TW200948849A - Redispersible functional particles - Google Patents

Abstract

A novel class of layered microparticles comprises a thermoplastic or crosslinked polymeric core containing anionic functional corona groups bonded to the core particle surface, and an oxidatively polymerized shell such as a polypyrrole embedded in the corona. The particles are useful e.g. as conductor material or electrophoretic or colloidal dye; they may be dried and redispersed in polar solvents by conventional means without changing the particles' properties.

Description

200948849 VI. INSTRUCTIONS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to novel functional particles, methods for preparing such particles, and the use of such particles for preparing electrically conductive structures, electronic devices, such as OLEDs. Or its use as, for example, a conductor in an optical or acoustic filter, an electronic device or a light control system, a conductor precursor, an electrical (dye) particle, or a collector. [Prior Art] Conductive layers (such as indium tin oxide) or germanium (=yttrium tin oxide) in today's electronic devices are usually applied by pvD (physical vapor deposition) or CVD (chemical vapor deposition). Coffee or (4) is expensive and slow = program and usually only works on rigid and flat substrates (#, glass). So far, conductive organic polymers have not been used because of their lack of processability and stability and generally conductivity. Too low and lack of transparency, with one exception: PEDOT: PSS is used as a hole injection and smoothing layer in, for example, a 〇led device. However, solutions of this material are strongly acidic and "corrupt" other layers, which have a negative impact on the life of the device. Furthermore, the product is delivered as a diluted aqueous solution and may not be isolated in powder form. WO 01/92377 discloses the preparation of a conductive microgel containing a conductive polymer physically adsorbed onto a core particle. It has now been found that it can be bonded to the particle surface by corona comprising an anionic polyelectrolyte (for example comprising a sulfonate group which can be linked by reaction with a stupid ethylene sulfonate) and optionally other neutral groups. A functional polymer shell obtained by oxidative polymerization is deposited on the corona and/or embedded in its 200948849 to obtain particles having strongly modified properties such as stability, narrow particle size distribution, colloidal properties (such as Redispersibility), properties of particles containing or films formed by the particles (such as 'adhesion of film to substrate, electrical and optical properties of film roughness' film). SUMMARY OF THE INVENTION Providing even finely dispersible properties of previously concentrated or dried particulate matter is different from prior art materials using one-step preparation (eg, 1780233), the particle core and particle shell of the present invention, and generally intermediate corona Obtained in separate steps; due to &, clear structure of the particles can be achieved (generally, there is no outer shell or corona substance in the core, and there is no core material in the particle shell). The layered particles of the present invention contain an anionic moiety that is normally chemically bonded to the surface of the core of the organic polymer. By conventional means, such as mixing a mixture of particles with a polar solvent (for example, as listed below) (four) and/or ultrasonic treatment, the dried particles can be easily redispersed in a polar solvent; The particles do not aggregate 'without additional processing such as freeze drying. For example, as shown in FIG. 9, the anion corona of the composite particles can be retained by polymerizing the pore ratio (py) oxidation in a suspension of core/shell particles having a polyelectrolyte corona. Forming the layered particles of the present invention. Optionally, the particles of the present invention may contain other functional groups covalently bonded to the core particles (see Figure 10)' for example to enhance electrical space or steric properties to prevent coagulation/flocculation and to retain colloidal enthalpy. As indicated in Figures 9 and 1Q, the preferred particles retain a small portion of the electrical 200948849 halo group on their surface even after the outer shell forming step. The particles of the present invention exhibit only a small tendency to aggregate or a tendency to aggregate (e.g., less than 40% by weight, especially less than 1% by weight of aggregated particles after reforming the dispersion). The size is typically in the nanometer range, e.g., in the range of 5 nm to about nm, especially about 15 nm to about 1 Torr.

The particles of the present invention generally do not contain any low molecular stabilizers as compared to some of the previously reported core shell particles. This contributes to the long-term stability of the particles in the dispersion medium; t-ability and its redispersibility as a dry powder. Advantages of films formed from such core shell particles include: high light transmission (due to dilution of the core polymer); b) high adhesion of the film to the substrate (because surfactants are typically not used) and due to Excellent film formation of the core of the particle (low-thickness; #彳.N, „supply degree), C) South economy due to the incorporation of core polymer. The advantages of this month's particles include the following Modifications of the nature: 1 • Mechanical Tension Elongation Elongation Elongation Bomb Deformation (including temperature dependence) Creep behavior Hardness 2.! Academicity t: DC Conductive AC Conductivity) Conductivity (including its temperature dependent impedance) (including its frequency dependence; aging (including temperature dependence) 5 200948849 Water content (NMR)-dependent voltage strain (electromigration property) of the layer between ITO and organic layer in air (dry) in vacuum Uniformity of properties, local variation (STM) 3. Optical properties transmission 400-800 nm Transmission aging behavior Light scattering (translucent, hazy) Reflectivity 4. Chemical properties / processing properties Thermal stability / drop /crosslinking solubility in various media, viscosity, etc. Crosslinkability Construction machinery using common methods (eg, embossing) Thermal (eg, laser) Photochemical expansion behavior, solvent retention and adjacent layers (Low) Reactivity 5. Interface properties and adhesion of ITO to the adhesion of the organic layer to the wettability (contact angle) 6 200948849 (low) roughness of the film 6. General application of particle size and particle size distribution (about 30 -100 nm) Stability of Conductivity (infinite) Water content (low) and pH ("Neutral") of the material. Dispersibility of the polymer in organic solvents (also in the background of printing) Properties and film-forming properties ❹ Hydrophobicity (high) Solvent resistance (high) homo energy level (electron blocking) [Embodiment]: Sub: favored by emulsion polymerization (for example, seed emulsion, microemulsion). The product is narrowly dispersed (= very large in size and composition); its size can be adjusted in the range of a few nanometers to tens of micrometers, and it is adjusted within the circumference (preferably small particles smaller than 1 〇〇 nm). θ double, sum, and repeat ratio It varies within a wide range from 1·1〇〇 to 1 00:1. J also uses a mixture of particles of different sizes and compositions and it is even better preferably to obtain excellent film formation and close packing. The particles of the child can be dried and the powder can be easily redispersed. It can be dry: the powder application or preferably in the form of a dispersion in a wide range of solvents should be in the form of a little = suitable, which is very suitable for printable electronics. Film/printing removes solvent and increases stacking and conductivity. Other additives such as light and heat: dispersants, smoothing agents, etc. can be used in dispersions or core materials to improve the formation and final properties. ^ 7 200948849 The core particles can be obtained according to methods known in the art for preparing polymer particles, for example by emulsion polymerization (for example, monomer-based half-batch emulsion polymerization can be advantageously used, this system Because it requires the use of a lower amount of surfactant to form the core particles). The polymers are usually synthetic, examples of which are further listed below. For a large number of applications of the final particles, it is advantageous to have a soft particle core or a particle core that softens or melts at relatively moderate temperatures (e.g., below 2 Torr, especially below 150 C). For example, the core forming organic polymer is crystalline or amorphous at 2 (TC) and has a glass transition temperature of 150 ° C or lower. This type of soft core particle usually contains ruthenium at 20 ° C for crystallization or non- Crystalline and having a typical unorganized and nonionic thermoplastic polymer of 200 ° C, especially ι 5 (Γ or lower glass transition temperature or a latent similar organic polymer with low parental affinity (eg nonionic a polymer such as polystyrene, a polyacrylate (such as poly(fluorenyl) acrylate or its copolymer), or even an allyl ether. If necessary, core crosslinking can be achieved by The difunctional or polyfunctional monomer or polymeric polymer (e.g., divinylbenzene, butadiene, etc.) is copolymerized to achieve. For clarity, in addition, the soft core polymeric material generally does not contain anionic functional moieties. The anionic monomer may still be present in minor amounts during the (co)polymerization of the core particles (eg, less than 50% by weight monomer, preferably less than 20% by weight, especially less than 10% by weight of monomer; examples are (曱基)propyl acetoin or A smaller amount of sulfonated styrene is present, however its presence is not necessary at this stage. The core particles obtained at this stage are usually in the range of about 5 to 1 〇〇 nm, especially 10 to 60 nm. 8 200948849 Corona - the "corona" of the particles formed by the copolymerization of the core particles with a suitable functional monomer to the anion of the particle and, if necessary, other functional groups. Officer: The monomer may have been added before or during the formation of the core particle. Alternatively, the core particles obtained as described above may be functionalized with: or a plurality of monomers providing anionic functional groups and optionally other monomers. The corona usually comprises a plurality of selected from the group consisting of a tallow group and a benzene group. a cationic group of an anionic group and, in particular, an anion functional group of a sulphonate group and/or a sulphate group. In some preferred particles, one or more anionic functional groups comprise an anionic or latent anionic function. The homopolymer chain of the monomer unit or the corresponding copolymer chain containing other comonomers and/or crosslinked fresh elements is attached to the core to the particle. An example of a useful polyanion chain is provided by The monomer of the ionic functional group is co-oligomerized/polymerized with the core particles, and the monomers which provide the anionic functional group of the polyanthracene are mainly PG-Sp-Ra of the following formula, wherein PG represents polymerizable a group such as vinyl-ch=ch2 or a vinyl group, especially an ethyl group; h is a residue selected from -coox and especially _S03X, _p(9)(ox)2 providing an anionic functional group; printed as a direct bond or a σ-suitable spacer having a valence of from 1 to about 5 G carbon atoms of (a+1), and Sp is particularly selected from the group consisting of a stretching group, a stretching group and an aryl group, and a combination of the groups 9 200948849 Aerobic or sulfur or nitrogen and/or substituted by ο, s; X is a group suitable for dissociation in the form of a cation; examples of such groups are Η, M, Rl, N(Rl)4, wherein Μ represents one Equivalent metals, such as alkali or alkaline earth metals or zinc, and Ri represent an ere "hydrocarbon residue, such as 〇1_6 fluorenyl, especially styrene sulfonic acid or a suitable salt or ester thereof. Examples of such preferred monomers include acids selected from the group consisting of vinegar and salts: vinyl benzene sulfonic acid 'C2_CS alkenyl sulfonic acid, (meth) acryl decyloxy-C2-Cs alkyl sulfonic acid , (meth) acrylamido-yl-C2_C8 alkyl sulfonic acid, vinyl phenylphosphonic acid, alkenylphosphonic acid, (meth) acryloyloxy _c2_c8 alkylphosphonic acid, (meth) acrylamide Base - c2_c8 alkylphosphonic acid derivative. If vinegar is used, it is preferred to convert the esters to the corresponding anionic moieties (acids or especially salts) prior to the final step (deposition of the peripherals) described below. Examples of suitable anionic monomers or monomers which can be converted to anionic moieties include the following:

