printing 6 3 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

Patent Application No. 90117385 ROC Patent Appln. No.90117385 Amendment to the scope of application for patent replacement page - Annex (II) Amended Claims in Chinese - Encl/II) (Submitted on August, Republic of China, August 20, 1997) (Submitted on August 20,2008) A further product or paste obtained by substituting an aqueous dispersion of a substituted or unsubstituted thiophene polymer gelatin which can be lyophilized to contain yt~·-〇〇r&quot ; 2 5 10 Ministry of Economic Affairs Intellectual Property Bureau 15 Cooperation 2〇(工) where the η system is greater than i, and each...with the R2 generation or the substituted Ci4 group hydrogen or unsubstituted h animal feed is not reduced or taken ί ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο a substituted alkyl group or a phenyl substituted exo group, an exoethyl group, a cyclohexyl group, an A, a 3-propyl group or a 1,2- 4 ·, according to the product of the scope of the application of the + Its * #(benzene (4)) anion knot, the finger ion is an anion. - / ~, the hexene The product of the 6th agent of the polymer, wherein the aqueous dispersion is prepared to produce an antistatic layer, and the package is transferred by adding water or an organic solvent to re-sequence: the product of the second product is obtained to obtain a solution. Or = Shen: Special -37 - ^ϊΪ(€Ν8)α75^(21〇χ297 90298Β-接3订S] AS B8 A8 B8 C8 D8, 1306109 VI. Patent application scope The printed layer or pattern of the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative has a surface resistivity of at least 106 Ω/square. 16. A coating solution comprising the product according to item 1 of the scope of the patent application. 17. The coating solution according to claim 16 of the patent application, which further comprises 5 water or an organic solvent. 18. The coating solution according to claim 16 wherein the latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene is at a concentration of at least 5% by weight of the coating solution. 19. The coating solution according to claim 16 wherein the latex comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene is at a concentration of at least 10% by weight of the coating solution. 20. The coating solution according to claim 16 of the patent application, further comprising a binder or a thickener. 21. The coating solution according to claim 16 of the patent application further comprising a surfactant. 22. The coating solution according to claim 21 of the patent application further comprising an organic solvent. 23. A coating dispersion comprising the product according to item 1 of the scope of the patent application. 20 24. The coating dispersion according to claim 23, which further comprises water or an organic solvent. 25. The coating dispersion according to claim 23, wherein the polyanion and the substituted or unsubstituted thiophene have a latex concentration of at least 5% by weight of the coating dispersion. 25 26. The coating dispersion according to Clause 23 of the patent application, wherein the latex concentration of the polyanion and the substituted or unsubstituted thiophene is -39 - the paper size applies to the Chinese National Standard (CNS) A4 specification (210x297) PCT) 0606109 Λ 至少 At least 10% by weight of the patented dispersion. 27. A coating dispersion according to claim 23, which further comprises a binder or a thickener. 28. A coating dispersion according to claim 23, which further comprises 5 a surfactant. 29. A coating dispersion according to claim 28, which further comprises an organic solvent. 30. A coating solution comprising the product according to item 5 of the scope of the patent application. 31. The coating solution according to claim 3, further comprising an organic solvent. 32. A coating dispersion comprising the product according to item # of the scope of the patent application. 15 33. A coating dispersion according to item 32 of the patent application, which further comprises an organic solvent. 34. A printing ink comprising the product according to the scope of the patent application. 35. A printing ink according to the scope of application of the patent application, which further comprises water or an organic solvent. The printing ink according to claim 34, wherein the latex comprising a polymer or a copolymer of a polyanion and a substituted or unsubstituted porphin is at a concentration of at least 5% by weight of the printing ink. . 37. The printing ink according to claim 34, wherein the latex comprising a polyanion and a substituted or unsubstituted sinus polymer or copolymer is at a concentration of at least 1% by weight of the printing ink. . __- 40 - This paper scale is applicable to China National Standard (CNS) A4 specification (21() χ 297 gong) I 1306109 VI. Patent application scope A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 38. According to patent application The printing ink of the range 坌h yoke, which further comprises a binder or a thickener. 39. ΐ, υ利(4) The printing ink of item 34, wherein the printing ink is a lithographic dry printing ink. 4. A method of using a printing ink according to claim 34 of the patent application, which is used for preparing an antistatic layer. A method of producing a conductive layer using a printing ink according to claim 34 of the patent application. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm)