JP2013522401A - Sulfonated polyketones as counterions for conducting polymers. - Google Patents

Abstract

The present invention is a complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, wherein the polyketone is a polymer comprising (—CO—) groups in repeating units. This (—CO—) group relates to a complex, characterized in that it is bound to two aromatic groups. The present invention relates to a process for the preparation of a complex, the complex obtainable by this process, the use of this complex, the use of a sulfonated polyketone, a coated substrate, a process for the production of a coated substrate, this process It also relates to coated substrates and electronic components that can be obtained by:
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Description

  The present invention relates to a novel polyelectrolyte complex comprising a functionalized polyketone and a conducting polymer, a process for the preparation of the complex, a complex obtainable by this process, the use of this complex, the use of a sulfonated polyketone, a coated Relates to a process for the manufacture of coated substrates, coated substrates, coated substrates obtainable by this process, and electronic components.

  Conductive polymers are becoming increasingly economically important because polymers have advantages over metals in that they can be tailored to properties through processability, weight, and chemical modification. Examples of known π-conjugated polymers are polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene and poly (p-phenylene vinylene). Conductive polymer layers are widely used in industry, for example, as a polymer counter electrode in capacitors or for through-plating of electronic circuit boards. Conductive polymers are made by chemical or electrochemical oxidation from monomeric precursors such as optionally substituted thiophene, pyrrole and aniline, and certain optional oligomeric derivatives thereof. Polymerization by chemical oxidation is particularly widespread because polymerization by chemical oxidation can be carried out in an industrially simple manner in a liquid medium or on a wide range of substrates.

  A particularly important and industrially used polythiophene is, for example, poly (ethylene-3,4-dioxythiophene) (PEDOT or PEDT) described in Patent Document 1, which is ethylene-3,4. -Manufactured by chemical polymerization of dioxythiophene (EDOT or EDT) and exhibits very high conductivity in its oxidized form. A review of a number of poly (alkylene-3,4-dioxythiophene) derivatives, particularly poly (ethylene-3,4-dioxythiophene) derivatives, their monomeric units, synthesis and use is given by Non-Patent Document 1. ing.

  For example, a dispersion of PEDOT having a polyanion such as polystyrene sulfonic acid (PSS) disclosed in Patent Document 2 is particularly industrially important. Transparent conductive membranes can be made from these dispersions; such membranes are positive for organic light emitting diodes (OLEDS), for example as antistatic coatings or as disclosed in US Pat. As a hole injection layer, it has found many uses.

  In this regard, the polymerization of EDOT is carried out in an aqueous solution of a polyanion to form a polyelectrolyte complex. Cationic polythiophenes containing polymeric anions as counterions for charge compensation are often referred to in the art as polythiophene / polyanion complexes. Due to the polyelectrolyte nature of PEDOT as polycation and PSS as polyanion, this complex is not a pure solution in this respect, but rather a dispersion. The extent to which the polymer or part of the polymer dissolves or disperses in this case depends on the weight ratio of polycation and polyanion, the charge density of the polymer, the salt concentration of the environment and the nature of the surrounding medium (Non-Patent Document 2). ). This transition can be fluid in this respect. Therefore, in the present specification, there will be no distinction between the terms “dispersed” and “dissolved” hereinafter. There is little difference between “dispersion” and “solution” or “dispersant” and “solvent”. On the contrary, these terms will be used hereinafter as synonyms.

  As noted above, PEDOT and PSS complexes have found a wide range of uses. Nevertheless, these complexes are characterized by their inherently high acidity. This is due to the high acidity of PSS. The equivalent weight of PSS is 184 g / mol. The pH of the PEDOT: PSS dispersion is correspondingly low. Thus, a typical PEDOT: PSS dispersion used as a hole injection layer in an OLED has a pH of 1.5. This low pH can lead to the etching of transparent electrodes made of indium tin oxide (ITO), for example in OLEDs. As a result, In and Sn ions become mobile and can diffuse into adjacent layers (Non-Patent Document 3), and thus can adversely affect the lifetime of the OLED.

  Non-Patent Document 4 and Non-Patent Document 5 report that PSS is thermally decomposed, thereby liberating sulfate, that is, PSS is not stable. For example, this sulfate can adversely affect the lifetime of the OLED.

  In US Pat. Nos. 6,099,069 and 5,099, Elschner et al. Describe a mixture of a perfluorinated sulfonic acid polymer and a conductive polymer as a hole injection layer in an OLED. When using these mixtures to produce hole injection layers in OLEDs, it was possible to demonstrate that the presence of this fluorinated polymer leads to an improvement in OLED lifetime. However, the presence of a layer comprising a fluorinated polymer is characterized by a high contact angle. This prevents the deposition of further solvent-based layers. This is because a large contact angle makes it difficult to form a film.

European Patent Application No. 0 339 340 (A2) Specification European Patent Application No. 0 440 957 (A2) Specification European Patent Application Publication No. 1 227 529 (A2) European Patent Application Publication No. 1 564 250 (A1) Specification International Publication No. 2004/032306 (A2) Pamphlet

L. Groendaal, F.M. Jonas, D.C. Freitag, H.C. Pieartzik and J.M. R. Reynolds, Adv. Mater. 2000, Vol. 12, pp. 481-494. V. Kabanov, Russian Chemical Reviews, 2005, 74, 3-20 M.M. P. de Jong et al., Appl. Phys. Lett. 2000, 77, 2255-2257. Si-Jeon Kim et al., Chem. Phys. Lett. 2004, 386, 2-7. Jaengwan Chung et al., Organic Electronics, 2009, Vol. 9, pages 869-872.

  Thus, there was a need for novel complexes containing conductive polymers and polyanions. In particular, there was a need for complexes in which the polyanion is characterized by low acidity and improved stability compared to PSS. Furthermore, there was a need for complexes suitable for producing hole injection layers for OLEDs where the hole injection layer is characterized by a low contact angle and the OLED is characterized by a long lifetime.

  In the present invention, surprisingly, complexes of conducting polymers and functionalized polyketones are suitable as polyanions for producing transparent conducting membranes, and these complexes are characterized by high stability. It was found. Furthermore, such conductive films are suitable as a hole injection layer in OLEDs, and it is found that the lifetime of such OLEDs is particularly long when the pH of the dispersion is increased by adding a base. It was issued.

  Thus, the present invention is a complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, wherein the polyketone has at least one (—CO in its repeat unit. A polymer comprising a-) group (keto group), and in these repeating units, the (-CO-) group is bonded to two aromatic groups.