^^〇^^so3- k+ X^il^-s〇3H

Wherein the potassium ion may also be replaced by other suitable cations (such as sodium ions), or the propylene sulfhydryl residue may be replaced by a mercapto acryloyl group, and is selected from hydrazine, a suitable cation or preferably as defined above for & . 200948849 The graft density of an anionic chain on the surface of a particle is typically in the range of 0.001 to about 1 bond per square nanometer. Other monomers may be copolymerized/attached to the particle core in the same manner; such copolyesters may be used to modify other properties of the final particle, such as hydrophilicity/hydrophobicity, solubility properties, electrical space or space properties, corona stiffness/stability (Example by cross-linking between the parts forming the corona). The s, ', which is used to form the corona, is substantially selected from the group of ruthenium provided for the formation of the core particles. The limitation is that the dispersion medium is suitable as a solvent for the desired product. Such preferred comonomers include (mercapto)acrylic acid and salts thereof and vinegars such as (poly)ethylene having various (poly)ether/polyglycol chain lengths (eg, comprising L400, especially 2_1(9) monomer units) Alcohol, glycerin and methacrylic acid vinegar of poly(ethylene glycol) or polydecyl alcohol; or divinylbenzene or butadiene used for crosslinking. The copolymerization reaction for forming a corona is preferably carried out in the liquid phase in the presence of a polar solvent or a dispersed phase. The reaction can be carried out in a free-radical polymerization form, preferably by adding a free radical primer and/or applying heat and/or actinic radiation to induce a typical reaction in the hair, as described above, the uncharged or charged core particles are dispersed in the polar phase. In the solvent. Adding an anion functional group-containing monomer (preferably in an amount ranging from i parts by weight to about 1 part by weight based on 100 parts by weight of the core particles) and other optional components (such as comonomer) After the interface is activated, the copolymerization is initiated by applying heat (for example, 1 (10), inert gas, mixing) and/or adding a polymerization initiator such as a radical initiator. The copolymerization reaction is carried out according to a method known per se, for example, by adding a suitable monomer to the core particle dispersion under the conditions for initiating the desired reaction. In the case of using an ethylenically unsaturated monomer (especially in the case where PG represents a vinyl group), the reaction can be conveniently initiated by the addition of a radical initiator. The ratio of the monomer to the core particle starting material (dry mass) is usually in the range of from 0.02:1 to about 1000:1 (parts by weight).

Each copolymerization reaction may be carried out in a crosslinking agent such as a monomer containing two or more vinyl moieties ("hydrogel corona"; examples: divinylbenzene, butadiene mono or di(meth)acrylate In the presence of a light or thermally degradable crosslinker. The ratio of crosslinker (if present) to the monomer forming the corona is typically in the range of from 〇 (no crosslinker) to about 0_05:1 (parts by weight). The resulting material already contains a negative charge on its surface; the treatment can be carried out according to procedures known in the art, including separation and/or drying of the intermediate particles. For the subsequent step (forming the outer casing), the thus obtained knife-dried/dried particles may be redispersed, or the obtained particle dispersion may be used as it is. For example, a thermoplastic or micro-crosslinked organic polymer (such as crystalline or amorphous at 2 ° C and having a melting temperature of 15 (rc or lower)

Suitable core nanoparticles of a polymer, especially polystyrene, can thus be copolymerized with a suitable monomer having 3 functional groups S〇3H, S〇3M or SOsR!, wherein Μ represents one equivalent of metal cation and Ri represents A Ci_C2Q hydrocarbon residue, such as an alkyl group, is especially copolymerized with styrene sulfonic acid or a suitable salt or ester thereof, and an acid group, especially (10)" and S〇3Rl (if the bow is converted to S03M, especially S03Na, as appropriate in a subsequent step). The ester and/or acid are converted to the corresponding salt as appropriate, usually by an additional heating step or without additional heating steps, and the ester is typically applied in the form of an aqueous solution (eg, an anthracene hydroxide such as Na〇) H aqueous solution) solution)." 7 Shell❹

A monomer suitable for oxidative polymerization (also referred to as oxidative coupling) may be added to the particle dispersion obtained in the previous step or may be added after the particles are redispersed in the solvent. The polymerization and deposition of the corresponding deuterated polymer are in combination with a suitable oxidizing agent (such as a metal cation (especially iron (10)), a peroxy compound (such as 'peracid, peroxodisulfate (eg, peroxodisulfate, h2〇2) The reaction occurs. Although (4) the conductive polymer shell provides a polyelectrolyte functional group, the corona functional group remains after the step of forming the outer shell; therefore, the particles can still be easily redispersed. For example, "called on the surface of the particle Polymerization, & usually is achieved by the addition of H and a suitable oxidizing agent such as Fe(III) salt, FeCh, iron toluenesulfonate (111). Other examples of suitable monomers for this step include aniline, thiophene, acetylene and It is known to carry out oxidative polymerization of substituted derivatives (substituted, for example, by substituents selected from lower alkyl groups such as Ci-C6 alkyl). The amount of oxidized polymer (shell) on the particles is usually at least 5 weights of the final particles. % (for example, 5 to 90% by weight). In a preferred method, 'the dispersion obtained after the above oxidation step is subsequently subjected to desalting, for example, by ultrafiltration. The present invention further relates to The method for preparing the layered particles of the present invention is generally described as "this method comprises the addition of an oxidizing agent in the presence of a polar solvent and intermediate particles dispersed in the solvent J (such as in the case of pyrrole deposition 13 200948849) The lower iron-III) polymerizes a suitable monomer such as pyrrole. The intermediate particle is a core particle of the invention comprising an anion corona as described above: that is, an anionic function comprising a covalent bond to its surface Particles of a thermoplastic or crosslinked polymer core. The particles obtained in this way are usually in the form of a dispersion; these particles are typically subjected to a desalting step (eg, ultrafiltration, ion exchange) prior to use or storage. The intermediate particles of the method step are usually prepared by emulsion polymerization of an ethylenically unsaturated monomer to form core particles. As mentioned above, a suitable comonomer containing a carboxylate group or especially a sulfonate group or a phosphonate group is used concomitantly. To provide an anionic functional group; an example is an acid or an ester or a salt thereof selected from the group consisting of vinylbenzenesulfonic acid, CrC:8 alkenylsulfonic acid, (meth)acrylic acid oxy-C2-Cs alkyl sulfonic acid, (meth) acrylamido yl-c2_c8 alkyl sulfonic acid, vinyl phosphinic acid, C2_CS alkenylphosphonic acid, (meth) acryl yloxy _CVC8 a pyridylphosphonic acid, (meth) acrylamido-c2-c8 alkylphosphonic acid derivative. This comonomer can be added during the polymerization step to form the core particles and/or in the subsequent step of forming a corona. Copolymerization of core particles (see above). Electroneutral groups (such as acid 'esters, salt groups) are usually added in subsequent steps (for example) by addition (eg 'alkaline hydroxides') and/or ion exchange Instead, it is converted to the corresponding anionic group. A chain transfer agent may be present to adjust the molecular weight. Purification of each step can be accomplished by known methods such as precipitation, ultrafiltration (UF) or other methods. As noted above, it is common to use/add more parental agents (see core particles and corona portions) as appropriate. Some preferred particles comprise a core of uncrosslinked or crosslinked polystyrene 200948849 1 or poly(?) acrylate or copolymer thereof characterized by a low Tg, a crosslinked polystyrene _ corona and a polypyrrole shell . Core: The ratio of corona is usually in the range of about i: 〇.5 to 1:1 〇 (for example, 'about 1:2); the ratio of particles: conductive outer shell is usually about 1: 〇. 1 to 1: i (eg, about 1: 〇·3). In an advantageous method, the core particle consists essentially of synthetic organic at 2 (TC is crystalline or amorphous and has a glass transfer temperature of 15 (rc or lower).

Poly S, especially polystyrene. This can be converted to the final particles by subsequent steps: a) copolymerization with a suitable monomer containing a functional group SC^H, SC^M or S〇3Ri, wherein Μ represents one equivalent of metal cation and Ri represents Ci_C2 〇 hydrocarbon a residue, such as an alkyl group, especially copolymerized with styrenesulfonic acid or a suitable salt or ester thereof, 曰', b) optionally incorporating a sulfonic acid group, in particular s〇3H and S〇3Ri, in step (a) (if The conversion) is converted to s〇3M, in particular S03Na, and c) the pyrrole is polymerized on the surface of the particles. In one of the specific methods of this type, i) steps (a), (b) and (c) are carried out in a dispersant selected from the group consisting of water and polar organic solvents and mixtures thereof; ii) sulfonic acid or sulfonate of step (b) The conversion of the acid ester group (if any, ^,) is carried out by introducing an alkali hydroxide such as NaOH. Q, 111) The polymerization of step (C) is carried out by adding hydrazine and a suitable oxidizing agent (such as, The Fe(III) salt, FeCl3, and iron (toluenesulfonate) are carried out; iv) the dispersion obtained after the step (c) is subjected to, for example, desalination (d) by super-transport. 15 200948849 In each of the above processes, the copolymerization step (a) forming a corona can be carried out in the presence of a crosslinking agent as further described above. Generally, no dopants or surfactants are used or present during the shell deposition reaction. The particles thus obtainable can be dried (e.g., by lyophilization or evaporating the solvent under reduced pressure), in the form of a dispersion in a polar solvent.

