TW201139506A - Sulphonated polyketones as a counter-ion of conductive polymers - Google Patents

Abstract

The present invention relates to a complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the polyketone is a polymer which comprises a (-CO-) group in its recurring units and in which this (-CO-) group is linked with two aromatic groups. The present invention also relates to a process for the preparation of a complex, a complex obtainable by this process, the use of the complex, the use of sulphonated polyketones, a coated substrate, a process for the production of a coated substrate, the coated substrate obtainable by this process and an electronic component.

Description

201139506 VI. INSTRUCTIONS: The present invention relates to a novel composite electrolyte comprising a functionalized polycopper and a conductive polymer, and a composite obtained by the method, the use of the composite The use of the sulfonated polyruthenium, the coated substrate, the side of the coated substrate, the coated substrate and the electronic component obtained by the method. The economic importance of conductive polymers is increasing because high knives have advantages over metals in terms of processability, weight and targeted property adjustment by chemical modification. Examples of known π-binding polymers are polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene and poly(p-phenylene-vinylene). The conductive polymer layer can be used in various industrial applications, for example, as a polymer counter electrode in a capacitor or as a through-plated electronic circuit board. The conductive polymer is prepared chemically or electrochemically by a monomer precursor (e.g., an optionally substituted thiophene, pyrrole, and aniline, and an oligomeric derivative thereof, which is optionally present). In particular, chemical oxidative polymerization is widely used because it is easily industrially implemented in a liquid medium or on a different substrate. A particularly important polythiophene for industrial use is poly(extended ethyl-3,4-dioxythiophene) (PED〇T or PEDT), which is described, for example, in ΕΡ0339340Α2 and is extended by chemical polymerization of ethyl _3. , 4-dioxythiophene (EDOT or EDT) to prepare 'and its very high conductivity in the oxidized form. Overview of various poly(alkyl-3,4-dioxythiophene) derivatives (especially poly(extended ethyl-3,4-dioxythiophene)' in organisms) and their early units, synthesis and use By L. Groenendaal, 201139506 F· J嶋s, D. Freitag, η. Pielartzik and 】r is fairy, 仏

Mater. 12, (2000) is given on page 48M94. For example, PED〇T (e.g., polystyrene acid (pss)) @dispersion having a polyanion disclosed in EP 440 440 95 7 a? Φ μ 7 Α 2 has been specified. Important hygiene [a transparent conductive film with many uses (for example, as an antistatic coating or as a hole injection in an organic light-emitting diode (OLED) 曰ΈΡ 1 227 5 29 A2) can be dispersed accordingly Liquid manufacturing. At this time, the polymerization of ed〇t was carried out in an aqueous polyanion solution to form a polyelectrolyte composite. In the technical field, a polymer anion for charge compensation is included as a cationic cation of a relative ion. The phenotype is also commonly referred to as a polythiophene/polyanion complex. Due to the polyelectrolyte nature of PED〇T as a polycation and pss as a polyanion, in this case the complex is not a true solution but a dispersion. In this case, the degree of partial dissolution or dispersion of the polymer or polymer depends on the weight ratio of the polycation to the polyanion, the charge density of the molecule, the salt concentration of the environment, and the nature of the surrounding medium (V. Kabanov, Russian Chemical). Reviews 74, 2005, 3-20 ) 〇 In this case, the transitional form can be a fluid. Therefore, there is no difference between the terms "dispersed" and "dissolved" hereinafter. Similarly, the difference between "dispersing" and "solution (s〇iui: i〇n)" or between "dispersing agent" and "solvent" is minimal. Rather, these terms are equally used hereinafter. The complex of PEDOT and PSS has been used in a variety of applications as described above. However, such composites are characterized by inherently high acidity. This is based on the high acidity of pss. The equivalent of PSS is 184 g/mo, and the pH of the PEDOT:PSS dispersion is relatively low. Therefore, the typical PEDOT:PSS dispersion used as the hole injection layer in the 〇lED has a pH of 1.5. This low pH can, for example, result in etching the indium tin oxide (ιτο) transparent electrode in the OLED. Therefore, In and Sn ions move and can diffuse in adjacent layers (M p de J〇ng et al., App丨

Phys· Lett. 77, (2000), 2255-2257), thus having an adverse effect on the lifetime of OLEDs.

Si-Jeon Kim et al., Chem. Phys. Lett· 386', (2004), 2-7 and

Jaengwan Chung et al., 〇rganic Eiectr〇nics 9, (2009) 869-872 have reported thermal decomposition of PSS, which splits out sulfate, ie PSS is unstable. This sulphate can have an adverse effect, for example, on the lifetime of 〇LEDs. In EP 1 564 250 A1 and WO 2004/032306 A2, Elschner et al. have described mixtures of perfluorinated sulfonic acid polymers and conductive polymers as OLEDs. The hole is injected into the layer. The use of such a mixture to produce a hole injection layer in the ’led has the potential to prove that the presence of the vaporized polymer improves the lifetime of the #0LED. Then, the layer containing the fluorinated polymer is characterized by a high contact angle. This makes it difficult to deposit other solvent-based layers because the film is difficult to form. m should contain a new polymer of conductive polymer and polyanion. It is desirable that the polyanion be characterized by a complex having an acidity below m and having increased stability. In addition, 'need to be suitable for & curry

It is characterized by a long life. The layer is characterized by a low contact angle and 〇LED 201139506 has now surprisingly found that a composite of a conductive polymer and a functionalized polyketone is suitable for use as a polyanion for the production of a transparent conductive film, and such composites are characterized by high stability. . Further, it has been found that the conductive films are suitable for use as a hole injection layer in a ruthenium LED. If the pH of the dispersion is increased by addition, the lifetime of the OLEDs is particularly long. Accordingly, the present invention provides a composite comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the polyketone comprises at least one (_c〇_) group in its repeating unit. A polymer of (keto group) and in this repeating unit, the (_c〇_) group is bonded via two aromatic groups. In a preferred embodiment of the complex of the present invention, the functionalized polyketone comprises a repeating unit of formula (I)

among them

An and Αι*2 may be the same or different and are optionally substituted as a goose group.