（式中、
Ａｒ_１およびＡｒ_２は、同じであってもよいし異なっていてもよく、かつ芳香族の任意に置換されたラジカルであり、
Ｒ_１は、１〜８０個の炭素原子を有する任意に置換された有機ラジカル、（−ＣＯ−）基または酸素原子であり、
ｎは、５〜５，０００、好ましくは１０〜３，０００、特に好ましくは２０〜２，０００の整数である）
を含む。 In a preferred embodiment of the complex according to the invention, the functionalized polyketone is a repeating unit of the general formula (I)

(Where
Ar ₁ and Ar ₂ may be the same or different and are aromatic optionally substituted radicals;
R ₁ is an optionally substituted organic radical having ₁ to 80 carbon atoms, a (—CO—) group or an oxygen atom,
n is an integer of 5 to 5,000, preferably 10 to 3,000, particularly preferably 20 to 2,000)
including.

  In the context of the present invention, the aromatic is a cyclic conjugated system, preferably benzene, naphthalene, anthracene and biphenyl, particularly preferably benzene, and the above compounds may be optionally substituted.

  Furthermore, in the context of the present invention, organic radicals having 1 to 80 carbon atoms are preferably, for example, ethers, ketones, sulfones, sulfides, esters, carbonates, amides, imides and aromatic groups—especially phenylene, biphenylene. And naphthalene- and a radical composed of one or more groups selected from the group consisting of aliphatic groups, in particular methylene, ethylene, propylene and isopropylidene, each group may repeatedly appear in the radical . These aromatic groups and aliphatic groups may be further substituted.

Unless expressly stated otherwise, in this and the rest of this application, “substituted” is an alkyl group, preferably a C ₁ -C ₂₀ -alkyl group, still more preferably methyl. group or an ethyl group, a cycloalkyl group, preferably a _C 3 _{-C 12} - cycloalkyl group, an aryl group, preferably a _C 6 _{-C 14} - aryl group, a halogen atom, preferably Cl, Br or I, an ether group, a thioether Group, disulfide group, sulfoxide group, sulfone group, sulfonate group, amino group, aldehyde group, keto group, carboxylic acid ester group, carboxylic acid group, carbonate group, carboxylate group, phosphonic acid group, phosphonate group, cyano group, alkyl Selected from the series consisting of silane group, alkoxysilane group and carboxylamide group It refers to the replacement by.

The term “C ₁ -C ₂₀ -alkyl” refers to a linear or branched C ₁ -C ₂₀ -alkyl radical, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- Or tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl N-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n -Represents octadecyl, n-nonadecyl, n-eicosyl and the like. The term “C ₃ -C ₁₂ -cycloalkyl” refers to a cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, and the term “C ₆ -C ₁₄ -aryl”. “Represents a C ₆ -C ₁₄ -aryl radical, for example phenyl or naphthyl.

  The functionalized polyketone contained in the complex according to the invention is preferably 5,000 to 500,000 g / mol, particularly preferably 10,000 to 100,000 g / mol, even more preferably 20,000 to 50,000 g / mol. It is characterized by a molecular weight (Mw) in mol. These functionalized polyketones have been disclosed in substantially known processes (S. Swier, Y. S. Chun, J. Gasa, M. T. Shaw and R. A. Weiss, Polym. Engin. Sci., 2005, 1081-1109; S. Vetter, B. Ruffmann, I. Buder and SP Nunes, J. Membrane Sci., 2005, 260, 181-186; L. Li, J. Zhang and Y. Wang, J. Membrane Sci., 2003, 226, 159-167; B. Bauer, DJ Jones, J. Roziere, L. Tchicaya, G. Alberti, M. Cassiola, L. Massinelli. A. Peraio, S. Besse and E. Ramni, J. New Mater. Electrochem. Systems, 2000, 3, 93-98; F. Trotta, E. Drioli, G. Moraglio and EB Poma, J. Appl. Poly. Sci. 1998, 70, 477-482; SMJ Zaidi, SD Mikhailenko, GP Robertson, MD Guiber and S. Kagliaguine, J. Membrane Sci., 2000. 173, 17-34; C. Baily, DJ Williams, FE Kharasz and WJ MacKnight, Polymer, 1987, 28, 1009-1016; X. Jin MT Bisho p, T.S. Ellis and FE Kharasz, Br. Polymer J., 1985, 17, No. 1, pages 4-10).

（式中、
Ａｒ_１およびＡｒ_２は、同じであってもよいし異なっていてもよく、かつ任意に置換された芳香族を表し、
Ｘ_１およびＸ_２は、同じであってもよいし異なっていてもよく、かつ各々、スルホン酸、スルホネート、ホスホン酸、ホスホネート、カルボン酸またはカルボキシレート基を表し、
ａおよびｂは、同じであってもよいし異なっていてもよく、かつ各々、互いに独立に、０〜２の範囲の整数または非整数を表し、非整数は、上記の酸が繰り返し単位ごとに現れるわけではなく、対応する割合の繰り返し単位の中でのみ現れるということを意味し、
Ｒ_２はＲ_１と同じ意味を有し、
ｎは、５〜５，０００、好ましくは１０〜３，０００、特に好ましくは２０〜２，０００の整数である）
を含む。 In a preferred embodiment of the complex according to the invention, the functionalized polyketone is a repeating unit of the general formula (II)

(Where
Ar ₁ and Ar ₂ may be the same or different and represent an optionally substituted aromatic,
X ₁ and X ₂ may be the same or different and each represents a sulfonic acid, sulfonate, phosphonic acid, phosphonate, carboxylic acid or carboxylate group,
a and b may be the same or different, and each independently represents an integer or non-integer in the range of 0 to 2, wherein the non-integer represents the above acid for each repeating unit. Means that it only appears in the corresponding proportion of repeat units,
R ₂ has the same meaning as R ₁ ,
n is an integer of 5 to 5,000, preferably 10 to 3,000, particularly preferably 20 to 2,000)
including.

Functionalization of the polyketone containing the repeating unit of formula (II) can appear in all or only some of the corresponding repeating units, ie non-integers for a and b are This means that the group X ₁ or X ₂ does not appear for each repeating unit, but only in the corresponding proportion of repeating units (the same applies hereinafter).

Still particularly preferably, the functionalized polyketone is a sulfonated polyketone (X ₁ and X ₂ = sulfonic acid or sulfonate group), the preparation of which, for example, Schuster et al. (Macromolecules, 2009, Vol. 42, No. 8). 3129-3137).

（式中、
ａ、ｂおよびＲ_２は、一般式（ＩＩ）について与えられた意味を有し、
Ｍは、金属カチオンまたはＨ、好ましくはＮａ、Ｋ、ＬｉまたはＨ、特に好ましくはＨを表す）
を含む。 In a still particularly preferred embodiment of the complex according to the invention, the functionalized polyketone is a repeating unit of the general formula (IIa) in which the aromatic Ar ₁ and Ar ₂ both represent a benzene ring:

(Where
a, b and R ₂ have the meaning given for general formula (II);
M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H)
including.