The subject matter of the present invention therefore includes particles and particle dispersions obtainable in the process as described above.较佳 Preferred particle dispersions contain a crystalline or amorphous form that is captured and has: 150. . Or a lower glass transition temperature synthetic organic polymer, especially a soft core of polystyrene ~ (with or without a plasticizer) & a layered particle of a polyfluorene shell, characterized by the number of such dry particles The average diameter is within the range of thieves to 120 coffee. Generally, particles of the invention having a narrow particle size division fabric are obtained; therefore, at a filament dispersion wipe, at least 90% or more of the particles of the dispersion have a range of sails above or below the number average diameter: diameter; Preferably, the standard deviation of the particle diameter (as determined by I·) is less than the average particle diameter of @3()%', especially less than about 25 〇/〇 of the average particle direct control of the particle or particle dispersion. More preferred particles for electronic devices (OLEDs) have particle sizes below 1 Å, for example in the range of _. Earthquake and General Remarks "Excessive negative charge" on a particle means the amount of anionic group exceeding the amount of the cationic group (if such a cationic group is present). In fact, the anionic group on the surface is separated from its relative cations in a suitable environment. The relative cation or "free cation" is a cation which is separable from the anionic group, preferably selected from protons or especially cations of base, ammonium or scale. The particle size is designated as the hydrodynamic radius (Rh' is determined by dynamic light scattering (then)), unless otherwise stated. The dried particle diameter was determined by TEM. ^Polar liquids for use as solvents and/or dispersion media, especially for the preparation and/or (re)dispersion of particles of the invention, include: water; alcohols, including mono-, di- or polyhydric alcohols; ethers; esters; / or anhydride; ketone; guanamine; amine; ionic liquid. Examples are water, ethanol, methanol, hydrazine-propanol, 2-propanol, butanol, 2-butanol, tert-butanol, pentanol, cyclopentanol, cyclohexanol, ethylene glycol, glycerol, a shout , B, methyl butyl ether, cough, dioxane, tetraammine, diketone, methyl-ethyl ketone, methyl-butyl-ketone, cyclopentane, cyclohexyl, mouth ratio An anthracene, a piperidine or the like and a mixture thereof or a mixture containing a polar solvent and a less polar solvent, and a dispersant selected from the above-mentioned water and a polar organic solvent are preferably used for the corona forming step and the outer shell forming step. The polymer which can be used for preparing the core particles can be, for example, a compound: an early olefin and a diene, a hydrazine, a butyl sulphide, a poly(4-methyl pentane-i-thin, a polyisoprene Alkene or polybutadiene and: polymer of olefin (such as cyclopentene or norbornene), polyethylene (contiguous 2 crosslinkable), such as high density polyethylene (HDPE), high density 刀 knife Dilute (HDPE-HMW), high density and (4) molecules 4^ 17 200948849 olefin (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDpE), (VLDpE) and (ULDPE). The polyolefin (i.e., the polymer of the monoolefin exemplified in the preceding paragraph, preferably polyethylene and polypropylene) can be prepared by various methods and especially by the following methods: a) Free radical polymerization (usually at south and high temperatures). b) Catalytic polymerization using a catalyst which typically contains one or more metals of Group lvb 'vb, VIb or VIII of the Periodic Table. These metals typically have one or more ligands, typically ruthenium, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryl groups which may be coordinated in the π or ^. These metal complexes may be in free form or fixed to a substrate, typically activated magnesium oxide, vaporized titanium (III) alumina or cerium oxide. These catalysts are soluble or insoluble in the polymerization medium. The catalyst may be used alone in the polymerization, or other activators may be used, typically metal alkyls, metal hydrides, metal alkyl dentates, metal alkyl oxides or metal alkyl fluorenes. The metal is an element of the periodic table Ia, na and/or nia. The activator can be easily modified by other ester group 'ether groups, amine groups or alkylene ether groups. Such catalyst systems are commonly referred to as phniips, Standard OiUndiana, Ziegler (-Nata), TMZ (DuP〇nt), metallocene (metall) 〇cene) or a single site catalyst (ssc). 2 · Mixtures of polymers mentioned in 1), such as mixtures of polypropylene with polyisobutylene, I propylene with polyethylene (eg PP/Hdpe, PP/LDPE) and mixtures of different types of vinyl (eg LDpE/ HDpE). 18 200948849 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), Propylene/but-1-ene copolymer, propylene/isobutylene copolymer, ethylene/butyl-nonene copolymer, ethylene/hexene copolymer 'ethylene/methylpentene copolymer, ethylene/heptene copolymer, ethylene /octene copolymer, propylene/butadiene copolymer, isobutylene/isoprene copolymer, ethylene/alkyl acrylate copolymer, ethylene/alkyl methacrylate copolymer, ethylene/vinyl acetate copolymer and Copolymer with carbon monoxide or ethylene/acrylic acid copolymer and its salt (ionic polymer) and ethylene with propylene and diene (such as hexadiene, dicyclopentadiene or ethylene-norbornene) Polymers, and mixtures of such copolymers with each other and with the polymers mentioned in 1) above, such as polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymer (EVA), LDPE/ Ethylene-acrylic copolymer (ΕΑΑ), LLDPE/EVA, LLDP E/EAA and alternating or random polyalkylene/tin oxide inverse copolymers and mixtures thereof with other polymers (e.g., polyamines). 4. A hydrocarbon resin (for example, Cs_C9), including a hydrogenated upgrade thereof (for example, a tackifier) and a mixture of a polyalkylene group and a starch. 5. Polystyrene, poly(p-methyl stupid ethylene), poly(7)·methylstyrene). 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butyl Diene/alkyl acrylate, styrene/butadiene/methacrylic acid, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; high impact strength styrene copolymer and, for example, poly Mixture of acrylic acid, diene polymer or another polymer of ethylene/propylene/diene terpolymer 19 200948849; and block copolymer of styrene, styrene/isoprene/styrene , styrene / ethylene / propylene / styrene. , such as styrene/butadiene/styrene/styrene/ethylene/butylene/styrene or

7. A graft copolymer of styrene or methyl styrene, such as polybutadiene: upper styrene, polybutadiene-styrene or polybutadiene-acrylonitrile copolymer on the present ethylene; Styrene and acrylonitrile (or styrene, acrylonitrile and methacrylate on decyl propylene polybutadiene; styrene and maleic anhydride on polybutadiene; styrene on polybutadiene) , acrylonitrile and maleic anhydride or maleimide; polybutadiene on styrene and maleimide; polybutadiene on styrene and alkyl acrylate or alkyl methacrylate Ester; styrene and acrylonitrile on ethylene/propylene/diene terpolymer; styrene and acrylonitrile on styrene and acrylonitrile, acrylate/butadiene copolymer on polyalkyl acrylate or polyalkyl methacrylate And mixtures thereof with copolymers listed under 6), for example copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Pixel-containing polymers, such as polychloroprene, gasified rubber, isobutylene-isoprene gasification and brominated copolymers (butyl butyl rubber), gasification or chaotication a copolymer of ethylene and vaporized ethylene, a gas alcohol homopolymer and a copolymer, especially a polymer of a dentate-containing vinyl compound, such as polyvinyl chloride, polydiethylene vinylene, polyvinyl fluoride, polydifluoro Ethylene and copolymers thereof such as ethylene/diethylene vinylene, ethylene/vinyl acetate or diethyleneethylene/vinyl acetate copolymer. 9. Polymers derived from α,/5· unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; impact modified by butyl acrylate 20 200948849 Polymethyl methacrylate, polypropylene Indoleamine and polyacrylonitrile. 10. Copolymers of monomers mentioned in 9) with each other or with other unsaturated monomers, such as acrylonitrile/butylene dilute copolymer, acrylonitrile/acrylic acid ester copolymer, acrylonitrile/alkyl acrylate Ester or acrylonitrile / i ethylene copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer. 11. Polymers derived from unsaturated alcohols and amines or their vat derivatives or mentores, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl polystearate, poly(vinyl benzoate), polysuccinene Vinyl acetate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and copolymers thereof with the olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides, polypropylene oxide or copolymers thereof with bisglycidyl ether. 13. Polyacetals, such as polyacetal and their polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or mbs. 14. Polyphenylene ether and polyphenylene sulfide, and mixtures of polyphenylene ether with styrene polymers or polyamines. 15. The aspect is derived from a hydroxyl terminated polyether, polyester or polybutadiene and, on the other hand, a polyaminocarbamic acid derived from an aliphatic or aromatic polyisocyanate and a precursor thereof. 16. Polyamines and copolyamines derived from diamines and dicarboxylic acids and/or derived from aminocarboxylic acids or corresponding internal amines, such as polyamides 4, polyamines 6, polyamines 6/6 , 6/10, 6/9, 6/12, 4/6, 12/12, polyamidoxime, polyamidamine 12, aromatic polyamine starting from meta-xylene diamine and adipic acid; Own 21 200948849 Diamine and isophthalic acid or/and polyammonium prepared in the presence or absence of stearic acid and in the presence of an elastomer as a modifier, such as poly 2,4,4-trimethyl Benzyl phthalamide or poly(phenylene phthalamide); and the above-mentioned polyamine and polyolefin, olefin copolymer, ionic polymer or chemically bonded or grafted elastomer embedded a segment copolymer; or a block copolymer of the above-mentioned polyamine and polyether, such as polyethylene glycol, polypropylene glycol or polybutylene glycol; and polyamine or copolymerized decylamine modified by EPDM or ABS And polyamines (RIM polyamine system) that condense during processing. 17. Polyurea, polyimine, polyamine-quinone imine, polyether quinone imine, oxime polyester quinone imine, polyhydantoin and polyphenyl hydrazine. Rice bran. 1 8 _ derived from dicarboxylic acids and diols and / or polyesters derived from hydroxy carboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4 - dimethylol cyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoate and block copolyetherester derived from hydroxyl terminated polyether; Polycarbonate or MBS modified polyester. 1 9. Polycarbonate and polyester carbonate. 20. Polyfluorene 'polyether sulfone and polyether ketone. 〇 21. - Crosslinked polymers derived from aldehydes and on the other hand derived from phenol, urea and melamine, such as phenol/furfural resins, urea/formaldehyde resins and melamine/formaldehyde resins. 22. Dry and non-dry alkyd resins. 23. An unsaturated polyester resin derived from a copolyester of a saturated and unsaturated dicarboxylic acid and a polyhydric alcohol and a vinyl compound as a crosslinking agent, and a modification thereof containing a low flammability. 22 200948849 2 4. Crosslinkable acrylic resin derived from substituted acrylic vinegar, such as epoxy acrylic, acrylic acid acrylate or polyester acrylate. 25. Alkyd resins, polyester resins and acrylic acid vinegar resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 26. A crosslinked epoxy resin derived from an aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compound, such as a product of bisphenol A and a diglycidyl ether of bisphenol F, which is conventionally used as a hardener (such as The anhydride or amine) is crosslinked in the presence or absence of a promoter. 27. Natural polymers, such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as fluorenyl cellulose; And rosin and its derivatives. 28. Blends (poly blends) of the above-mentioned polymers such as PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS > PC/ABS, PBTP /ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylic acid, POM/thermoplastic PUR, PC/thermoplastic PUR 'POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 And copolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC. 29. Naturally occurring and synthetic organic substances which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or synthetic ester based oils, fats and waxes (for example, phthalic acid) Formates, adipates, phosphates or trimellitates) and synthetic esters and mineral oils 23 200948849 A mixture of any weight ratios and aqueous emulsions of such materials are generally used as the spinning composition, An emulsion of an aqueous emulsion of styrene/butadiene polymer of 30. Natural or synthetic rubber. For example, a preferred olefinic polymer which is a major component of the core of the particle is a polymer which is listed in the above knives 1 to 3, 5 to 7 and 9 to 11.

Any additives conventionally used in the plastics industry (such as plasticizers or stabilizers) can be added to the polymer in conventional amounts; examples are listed in (3) by way of citation and by us_6184375 in this article" shed 57 to 2 5 rest in 3 5 rows. Dajin Zhao will enter, in the seven-order r 罝 罝 non-Wei suitable core f can be purchased in latex form (such as poly (styrene butadiene) latex). The particles contain a plasticizer in particular in the core of the particle; the agent can be added to the latex by or before the polymerization or by adding to the core of the human particle, preferably the particles have a uniform size (also That is, a narrow knife and a very low residual amount of solvent and/or monomer.