Ri is an optionally substituted organic group having 1 to 80 carbon atoms, a (_C0_) group or an oxygen atom, and η is 5 to 5, _, preferably 1 Å to 3 Å, particularly preferably 2 〇 to 2, the integer of the discussion. 201139506 In the case of the present invention, the poor test "private ring conjugate system, preferably 盍 - Cai, 蒽 and biphenyl, especially preferably A - Bi Yijia is stupid, this 'the above compounds are likely to taste Further, in the present case, in the case of the present invention, the organic group having 1 to 80 carbon atoms is preferably a group consisting of, for example, - or a plurality of = selected from the group consisting of: Ethers, ketones, sulfones' sulphides, vinegar's carbonated vinegars, enriched amines, quinones and aromatics (iv) (especially extended, extended biphenyls and naphthalenes) and aliphatic groups (especially methylene, ethylidene) Prolonged propyl and isopropylidene groups, individual groups may also be repeatedly present in the group. The aromatic and aliphatic groups may be additionally substituted. Unless otherwise explicitly mentioned, in this article and below Substituted" means substituted by a group selected from the group consisting of alkyl, preferably cI_C20 alkyl 'very, particularly preferably fluorenyl or ethyl; cycloalkyl, preferably C^Ci2 ring' An aryl group, preferably a C^-Ci4 aryl group; a halogen atom, preferably Cl, Br or I; a mystery group; a sulfur bond group, a sulfur bond, a subscript ;; kiln; sulfonate; amine; aldehyde; keto; carboxylate; carboxylic acid; carbonate; carboxylate; phosphonic acid; Alkyl fluorenyl; alkoxy fluorenyl; and carboxy guanylamino. The term "Ci-Cw-alkyl" means a straight or branched ci-C2 alkyl group, such as decyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, Dibutyl or tert-butyl, n-pentyl, 1-methylbutyl, 2-mercaptobutyl, 3-methylbutyl, 1-ethylpropyl, hydrazine, 1-diisopropylpropyl 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 8 201139506 2-ethylhexyl, n-decyl, n-decyl, n-ten Monoalkyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecane Base or n-icosyl. The term "C3-C12-cycloalkyl" means a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or "Cyclohexyl" and the term "C6-C14 aryl (C6-Cl4-aryl)" denotes a C6-Ci4 aryl group such as phenyl or naphthyl. The functionalized polyketone contained in the composite of the present invention is preferably characterized by from 5.000 g/mol to 500,000 g/mo, particularly preferably i〇, 〇〇〇g/m〇1 to 100.000 g/mol and more preferably Molecular weight (Mw) of 20,000 g/mol to 50,000 g/mol. Such functionalized polyketones can be prepared by a substantially known method (S. Swier, YS Chun, J. Gasa, Μ. T. Shaw A RA Weiss, Polym. Engin. Sci. 2005, pp. 1081-1091; S. Vetter, B. Ruffmann, J. Buder and SP Nunes, J. Membrane Sci. 260 (2005), 181-186; L. Li, J. Zhang and Y. Wang, J. Membrane Sci. 226 (2003) , 159-167 ; B. Bauer, DJ Jones, J. Roziere, L.

Tchicaya, G. Alberti, M. Casciola, L. Massinelli, A. Peraio, S, Besse Sl E. Ramunni, J. New Mater. Electrochem. Systems, 3, 93-98 (2000); F. Trotta, E. Drioli, G. Moraglio and EB Poma, J. Appl. Polym. Sci. 70, 477-482 (1998); SMJ Zaidi, SD Mik-hailenko, GP Robertson, MD Guiver A S. Kaliaguine, J. Membrane Sci. 173 (2000 ), 17-34; C. Bailly, DJ Williams, FE Kharasz and WJ MacKnight, Polymer 1987 (28), 3009-1016; X. Jin, Μ. T. Bishop, T. S. Ellis and F. E. Kharasz , 9 201139506

Br. Polymer J. 17(1), 4-10 (1985)). In a preferred embodiment of the complex of the present invention, the functionalized polyketone comprises a repeating unit of the formula (II) 0 _R2 - ^ATf η

(II wherein ΑΓ| and Ah may be the same or different and represent an optionally substituted aromatic, \, and X2 may be the same or different and each represents a sulfonium, sulfonate, phosphonic acid, phosphonate a carboxylic acid or a carboxylate group, a and b may be the same or different and each independently represents an integer or a non-integer in the range of 〇 to 2, and a non-integer means that the acid mentioned does not exist. In each repeating unit, but only in the corresponding portion of the repeating unit, R2 has the same meaning as R, and η is 5 to 5,000, preferably 10 to 3,000, particularly preferably 汕 to 2 〇〇〇 Integer. ^ The functionalization of a polyketone containing a repeating unit of the formula (Π) can occur on all repeating units or only on some corresponding repeating units, that is, the non-integer meanings of & and 匕 (including the following) The functional groups & or & mentioned are not present in each repeating unit, but only in the corresponding part of the repeating unit. Very particularly preferably, the functionalized polyketone is a sulfonated polyketone (& Χ2 = sulfonate 201139506 acid or acid vinegar base), its preparation is for example by Schuster et al. (Macromo Lecules 2009, 42(8), pp. 3129-3 137). In a particularly preferred embodiment of the complex of the present invention, the functionalized polyketone comprises a repeating unit of formula (IIa) wherein aromatic仏 and A. In each case, it means benzene ring:

Wherein a, b and R_2 have the meanings given for the formula (π), and Μ represents a metal cation or η, preferably Na, K, Li or ruthenium, particularly preferably ruthenium. One or two benzene rings in the repeating units of the formulae (II) and (Ila) may optionally be mono- or polysubstituted with a substituent different from the SOsM group, and a fluorenyl group or an ethyl group may especially exist as a substituent (formula ( Not shown in π) and (IIa). In another particularly preferred embodiment of the complex of the present invention, the functionalized polyketone comprises a repeating unit of the formula (ΙΠ), wherein the repeating unit comprises three benzene rings bridged via a keto group and two ether groups, Each stupid ring may have a sulfonic acid group: 201139506

Wherein C has the same meaning as a and oxime and a&b has the meaning given to the formula (II), and the oxime is not a metal cation or H, preferably η, which is preferably ruthenium. In the case of the present invention, the contiguous polyketone of the formula (111) is also referred to as a continuation polystyrene (s-PEEK). Also herein, one or two or all three benzene rings in the repeating unit of formula (111) may optionally be mono- or polysubstituted with a substituent different from the SAM group, and methyl or ethyl may especially be used as a substituent. Existence (not shown in (式)). In another particularly preferred embodiment of the composite of the present invention, the functionalized polyketone comprises a repeating unit of the formula (IV), wherein the repeating unit comprises four stupid bridges by a ketone group and two substituents. The ring 'each benzene ring may have a sulfonic acid group:

SOjM S〇3M b [SOjM S〇3M jd 12 (IV), 201139506 where ΠΙ) gives d with the same meaning as a, b and c and a, b, c and Μ have the formula (II) Or also herein, in the formula (no one or two, three or all four benzene rings in the repeating unit may be substituted by a substituent different from the s〇3M group, and the 'f group or the The base is especially likely to be present as a substituent (not shown in (IV)). In the present invention. Further, in a particularly preferred embodiment, the functionalized plurality contains a repeating unit of the formula (7), wherein the repeating unit comprises two benzene rings bridged by a keto group and a fluorenyl group, each of which may have an item Acid base:

Wherein and b have the meaning given to the formula (η) and the oxime is not a metal cation or η, preferably ^^, 逆, [丨 or ^, which is preferably jj. In the case of the present invention, one or two of the repeating units of the polyether (v) of the formula (ν) may be optionally substituted by a substituent different from the 13 201139506 S〇3M group. Or polysubstituted, fluorenyl or ethyl is especially possible as a substituent (not shown in formula (V)). In another very particularly preferred embodiment of the complex of the invention, the functionalized polyketone comprises a formula ( VI) a repeating unit, wherein the repeating unit comprises three benzene rings, one of which may be bridged in the meta or para position via two adjacent carbonyl substituents corresponding to the group of formula (VI), each benzene ring It is possible to have a sulfonic acid group:

(VI), giving the meaning. In the case of the present invention, the polyoxan of the formula (VI) is also referred to as the polyketene ketone (s-PEKK). Also herein, one or two of the three benzene rings in the repeating unit of the formula (VI) may be optionally substituted by a substituent of the group "3", especially if it is present as a substituent (not shown). ’

In the context of the present invention, a pharmaceutically acceptable polyketone is also understood to mean a mixture of the above-mentioned polyketides or a condensed compound which is present in the form of a polycation and a left-form of the above functionalized polyketone. The composite of the present invention 14 201139506 comprises at least one electrically conductive polymer which is optionally substituted as a polycation. The conductive polymer is, for example, a polystyrene which is optionally substituted, a polypyrole which is optionally substituted, and a poly(sigma) which is optionally substituted. In a preferred embodiment of the composite of the present invention, the conductive polymer is an optionally substituted polyseptene comprising a repeating unit of the formula (VII)

(VII) wherein R4 and R5 each independently represent Η, optionally substituted c, -C, 8 alkyl or optionally substituted C! -C|8 alkoxy, r4 together with R5

The C?-Cs extended alkyl group may be substituted by one or more of the same or different heteroatoms selected from hydrazine or S, preferably 匕{8 Ο or S.