One or both of the benzene rings in the repeating units of formulas (II) and (IIa) may optionally be mono- or polysubstituted by substituents different from the SO ₃ M group, Methyl or ethyl groups can be present as substituents (not shown in formulas (II) and (IIa)).

（式中、
ｃは、ａおよびｂと同じ意味を有し、
ａおよびｂは、一般式（ＩＩ）について与えられた意味を有し、
Ｍは、金属カチオンまたはＨ、好ましくはＮａ、Ｋ、ＬｉまたはＨ、特に好ましくはＨを表す）
を含む。 In an even more particularly preferred embodiment of the complex according to the invention, the functionalized polyketone comprises three benzene rings in which the repeating units are bridged via a keto group and two ether groups, each benzene ring being Repeating unit of general formula (III) which can have a sulfonic acid group:

(Where
c has the same meaning as a and b;
a and b have the meaning given for general formula (II);
M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H)
including.

  In the context of the present invention, the sulfonated polyketone according to general formula (III) is also called sulfonated polyetheretherketone (s-PEEK).

Again, one or two or all three of the benzene rings in the repeating unit of formula (III) are optionally mono- or polysubstituted by substituents different from the SO ₃ M group. In particular, a methyl or ethyl group can be present as a substituent (not shown in formula (III)).

（式中、
ｄは、ａ、ｂおよびｃと同じ意味を有し、
ａ、ｂ、ｃおよびＭは、一般式（ＩＩ）または（ＩＩＩ）について与えられた意味を有する）
を含む。 In an even more particularly preferred embodiment of the complex according to the invention, the functionalized polyketone comprises four benzene rings whose repeating units are bridged by a keto group and three ether groups, each benzene ring being a sulfonic acid Repeating units of the general formula (IV) that can have groups:

(Where
d has the same meaning as a, b and c;
a, b, c and M have the meanings given for general formula (II) or (III))
including.

Again, one or two, three or all four of the benzene rings in the repeating unit of formula (IV) are optionally mono- or polysubstituted by substituents different from the SO ₃ M group. In particular, it is possible for a methyl or ethyl group to be present as a substituent (not shown in formula (IV)).

（式中、
ａおよびｂは、一般式（ＩＩ）について与えられた意味を有し、
Ｍは、金属カチオンまたはＨ、好ましくはＮａ、Ｋ、ＬｉまたはＨ、特に好ましくはＨを表す）
を含む。 In a still further particularly preferred embodiment of the complex according to the invention, the functionalized polyketone comprises two benzene rings whose repeating units are bridged by a keto group and an ether group, each benzene ring being a sulfonic acid Repeating units of the general formula (V) that can have groups:

(Where
a and b have the meaning given for general formula (II);
M represents a metal cation or H, preferably Na, K, Li or H, particularly preferably H)
including.

  In the context of the present invention, the sulfonated polyketone according to general formula (V) is also referred to as sulfonated polyetherketone (s-PEK).

One or both of the benzene rings in the repeating unit of formula (V) may optionally be mono- or polysubstituted by a substituent different from the SO ₃ M group, in particular a methyl or ethyl group Can be present as a substituent (not shown in formula (V)).

（式中、ａ、ｂ、ｃおよびＭは一般式（ＩＩ）または（ＩＩＩ）について与えられた意味を有する）
を含む。 In an even more particularly preferred embodiment of the complex according to the invention, the functionalized polyketone is a repeating unit of the general formula (VI), the repeating unit comprising three benzene rings, One may be bridged by two adjacent carbonyl substituents in the meta or para position corresponding to the repeat unit shown in formula (VI), and each benzene ring may have a sulfonic acid group. Possible repeating units of the general formula (VI):

Wherein a, b, c and M have the meanings given for general formula (II) or (III)
including.

  In the context of the present invention, the sulfonated polyketone according to general formula (VI) is also referred to as sulfonated polyetherketoneketone (s-PEKK).

Again, one or two or all three benzene rings in the repeating unit of formula (VI) may optionally be mono- or polysubstituted with a substituent different from the SO ₃ M group. In particular, a methyl or ethyl group can be present as a substituent (not shown in formula (VI)).

  In the context of the present invention, functionalized polyketones are also understood to mean mixtures or copolycondensates of the above functionalized polyketones.

  In addition to the above functionalized polyketones present as polyanions, the complexes according to the invention comprise at least one optionally substituted conductive polymer as polycation. Such conductive polymers are, for example, optionally substituted polyaniline, optionally substituted polypyrrole and optionally substituted polythiophene.

（式中、
Ｒ_４およびＲ_５は、各々互いに独立に、Ｈ、任意に置換されたＣ_１−Ｃ_１８−アルキルラジカルまたは任意に置換されたＣ_１−Ｃ_１８−アルコキシラジカルを表すか、Ｒ_４およびＲ_５は、一緒に、任意に置換されたＣ_１−Ｃ_８−アルキレンラジカル（この基において、１以上のＣ原子が１以上の同一のもしくは異なる、ＯもしくはＳから選ばれるヘテロ原子によって置き換えられてもよい）、好ましくはＣ_１−Ｃ_８−ジオキシアルキレンラジカル、任意に置換されたＣ_１−Ｃ_８−オキシチアアルキレンラジカルまたは任意に置換されたＣ_１−Ｃ_８−ジチアアルキレンラジカルを表すか、または任意に置換されたＣ_１−Ｃ_８−アルキリデンラジカル（この基において、任意に、少なくとも１つのＣ原子はＯまたはＳから選ばれるヘテロ原子によって置き換えられる）を表す）
である。 In a preferred embodiment of the complex according to the invention, the conducting polymer is an optionally substituted polythiophene comprising repeating units of the general formula (VII)

(Where
R ₄ and R ₅ each independently of one another represent H, an optionally substituted C ₁ -C ₁₈ -alkyl radical or an optionally substituted C ₁ -C ₁₈ -alkoxy radical, or R ₄ and R ₅ Together are optionally substituted C ₁ -C ₈ -alkylene radicals in which one or more C atoms may be replaced by one or more heteroatoms selected from the same or different O or S. Preferred), preferably represents a C ₁ -C ₈ -dioxyalkylene radical, an optionally substituted C ₁ -C ₈ -oxythiaalkylene radical or an optionally substituted C ₁ -C ₈ -dithiaalkylene radical or an optionally substituted C ₁ -C 8, _- the alkylidene radicals (this group, optionally, at least one C atom from O or S Represents barrel is replaced by a heteroatom))
It is.