The particles of the present invention can be used to prepare electrically conductive structures such as layers, electronic devices such as OLEDs. Such particles can be used, for example, as conductor materials in optical or acoustic transducers, electronic devices or light control systems, conductor or semiconductor precursors, particles in capacitor applications, electrophoretic (dye) particles, absorbents. For example, the particles of the present invention may be included in a germanium LED device or form a major component of a hole injection layer in an OLED device. Another important application is to replace the IT〇 that is currently widely used as an electrode material. Other electrical or electronic devices in which the particles of the invention may be used thus include integrated circuits, displays 24, 200948849, RFID tags, electroluminescent or photoluminescent devices, backlights for displays, optoelectronic or sensor devices (such as solar cells) , charge injection layer, planarization layer, antistatic agent, conductive substrate or pattern, photoconductor or electrophotographic application or recording material.

❹ In an important application, the particles of the invention are used to form conductive or semiconductive layers in a known manner, for example by applying dry particles or by coating or printing techniques using dispersion in a suitable solvent (eg 'water, The particles in the alcohol or its &) are dried and the particles as described above are applied to the substrate. The conductive or semiconductive layer is then conveniently obtained by applying heat, e.g., to a temperature above the glass transition temperature of the synthetic organic polymer of the core particles. Typical temperatures for conversion into layers are in the range of 8 〇 25 (rc, eg 8 〇 2 。). In the case where the particles are applied by applying a (unidirectional) M force printing method (eg 'in Electrostatic printing/laser printing or in the transfer printing or compression bonding method of _7105462 or US-7176052), a combination of pressure and temperature can be used to convert the particles into a desired layer, which allows for a lower conversion temperature. A uniform layer. Thus the invention includes an electrically or semiconductive layer electronic device or optical or acoustic filter comprising one or more types of particles as described above and/or obtained by converting particles as described above. It can also be used as it is (i.e., as a pigment) or as a conductive ink or electrophoretic dye/pigment application. In another embodiment, the particles of the invention may be coated with a conductive metal such as silver, copper and/or gold, and thus The obtained composite particles are used for a conductive ink. In another application, silver or copper particles may be coated with the layered polymer particles of the present invention as a conductive and anti-corrosion surname 25 200948849 layer; the composite particles of this form may also be used Some of the uses are described in more detail in the following examples. The following test methods and examples are for illustrative purposes only and are not to be construed as limiting the invention in any way. Room temperature (RT) is depicted at 2〇_ The temperature in the range of c. overnight means the time period within 12-16 hours. Unless otherwise indicated, the percentages and ratios of the examples and others are by weight. Abbreviations used in the examples or elsewhere: AIBN Azo Diisobutyronitrile DLS Dynamic Light Scattering OLED Organic Light Emitting Diode SDS Tetra-Sodium Sulfate GPC Gel Permeation Chromatography THF Tetrahydropyrene PS Polystyrene SSEE Styrene Ethyl Acetate PSS 1 Ethyl Ethyl Acetate PEGMA Poly(Ethyl Alcohol) Mercapto Acetate Methyl Ether Methyl Phenol PPy Poly D Biluo DVB Ethyl Phenyl PDI Polydisperse TEM Penetration Electron Microscopy pbw Parts by Weight TOSOH Representative Supplier Tosoh Corp., Tokyo ( JP ITO doped indium tin oxide 200948849

FTO UF doped fluorine tin oxide ultrafiltration. Left Ajg particle. Micro-crosslinked polystyrene core; sodium benzene sulfonate corona Ο

SDS KPS 1-pentment

S〇3Na SSS h2o 6h, 90 °c

The latex in water will be 7.84 g (75·3 mmol) of styrene (Fluka purum), 160 mg (〇·77 mmol) of 4-vinylbenzoic acid sodium salt (Fluka teChn·), 〇.20 g during 15 min. (h5 mmol) divinylbenzene (Fluka techn.), 2.5 g of sodium decyl sulfate (SDS, Fluka techn.) and 250 ml of water were introduced into a 1 L round bottom flask with mechanical stirring and flushed with nitrogen. During the 丨h period, 1.75 g of 1-pentanol (Flukapurum) was added and the entire mixture was homogenized at 3 rpm under n2. The homogeneous emulsion was heated to 9 Torr using an oil bath (>c and using a /ejector to add 〇.2 〇g to potassium peroxydisulfate (KPS, Fluka microselect) dissolved in 10 ml of water. At 90° Polymerization at C for 6 h. After cooling to room temperature, use ultrafiltration dispersion of cellulose membrane (Amicon® cell, diameter 76 mm, cut-off: lOO'OOO Da) until permeate (full permeate: 1 · 6 L) SDS (=activator) is no longer detectable. Analysis: Solids content of the dispersion (weight analysis after evaporation of water). 3.03%. 27 200948849 Dynamic Light Scattering (DLS): Average Diameter (Z Average): 12.8 nm. Example 2: polystyrene core; micro-crosslinked besylate sodium corona

No extra SDS! kps (0.2 g added within 4 h) 120 ml Ming 4+2 h, 70eC

PS latex in water 1〇 g 0.2 g (=2%) 4.36 Palace? 5 (50 Palace Latex) (47.2111 Yangshuo) (1.54〇^〇1) Add SSEE in parallel with the initiator within 4 h. 9/r... Ming consists of poly (SSEE-co-DVB) micro (2%) Cross-linked corona

NaOH (2.26 g; 56.6 mmol) 15 h, 90 °C Micro (2%) crosslinked corona consisting of poly(SSS-co-DVB) a) Core: 5 g of 12-alkyl sulphuric acid during 15 min Nano (SDS, Fluka techn.) and 500 ml of water were introduced into a 1 L round bottom flask with mechanical disruption and flushed with nitrogen. The mixture was stirred at 300 rpm under N2, heated to 50 - 5 5 ° C with an oil bath and 〇 · 25 g of potassium peroxydisulfate (KPS, Fluka microselect) dissolved in 6 ml of water was added. During the 8 h period, 50 g (480.1 mmol) of styrene (Fluka purum) was continuously added with a pump. After 3 h, another portion of 0.25 g of potassium peroxodisulfate (KPS, Fluka microselect) dissolved in 6 ml of water was added. After all the styrene was added, the reaction was continued at 50 ° C for 14 h. 567.9 g of latex having a solids content of 8.72% were obtained. Analysis: DLS (after dilution with water to 1.5%): average diameter (Z average): 39.7 nm. GPC (THF, PS standard): Mn=202000, Mw=615000, 28 200948849 PDI=3.05 〇b) Corona: During the 1 h period, in a 35 〇ml round bottom flask with mechanical stirring '50 g above The emulsion (4.36 g solids) was diluted with 12 mL of water and flushed with nitrogen. During 4 h, the mixture was mixed at 3 rpm, heated to 70 ° C with an oil bath and continuously added with pump 0.20 g (1_54 mmol) of divinylbenzene (Fluka techrJ) dissolved in 1 〇mi water. 1 〇g (47 2 mmol) of ethyl ethano-4-ethyl acrylate (TOSOH techn·) mixed with 2 〇g potassium peroxodisulfate (KPS, Fluka microselect). After adding all of the ® monomer and initiator, continue to react at 7 (TC for 2 h (= supplementary reaction). Then by adding 2.26 g (56.6 mmol) NaOH and disturbing the mixture at 90 C for 2 h ' Hydrolysis of vinegar. Treatment: Dissolve 5 g of NaCl in 600 ml of MeOH and add the above reaction mixture and stir at room temperature for 1 min, then centrifuge (3 rpm) 10 mm. Discard the supernatant and The remainder was again added to a solution of $g Naci in 600 ml MeOH, stirred and centrifuged as described above. This oxime procedure was repeated 2 more times and then the precipitate was redispersed in 44 〇ml water. The receiver was in AmiC〇 The cellulose film (diameter 76 mm, cut-off: 100,000 Da) in n Cel1 exceeds the dispersion' until the SDS (= surfactant) is no longer detectable in the permeate (all permeate: 75 〇ml) Analysis: The knife dispersion was dried cold and the solid content was determined to be 2.56%. It was then easily redispersed in water. Teeth Electron Microscopy (TEM): average diameter d = 28_39 nm.) Shell, core/shell Synthesis of Nanoparticles 29 200948849

Micro-(23⁄4) cross-linked first shell by poly(SSS total DVB)

FeCI3 6H20 3.67 g (13.6 mmol; 2, 3 equivalents relative to pyrrole) 0.5 h continuous addition at room temperature

Emulsion in water by UF; lyophilized 1·41 g (45 g lotion) AM-3445/1 containing 23.6 mmol-SChNa

0.39 g (5.9 mmol) 100+50 ml I^O (= core 283⁄4) Polypyrrole (PPy) coating Disperse 45 g of core shell particles of Example ❹ 2 in a 350 ml round bottom flask with mechanical stirring The solution (i 41 g solid) was decanted with 丨〇〇ml water and degassed by rinsing with Ar for 1 h. 0.39 g (5.9 mmol) of pyrrole (Fluka purum) was added and the mixture was stirred at 3 rpm. During the 30 min period, 3.67 g (13.57 mmol) of vaporized iron (ruthenium) hexahydrate (Fluka Puriss p.a') dissolved in 5 ml of water and flushed with Ar was continuously added by a pump. Thereafter, the reaction mixture was kept under aj· and stirred at room temperature for further 30 min. Note: The reaction mixture turns black after the addition of the iron salt, that is, polypyrrole is formed on the surface of the nanoparticles. ❹ Treatment • Homogenization by super-wave ’ followed by ultrafiltration with a cellulose membrane (diameter 76 mm, cut-off: 100, 〇〇〇 Da) in the octopus con®ceii until the total permeate amount was 300 ml. Analysis: Freeze dry liquid and determine solid content: 〇 85%. The lyophilized material can be easily redispersed in water. Alizarin analysis; calculated values (experimental values): c 62 9 (57 〇), Η 4·93 (5.20), Ν 4·57 (4.65), S 8.59 (6·〇9). 30 200948849 Penetrating electron microscopy (ΤΕΜ) ·• Average diameter d = 30-40 nm. Example 4: Crosslinked polystyrene core / crosslinked sodium sulfonate corona