A Ci-C8 alkylene group in which at least one of the hetero atoms is substituted.

The base or the atom that is optionally replaced is selected from 〇 or S.

(VII-a) and / especially more than f · or (VII-b ) 15 201139506

Wherein A represents an optionally substituted Ci_C5 alkylene group, preferably a C2-C3 alkylene group which is optionally substituted, represents Y or S, and R6 represents a straight or branched chain, optionally substituted Ci-Cis An alkyl group, preferably a straight or branched chain, optionally substituted C1-C i4 alkyl; optionally substituted Cs-C, 2 cycloalkyl; optionally substituted c6-c14 aryl; a substituted C7-C1S aralkyl group; optionally substituted c7_Ci8 alkaryl; optionally substituted c, -c4 hydroxyalkyl; or hydroxy, and y represents 0 to 8, preferably 0'1 or 2, particularly preferably 〇 or an integer of 1, and wherein in the case where several groups R_6 are bonded to A, such groups may be the same or different. The formula (VII-a) is understood to mean that the substituent & can be bonded to an alkylene group a y : owed. In other very particularly preferred embodiments of the complex of the present invention, the (iv) phene comprising a repeating unit of the formula (νπ) is such that they comprise repeating units of the formula (vn_aa) and/or (Vn-ab) Polythiophene 16 201139506

Among them, 6 and 丫 have the above meanings. In still another highly preferred embodiment of the complex of the present invention, the polythiophene comprising a repeating unit of the formula (VII) is a repeating unit comprising the formula (νπ-aaa) and/or the formula (νπ-aba) These polythiophenes>«w • - r^\ r^\ --本 (VII-aaa) (VII-aba) In the case of the present invention, the prefix "poly(p〇ly_)" should be understood as meaning The thiophene contains more than one identical or different repeating unit. The polythiophene comprises a total of f η repeating units of the formula (VII), wherein n can be 2 to 2, 〇〇〇, an integer of 2, 100. In each case, the repeating units of the formula (VH) in one polythiophene may be the same or different. Polythiophenes containing repeating units of the same general formula (Vn) in each case are preferred. ^ Polythiophene preferably has a ruthenium on each end group. In a particularly preferred embodiment, 17 201139506 polythiophene having the general formula (νπ) repeating unit is poly(3,4-extended ethyldioxythiophene), poly(3,4-ethylhexyloxythio)嗟 )) or poly(thieno[3,4-b]thiophene), that is, a homopolythiophene of a repeating unit of the formula (VII-aaa), (Vll-aba) or (VII-b) wherein γ = s . In other particularly preferred embodiments of the complex of the present invention, the polythiophene having a repeating unit of the formula (VII) is a formula (VII_aaa) and (VII aba), (VII-aaa) and (VII-b), Copolymers of VII_aba) and (VII b) or (Vli aaa), (vil-aba) and (VII-b) repeating units, formula (vn_aaa) and (Vll-aba) and (VII-aaa) and (vn_b) The copolymer of the repeating unit is preferred. In the context of the present invention, c1-C5 alkylene A is preferably methylene, ethylidene propyl, n-butyl or n-pentyl, and 〇1-(:8 alkyl is additionally In the case of the present invention, the K8 alkylene group is preferably the above-mentioned Ci_c8 alkylene group containing at least one double bond. In the case of the present invention, 'Cl_C8 dioxyalkylene alkyl group , C|_C8 oxythiazole alkyl and CrC8 dithioheteroalkyl preferably denotes Ci_c8: oxy-extension base, C|_c8a-based thiazepine and Ci_C8 dithia-extension correspond to the above (^( : 8 alkylene. Cl_Cl8 alkyl, C|_Cu alkyl and c5_Ci2 cycloalkyl represent alkyl and Cs-C, 2 naphthenic as mentioned for the substituents of the groups Arl, ^ and R1 in the formula (1) Correspondingly, in the case of the present invention, 'C,-Cl8 alkoxy represents an alkoxy group corresponding to the above Ci-Ci8 alkyl group, and CVC, 4 aryl group has a group A in formula (1) Further, in the case of the present invention, the c7_Ci8 aryl group preferably represents the following c7-c, 8 aryl group, such as benzyl or alkyl benzyl, O-methyl Methyl, m-methylbenzyl, p-methylbenzyl, 18 201139506 C7-Cu aralkyl represents o-nonyl, m-tolyl, p-phenyl, 23-phenyl, 2,4- Dimethyl, 2,5-dimethylphenyl, 2,6. xylyl, '3 didimethylphenyl, 3,5-diphenylphenyl or 2,4,6-trimethylphenyl, and In the case of the invention, C "C4 is preferably understood to include (4) as a base c, -c4 alkyl group and wherein the Ci_C4 alkyl group may represent, for example, methyl, ethyl, n-propyl or iso- a propyl, n-butyl, isobutyl, t-butyl or t-butyl group. The foregoing list is intended to illustrate the invention and is not considered to be deterministic. The polythiophene which is optionally substituted is cationic. "Cationality is only related to the charge on the polybenzazole backbone. Polythiophenes can have (four) positive and negative charges in the structural unit, and positive charges on the substituents on the group are located on the polystyrene backbone. The charge is optionally located on a group R substituted with a succinic acid or a phenolic acid group. In this case, the positive charge of the ten gram main chain may be partially or completely an anion present on the substrate as appropriate. In general, in these cases, the polythiophene may be cationic, neutral or even anionic. However, in the case of the present invention, all of them are regarded as cationic poly. The positive charge on the main chain of the phenotype is decisive. The positive charge is not shown in the formula 'because it is meso-delocalized. However, the number of positive charges is at least 1 and at most η, where all repeats in the 4 polythiophene The total number of units (identical or different). To replenish the positive charge, the right is not yet achieved by the acid or phenolic acid vinegar, and thus the negatively charged group RdR5, the cationic polyporphin anion is used as the relative The ion 'in this context is at least partially assumed by the functionalized polyketone. According to a rather specific embodiment of the complex of the present invention, the polythiophene having the repeating unit of the formula (20113506) is poly(3,4-ethylhexyloxythiophene), poly(3,4-ethylidene) Oxythiothiathiophene) or poly(thieno[34_b]thiophene), very particularly preferably poly(3,4-extended ethyldioxysinter), and the polyketone is a repeating unit of formula (II) Sulfonated polyketone, very particularly preferably a sulfonated polyetheretherketone having a repeating unit of the formula (ΠΙ), a sulfonated polyketone having a repeating unit of the formula (IV), a polyether having a repeating unit of the formula (v) A ketone or a poly-light ketone having a repeating unit of formula (VI). According to the present invention, it is more preferred that the above-described composite of the present invention is dissolved or dispersed in one or more solvents or dispersants, and thus exists in the form of a solution or dispersion. The solid content of the conductive polymer in the dispersion or solution (especially the optionally substituted polythiophene comprising the repeating unit of the formula (VII)) is preferably 0.05% by weight (% by weight) and 20% by weight (% by weight) In particular, it is preferably between (Μ% by weight and 5% by weight and optimally between 0.3% by weight and 4.0% by weight' in each case based on the total weight of the solution or dispersion. The solvent and dispersing agent are, for example, the following liquids: aliphatic alcohols, various methanols, alcohols, isopropanols and butanols; aliphatic hydrazines such as propylene and methyl groups; ethyl ketones; Such as ethyl acetate and butyl acetate; aromatic smoke, toluene and mono-benzene, aliphatic hydrocarbons such as hexane heptane and cyclohexane; gas hydrocarbons such as two gas, gas and 1,2 _ 2 gas e-sinter; aliphatic nitrile, such as acetonitrile; aliphatic hydrazine and stone wind, such as dimethyl sulfoxide and sulfolane; aliphatic carboxylic acid guanamine, such as methyl acetamide, dimethyl acetamide, 〕 methyl ketoamine or N-methyl beeidine _; and lipid (four) and araliphatic ethers, such as the test and benzene 20 201139506 In addition, or a dispersing agent. Water or a mixture of water and the above organic solvent may also be used as a solvent. A preferred solvent or dispersing agent is water or other protic solvent such as an alcohol such as methanol, ethanol, isopropanol and butanol, and A mixture of water and such an alcohol is particularly preferred as a solvent or dispersant. The complex of the invention (i.e., a conductive polymer (especially comprising a repeating unit of the formula (VII) is optionally substituted in the solution or dispersion) The total content of the polybenz and the functionalized polyketone) is, for example, between 5% by weight and 10% by weight of GQ, preferably between 5% by weight and 5% by weight, in each case in solution or dispersion. The solution or dispersion may comprise a conductive high score, especially an optionally substituted polythiophene comprising a repeating unit of the formula (VII), and a functionalized polyketone in a weight ratio of 1:0.3 to 1:100. Within the range of 1:1 to 1:4 Torr, it is particularly preferably in the range of 1:2 to 1:20 and extremely in the range of 1:2 to 1:15. Here, assuming that the complete conversion is carried out during the polymerization, the weight of the conductive polymer is roughly equivalent to the weight of the monomer used. The preparation of the above solution or dispersion is carried out by first preparing the conductive in the presence of a counter ion, preferably in the presence of the above-mentioned functionalized polyketone, for example, similar to the conditions mentioned in EP 0 440 957 A2. Preparation of a corresponding solution of a polymer solution or a conductive polymer dispersion. An improved variation of the preparation of this solution or dispersion is the use of an ion exchanger to remove the inorganic salt content or a portion thereof. This variant is described, for example, in DE i96 27 〇7i ai. For example, the ion exchanger can be agitated with the product or delivered to a column packed with an ion exchanger. For example, the low metal 21 201139506 inclusion can be achieved by using an ion exchanger. The particle size in the dispersion can be reduced after demineralization, (10) Pressure homogenizer. This operation can also be repeated to increase the effect. The high pressure between 1 and bar has been especially proven to be particularly advantageous in this paper to greatly reduce the particle size. Alternatively, the particle size can also be reduced by ultrasonic processing. Processes for preparing monomeric precursors for the preparation of polybenzazoles and derivatives thereof comprising repeating units of the general formula (VII) are known to those skilled in the art and are examples of L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik and J. R. Reynolds, Adv. Mater. 12 (2000) 481·494 and the literature cited therein. Mixtures of various precursors can also be used. In the context of the present invention, the above derivatives of ° phenophene are understood to mean: dimers or trimers of such thiophenes. The higher molecular weight of the monomer precursor, the two organisms (i.e., tetramers, pentamers, etc.) may also be used as derivatives. The derivatives may be constructed from the same or different monomer units and may be in pure form and in admixture with one another and/or with the above. Used in the form of a mixture of phenotypes. In the case of the present invention, the oxidized or reduced form of the & isoprene and porphin derivatives is also included in the "η" + ° ° plug" and thiophene derivatives, as long as they are concentrated. The same conductive polymer may be formed in the middle, for example, in the case of the above thiophene and thiophene derivatives. Preparing a monomeric precursor comprising a repeating unit of the formula (νπ), particularly suitable for use as a monomeric precursor, optionally substituted 3,4-extended alkyloxythiophene, which may, for example, be of the formula (VIII) indicates 22 201139506