（式中、
Ａは、任意に置換されたＣ_１−Ｃ_５−アルキレンラジカル、好ましくは任意に置換されたＣ_２−Ｃ_３−アルキレンラジカルを表し、
Ｙは、ＯまたはＳを表し、
Ｒ_６は、直鎖状もしくは分枝状の、任意に置換されたＣ_１−Ｃ_１８−アルキルラジカル、好ましくは直鎖状もしくは分枝状の、任意に置換されたＣ_１−Ｃ_１４−アルキルラジカル、任意に置換されたＣ_５−Ｃ_１２−シクロアルキルラジカル、任意に置換されたＣ_６−Ｃ_１４−アリールラジカル、任意に置換されたＣ_７−Ｃ_１８−アラルキルラジカル、任意に置換されたＣ_７−Ｃ_１８−アルカリールラジカル、任意に置換されたＣ_１−Ｃ_４−ヒドロキシアルキルラジカルまたはヒドロキシルラジカルを表し、
ｙは、０〜８、好ましくは０、１または２、特に好ましくは０または１の整数を表し、
いくつかのラジカルＲ_６がＡに結合されている場合、これらは同じであってもよいし異なっていてもよい）
である。 Particularly preferably, these are polythiophenes comprising repeating units of the general formula (VII-a) and / or (VII-b)

(Where
A represents an optionally substituted C ₁ -C ₅ -alkylene radical, preferably an optionally substituted C ₂ -C ₃ -alkylene radical;
Y represents O or S;
R ₆ is a linear or branched, optionally substituted C ₁ -C ₁₈ -alkyl radical, preferably a linear or branched, optionally substituted C ₁ -C ₁₄ -alkyl. substituted aralkyl radical, optionally - radical, optionally substituted _C 5 _{-C 12} - cycloalkyl radical, optionally _{-C 14 C} 6 substituted - aryl radicals, _C 7 _{-C 18} optionally substituted Represents a C ₇ -C ₁₈ -alkaryl radical, an optionally substituted C ₁ -C ₄ -hydroxyalkyl radical or a hydroxyl radical;
y represents an integer of 0 to 8, preferably 0, 1 or 2, particularly preferably 0 or 1;
When several radicals R ₆ are attached to A, these may be the same or different)
It is.

The general formula (VII-a) should be understood as meaning that the substituent R ₆ may be bonded to the alkylene radical A y times.

式中、Ｒ_６およびｙは上記の意味を有する。 In a still further particularly preferred embodiment of the complex according to the invention, the polythiophene comprising a repeating unit of the general formula (VII) contains a repeating unit of the general formula (VII-aa) and / or the general formula (VII-ab) Polythiophene is:

In which R ₆ and y have the meanings given above.

In an even more highly preferred embodiment of the complex according to the invention, the polythiophene comprising a repeating unit of the general formula (VII) contains a repeating unit of the general formula (VII-aaa) and / or the general formula (VII-aba) Polythiophene.

  In the context of the present invention, the prefix “poly” should be understood to mean that the polythiophene comprises a plurality of identical or different repeating units. The polythiophene comprises a total of n repeating units of general formula (VII), where n can be an integer from 2 to 2,000, preferably from 2 to 100. All of the repeating units of the general formula (VII) may be the same or different in one polythiophene. In any case, polythiophene containing the same repeating unit of the general formula (VII) is preferable.

  The polythiophene preferably has H at each of the end groups.

  In a particularly preferred embodiment, the polythiophene having a repeating unit of the general formula (VII) is poly (3,4-ethylenedioxythiophene), poly (3,4-ethyleneoxythiathiophene) or poly (thieno [3,4] -B] thiophene), i.e. a homopolythiophene of the repeating unit of formula (VII-aaa), (VII-aba) or (VII-b) wherein Y = S.

  In a further particularly preferred embodiment of the complex according to the invention, the polythiophene having a repeating unit of the general formula (VII) has the formulas (VII-aaa) and (VII-aba), (VII-aaa) and (VII-b) , (VII-aba) and (VII-b), or a copolymer of repeating units of (VII-aaa), (VII-aba) and (VII-b), of formulas (VII-aaa) and (VII -Aba) and copolymers of repeating units of (VII-aaa) and (VII-b) are preferred.

In the context of the present invention, the C ₁ -C ₅ -alkylene radical A is preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene, and the C ₁ -C ₈ -alkylene radical is n- Hexylene, n-heptylene and n-octylene. In the context of the present invention, a C ₁ -C ₈ -alkylidene radical is preferably a C ₁ -C ₈ -alkylene radical as defined above containing at least one double bond. For the present _invention, C 1 -C ₈ - dioxyalkylene _radicals, C 1 -C ₈ - oxy thiaalkylene radicals and _C 1 -C ₈ - di thiaalkylene radical, preferably above _C 1 -C ₈ - It represents a C ₁ -C ₈ -dioxyalkylene radical, a C ₁ -C ₈ -oxythiaalkylene radical and a C ₁ -C ₈ -dithiaalkylene radical corresponding to the alkylene radical. C ₁ -C ₁₈ -alkyl, C ₁ -C ₁₄ -alkyl and C ₅ -C ₁₂ -cycloalkyl are described in relation to the substituents of the groups Ar ₁ , Ar ₂ and R ₁ in formula (I) Represents the corresponding selection from C ₁ -C ₂₀ -alkyl and C ₃ -C ₁₂ -cycloalkyl radicals. In the context of the present invention, a C ₁ -C ₁₈ -alkoxy radical represents an alkoxy radical corresponding to the above C ₁ -C ₁₈ -alkyl radical, and C ₆ -C ₁₄ -aryl is a group in formula (I) Has the meaning given in relation to the substituents Ar ₁ , Ar ₂ and R ₁ . Furthermore, in the context of the present invention, C ₇ -C ₁₈ -aralkyl is preferably a C ₇ -C ₁₈ -aralkyl radical (eg benzyl etc.) or an alkylbenzyl radical (o-, m-, p-methylbenzyl). And C ₇ -C ₁₈ -aralkyl is o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3 , 5-xylyl or mesityl, and in the context of the present invention C ₁ -C ₄ -hydroxyalkyl is preferably understood to mean a C ₁ -C ₄ -alkyl radical containing a hydroxyl group as a substituent, _{A 1} -C ₄ -alkyl radical can represent, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl. The above list serves to illustrate the invention by way of example, but should not be considered exclusive.