55 DVB 6g 2g

=PS-DVB 2.73+ 18 g

NaOH (2.26 g; 56.6 mmol) 15 h, 90 °C

S03Na sss S〇3Na is attached to the first shell of the (highly) crosslinked core composed of poly(S-co-DVB). During 30 min, 6.0 g (57.6 mmol) of styrene (Fluka purum), 2.0 g ( 15.4 mmol) diethylbenzene benzene (Flukatechn.), l.Og sodium dodecyl sulfate (SDS, Fluka techn.) and 200 ml of water were introduced into a 1 L round bottom flask with mechanical stirring and degassed with nitrogen and rinse. The mixture was homogenized by stirring during 1 h, and the emulsion was heated to 70 ° C with an oil bath. 80 mg of potassium peroxydisulfate (KPS, Fluka microselect) dissolved in 5 ml of water was added via a septum using a syringe. After prepolymerization at 70 °C for 30 min, add 2.73 g ( 13.2 mmol) of 4-ethylphenylbenzoate in 15 ml of water via a septum (Fluka techn.), followed by a second addition. A portion of 40 mg of potassium peroxodisulfate (KPS, Fluka microselect) was dissolved in 5 ml of water. Polymerization was carried out at 70 ° C for 15 min with thorough stirring (300 rpm). During the 4 h period, another 18 g (87.3 mmol) of 4-vinylbenzoate sodium 31 200948849 salt (Fluka techn.) dissolved in 100 ml of water was continuously added by means of a pump. Thereafter, a third portion of 80 mg of potassium peroxodisulfate (KPS, Fluka microselect) dissolved in 5 ml of water was added and polymerization was continued at 70 ° C for 16 h. After cooling to room temperature, the dispersion was ultrafiltered in a Amicon® cell with a cellulose membrane (diameter 76 mm, cut-off: 300'000 Da) until the total permeate was 3 L. Analysis: The dispersion was freeze-dried and the solid content was determined to be 6.2%. It can be easily redispersed in water. Elemental analysis; calculated values (experimental values): C 60.3 (51.4), Η 4.72 (5.51), S 10.85 (9.30). Penetrating electron microscopy (ΤΕΜ): mean diameter d = 18-28 nm. Example 5: Synthesis of Conductive Core/Shell Nanoparticles

Connected to the first outer shell of the (high) crosslinked core composed of poly(S-co-DVB) S〇3Na

FeCI3 6 H20 3.67 g (13.6 mmol; 2.3 mol equivalent to pyrrole) continuously added at room temperature for 0.5 h

[•PS-DVBI Poly 0 to 1 each (PPy) coating 0.39 g (5.9 mmol) 100+50 ml H2 〇 (= 28% of the core) 1.41 g (22.7 g emulsion) containing 5. 9 mmol -S03Na -3449/1 The emulsion in water was purified by "Jumbosep"; lyophilized in a 350 ml round bottom flask with mechanical stirring, 22.74 g of the core shell particle dispersion of Example 4 (1.41 g solids) was used in 100 ml The water was diluted and degassed by rinsing with Ar for 1 h. 0.39 g (5.9 mmol) π ratio B (Fluka purum) was added and the mixture was scrambled at 300 rpm. During the 30 min period, 3.67 g (13.57 mmo 1 ) of gasified iron(III)-hexahydrate (Fluka 32 200948849 puriss p.a.) dissolved in 50 ml of water and flushed with Ar was continuously added by means of a pump. Thereafter, the reaction mixture was kept under Ar and stirred at room temperature for further 30 min. Note: The reaction mixture turns black after the addition of the iron salt, that is, polypyrrole is formed on the surface of the nanoparticles. Treatment: homogenize with ultrasound, then use a jumb〇sep ( pal ) filter unit (membrane retention: 10 (V000 Da) ultrafiltration in a centrifuge (3000 rpm, 2 X120 min) with uitra-Turrax in the middle And the ultrasonic bath is redispersed. Analysis: The dispersion is freeze-dried and the solid content is determined to be 0.4% by weight. It can then be easily redispersed in water. Elemental analysis; calculated value (experimental value): C 63.1 (55.0), Η 4.70 (5.47), Ν 4.53 (4.25), S 8.57 (7.04) 〇 Penetrating electron microscopy (ΤΕΜ): average diameter d = 34 nm. Styrene (PS) core nevi granules in a magnetic stirrer 500 In a mL round bottom flask, 3·〇g of sodium dodecyl sulfate (SDS, Fluka 99%) was dissolved in 300 mL of water. The transparent solution was heated to 5 Torr using an oil bath. (: and argon was flushed for 1 hour. Introduce i 5 〇mg (0.55 mmol) of potassium persulfate (Kps, Fluka 99%) in 1 mL of water. Add 3 〇g (288 mmol) of benzene in 1 〇h after adding KPS solution for 1 〇min. Ethylene (Fiuka 99〇/〇). After introducing KpS for 3 hours, add another 15 mg in 1 〇 water via a septum using a syringe. Kps. After complete addition of styrene, the polymerization was continued for another 3 hours. The resulting suspension was used for shell coating without purification. Features: 33 200948849 Dispersion solid content (weight analysis): 9.8% 'Scanning electron display Microscopy (SEM): 23.6 nm (number average diameter) Dynamic Light Scattering (DLS): Rh = 20.5 nm (hydrodynamic radius) Suitable for example ~L: Polystyrene-core polystyrene sulfonate shell (PS) -PSS) Nanoparticles 50 mL of the suspension obtained in Example 6 (solids content 49 g) and 400 mL of water were introduced into a 1 l round bottom flask with a magnetic stirrer. The suspension was heated to 70 with oil. C and flushed with argon for J hours. Introduce 1 〇〇mg of KPS in 10 mL of water, and then add 1 〇g of benzoquinone ethyl methacrylate (SSEE, TOSOH, 91%) and 1 逐 dropwise over 4 hours. Mixture of 〇mg diethylbenzene (DVB, Fluka, 80%). After the addition of the mixture of SSEE and DVB, the polymerization was continued for another 6 hours. The nanoparticle/KOH/water suspension was refluxed for 12 hours. PS/PSSEE core/shell nanoparticle hydrolysis produces ps_pss core shell nanoparticles. Hydrolysis times from 4 Yue alcohol precipitation of a solid proton NMR confirmed. Redispersed in and circulating water for the purified PS-PSS aqueous solution of the square particles. Features: DLS : Rh = 57 nm (PS-PSSEE core shell particles)

Rh = 330 nm (PS-PSS core shell particles) Example 8: PS-PSS-PPy nanoparticles In a 500 mL round bottom flask, 20 mL of PS-PSS suspension (obtained as in Example 7; solids content) 7〇〇mg) was diluted with 300 mL of water and rinsed with 34 200948849 argon for 1 hour. After adding 1 70 mg β σ (Py, 2.5 mmol, Fluka 97%) for 10 min, 986 mg of iron (III) in 20 mL of water (6.1 mmol, Fluka 97%) was introduced dropwise over 2 hours. ). After the complete addition of gasified iron, the reaction continued for another half an hour. Four cycles of precipitation from methanol and redispersion in water were used to purify PS-PSS-PPy nanoparticles. Characteristics: DLS: Rh = 83 nm TEM: average diameter 52 nm, standard deviation 8 nm. Example 9: Transmittance of a film composed of PS-PSS-PPy nanoparticles: PS-PSS-PPy nanoparticles were prepared as in Example 8, except that the ratio of PPy/(PS + PSS + PPy) was 16 % ( w/w ). A film having a thickness of 87 nm was prepared by spin coating on a microscope slide, and the transmittance was measured by Lambda UV/VIS/NIR and UV/VIS spectrometer (Perkin-Elmer). The transmittance was determined to exceed 82% throughout the visible region (see Figure 1). Example 10: Redispersibility using dynamic light scattering (DLS; with ALV 5000 correlator [ALV, Langen, DE], ALV-SP81 goniometer, sag photodiode and helium ion laser (647 · 1 nm) Light Scattering Line) The redispersibility of the particles after cooling and drying was examined by comparing the size and particle size distribution of the respective suspensions before and after freeze drying. The experiment was based on the particles of Example 8. After the suspension was freeze-dried for 4 days, the material was redispersed in water by ultrasonic waves. By 35 200948849 DLS measurement of particle size and particle size distribution distribution phase " 2 proved that the particle size and particle size distribution remained the same in the cold _=== suspension, which means that the stomach (10) = rice particles have excellent redispersibility. Similar results were obtained using any of the particles of Examples 1 and 2. More Example 11: Conductivity The conductivity measurement is based on a four-point probe method as shown in Figure 3. Assume that (1) the thickness d of the sample is much smaller than the distance between the electrodes χΐ, χ, 3, (") © ^ has (4) the distance U1 = X2 = ..., (called the sample on the non-conductive surface '(iv) and Compared with the distance between the electrodes, the direct contact of the electrode is small, and (7) the distance between the electrode and the sample boundary is larger than the distance between the electrodes, and the conductivity at the time of the quality can be detected by the detected side. And the current is calculated using the following equation (~=inherent resistivity, which is the reciprocal of conductivity): ΛAVχπχά 制备 The sample is prepared by pressing the dry powder of the substance obtained in Example 8 into pellets having a thickness of 0.679 mm. The measured conductivity is 3.8χ1〇·2 s/cm. Example 12: Conductive behavior is designed with temperature and time to design a specific device to monitor the conductivity (σ) of PPy composite pellets with temperature and time. Development. Figure 4 shows a photograph of the device. With this device, it is possible to measure the conductivity at different temperatures (20 ° C - 250 ° C) and in different environments (such as air 36 200948849 gas, nitrogen or argon). /, has the same complex as the specific particles of Example 8, but PPy nanoparticles prepared in the same batch were used for these experiments. Figure 5 &) shows that the resistivity of PPy composite pellets decreases as the temperature increases from 25 C to 200 C. In other words, the conductivity increases with temperature. The aging behavior of the ppy composite pellet in the air under the armpit is shown in 5b). The master curve can be extracted based on this graph according to H. Muenstedt et al. Thus, the aging behavior at different temperatures is inferred. : Roughness 〇> by using a spin coater of Headway Research. Inc. - a colloidal film of particles. The particles used were the example particles. The concentration was 2% (w/w). The rotation speed was adjusted to obtain the desired Film thickness, film thickness was measured by a TENCOR® Ρ-10 surface profiler. These colloidal films were examined by intermittent contact atomic force microscopy (AFM) Dimension 3100 closed loop (Digital inStrument Veeco metr〇1〇gy gr〇up) Surface quality. High and phase images are obtained during sample scanning. 般 Normally, the image reflects the topographical changes across the surface of the sample, while the phase image reflects the change in hardness of the material. The arithmetic mean of the deviation of the face: z.