(VIII) wherein A, R0, and y have the meanings given by formula (VII-a) wherein, in the case where several groups R are bonded to A, the same or different. It is especially preferred that the monomer precursor is an optionally substituted 3,4-extended ethyl-lactylthiophene' and, in a preferred embodiment, an unsubstituted bis-dioxythiophene. ' ^ In addition to the complex of conductive polymer and functionalized, the solution or dispersion can contain other polymers, such as polystyrene, II or perfluorinated ~ Western, polyethylene, $ Ethylene n (four) (four), polyethylene gas, polyvinyl acetate S, polybutyl butyrate, % acrylate, polyacrylamide, polymethacrylate, polymethyl methacrylate, polyacrylonitrile, styrene / propylene驮s曰 vinyl acetate/acrylate and ethylene/vinyl acetate copolymer, poly:, polyester, polyamino phthalate, polydecylamine, polyimide, non-functional ketene, polylith, Melamine road resin, epoxy resin, polyoxin or cellulose. The solution or dispersion may additionally comprise other components, such as surface active substances such as ionic and nonionic surfactants; or adhesion promoters, such as organic functional money or hydrolysates thereof, such as 3-glycidoxypropyl three Alkoxydecane, 3-aminopropyltriethoxydecane, 3·mercaptopropyltrimethyl 23 201139506 Oxygen oxysphate, 3-mercaptopropyloxypropyltrimethoxy sylvestre, vinyl II Methoxydecane or octyltriethoxydecane. In the case of the present invention, in addition, the pH of the solution or dispersion may be in the range of 1 to 8, preferably in the range of 2 to 7, particularly preferably in the range of 4 to 7. A base may be added to the intermediate dispersion to adjust the corresponding pH, such as an amine, ammonium hydroxide or metal hydroxide, preferably ammonia or an alkali metal hydroxide. Herein, the pH is measured by means of a pH electrode (KnickLab〇r pH meter 766) at 25 °C. Therefore, the present invention also relates to a conductive polysiloxane, preferably a conductive polythiophene comprising a repeating unit of the formula (VII), and a functionalized, preferably transversely multi-dimensional, particularly preferably having a structure (III), (IV). a method for preparing a complex of a sulfonated polyketone of a repeating unit of (V) or (VI), wherein the polymerization is carried out in the presence of a sulfonated polyketone for preparing a conductive polymer, preferably 3, 4_ Ethyloxy thiophene, very particularly preferably a 3,4-extended ethyldioxythiophene precursor. The composite of the present invention is surprisingly suitable for the fabrication of hole injection layers or hole transport layers in tantalum LED or organic solar cells (OSC), or for the manufacture of transparent conductive coatings. Accordingly, the present invention also provides the use of the composite of the present invention for the manufacture of transparent conductive coatings or for the fabrication of hole injection layers or holes in organic light-emitting diodes (ITO) or organic solar cells (OSC). Transport layer. For the production of transparent conductive coatings, for example by known methods, such as by spin coating, dipping, pouring, dripping, spraying, spraying mist, knife coating, brushing or printing, for example by inkjet, screen printing , gravure, lithographic or mobile printing, 24 201139506 The above solution or dispersion is applied to a suitable substrate at a wet film thickness of from 0 5 μm to 250 μm, preferably from 2 μm to 50 μm, followed by at least 20 Dry at temperatures from °C to 200 °C. The importance of organic light-emitting diodes (OLEDs) in applications such as displays and planar antennas is increasing. The construction and function of 〇LEDs are known to those skilled in the art and are described, for example, in D. Hertel and K, Meerhdz Chemie in unserer Zeit, 39 (2〇〇5), p. 336 347. The composite of the present invention can be used as an intermediate layer in such applications. Thus, for example, it is conceivable to construct a transparent conductive electrode (for example made of indium tin oxide (IT〇), doped zinc or tin oxide) or a conductive polymer (for example a conductive comprising a repeating unit of structure (VII) The polymer is coated on a transparent substrate of glass, poly(p-benzoic acid ethyl ester) (pET) or other transparent plastic. The composite of the present invention is deposited as a thin layer thereon. One or more organic functional layers are then applied thereto. Such materials may be conjugated polymers, such as polyphenylene vinyl or poly; or vapor deposited molecular layers, such as are known to those skilled in the art and such as, for example, by D. Hertel and K.