The optionally substituted polythiophene is cationic and “cationic” relates only to the charge present on the polythiophene backbone. Depending on the substituents on the radicals R ₄ and R ₅ , the polythiophene can have a positive and negative charge in its structural unit, this positive charge being present on the polythiophene main chain and the negative charge being Optionally present on a radical R substituted by a sulfonate or carboxylate group. In this case, the positive charge of the polythiophene main chain may be partially or completely saturated by an anionic group on the radical R which is present optionally. Overall, the polythiophene may be cationic, neutral or even anionic in these cases. Nevertheless, in the context of the present invention, they are all considered to be cationic polythiophenes. This is because the positive charge on the polythiophene main chain is very important. This positive charge is not shown in the above equation. Because they are delocalized by resonance. However, the number of positive charges is at least 1 and at most n (n is the total number of all (same or different) repeat units in the polythiophene).

In order to balance this positive charge, this cationic charge, unless it is already balanced with this positive charge by radicals R ₄ or R ₅ optionally substituted with sulfonate or carboxylate and thus negatively charged Polythiophenes require anions as counterions, and in the context of the present invention, this role is at least partially played by functionalized polyketones.

  According to a more specific embodiment of the complex according to the invention, the polythiophene having a repeating unit of the general formula (VII) is poly (3,4-ethylenedioxythiophene), poly (3,4-ethyleneoxythiathiophene) ) Or poly (thieno [3,4-b] thiophene), particularly preferably poly (3,4-ethylenedioxythiophene), the polyketone being a sulfonated polyketone having a repeating unit of the formula (II), Particularly preferably, a sulfonated polyether ether ketone having a repeating unit of the formula (III), a sulfonated polyketone having a repeating unit according to the formula (IV), a sulfonated polyether ketone having a repeating unit of the formula (V), or a formula It is a sulfonated polyether ketone ketone having a repeating unit of (VI).

  According to the invention, it is further preferred that the complex according to the invention as described above is dissolved or dispersed in one or more solvents or dispersants and therefore exists in the form of a solution or dispersion.

  The solids content of the conductive polymer in the dispersion or solution, especially the optionally substituted polythiophene containing repeating units of general formula (VII), is preferably based on the total weight of the solution or dispersion. Is 0.05 to 20.0 weight percent (% by weight), particularly preferably 0.1 to 5.0% by weight, and most preferably 0.3 to 4.0% by weight.

  Solvents and dispersants that may be mentioned are, for example, the following liquids: aliphatic alcohols such as methanol, ethanol, i-propanol and butanol; aliphatic ketones such as acetone and methyl ethyl ketone; fats such as ethyl acetate and butyl acetate Aromatic carboxylic acid esters; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane; aliphatic nitriles such as acetonitrile Aliphatic sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; aliphatic carboxylic acid amides such as methylacetamide, dimethylacetamide, dimethylformamide or N-methylpyrrolidone; and Aliphatic ethers and aromatic aliphatic ethers such as ethyl ether and anisole. Furthermore, water or a mixture of water and the above organic solvent can also be used as a solvent or a dispersant.

  Preferred solvents or dispersants are water or other protic solvents such as alcohols (such as methanol, ethanol, i-propanol and butanol), and mixtures of water and these alcohols, where water is the solvent or dispersant. Is particularly preferred.

  The total content of the complex according to the invention in the solution or in the dispersion, i.e. the conductive polymer, in particular an optionally substituted polythiophene comprising a repeating unit of the general formula (VII), and the functionalized polyketone, For example, all are 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the solution or dispersion.

  This solution or dispersion comprises a conductive polymer, in particular an optionally substituted polythiophene comprising a repeating unit of general formula (VII) above, and the functionalized polyketone in the range of 1: 0.3 to 1: 100, preferably Can be included in a weight ratio in the range of 1: 1 to 1:40, particularly preferably in the range of 1: 2 to 1:20, very preferably in the range of 1: 2 to 1:15. As used herein, the weight of the conductive polymer roughly corresponds to the weight of the monomer used, assuming complete conversion occurs during polymerization.

  The above dispersion or dispersion is first prepared from a corresponding precursor for the preparation of the conductive polymer, from a solution or dispersion of the electrically conductive polymer, for example EP 0 440 957 (A). Similar to the conditions mentioned in the specification, it is produced by preparing in the presence of a counter ion, preferably in the presence of the functionalized polyketone. An improved variant for the preparation of this solution or dispersion is the use of an ion exchanger to remove the inorganic salt content or part thereof. Such a variant is described, for example, in German Offenlegungsschrift 196 27 071 (A). The ion exchanger can be stirred with the product, for example, or the product is conveyed through a column packed with ion exchangers. The use of ion exchangers makes it possible, for example, to achieve a low metal content.

  The size of the particles in the dispersion can be reduced after desalting using, for example, a high-pressure homogenizer. This operation may be repeated to enhance the effect. In order to greatly reduce the particle size, it has been found that a particularly high pressure between 100 and 2,000 bar is particularly advantageous in this case. Alternatively, the particle size can be reduced by sonication.

  Processes for the preparation of monomeric precursors and their derivatives for the preparation of polythiophenes comprising recurring units of the general formula (VII) are known to the person skilled in the art, see for example L. Groendaal, F.M. Jonas, D.C. Freitag, H.C. Pieartzik and J.M. R. Reynolds, Adv. Mater. 2000, Vol. 12, pp. 481-494 and the references cited therein. Mixtures of various precursors can also be used.

  In the context of the present invention, the above thiophene derivatives are understood to mean, for example, dimers or trimers of these thiophenes. Higher molecular weight derivatives of this monomeric precursor, ie, tetramers, pentamers, etc. are also possible as derivatives. This derivative may be constructed either from the same monomer unit or from different monomer units, may be used in pure form, and mixed with each other and / or thiophene as described herein above May be. In the context of the present invention, the oxidized or reduced forms of these thiophenes and thiophene derivatives are also encompassed by the terms “thiophene” and “thiophene derivative”, provided that the polymerization is thiophene as described above. And to give the same conducting polymer as in thiophene derivatives.

（式中、Ａ、Ｒ_６およびｙは、式（ＶＩＩ−ａ）に関連して与えられる意味を有し、いくつかのラジカルＲがＡに結合されている場合、これらは同じであってもよいし異なっていてもよい）
によって表すことができる任意に置換された３，４−アルキレンジオキシチオフェンである。 Particularly suitable monomeric precursors for the preparation of optionally substituted polythiophenes comprising repeating units of the general formula (VII) include, by way of example, the general formula (VIII)

Wherein A, R ₆ and y have the meaning given in connection with formula (VII-a), and if several radicals R are attached to A, they may be the same Good or different)
Is an optionally substituted 3,4-alkylenedioxythiophene that can be represented by:

  A particularly preferred monomeric precursor is optionally substituted 3,4-ethylenedioxythiophene, and in a preferred embodiment is unsubstituted 3,4-ethylenedioxythiophene.