R

N Here, zcp is the Z value of the center plane. A representative ppy composite film having a thickness of 60 nm is shown in Figure 6, which is at 15. . Prepared at rpm spin speed. According to the above equation, the average is 37 200948849 . The crude sugar is 9 nm. 'f旌Example 14: Film formation of PPy composite nanoparticle was examined by film formation of PPy composite film, and film was prepared by spin coating (20 (TC, vacuum, 1 〇min) with the substance from Example 8. Comparative heating SEM images before and after: Figure 7 (left) demonstrates the SEM image of the ppy film before annealing. The individual nanoparticle morphology remains. Figure 7 (right) shows the SEM image of the same PPy film after annealing, The particle boundary is not as clear as the particle boundary before annealing and forms a continuous film. Free mask 1 5 : PS-PSS-PPy film and substrate adhesion 〇 PPy film adhered to the substrate (here test glass and fto cover glass) is based on the figure The adhesive tape test method is schematically illustrated in 8. The material obtained as in Example 9 was used to form a film by spin coating the Naiqi particles on a microscope slide. The formed film was placed at 15 Torr. In a vacuum oven, the water was removed for 5 mm. Then the adhesive tape was placed over the ppy composite film. Then the sample was placed in a vacuum oven for 5 min to make the adhesive tape in good contact with the PPy film. 8 SEM is used to check how much remains after the adhesive tape is slowly lifted from the PPy composite film (the following). 〇 The position of the adhesive tape protruding from the red circle in the left photomicrograph is the position of the previous magnification. The photo shows that the PPy composite film is intact, and some substances are peeled off by the adhesive tape. This experiment proves that the adhesive film of the PPy composite film and the substrate is excellent. 宜·. Rod example ^: Preparation of the light-emitting device will be used for the glass substrate with patterned ITO Acetone, propanol and water were washed in an ultrasonic bath. The dried substrate was treated with oxygen for 2 min. The compound of Example 8 was spin coated (5〇〇〇38 200948849 * rpm) to obtain a 70 nm film. Thickness. A reference sample was prepared in a similar manner (15 rpm, 55 nm), but using PED0T AL4083 (supplier: H c starck) instead of the compound of the invention. The film was placed on a hot plate (10 min, 200 t:, environment) Drying over the atmosphere. The blue-emitting polymer (the compound of Example 1-7 of WO 06/097419) was spin-coated under nitrogen to have a layer thickness of 80 nm. by evaporation from 5 nm Ba and 70 Nm A丨 group The two-layer cathode is used to complete the device. The 〇led device is not intended to be shown in Figure 11. The device is characterized by an inert atmosphere. The results are shown in Figure 12 (left: current density [A/cm2]; lower half Part / Right: Brightness [cd/m2]) Example 1 7 ^-Polystyrene (PS) Core Nanoparticles In a 500 mL round bottom flask with a mechanical stirrer, 2 〇g of 12 sulphur-based sulphuric acid Sodium (SDS, Fluka 99%) was dissolved in 300 mL of water. The clear suspension was heated to 5 (TC and argon purged for 1 hour using an oil bath. Introduced ❹100 mg (0.37 mmol) of potassium persulfate (KPS, Fluka 99%) in 10 mL of water. Add KPS solution for 10 min. Then, within 2 hours, add 2〇g (192111111〇1) styrene (17111]^99%) while stirring (350 卬111). After introducing KPS for 3 hours, add 100 mg to the membrane via a septum. KPS in 10 mL of water. After complete addition of styrene, polymerization was continued for another 3 hours. The resulting suspension was filtered through a glass fiber filter. Features: Solids content of the dispersion (weight analysis): 5.40/〇 Dynamic Light Scattering (DLS) : Rh = 21.4 nm b ) Polystyrene-core polystyrene sulfonate shell (PS_PSS) Nano 39 200948849 Particles Introduced 148.15g of product (solid content 8g) and 700 mL of water into a mechanical stirrer 1 L round bottom flask. The suspension was heated to 50 C using an oil bath and flushed with argon for 1 hour. Go mg azobisisobutyronitrile (AIBN, Fluka 98%) was introduced, and then 4 g of ethyl styrene sulfonate (88 £, D, 08011, 91%) and 12 〇 11 ^ were added dropwise over 4 hours. A mixture of divinylbenzene (DVB, Fluka, 80%) was stirred simultaneously (45 rpm). After the mixture of SSEE and DVB was completely added, the polymerization was continued for another 6 hours. The PS/PSSEE core/shell nanoparticle was hydrolyzed to produce PS_PSS core-shell nanoparticle by adding 3 g of KOH and refluxing the suspension for 24 hours. Complete hydrolysis was demonstrated by solid proton NMR and FTIR. The resulting suspension was purified by 5 cycles of precipitation and redispersion in methanol followed by 3 ultrafiltration cycles. Characteristics: DLS : Rh=142 nm C) PS-PSS-PPy nanoparticles in a 2 L round bottom flask, 150 g ps_pss suspension (as obtained according to (b); solid content 3 g) diluted with i.4 L water Rinse with argon for 1 hour. After adding 350 mg of distilled pyrrole (Py, 5 21 〇1, Fluka 97%) 1〇11^11, 8 236 8 of p-toluene iron in 2〇11^ water was introduced dropwise within 3 hours. (m) hexahydrate (12. 丨mm〇1, Aldrich tech.). After the complete addition of iron (rhodium) p-toluenesulfonate hexahydrate, the reaction was continued for another half an hour. Three cycles of precipitation and redispersion from methanol and three cycles of ultrafiltration were used to purify the PS-PSS-PPy nanoparticles. 40 200948849 Features: DLS . Rh-81.2nm ; ΤΕΜ : average diameter 51 nm, standard deviation 10 nm 〇d) Conductivity of PPy complex obtained in (c): using four-point method: 2.8*1 〇 · 5 s/em spheroids using dielectric spectrum: 8.4*1 (r5 s/cm; film using four-point method: 1.5*10·6 S/cm e) Film properties of the composite obtained in (c) : Roughness and Transmittance 胶 A colloidal film of ps-pss-ppy particles was prepared by spin coating using a spin coater of Headway Research. The particle concentration is 2% (w/w). The rotation speed was adjusted to obtain the desired film thickness, and the film thickness was measured by a TENCOR® P-10 surface profiler. The surface quality of these colloidal films was examined by a batch contact atomic force microscope (AFM) Dimension 3100 closed loop (Digital instrument Veeco metrology group). An annealed PPy composite film having a thickness of 152 nm was prepared at a spin coating speed of 1500 rpm. Θ Result·’The average crude chain is 5 nm. f) Transmittance of PPy composite film obtained in (e) Transmittance was measured by Lambda UV/VIS/NIR and UV/VIS spectrometer (Perkin-Elmer). Results: The transmittance was determined to be more than 8 8% throughout the visible region, with a maximum of 92% at 550-570 nm. Example 18 a) Polystyrene-core polystyrene sulfonate shell (PS-PSS) nanoparticle 200948849 129.63 g of ps nanoparticle·subsequent obtained in part (a) of Example 17 (solid content) 7 g) and 600 mL of water were introduced into a 1 L round bottom flask with a mechanical stirrer. The suspension was heated to 5 (rc with an oil bath and flushed with argon for 1 hour. 35 mg of azobisisobutyronitrile (AIBN, Fluka 98%) was introduced and then 1.75 g of styrene was added dropwise over 4 hours. A mixture of ethyl acrylate (SSEE, TOSOH, 91%) and 52.5 mg of divinylbenzene (DVB, Fluka, 80%) was simultaneously spoiled (450 rpm). After the complete addition of the mixture of SSEE and DVB, continue Polymerization for 6 hours. The 〇PS/PSSEE core/shell nanoparticle was hydrolyzed to produce ps_pss core-shell nanoparticle by adding I·4 g KOH and refluxing the suspension for 24 hours. The complete hydrolysis was confirmed by solid proton NMR and FTIR. The suspension was purified by 5 cycles of precipitation and redispersion in decyl alcohol, followed by 3 ultrafiltration loops. Features: DLS · Rh ==120 nm b) PS-PSS-PPy nanoparticles in 1 In an L round bottom flask, 42.70 g of a PS-PSS suspension (solid content of 1.2 g) was diluted with 600 mL of water and rinsed with argon for 1 hour. After adding 15 (h3 mg of distilled fluorene (Py, 2.24 mm 〇 1, Fluka 97%) ι〇 min, 5181 g of Baytr〇nC B4 引入 (Hc Starck, 1-butanol in p-toluene) was introduced dropwise over 3 hours. The content of iron (III) sulfonate hexahydrate is 40.4%. After the addition of Baytr〇nC_B4〇, the reaction is continued for another half an hour. Three cycles of re-dispersing from methanol and redispersing in water and three ultrafiltrations 42 200948849 Cycle for purification of PS-PSS-PPy nanoparticles. Features: DLS: 78.9 nm Conductivity: Use of four-point pellets: pellets using dielectric crucibles: Example ΐ 9 a) PS-PSS/PEGMA Core Shell 2 g of the PS nanoparticle suspension (solids content) obtained in part (a) of Example 17 and 150 mL of water were introduced into a 250 mL round bottom flask with a magnetic stirrer. The suspension was heated to 60 ° C using an oil bath and flushed with argon for 1 hour. Introducing 20 mg of azobisisobutyronitrile (AIBN, Fluka 98%), and then adding 〇·6 g of phenelzine (Fluka 99%) and 〇·4 g of divinylbenzene (DVB, dropwise) over 1.5 hours. a mixture of Fluka, 80%) while stirring (450 rpm) ^ continued polymerization for 1.5 hours, followed by 3 g of sodium styrene sulfonate (NaSS, Fluka > 90%) and 0 in 10 mL of water in the hour. · 50 g of poly(ethylene glycol) methacrylate decyl ether (50 〇 / 〇 in water,

Aldnch, Mw: 2080). Thereafter, the reaction was continued for another 1 hour.

The incorporation of NaSS and PEGMA is evidenced by FT-IR. The resulting suspension was purified by 5 cycles of precipitation and redispersion in a cycle saturated with sodium chloride followed by 3 ultrafiltration cycles. Characteristics: DLS : Rh=87 nm TEM . 67 nm b) PS-PSS/PEGMA-PPy 43 200948849 In a 100 mL round bottom flask, 5.128 g of PS-PSS/PEGMA suspension (as obtained in part (a)' The solids content (1 mg) was diluted with 8 mL of water and flushed with argon for 1 hour. After adding 42.9 mg of deuterium (Py, 0.639 mmol, Fluka 97%) for 1 〇 min, 2.1 1 1 g of Baytron CB 40 (H_C. Starck, 1-butyric acid) was introduced dropwise over 3 hours. The content of iron (III) p-toluenesulfonate hexahydrate (1.490 mmol) was 40.4%). After the addition of Baytron C-B 40 was completed, the reaction was continued for another half an hour. Three cycles from methanol precipitation and three ultrafiltration cycles were used to purify PS-PSS/PEGMA-PPy nanoparticles. ❹ Features: DSL: 83.4 nm Spherical conductivity using four-point method: 〇·Π S/cm Sword 20-22: Has a softer core and a softer shell 夕心心/Shell Nanoparticles to make the core and shell softer (To make it easier to penetrate the core material and gradually establish a continuous PS copolymer phase and PPy phase after annealing), use various amounts of other comonomers (see also Scheme 1-3):

44 200948849 ❹

ALMA 8 wt.% Core: 12.. 1. 1. Shell: 12 2: .2 wt.% 12.2 wt.% 2. Shell: 75.6 wt·% S (calculated value): 11.79% S (experimental value): 9.85% TEM: d=30 nm (approx.) Tg: cannot be measured by DSCt