Meerholz, Chemie in unserer Zeit, 39 (2005), pp. 336-347. The OLED is terminated by depositing a final metal electrode, such as a metal ruthenium or LiF//Al. After applying a 2 〇 直流 dc voltage, current flows through the configuration and produces electroluminescence in at least one of the functional layers. The advantages of the polymeric interlayer in OLEDs are: 1) Simple deposition of a polymeric intermediate layer from a solution without the need for a time consuming and expensive vacuum process. 2) The polymeric intermediate layer is highly transparent and allows efficient optical decoupling. 25 201139506 3) The middle layer of the aggregation smoothes the layer below. There is less short-circuit in the OLED of this process, so the yield of component manufacturing is higher. 4) The electrical properties of the OLED are improved because the charge carriers are improved from the transparent electrode to the subsequent organic layer. The composite of the present invention can also be similarly used in the manufacture of organic solar cells (OSC) and produces similar advantages. In 纟osc, electric dust is generated by absorbing light at the electrodes. It is known to be familiar to those skilled in the art and has been repeatedly described, for example, in S. Sensfuss et al., Kunststoffe 8 (2007), p. 136. Furthermore, the invention relates to the use of a functionalized polyketone which functionalizes a preferred sulfonated polyketone, particularly preferably a repeating unit of structure (m), (IV), (v) or (VI), as a poly The anion forms a complex with a conductive polymer as a polycation, preferably a conductive polymer having a repeating unit of structure (VII). Further, the present invention relates to a coated substrate on which a preferred transparent conductive coating comprising the composite of the present invention is applied. The substrate may be especially a film, particularly preferably a polymer film, and particularly preferably a polymer film or a glass plate of a thermoplastic polymer. Further, the present invention relates to a method for producing a coated substrate, which comprises the following processing steps. : i) providing a substrate; η) coating the substrate with a composition comprising the composite of the invention. In the processing step i) of the method for producing a coated substrate of the present invention, a substrate is first provided, and the substrate is preferably one of the above substrates. In process step ii), the substrate is then coated with composition 26 201139506 comprising the composite of the invention. In this connection, it is preferred that the liquid or dispersion containing one or more solvents or dispersants and the composite of the present invention be applied to certain regions of the substrate or substrate, and then evaporate at least - ^ Some solvents or dispersants, which may be carried out, for example, by simply air drying, drying in an oven, as appropriate. Further, the present invention relates to a coated substrate obtainable by this method. The present invention also relates to an electronic component comprising the coated substrate of the present invention or a coated substrate obtainable by the method of the present invention for producing a coated substrate. The electronic component is preferably an organic light emitting diode or Organic solar cells. In the organic light-emitting diode, the coating of the substrate may particularly serve as a hole injection layer or a hole transport layer. However, it is also conceivable that the composite of the present invention is used in other electronic components such as capacitors. The following examples are merely illustrative of the invention and should not be construed as limiting. Example fA^J__LA_±gD〇T and s-ΡΕΕΚ He borrowed the public survey φ. 25.25g polyetheretherketone Victrex® PEEK·TM 150 PF (supplier: VlCtreX EUr〇pa GmbH, Hofheim/Ts.) Measured to 250.0 g of 95% sulfuric acid. After heating the mixture at 5 Torr under 1 Torr, the reaction mixture was cooled to 0 ° C and stirred at this temperature in a mixture of 650 mi water and 325 ml of n-butanol while cooling. . Discard the aqueous phase. The m 1 water was washed with butanol phase twice and the wash water was discarded. Subsequently, 15 0 m 1 of water was added to the butanol phase and the pH of the mixture was 27 201139506 and to a pH of about 6 with 12 ml of 30% strength NaOH. Then, the butanol was distilled off on a rotating burr 3! μ stone, and the water was gradually replaced with water, and finally the volume was concentrated to about 1/3. Jiang, 300 ml of methanol was added to this aqueous solution and the sodium sulfate which had been precipitated was filtered out. The filtrate was treated 3 times with M> milk ion exchanger (Lewatit MP® 62 and Lewatit® Monoplus S 1〇〇, **. τ 仏 · Lanxess AG) to remove sulfate and sodium ions, followed by evaporation to The residue was dried and dried at 0.5 mbar. The yield was 23 6 gs_pEEK. The degree of sulfonation of each repeating unit of the polymer was 1.09 (determined by titration with 〇.1N sodium hydroxide solution), which corresponds to an equivalent of 286 g/mol. 1.5 1 glass container is equipped with a stirrer and a thermometer. At 25. Under the arm, 1,338 g of water, 10 g of polyfluorene ketone' 2.36 gi〇〇/0 concentration of iron (III) sulfate solution and 1.91 g of ethyldioxythiophene EDT (Clevios®) M V2, HC Starck Clevios GmbH, Germany) Mix thoroughly for 15 minutes. Subsequently, add 4.66 g of sodium peroxodisulfate and stir the mixture at 25 hours for 24 hours. Then add 57 g of anion exchanger (Lewatit® MP 62, Lanxess AG, Leverkusen, Germany) and 111 g of cation exchanger (Lewatit® S 100 H, Lanxess AG, Leverkusen, Germany). The mixture was stirred for 2 hours. The ion exchange was then separated through a filter paper and the dispersion was passed through a 0.2 μm filter. Solid content: 0.61% Viscosity: 2 mPas (Haake RV 1,20 ° C, 700 s·1) Example 2: 劁i tells that the layer of the PEDOT/s-PEEK is on the rotary evaporator from the example The dispersion of 1 was concentrated to a solids content of 1.36%. The cleaned glass substrate was placed on a rotary paint coater (lacquer whirler 28 201139506 coater) and 5 ml of the concentrated dispersion was distributed on the substrate. The excess dispersion was then separated by rotating the plate at 500 rpm for 30 seconds. Thereafter, the substrate coated in this manner was dried on a hot plate at 200 ° C for 3 minutes. The layer thickness is 65 nm (Tencor, Alphastep 500). Conductivity was determined by vapor deposition of a 2.5 cm length Ag electrode at a distance of 0.5 mm through a mask. The surface resistance measured by an electrometer was multiplied by the layer thickness to obtain a specific resistance. The specific resistance of the layer was 1,760 0 hm.cm. This layer is transparent. Solution 3: Storage at high temperature 50 g of the dispersion from Example 1 was stored at 50 ° C for 16 days. The sulfate content after storage is 7 ppm. Therefore, the sulphate concentration remains constant in terms of measurement accuracy. The resulting composite did not separate sulfate at a temperature of 50 °C. Comparative Example 1: Storage at a high temperature A conventional PEDOT:PSS dispersion (cievi〇s® p vp AI 4083, H_C. Starck Clevios Co., Ltd.) was used for reference experiments: solid content 1.6% Sulfate content 5 ppm pH 1. 5 50 g of this material was also stored at 50 ° C for 16 days. The sulfate content after storage was 22 ppm and therefore increased significantly. Example 3 shows that the dispersion of the present invention from Example 1 did not separate sulfate at room temperature compared to the known PEDOT:PSS complex.