  In addition to the conducting polymer and functionalized polyketone complex, the solution or dispersion can be further polymerized, for example polystyrene sulfonic acid, fluorinated sulfonic acid or perfluorinated sulfonic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, polyacetic acid. Vinyl, polyvinyl butyrate, polyacrylic acid ester, polyacrylic acid amide, polymethacrylic acid ester, polymethacrylic acid amide, polyacrylonitrile, styrene / acrylic acid ester, vinyl acetate / acrylic acid ester and ethylene / vinyl acetate copolymer, Polyether, polyester, polyurethane, polyamide, polyimide, non-functionalized polyketone, polysulfone, melamine-formaldehyde resin, epoxy resin, silicone resin or cellulose derivative Mukoto can.

  The solution or dispersion further comprises a surface-active substance, such as an ionic surfactant and a nonionic surfactant, or, for example, an organofunctional silane or a hydrolysis product thereof, such as 3-glycidoxypropyltrialkoxy. It may contain further components such as silane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, adhesion promoters such as vinyltrimethoxysilane or octyltriethoxysilane it can.

  In the context of the present invention, the solution or dispersion can further have a pH in the range 1-8, preferably in the range 2-7, particularly preferably in the range 4-7. For example, a base such as amine, ammonium hydroxide or metal hydroxide, preferably ammonia or alkali metal hydroxide, can be added to the dispersion to adjust the corresponding pH. In the present invention, pH is measured at 25 ° C. using a pH electrode (Knick Labor pH-meter 766).

  Accordingly, the present invention relates to electrically conductive polymers, preferably from electrically conductive polythiophenes comprising repeating units of the general formula (VII), and functionalized, preferably sulfonated polyketones, particularly preferably the structure (III) A process for the preparation of a complex from a sulfonated polyketone having a repeating unit of (IV), (V) or (VI), the precursor for the preparation of the conducting polymer, preferably optionally substituted It also relates to a process in which 3,4-ethylenedioxythiophene, more particularly preferably 3,4-ethylenedioxythiophene, is polymerized in the presence of the sulfonated polyketone.

  The complexes according to the invention are surprisingly suitable for the production of hole injection or hole transport layers in OLEDs or organic solar cells (OSC) or for the production of transparent conductive coatings.

  Accordingly, the present invention provides a complex according to the invention for the production of transparent conductive coatings or for the production of hole injection layers or hole transport layers in organic light emitting diodes (OLEDs) or organic solar cells (OSCs). The use of is also provided.

  For the production of transparent conductive coatings, the above solutions or dispersions can be prepared, for example, by known processes, for example by spin coating, impregnation, pouring, dripping, spraying, misting, knife coating. , By brushing or printing, such as inkjet printing, screen printing, gravure printing, offset printing or tampon printing, with a film thickness before drying of 0.5 μm to 250 μm, preferably with a film thickness before drying of 2 μm to 50 μm It is applied to a suitable substrate and then dried at a temperature of at least 20 ° C to 200 ° C.

  Organic light emitting diodes (OLEDs) are becoming increasingly important in applications such as displays and flat-top antennas. The construction and function of OLEDs are known to those skilled in the art, for example as described in D.C. Hertel and K.H. Meerholz, Chemie in unserer Zeit, 2005, Vol. 39, pages 336-347. The complex according to the invention may be used as an intermediate layer in these uses.

  Thus, for example, the following construction is conceivable: for example made of indium tin oxide (ITO), doped zinc oxide or tin oxide, or a conductive polymer, for example a conductive polymer comprising a repeating unit of structure (VII) A transparent electrically conductive electrode, such as one, is applied to a transparent substrate made of glass, poly (ethylene terephthalate) (PET) or other transparent plastic. The complex according to the invention is deposited thereon as a thin layer. Thereafter, one or more organic functional layers are applied thereto. These include conjugated polymers such as polyphenylene vinylene or polyfluorene or those known to those skilled in the art, as well as for example D.I. Hertel and K.H. It may also be a layer of vapor deposited molecules such as those described by Meerholz, Chemie in unserer Zeit, 2005, 39, 336-347. The OLED is completed by deposition of a final metal electrode, for example metal barium or LiF // Al. When a DC voltage of 2-20V is applied, current flows through the structure and electroluminescence is generated in at least one of the functional layers.

The advantages of the polymer interlayer in OLED are as follows:
1. 1. Easily deposit polymer interlayers from solution without using time-consuming and expensive vacuum processes. 2.) The polymer interlayer is very transparent and enables efficient light decoupling. ) The polymer interlayer smoothes the underlying layer. This means fewer shorts in the finished processed LED and thus higher yield in component manufacturing. ) Improved electrical properties of the OLED as a result of improved charge carrier injection from the transparent electrode into the subsequent organic layer.

  The complexes according to the invention may likewise be used to produce organic solar cells (OSC), where the complexes according to the invention lead to similar advantages. In OSC, a voltage is generated by absorption of light at an electrode. This construction is known to those skilled in the art, for example S. This is widely described in Sensfuss et al., Kunststoffe, 2007, Vol.

  The present invention further provides a functionalized, preferably sulfone, as polyanion in a complex with an electrically conductive polymer as a polycation, preferably with an electrically conductive polymer having a repeating unit of structure (VII). Of sulfonated polyketones, particularly preferably sulfonated polyketones having repeating units of structure (III), (IV), (V) or (VI).

  The invention further relates to a coated substrate, preferably provided with a transparent, conductive coating comprising a complex according to the invention. Possible substrates are in particular films, particularly preferably polymer films, even more particularly preferably polymer films of thermoplastic polymers, or glass plates.

The present invention is further a process for the manufacture of a coated substrate comprising:
i) preparing a substrate;
ii) coating the substrate with a composition comprising a complex according to the invention.

  In step i) of the process according to the invention for the production of a coated substrate, a substrate is first prepared, which is preferably one of the abovementioned substrates.

  In step ii), the substrate is then coated with a composition comprising the complex according to the invention. In this regard, a solution or dispersion comprising one or more solvents or dispersants and a complex according to the invention is applied to the substrate or to a predetermined area of the substrate and then at least one of the solvents or dispersants. It is particularly preferred that the part is evaporated, this evaporation can be carried out, for example, by simply drying in air or optionally drying in an oven.

  The invention further relates to a coated substrate obtainable by this process.

  The invention also relates to an electronic component comprising a coated substrate according to the invention or a coated substrate obtainable by a process according to the invention for the production of a coated substrate, which electronic component comprises: Organic light emitting diodes or organic solar cells are preferred. In organic light emitting diodes, the coating applied to the substrate can function in particular as a hole injection layer or a hole transport layer. However, the use of the complex according to the invention in other electronic components, for example capacitors, is also conceivable.