S〇3Na PSS as the second shell

SDS / KPS -5 h2o; n2 2h, 70〇C

Core uncrosslinked

d=22 nm (DLS) d=14 nm (TEM) , ,DSC: n [PS-BA-ALMA) Tg=28 C Emulsion

KPS

0^0 h2o; n2 30 min, 70° (^ DVB 50 wt, % BA 50 wt.%

Scheme 1: Synthesis of anionic core/shell nanoparticles with a more flexible core and crosslinked first and second outer shells with 42% BA: Examples 20 and 21 During the 15 min period, 5·0 g twelve Sodium alkyl sulfate (SDS, Fluka techn.) and 200 ml of water were introduced into a 1 L round bottom flask with mechanical stirring and degassed and flushed 3 times with nitrogen. The mixture was heated to 55 ° C using an oil bath and stirred at 200 rpm, and a first portion of 25 0 mg of potassium peroxydisulfate (KPS, Fluka microselect) dissolved in 6 ml of water was added via a septum using a syringe. During the 8 h period, the monomer 2 1 ·0 g (20 1 _6 mmol ) of styrene (Fluka purum), 25.0 g ( 195.1 mmol ) of butyl phthalate (Fluka purum) and 4.0 g ( 31.7 mmol ) The acrylic acid acrylonitrile (Fluka purum) was mixed and added dropwise using a syringe and a pump. After 3 h 45 200948849 reaction time, another portion of 25 mg of potassium peroxydisulfate (Kps, Fluka) dissolved in 6 ml of water was added via a septum using a syringe. After all the monomers were added, the polymerization was continued for another 14 hours at 55t:. After cooling to room temperature, 576.6 g of a latex having a solids content of 7.3% was obtained. analysis:

DSC : Tg = 28 〇 C Dynamic Light Scattering (DLS) : d (z average) = 22 nm. Penetrating electron microscopy (TEM): mean diameter d = 14 nm. Example 21: ❹ During 15 min 'in a 1 l round bottom suspension with mechanical disruption, 41.1 g of the dispersion according to Example 17 was diluted with 200 ml of water, degassed with nitrogen and rinsed 3 times . Add 1 _5 g (11.5 mmol) of divinylbenzene (DVB,

Flukatechn·, a mixture of isomers) and n-butyl acrylate (Fluka purum) followed by 40 mg of potassium peroxodisulfate (KPS, Fluka microselect) dissolved in 3 ml of water. The mixture was heated to 70 using an oil bath during 30 min. (: and polymerization 'at the same time stirring at 200 rpm. Then add 80 mg of peroxodisulfate in 6 ml of water (KPS, Fluka microselect) and add at the same time at 70 C for 3.5 h. 20.61 g (90 mmol) of sodium p-styrene sulfonate (Fiuka tech. 90 〇 / 〇) and 〇 · 37 g (1 · 9 mmol) of ethylene glycol dimercaptoacrylate (EDma, Fluka pimim) (= Monomer oxime and 13.34 g of n-butyl acrylate (=monomer 2) mixed with 〇27 g edmA. Thereafter, another portion of 40 mg of potassium peroxymonosulfate (KPS, Fluka microselect) dissolved in 3 ml of water was added and The polymerization was continued for another 16 h at 70 ° C. After cooling to room temperature, ultrafiltration latex was applied to Amicon® cells using 46 200948849 • cellulose membrane (diameter 76 mm, cut-off: 300'000 Da) until the total amount of permeate 3 L. The 10 g dispersion was freeze-dried and the solid content was determined to be 6.73%. It was easily redispersible in water. Analysis: Elemental analysis: Calculated value (experimental value): C58.35 (5 5·81) Η 6 .3 9 (6.71) S 7.40 (6.94) C/S 7.88 (8.04) Penetrating electron microscopy (ΤΕΜ): average diameter d = 33 nm. Example 22: ❹ In Examples 20 and 21, core shell nanoparticles having a core as in Example 20 and having different comonomers and varying amounts of polystyrene-sulfonate in the second shell were prepared, see Schemes 2 and 3. :

S03Na PSS as second outer casing 47 200948849 Scheme 2: Synthesis of a more flexible core and crosslinked first outer shell and an anionic core/shell nanoparticle having 100% polystyrene-sulfonate in the second outer shell: examples twenty two.

42 wt.% 50wt.%

SDS/KPS h20; n2 2 h, 70eC

8 wt. % core uncrosslinked eDSC: Tg=28 °c emulsion d=22 nm (DLS) d=14nm (TEM)

H2o; n2 30 min, 70 eC

DVB (10) 50wt.% 50wt.%

Core: 7.7wt.% 1. Housing: 7.7wt.% 2. Housing: 84.6 wt.%

S03Na S (calculated value): 2.38% S (experimental value): 2.41% DLS: d = 97.2 nm (z average) TEM: d = 28 nm (about) D9: Not more than BA by DSC measurement Second Shell Process of Toughener 3: Synthesis of anion core/shell nanoparticle with a more flexible core and crosslinked first and second shells with a high butyl acrylate content (81%): Example 23. Examples 24-26. Anionic nanoparticles having softer cores and outer shells according to Examples 21-23, which are not shown in Scheme 1-3, were coated with different thicknesses of pyrrole shells according to Scheme 4'. An embodiment (Embodiment 24) is given in detail. 48 200948849 ❹

Add H20 (2.5 equivalents to SSS) for 0.5 h at room temperature. S content: 9.65% d=30 r>m (TEM)

H20 (2.8 equivalents to SSS) was added continuously at room temperature for 0.5 h. S content: 6.94% d=33 nm (TEM)

Continuous addition of H20 at room temperature for 0.5 h (relative to SSS 2.75 equivalents) S content: 2.41% d=28 nm (TEM); 97 nm (DLS)

Fe(tos)3 (2.3 equivalents to Py)

Fe(tos)3 (relative to ?? 2.3 equivalents)

Fe(tos)3 (relative to ?? 2.3 equivalents)

Note: 0.001% dispersion corresponds to a dry layer thickness of about 100 nm. 001% dispersion; λ=450ηπι: OD=0.136; T=73.1% (calculated based on pure PPy: Τ=38.6%) TEM: d =40 nm Elemental analysis calculated value 6.99% S 6.43% Food test value N 6.77% S 6.13% The powder is fully redispersed! PPy content: 333⁄4 0. 001% dispersion of total particles; λ=450ηηι: OD=0.085; 1=82.2% (calculated value based on pure PPy: T=45.3%) TEM: d=41 nm Elemental analysis calculated value N 6.00% S 4.91% Experimental value N 5.11% S 5.51% Powder redispersible (some sedimentation) PPy content: 29% of total particles 0. 001% dispersion; λ=450ηηι: OD=0.038; T=91.6% (based on Calculated value of pure PPy: Τ=49.0%) TEM: d=55 nm Elemental analysis calculated value N 2.54% S 2.12% Experimental value N 1.92% S 2.24% Large particles, sedimentation PPy content: 12.2% of total particles 4: Synthesis of a polypyrrole (PPy) shell of different thicknesses. Example 24: Coating of particles according to Example 2 1 with polypyrrole in a 45 ml round bottom flask with mechanical mixing, 20.0 g The dispersion according to Example 21 was diluted with 100 ml of water, degassed with argon and rinsed 3 times. 0.543 g (8.1 mmol) ° of each of the B (Fluka purum) was introduced and homogenized. 12·62 g (18.63 mmol) of iron(III) tosylate hydrate (Fe(tos) 3 6 H20, Aldrich) dissolved in 40 ml of water was added dropwise via syringe and pump at room temperature for 30 min. After all the iron (III) toluenesulfonate was added, the reaction mixture was stirred for further 30 min. The reaction mixture was ultrafiltered in a Amicon® cell with a cellulose membrane (diameter 76 mm, cut-off: 300 Ό00 Da) until the total permeate amount was 3 L. Freeze 1 g of the dispersion was dried. 49 200948849 Dry and determined solid content: 0.62%. It can be easily redispersed in water. Analysis: Elemental analysis: Calculated value (experimental value): N 6.00 (5.1 1) S 4.91 (5.51) Penetrating electron microscopy (TEM): average diameter d = 41 nm. It is advisable to apply Example 1: Here, 'coating the core/shell nanoparticle according to Example 21 with polyaniline (instead of polypyrene): in a 350 round bottom flask with mechanical stirring during 45 min' 16.0 g of the dispersion according to Example 21 was diluted with i〇〇ml of water, degassed with argon and rinsed three times. 0.46 ml (0.47 g, 5_0 mmol) of benzoguanamine (Aldrich) was introduced, homogenized and cooled to an ice bath. During the 3 〇 min period, 1. 〇3 g (4.5 1 mmol) of ammonium peroxydisulfate (Merck) dissolved in 40 ml of water was added via <<> the main emitter and the chestnut, whereby the reaction mixture turned green. (Polylane of polyaniline). After all (NH4)2S2〇8 was added, the reaction mixture was stirred at 0 ° C for further 1 h, then stirred at room temperature for 1 h. The reaction mixture was ultrafiltered in a cellulose membrane (diameter 76 mm, cut-off: 300, 〇〇〇 Da) in AmiC〇n® Cell until the total permeate amount was 1 L. The i g dispersion was cold bundle dried and the solids content determined: 〇·74%. It can be easily redispersed in water. Analysis: Elemental analysis. Calculated value (experimental value): Ν 3.49 (3.21) S 5.32 (5.99) Penetrating electron microscopy (ΤΕΜ): average diameter d = 44 nm. A ^ p}. 28: thermogravimetric analysis (TGA; substance as in Example 8; 25-800 (:; 10 (: / 111111; > ^) shows 40. (: with 150. (: between 8.6 % water loss' and decomposition begins above 420 ° C. 50 200948849 29 : DC conductivity of composite pellets at 293.15 K is detected by dielectric spectroscopy as described in Example 17d. Similar to Example 17 c The other ones, the particles used were obtained, but various amounts of PPy outer shell material were deposited. The results were shown to contain less than the weight of the ppy particles (about 1 〇-8 s/cm) to about 10% to about 25 weight. The conductivity of the particles of % PPy (10 3 to 10 · 1 s / cm, see Figure i 3 ) is strongly increased. J J 30 : The first thin shell of highly crosslinked polystyrene / divinyl benzene And uncrosslinked poly(sodium styrene sulfonate) second shell® (ps_p(s/DVB)-pss) polystyrene-core 307.22 g of the suspension of Example 6 (solids content 16.59 g) and 1500 mL Water was introduced into a 2 L round bottom flask with a mechanical stirrer. The suspension was heated to 601 using an oil bath and flushed with argon for 1 hour. 580 mg of acetoisoisobutyronitrile (AIBN, Fluka 98%) was introduced. After 10 min, a mixture of 5.80 g of styrene (Acros 99%) and 1.45 mg of divinylbenzene (DVB, Fluka, 80%) was added dropwise over 1 hour while stirring (45 rpm) 0 © - After το total addition of styrene/DVB mixture, polymerization was continued for 70 min at 60 ° C. Add 5.32 g of sodium styrene sulfonate (NaSS, Fluka 92/〇) and 1·〇9 g of poly(E1) within 1 hour. Alcohol) a mixture of ketone methacrylic acid (pegma Aldrich' Mn = 2080 g/mol, 50% by weight aqueous solution) in 6 liters of machine water. The polymerization was continued for another 12 hours at 60 t: while stirring. The solution was purified by ion exchange (Amberjet 42 〇〇cr) and three ultrafiltration cycles, treated with ultrasound and first filtered through 〇8 and then via 51 200948849 0.45 μm membrane. Yield: 22.7 g (83.5%) Solids content of the dispersion (weight analysis): 2.65% C/H/S/Na Analysis (calculated/experimental): C (83.13% / 83.12%) Η ( 7.32% / 7.17%) S ( 2.74% / 1.99%) )