Paste Example 4: Fabrication of OLED 29 201139506 An organic light-emitting diode (OLED) was constructed using the dispersion of the invention from Example. The procedure for manufacturing an OLED is as follows: 1. Prepare a ITO coated ITO. Cut the ITO-coated glass into a 5 〇mm x 5 〇 mm piece (substrate) and structure it into four parallel lines with a photolacquer. Each is 2 mm wide and 5 cm long. Subsequently, the substrate was cleaned in a sonic bath with a 〇3〇/〇 concentration of Mucasol solution, rinsed with distilled water and spin dried in a centrifuge. The IT coating was cleaned in a UV/ozone reactor (PR_1〇〇, UVP, Cambridge, GB) for 1 minute immediately before coating. 2. Coating the hole injection layer to filter about 5 ml of the dispersion of the invention (MiUip〇re HV ' 0.45 μη〇 from Example 1. Place the cleaned ιτο-coated substrate on a rotary painting machine and The filtered solution was distributed on the IT coated surface of the substrate, and then the excess solution was separated by rotating the plate at 600 rpm for 30 seconds, and then dried at 200 ° C on a hot plate in this manner. The substrate was 5 minutes. The layer thickness was measured by a surface meter (Tencor, Alphastep 500), and the layer thickness was about 50 nm. 3. The coated hole transport layer and the emitter tray were coated with the ITO substrate from the dispersion of Example 1. Transfer to a vapor deposition unit (Uni vex 350, Ley bold). Under a pressure of 1 〇·3 Pa, the first 60 nm NPB (N,N'-bis(naphthalen-1-yl)-N,N, - Bis(phenyl)benzidine) hole transport layer, followed by 50 nm A1Q3 (8-hydroxyquinoline) aluminum emitter layer for continuous vapor deposition at a vapor deposition rate of 1 in / sec. The gold-coated 1 cathode then transferred the layer system to a glove box with an N2 atmosphere and integrated vapor deposition unit 201139506 (Edwards), and vapor deposition Metal electrode. To this end, the substrate is placed on the mask. The layer system is downward. The mask contains a 2 mm wide rectangular groove oriented with the IT 〇 parent fork and perpendicular to the sash. · Under the pressure of 3 Pa, a 0.5 nm thick LiF layer and a 200 nm thick A1 layer were sequentially vapor deposited from two vapor deposition vessels. The vapor deposition rate was 1 in / s for LiF and 1 intrusion for A1. /8. The area of individual 〇LED is 4.0 mm2. 5. OLED characterization The two electrodes of the organic LED are connected (contacted) to the voltage source via electrical leads. The positive electrode is connected to the ιτο electrode and the negative electrode is connected to the metal electrode. Current and electroluminescence intensity (detected by photodiode (EG & G C3〇8〇9E)) plotted against voltage. Then a constant current of j = 3.84 mA is passed through the configuration and Monitoring the voltage and light intensity as a function of time to determine the lifetime. Selecting the parent's ear 2: The beginning of the event; knowing the scattered stock Mi Si La U VII jj The procedure is the same as in Example 5, except that in the second processing step The intermediate layer used is not the dispersion of the present invention from the embodiment (4), but is usually made Clevis® P VP AI 4〇83 (Hc Plus) is used as a standard for OLED construction. For this purpose, filter ai, spin coating at 700° for 30 seconds, then dry on a hot plate at .c. $min. The layer thickness is 5〇nm, and the specific resistance is 1,290 Ohm.Cm. The middle P曰1 (1)叩 procedure is the same as the example 4 and $, τ η 士 士 ju 夂 夂 5, the difference is completely The polymerization intermediate layer is omitted and processing step 2 is absent. 31 201139506

Example 5: Comparison of PLEDs from Example 4 and Comparative Examples 2 and 3 to demonstrate improvement of OLEDs comprising the dispersion of the present invention from Example 1 compared to the standard material Clevios® P VP AI 4083, in various cases The substrates from Example 4 and Comparative Examples 2 and 3 were processed in parallel, that is, the vapor deposited layer and the cathode were deposited on all of the substrates under the same conditions. The OLEDs manufactured according to Example 4 and Comparative 2 show the typical diode properties of the organic light-emitting diode. On the other hand, the structures manufactured according to Comparative Example 3 all showed an electrical short. In the life measurement, the voltage and brightness at the time t = 0, U0 and L0, the current efficiency in the form of the quotient L0/1, the time when the brightness drops to 50% of L0, the t and L0 at L0/2 The voltage at time t of /2. ITO//HIL//NPB//ALQ//LiF//Al OLED lifetime I = 96 mA/cm2 uo [V] L0 [cd/m3] Efficiency [cd/Al L0/2 under t 『hi U (t0 under L0/2) m OLED of Example 4 (according to the invention) 5.8 2,200 2.3 225 6.3 OLED 6.0 of Comparative Example 2 2,400 2.5 15 6.2 OLED of Comparative Example 3 may not be measured for life due to electrical short It has thus been demonstrated that the polymeric intermediate layer is necessary to avoid OLED short circuits. Compared with the standard material Clevios® P AI 4083, the dispersion of the present invention from Example 1 as an intermediate layer in the OLED has a significant advantage in that its lifetime is 10 times and the time-dependent voltage increase can be reduced. Example 6: Determining the contact angle using the dispersion of the present invention Similar to the second point of Example 4, a dispersion layer of the present invention from Example 32 201139506 was deposited on a glass substrate by means of a rotary paint coater and Dry on a hot plate for 5 minutes at 2 〇〇〇c. Next, the contact angle of one of the benzophenones deposited on the layer (Krtiss MicroDrop) with the layer was measured. The wetting is so good that the contact angle is less than 3. Therefore, the measurement is not available.