  The following examples serve to illustrate the invention by way of example only and should not be construed as limiting.

Example 1: Preparation of dispersion from PEDOT and s-PEEK 25.0 g of polyetheretherketone Victrex® PEEK ™ 150 PF (supplier: Victrex Europe GmbH, Victrex Europe GmbH) Hofheim am Taunus (Hofheim / Ts.) Was weighed into 250.0 g of 95% strength sulfuric acid. The mixture was heated at 100 ° C. for 5 hours with vigorous stirring. The reaction mixture was then cooled to 0 ° C. and mixed at this temperature with cooling into a mixture of 650 mL water and 325 mL n-butanol. The aqueous phase was discarded. The butanol phase was washed twice with 200 mL of water each time and the wash water was discarded. 150 mL of water was then added to the butanol phase and the mixture was neutralized to a pH of approximately 6 using 12 mL of 30% NaOH. The butanol was then distilled off on a rotary evaporator and replaced in stages with water, finally concentrating the volume to approximately 1/3. 300 mL of methanol was added to this aqueous solution and the precipitated sodium sulfate was filtered off. The filtrate is treated 3 times with ion exchangers (Lewatit MP® 62 and Lewatit® Monoplus S 100, supplier: Lanxess AG) to remove sulfate and sodium ions. And then evaporated to dryness and the residue was post-dried at 0.5 mbar. The yield was 23.6 g s-PEEK. The degree of sulfonation per repeating unit of this polymer was 1.09 (determined by titration with 0.1N sodium hydroxide solution). This corresponds to an equivalent weight of 286 g / mol.

A stirrer and a thermometer were attached to a 1.5 L glass container. 1,338 g of water, 10 g of the sulfonated polyetheretherketone, 2.36 g of a 10% strength solution of iron (III) sulfate in water and 1.91 g of ethylenedioxythiophene, EDT (Clevios®) MV2, H.C. Stark Klevios GmbH (Germany) was thoroughly agitated in this glass container at 25 ° C. for 15 minutes. Thereafter, 4.66 g of sodium peroxodisulfate was added and the mixture was stirred at 25 ° C. for 24 hours. 57 g of anion exchanger (Lewatit® MP 62, Lanxess AG, Leverkusen, Germany) and 111 g of cation exchanger (Lewatit® S 100 H, LANXESS AG (Lanxess AG), Leverkusen, Germany) was added. The mixture was stirred for 2 hours. The ion exchanger was then separated with filter paper, and this 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: Preparation of a layer based on the complex PEDOT / s-PEEK The dispersion from Example 1 was concentrated on a rotary evaporator to a solids content of 1.36%.

  The cleaned glass substrate was placed on a spin coater, and 5 mL of the concentrated dispersion was spread on the substrate. The excess dispersion was then centrifuged by rotating the plate at 500 rpm for 30 seconds. Thereafter, the substrate thus coated was dried on a heating plate at 200 ° C. for 3 minutes. The layer thickness was 65 nm (Tencor, Alphastep 500).

  The electrical conductivity was measured by vapor deposition of a 2.5 cm long Ag electrode through a shadow mask at a distance of 0.5 mm. In order to obtain the specific resistance, the surface resistance measured using an electrometer was multiplied by the layer thickness and the layer thickness. The specific resistance of this layer was 1,760 Ohm · cm. The layer was transparent.

Example 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 was 7 ppm. Therefore, the sulfate concentration remained unchanged within the measurement accuracy range. The complex produced does not liberate sulfate even under exposure to a temperature of 50 ° C.

Comparative Example 1 Storage of Conventional Dispersion at High Temperature For reference experiments, PEDOT: PSS dispersion (Clevios® P VP AI 4083, H.C. Stark Klevios Gaembecher ( H. C. Stark Clevios GmbH)) was used:
Solid content: 1.6%
Sulfate content: 5ppm
pH: 1.5

  50 g of this material was similarly 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 according to the invention from Example 1 does not liberate sulfate at high temperatures, in contrast to the known PEDOT: PSS complex.

Example 4: Production of OLED The dispersion according to the invention from Example 1 was used to construct an organic light emitting diode (OLED). The procedure was as follows for the production of OLED.

1. Preparation of ITO coated substrates ITO coated glass was cut into 50 mm x 50 mm pieces (substrates) and structured with photoresist into 4 parallel lines each having a width of 2 mm and a length of 5 cm. Thereafter, the substrate was cleaned in a 0.3% strength Mucasol solution in an ultrasonic bath, rinsed with distilled water and centrifuged in a centrifuge. Immediately prior to coating, the ITO coated side was cleaned in a UV / ozone reactor (PR-100, UVP Inc., Cambridge, UK) for 10 minutes.

2. Application of hole injection layer About 5 mL of the dispersion according to the invention from Example 1 was filtered (Millipore HV, 0.45 μm). The cleaned ITO coated substrate was placed on a spin coater and the filtered solution was spread on the ITO coated side of the substrate. The excess solution was then centrifuged by rotating the plate for 30 seconds at 600 rpm. Thereafter, the substrate thus coated was dried on a heating plate at 200 ° C. for 5 minutes. When measured using a layer surface shape measuring device (Tencor, Alphastep 500), the thickness of the layer was 50 nm.

3. Application of Hole Transport Layer and Emitter Layer The ITO substrate coated with the dispersion from Example 1 was transferred to a vapor deposition apparatus (Univex 350, Leybold). 60 nm hole transport layer initially made of NPB (N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) benzidine) at a pressure of 10 ⁻³ Pa, then AlQ ₃ A 50 nm emitter layer made of (tris- (8-hydroxyquinoline) aluminum) was continuously vapor deposited at a vapor deposition rate of 1 kg / sec.

4). Application of the metal cathode The layer system was then transferred to a glove box system (Edwards) with an N ₂ atmosphere and an integrated vapor deposition apparatus, and metal electrodes were vapor deposited. For this purpose, the substrate was placed on a shadow mask with this layer system facing down. This shadow mask had a 2 mm wide rectangular groove that intersected and was orthogonal to the ITO strips. A 0.5 nm thick LiF layer and then a 200 nm thick Al layer were sequentially vapor deposited from two vapor deposition dishes at a pressure of p = 10 ⁻³ Pa. The vapor deposition rate was 1 Å / s for LiF and 10 Å / s for Al. The area of each OLED was 4.0 mm ² .

5. Characteristic analysis of OLED The two electrodes of this organic LED were connected (contacted) to a power source via a feeder line. The positive electrode was connected to the ITO electrode, and the negative electrode was connected to the metal electrode. The dependence of OLED current and electroluminescence intensity on voltage (detection made using a photodiode (EG & G C30809E)) was plotted. Thereafter, a constant current I = 3.84 mA was passed through the composition and the lifetime was measured by monitoring the voltage and light intensity as a function of time.