Na ( 1.97%/1.28%) DLS : rh = 37.4 nm

AjUL_3J_L_PS-P(S/DVB)-PSS-PPy Nanoparticles In a 2 L round bottom flask with a mechanical stirrer, 113.21 g of the suspension of Example 30 (solids content 3 g) was diluted with 1.7 L of water. It was rinsed with argon for 1 hour. After adding 158 mg of distilled pyrrole (Py, 2_36 mmol, Fluka 97 °/o) for 10 min, 3.139 g of iron (III) p-toluenesulfonate (5.48 mmol) in 25 water was introduced dropwise over 3 hours. HCStarck), while disturbing. After the complete addition of iron (p-toluenesulfonate), the reaction was continued for another half an hour. The resulting suspension was purified by ion exchange (Amberlite IR-120 H+) and a secondary ultrafiltration cycle and passed through a 〇 8 V m and 〇.45 a m filter. AAS : 56.9 pg Fe/g ρργ content obtained by nitrogen analysis: 4.7% DLS : rh = 48 nm Conductivity increases with PPy amount [Simplified illustration] Figure 1: UV/VIS of PS-PSS-PPy film Transmittance. Figure 2: DLS results for the 52 200948849 particle suspension of Example 8 prior to lyophilization and after 4 days of freeze drying. Figure 3: Graphical representation of the four-point probe method as in Example n and calculation of the intrinsic resistivity as the reciprocal of conductivity. Figure 4: Phase of the device used to monitor conductivity as a function of temperature and time. Figure 5. a) The resistivity of argon + ρργ composite pellets develops with temperature. b) aging of the conductive behavior of PPy composite pellets in air. Figure 6: AFM image of the film of Example 13, with a height image on the left and a phase image on the right. The rotation speed was 1500 rpm and the film thickness was 60 nm 〇 Ra = 9 nm 〇 Figure 7: SEM image of the ppy composite film (Example 14) before heating (left) and after heating (right). Figure 8. Center up, adhesive tape testing process. In the following, an SEM image of the PPy composite film after the adhesive tape was slowly lifted (Example 15). Figure 9. Flow of core/shell polyfluorene complex nanoparticles with a softer polymer core and an embedded anionic polyelectrolyte shell. Here some of the anionic polyelectrolytes act as counter ions to PPy, and the remaining polyelectrolytes provide electrical steric stabilization to prevent colloidal flocculation in water or water/organic mixed tannins. It is the remaining anionic polyelectrolyte that causes the ppy nanoparticle to redisperse. Thus, the prepared composite particles can be delivered and sold in powder form. Figure 1. 核心. Core/shell ppy composite nanoparticle with a softer polymer core and a polyelectrolyte containing the opposite ions of the polyfluorene shell and other chains providing (other) electrical space or space properties. Particle 53 The process of 200948849. Figure 11 is a schematic illustration of the OLED device of Example 16. Figure 12: Features of the apparatus of Example 16 (left: current density [A/cm2]; lower half/right: brightness [cd/m2]; horizontal axis: voltage). Figure 13: Contains various amounts of poly. The conductivity of the compound of the pyrrole. [Main component symbol description] None

54

Claims (1)

200948849 ' VII. Scope of application: 1. A layered particle comprising a thermoplastic or crosslinked unsubstituted (tetra) polymer core comprising an anionic functional group on the surface of the core, and an oxidatively polymerized outer shell, the particle being characterized by Easy to redisperse in polar solvents. 2 - a layered particle comprising a thermoplastic or crosslinked untetrazed polymer core having an anionic shell on the surface of the core, particularly as claimed in the patent scope, wherein the particle contains a prominent neutral The group and/or excess anionic cation functional groups covalently bonded to its core surface. 3. The layered particle of claim i or item 2, wherein the cough core consists essentially of a synthetic organic polymer 2 (the TC is crystalline or amorphous and has 彳15 ( The rc or lower glass transition temperature is preferably selected from the group consisting of olefinic polymers. 4. The layered particles of claim 2 or 2, wherein the core is substantially composed of polystyrene or polyacrylate Especially polystyrene composition. 5. The layered particle of claim 1 or 2, wherein the anionic functional group is selected from the group consisting of a decanoate group and a particularly acid group and a phosphonate group, preferably a polyanion In the form of a chain, such as by the core particle being co-linked with one or more suitable monomers (IV), & wherein PG represents a polymerizable group, such as a vinyl group; Ra is an anionic functional group as mentioned above Sp is a direct bond or a suitable organic spacer ring cyclist and a aryl group and a complex thereof, which are selected from the group consisting of an alkyl group, an alkyl group of about 50 carbon atoms, and a bond thereof. 55 200948849 Or sulfur or nitrogen and/or substituted by hydrazine or S, the monomers are preferably selected from the group consisting of ethylene benzoic acid, esters and salts, c2-c8 alkenyl acid, esters and salts, (mercapto) propylene Stable oxy-C2_C8 alkyl carboxylic acid, vinegar and salt '(mercapto) acrylamide-C2_C8 alkyl carboxylic acid, ester and salt, ethyl phenylphosphonic acid, ester and salt, c2-c8 olefin Phosphonic acid, ester and salt, (meth) propyl aryloxy-CrCs alkylphosphonic acid, ester and salt, (meth) acrylamido _C2_C8 alkyl phosphonic acid, ester Salt. 6. The layered particle of claim 1 or 2, wherein the oxidatively polymerized outer shell is obtained by oxidative coupling of unsubstituted or substituted pyrrole, aniline or styrene. 7. The layered particle of claim 1 or 2, wherein the oxidized polymeric shell consists essentially of polypyridinium. 8. The layered particle of claim 1 or 2, wherein the anionic group is on an oligomeric or polymeric hydrocarbon chain having from 8 to 100 carbon atoms. A method for producing a layered particle according to any one of the above claims, wherein the method comprises adding in the presence of a polar solvent and an intermediate particle dispersed in the mixture The oxidizing agent polymerizes a suitable monomer, characterized in that the intermediate particles comprise a thermoplastic or crosslinked polymer core. The core contains an anionic functional group covalently bonded to its surface. a method wherein the intermediate particles have been prepared by emulsion polymerization of a dilute unsaturated monomer to form a core, a particle in which a polyacid group or a particularly sulfonate group or a phosphonic acid is added during a polymerization step in which the core particle is formed a root group, such as a suitable comonomer selected from the group consisting of the following acids and their vinegars and salts: vinyl sulfonic acid '& carboxylic acid' (meth) acryloyloxy _c2-ce carboxylic acid, (Methyl ^ 56 200948849 Acryl-CrC8 alkyl sulfonic acid, vinyl phenylphosphonic acid, (^-. alkenylphosphonic acid, (meth) acryloyloxy-C2-Cs alkylphosphonic acid, ( Derivatization of methyl) acrylamide-based _C2_C8 alkylphosphonic acid Or copolymerizing it with the core particles in a subsequent step, and wherein a relatively small amount of cross-linking agent is present during or during the formation of the core particles or during the copolymerization of the core particles with the comonomer. · The method of applying the patent scope item 9 is for the preparation of soft 层 Core particles and layered particles of polypyrrole shell, the method is characterized in that the core particles are substantially composed of. Forming an organic polymer which is under the junction μ or amorphous and has a glass transition temperature of 丄5〇〇c or lower, especially selected from an olefinic polymer such as polystyrene or polyacrylic acid. The following steps are subsequently carried out: ^ 〇 is copolymerized with a suitable monomer containing a functional group S03H, S03M or S〇3R], wherein Μ represents one equivalent of metal cation and R 丨 represents Cl·. An alkane residue, such as a C?C8 alkyl group, especially copolymerized with styrenesulfonic acid or a suitable salt or vinegar thereof, b) the sulfonic acid group, especially s〇3H and S, introduced in step (a) 〇3Rl (if present) is converted to S03M, especially s〇3Na, and C). The specific polymer is polymerized on the surface of the particles. Wherein water and polar organic solvent 12· as in the method of claim 11 of the patent scope!) Steps (a), (b) and (c) are carried out in a dispersant selected from the group consisting of: ^) Step (b) The conversion of the sulfonic acid or sulfonate group, if any, is carried out by introducing an alkali hydroxide such as NaOH; 57 200948849 out: the polymerization of step (c) is by adding force σ H &amp Suitable oxidizing agent, = e(III) salt, FeCl3, iron benzene sulfonate (ΠΙ); iv) The dispersion obtained after step (e) is subjected to, for example, desalination (d) by filtration. A 13.-particle or particle dispersion obtained in the method of any one of claims 9-12. Human H. A method for preparing a conductive or semiconductive layer, comprising a package 3 or more types of particles as claimed in item i to item 8 or item η of the patent application, especially the layer force of particles of item 3 of the patent scope, '., to nucleus to particles The temperature above the glass transition temperature of the synthetic organic polymer. An electronic device or an optical or acoustic filter comprising one or more types of particles, such as a towel, in any one of the scope of the invention, to the eighth or third item, and/or by applying The conductive or semiconductive layer obtained by the method of claim 14 is selected, in particular, from an integrated circuit, a display, an RFID tag' Electro- or photoluminescent devices, backlights for displays, optoelectronic or sensor devices' electronic devices for solar cells. 16. The use of a dispersion of particles or particles as claimed in any of the scopes of the claims to the eighth or the third item, for use as a charge injection layer flattening layer, an antistatic agent, a conductive substrate or Patterns, photoconductors, electrophotographic t/applications, conductor materials in δ-recorded materials, conductor precursors, electrophoretic (dye) particles, pigments, IR absorbers, and/or used to prepare conductive structures, conductive inks, capacitors, Optical or acoustic filters, electronics, light control systems. 58