Ik. Comparative Example 4: Determination of Contact Angle Using Conventional Dispersions Similar to Example 6, the contact angle of the reference material cievios® P VP AI 4083 layer with toluene was determined. The wetting is so good that the contact angle is less than 30, so the amount is not measured. 1匕-敉Example 5: Determination of a contact preparation using a conventional dispersion based on a perfluorinated sulfonic acid polymer similar to Example 6 'determination of a reference material layer corresponding to EP 1 564 250 A1 (ie, perfluorinated sulfonate) Contact angle of a mixture of an acid polymer and a conductive polymer: a = 48 <. According to Example 6 and Comparative Examples 4 and 5, the wetting of the layer comprising the formulation of the invention with a toluene-based solution was as good as clevi〇s® p AI 4〇83, but on the other hand, it was significantly better than Corresponds to the reference material of Ep 1 564 250 A1. i Example 7: By PEDOT and s-ΡΕΚΚ唧, this product, 25 g of polyetherketoneketone (0xpekk® c, supplier: P〇iytron KUnstst0fftechnik GmbH, KG, Bergisch Giadbach, Germany) was added to 62.5 g 95% strength sulfuric acid in a mixture with 187 5 g fuming sulfuric acid (20% S〇3 content). The mixture was stirred under i 2 Torr for 3 hrs, then at 140 C for 15 hr. The cooled reaction mixture was then introduced into 1,800 ml of water and 5 ml of butanol was added to the resulting solution of 33 201139506. After separating the phases, the aqueous phase was extracted twice with 100 ml of butanol each time. The butanol phase was washed with water. The butanol phase was then combined, 2 mM ml of a 3% sodium hydroxide solution was added, followed by a 30% strength sodium hydroxide solution: the mixture was adjusted to a pH of 6.3. The aqueous phase was concentrated to 1 〇〇 ml and 25 〇 such as methanol was added. The sodium sulfate precipitated from the supernatant was decanted and evaporated. Dissolve the residue in 200 ml of water and use an ion exchanger (Lewam Mp® 62 and

Lewatit® M〇noplus S 100, supplier: Lanxess AG) treated the solution 3 times to remove the sulfate and sodium ions, followed by evaporation to dryness and drying the residue after 5 mbar. The yield was 17 g s-PEKK, and the degree of sulfonation of each repeating unit of the polymer was 0.97, equivalent to 389 g/mol equivalent, as determined by titration with a 〇N sodium hydroxide solution. 4. At 25 C 'in a 5 〇〇mi flask with a stirrer and a thermometer, 4.92 g of sulfonated polyetherketone ketone, 〇5 g of a 1% by weight aqueous solution of iron sulphate (ΠΙ) and 1.91 g of 3,4 • Ethyldioxythiophene (Clevi〇s® M v2, H c Starck Clevios, Germany) was thoroughly mixed in 248 g of water for 30 minutes and 4 minutes until a clear solution appeared. Subsequently, 〇·94 g of sodium persulfate was added and the mixture was stirred at 25 C for 24 hours. Then, 18 g of an anion exchanger (Lewatit MP® 62, Lanxess AG, Leverkusen, Germany) and 30 g of a cation exchanger (Lewatit® S 100 H, Lanxess AG, Leverkusen, Germany) were added. The mixture was stirred for 2 hours. The ion exchanger was then separated by filter paper and the dispersion was passed through a 0.45 μηη filter. A blue dispersion of the PEDOT:s-PEKK complex is obtained, and it is possible to manufacture a conductive layer therefrom by knife coating. Example 8: Organic solar thunder pool containing a formulation of the invention 34 201139506 An organic solar cell (OSC) was constructed using the formulation of the invention from Example 1. The procedure for manufacturing OSC is as follows. 1. Preparation of a substrate coated with ιτο The glass coated with enamel (Merck Balzers AG, FL, part number 253 674 XO) was cut into 25 mm x 25 mm sized sheets (substrates). The substrate was then cleaned with a 3% strength Mucasol solution in an ultrasonic bath for 15 minutes. The substrate was then rinsed with distilled water and spin dried in a centrifuge. The ITO surface was cleaned for 10 minutes in a UV/ozone reactor (PR-ioo, XJVP, Cambridge, GB) just prior to coating. 2. Coating the hole extraction layer (ΗΚΤΛ Filter about 1 ml of the formulation of the invention from Example 1 (Millipore HV, 0.45 μη〇. Place the cleaned ruthenium-coated substrate on a rotary painting machine and The filtered solution was distributed on the coated surface of the substrate, and then the excess solution was separated by rotating the plate at 500 rpm for 30 seconds, and then dried at 200 ° C on a hot plate. The substrate is 5 minutes. The layer thickness is about 50 nm (Tencor, Alphastep 500). 3. Coating the light absorbing layer (LAL) 50 mg of polymer P3HT (BASF, Sempiolid P 200) and 50 mg of Fule at room temperature The ene pCBm ( So-lenne [60] PCBM) is dissolved in 5 ml of di-benzene. To achieve complete dissolution of the material in the solution, the solution is stirred for about 1 hour using a stirring fish. (Millipore HV, 0.45 μηι) filtered solution, then distributed on a substrate on a rotary painting machine' and the excess solution was separated by rotating the plate at 750 rpm for 30 seconds. Then 'heated at l3〇t Drying on the board is applied in this way 35 201139506 cloth substrate Η) minutes. Layer thickness is l 〇〇nm (Tenc〇r 5(4). This operation and all the following operations were carried out in a glove box system under a pure P nitrogen atmosphere. 4. The cathode vapor-deposited the metal electrode as a cathode in a layered system ITO//HEL/ On the substrate of /LAL, a vacuum device equipped with two thermal vaporizers (5) medical ds) is used for this operation. The cover system is covered with a mask having a diameter of 2 5 _ and 5 faces: the substrate is placed in a rotating sample holding On the device, the installed mask is downward. The size of the sample holder allows four substrates to be accommodated at the same time. At P = 1〇·3 + τ ,

Under the pressure of Pa, 25nm thick CaJi»-hand waste and 8G nm thick "layers were vapor deposited from two thermal vaporizers. The vapor deposition rate was 1〇A/s for Ba(IV) and 2〇 for Ba(4). A/s. The area of the separated metal electrodes is 4.9 mm2 and 28 mm2, respectively. 5. The deuteration of P_SC is also characterized in the glove box system filled with nitrogen only, in which the bottom of the glove is inserted (4) The sun simulator (she s, (4) r Centest 575) and bows its monochromatic light upwards. The anchor with (10) is located in the light cone. The distance from the sample plane to the bottom is about 1 〇 coffee. The grating was attenuated by a light-emitting sheet. The intensity at the plane of the sample was measured with a pyranometer (Kipp & Z〇nen'CM10) and it was about 5 〇〇 w/m 2 . Measured with a thermal sensor (PT 丨 00) The temperature of the sample holder and its maximum is 40 ° C. By connecting the ITO electrode to the Au stylus (positive electrode) and pressing the flexible Au filament against one of the metal electrodes (negative electrode), the 〇sc is electrically contacted. 36 201139506 Cable to the current/voltage source (Keithley 2800) connects two contacts β first covers the light And measure the dark characteristic line. To this end, apply a voltage to the sample, change the voltage in the range of -2 to +2 V and record the current. Then, similarly, the current/voltage characteristic line is plotted under illumination. Parameters related to solar cells, such as conversion efficiency, open circuit voltage, short circuit current, and fill factor, are determined according to 〇n〇rM ΕΝ 60904-3. Example 9: OSC without HEL is similar to Example 8 construction without HEL The reference battery is different in that the processing step 2 "coating the hole extraction layer" is omitted. f Example 10: OSC with alternative HEL I_ping a Similar to Example 8 constructing a reference cell without HEL' is different in the processing step 2, using an alternative material, ie aevi〇s <g) p. 8408 (HC SUrck Clevios Co., Ltd., Leverkusen) replaces the formulation of the present invention. The conditions for processing m are: MU 遽 (MUiip〇re 1^, 0.45 / ^) about 1 „11^^1> 八14〇83 solution. The cleaned enamel-coated substrate is placed on the rotary painting machine. And the filtered solution is distributed on the coated surface of the substrate, and then the excess solution is separated by rotating the plate for 3 seconds under 75 Torr. Then, it is coated by drying on a hot plate under the boot. The substrate is 5 minutes. The layer thickness is about 5 〇 (3) (10),

Alphastep 500) ° f jfe Example 11: Comparative Example only 〇 ^ Under the same experimental conditions, the current/voltage characteristic lines from the OSC of Shen & A, 自 自 1-3 were plotted. In the results table, in the && & clothing, k take the parameters related to the evaluation; battery area (A), irradiance (P0), short circuit power Isc), open circuit voltage (Vm), 37 201139506 operating point Electrical output (Pmax), fill factor (FF), and conversion efficiency (r/). Result table: A/cm2 P0 /Wm·2 Λ Isc /mA/crn V〇c/V Pmax /mW/cm2 FF V Battery from Example 8 (present invention) 0.049 487 3.78 0.562 1.31 0.61 2.68 0.049 487 3.65 0.557 1.34 0.66 2.75 0.282 487 3.74 0.567 1.33 0.63 2.73 0.282 487 3.53 0.559 1.25 0.63 2.56 Battery from Example 9 (reference cell without HEL) 0.049 488 All batteries tested had a short circuit of 0.28 488 from the battery of Example 10 (refer to Clevios ® PAI4083) 0.049 4S7 4.62 0.532 1.47 0.6 3.02 0.049 487 4.54 0.531 1.47 0.61 3.02 0.282 487 4.48 0.54 1.28 0.53 2.62 0.282 487 4.44 0.538 1.25 0.53 2.57 According to the results table, the formulation of the invention is particularly suitable for use as an intermediate layer of OSC and improved Configure the resistance to the short circuit. A comparison with the reference Clevios® P AI4083 shows that similar OSC properties are achieved in principle, and the open circuit voltage and fill factor are improved. Another advantage of the formulations of the present invention over Clevios® P AI4083 is that the material has a higher thermal stability and, as expected, this results in a longer OSC life. [Simple diagram description] None [Main component symbol description] None 38

Claims (1)

201139506 VII. Patent application scope: 1. A composite comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, characterized in that the polyketone is contained in its repeating unit (-CO-) The polymer of the group and in this repeating unit the (-CO.) group is attached via two aromatic groups. 2. The composite according to claim 1, characterized in that the functionalized polyketone comprises a repeating unit of the formula (I) 0 _· [ Ί Ri-Arj-U-Arj-- L Jn wherein Ar, and Ai&quot ; 2 may be the same or different 'and an optionally substituted aromatic, Ri is an optionally substituted organic group having 1 to 80 carbon atoms, a (_c〇_) group or an oxygen atom and η is 5 to 5, an integer of 〇〇〇. 3. A composite according to claim 1 or 2, characterized in that the functionalized polyketone comprises a repeating unit of the formula (Π) 39 201139506 wherein Ar, and Ah may be the same or different and represent aromatic, 乂, and X2 may be the same or different and each represents a sulfonic acid, sulfonate, phosphonic acid, phosphonate 'carboxylic acid or carboxylate group The group, a and b may be the same or different and each independently represents an integer or non-integer 'non-integer in the range of 〇 to 2 means that the acid mentioned is not present in each repeating unit' Only in the corresponding portions of the repeating units, ~ has the same meaning as R1 in the second item of the patent application, and n is an integer from 5 to 5,000. 4. The composite according to any one of claims 1-3 to 3, characterized in that the functionalized polyketone comprises a repeating unit of the formula (Ila) Wherein a b and R 2 have the meanings given in item 3 of the scope of the patent application, and M represents a metal cation or ruthenium. 5. If the application of at least one of items 1 to 4 of the scope of the patent application is 40 so3m 201139506, characterized by the official I Formula (III) Formula (IV) p- so3m a Formula (V) or Formula (VI) -fU- so3M 201139506 wherein a, b, c and d may be the same Or an integer or non-integer 'non-integer, denoted in the range of 〇 to 2, means that the acid mentioned is not present in each repeating unit, but only in the corresponding part of the repeating unit, Μ represents a metal cation or ruthenium, and η is an integer from 5 to 5,000. 6_ The composite according to at least one of claims 1 to 5, characterized in that the conductive polymer comprises an optionally substituted polythiophene containing a repeating unit of the formula (VII) (VII) R·4 and Rs each independently represent Η 'optionally substituted c丨_cis alkyl or optionally substituted Cl-Cl8 alkoxy, and the heart together with & represents substitution as appropriate Crq alkyl, wherein - or a plurality of c atoms may be substituted by one or more of the same or different heteroatoms selected from 0 or S, preferably Ci_Cs dioxyalkylene, optionally substituted c-oxysulfide Heteroalkyl or 42 201139506 Heteroatom replacement. 7. A composite according to claim 6 which is characterized in that the polythiophene comprises a repeating unit of the formula (VII-a) and/or (VII-b) Wherein A represents an optionally substituted C!-C5 alkylene group, preferably a C2-C3 alkylene group which is optionally substituted, Y represents hydrazine or S, and Re represents a straight or branched chain, as the case may be substituted. Alkyl, preferably straight or branched, optionally substituted C,-CM alkyl; optionally substituted Cs-Cu cycloalkyl; optionally substituted c6-C14 aryl; Substituted C7-C1S aralkyl; optionally substituted c7-c18^ aryl; optionally substituted C, -C4 hydroxyalkyl or thiol, and y represents 0 to 8, preferably 0, 1 or 2, especially better 〇 or! An integer, and wherein in the case where several groups R_6 are bonded to A, such groups may be the same or different. 8. A composite according to claim 7, characterized in that the polyfluorene 43 201139506 is exemplified by poly(3,4-extended ethyldioxythiophene). 9. A composite according to at least one of claims 1 to 8, characterized in that the composite is dispersed or transferred to - or a plurality of dispersants. 10. The composite of claim 9, wherein the pH of the dispersion is in the range of 丨 to 8. -11. - A conductive polymer as defined in any one of claims 6 to 8 and a functionalized polyketone as defined in any one of claims 2 to 5 A method of preparing a composite, wherein the conductive polymer precursor is polymerized in the presence of the sulfonated polyketone. 12_ - A compound obtainable by the method of claim U of the patent application. 13. Use of a composite according to at least one of claims i to 1 and 12 for the manufacture of a transparent conductive coating. 14. Use of a composite according to any one of claims 1 to 1 and 12 for the manufacture of a hole injection layer or hole in an organic light-emitting diode or an organic solar cell Transport layer. 15. The use of a nucleating polyketone as defined in any one of claims 2 to 5, as defined in any one of claims 6 to 8 A composite of a conductive polymer is used as a polyanion. A coated substrate on which a coating comprising a composite according to at least one of the first to the first and fourth aspects of the patent application is applied. 1 7. A method of manufacturing a coated substrate, comprising the following processing steps: i) providing a substrate; 201139506 ii) comprising at least one of items 1 through 1 and 12 of the scope of the patent application The composition of the composite coats the substrate. 18_ A coated substrate obtainable by the method of the patent application 帛η帛. 19. An electronic component comprising a coated substrate as claimed in claim 3 or item 18. 20. The electronic component of claim 19, wherein the electronic implant is an organic light emitting diode or an organic solar cell. , eight, schema: no 45