Comparative Example 2: Production of OLED using conventional dispersion The procedure is the second step, the intermediate layer used is not a dispersion according to the present invention from the example [as is], but a standard product in the construction of OLED As in Example 5, except that it was Clevios® P VP AI 4083 (HC Stark Clevios GmbH), which is often used as is there. For this, AI 4083 was filtered, spin coated at 700 rpm for 30 seconds and then dried on a heating plate at 200 ° C. for 5 minutes. The thickness of the layer was 50 nm, and the specific resistance was 1,290 Ohm · cm.

Comparative Example 3: Production of OLED without polymer interlayer The procedure is as in Examples 4 and 5, except that the polymer interlayer was completely omitted and step 2 was not performed.

Example 5: Comparison of OLEDs from Example 4 and Comparative Examples 2 and 3 OLEDs comprising a dispersion according to the invention from Example 1 compared to the standard material Clevios® P VP AI 4083 In order to demonstrate the improvement, both the substrate from Example 4 and Comparative Examples 2 and 3 were processed in parallel, ie the vapor deposited layer and the cathode were deposited on all substrates under the same conditions . The OLEDs fabricated according to Example 4 and Comparative 2 showed typical diode characteristics of organic light emitting diodes. On the other hand, all the constructs produced according to Comparative Example 3 showed a short circuit.

  In lifetime measurements, the voltage and brightness at t = 0, U0 and L0, the current efficiency as a ratio L0 / 1, the time it takes for the brightness to drop to 50% of L0, t @ L0 / 2, and t @ L0 / 2 evaluate the voltage.

  Thus, it has been demonstrated that a polymer interlayer is required for OLEDs without short circuits. The dispersion according to the invention from Example 1 as an intermediate layer in an OLED has the obvious advantage of a lifetime greater than 10 times and an increase in voltage with respect to time compared to the standard material Clevios P AI 4083. Reduced.

Example 6: Measurement of the contact angle using the dispersion according to the invention As in Example 4, item 2, the layer of the dispersion according to the invention from Example 1 is applied onto a glass substrate using a spin coater. Deposited and dried on a heating plate at 200 ° C. for 5 minutes. The contact angle of a drop of toluene placed on the layer with respect to the layer was then measured (Kruess MicroDrop). The wetting was good and the contact angle was <3 ° and therefore could not be measured.

Comparative Example 4: Measurement of Contact Angle Using Conventional Dispersion In the same manner as in Example 6, the contact angle with toluene of the layer of the reference material Clevios (registered trademark) PVP AI 4083 was measured. The wetting was good and the contact angle was <3 ° and therefore could not be measured.

Comparative Example 5: Measurement of contact angle using a conventional dispersion based on a perfluorinated sulfonic acid polymer As in Example 6, a reference material corresponding to EP 1 564 250 (A1), ie perfluoro The contact angle of the layer of a mixture of sulfonated sulfonic acid polymer and conductive polymer was measured: a = 48 °.

  From Example 6 and Comparative Examples 4 and 5, the wetting of the layer containing the formulation according to the invention with the toluene-based solution is as good as the wetting for Clevios® P AI 4083, On the other hand, it can be seen that it is significantly better than the wetting for the reference material corresponding to EP 1 564 250 (A1).

Example 7: Preparation of dispersion from PEDOT and s-PEKK 25 g of polyether ketone ketone (Oppekk <(R)> C, supplier: Polytron Kunststofftechnik GmbH & Polytron Kunststofftechnik GmbH Co. KG), Bergisch Gladbach, Germany, was added to a mixture of 62.5 g of 95% strength sulfuric acid and 187.5 g of fuming sulfuric acid (SO ₃ content 20%). And stirred for 15 hours at 120 ° C. and 15 hours at 140 ° C. The cooled reaction mixture was then introduced into 1,800 mL of water and 500 mL of butanol was added to the formed solution. After that, the water phase Extracted twice with 00 mL butanol, the butanol phase was washed with water, the butanol phases were then combined, 20 mL 30% strength sodium hydroxide solution was added, and the mixture was then added to 30% strength sodium hydroxide. The solution was further adjusted to a pH of 6.3, the aqueous phase was concentrated to 100 mL and 250 mL of methanol was added, the supernatant solution was decanted and removed from the precipitated sodium sulfate and evaporated. Dissolve the residue in 200 mL of water and treat this solution 3 times with ion exchangers (Lewatit MP® 62 and Lewatit® Monoplus S 100, supplier: Lanxess AG). To remove sulfate and sodium ions, and then dry Evaporated until solid and the residue was post-dried at 0.5 mbar, yield 17 g, polymer with a degree of sulfonation per repeat unit of 0.97 (titration with 0.1 N sodium hydroxide solution). S-PEKK, which corresponds to an equivalent weight of 389 g / mol.

  4.92 g of the sulfonated polyetherketone ketone, 0.5 g of iron (III) sulfate in a 10% strength solution in water and 1.91 g of 3,4-ethylenedioxythiophene (Clevios® M V2 HC Starck Clevios GmbH, Germany) in a 500 mL flask equipped with stirrer and thermometer in 248 g of water at 25 ° C. for 30 minutes. Stir well until a clear solution appears. 0.94 g of sodium peroxodisulfate was then added and the mixture was stirred at 25 ° C. for 24 hours. Then 18 g anion exchanger (Lewatit MP® 62, Lanxess AG, Leverkusen, Germany) and 30 g cation exchanger (Lewatit® S 100 H, LANXESS) Addition of AG (Lancess AG), Leverkusen, Germany). The mixture was stirred for 2 hours. The ion exchanger was then separated on a filter paper, and the dispersion was passed through a 0.45 μm filter. A blue dispersion of PEDOT: s-PEKK complex was obtained, from which it was possible to produce a conductive layer by knife coating.

Example 8: Organic Solar Cell Containing Formulation According to the Invention The formulation according to the invention from Example 1 is used to construct an organic solar cell (OSC). The procedure was as follows for the production of OSC.

1. Preparation of ITO Coated Substrate ITO coated glass (Merck Balzers AG, FL, part number 253 674 XO) is cut into small pieces (substrate) of 25 mm × 25 mm size. The substrate is then cleaned for 15 minutes in a 3% strength Mucasol solution in an ultrasonic bath. Thereafter, the substrate was rinsed with distilled water and centrifuged in a centrifuge. Immediately prior to coating, the ITO coated side was cleaned in a UV / ozone reactor (PR-100, UVP Inc., Cambridge, UK) for 10 minutes.

2. Application of Hole Extraction Layer (HEL) About 1 mL of the formulation according to the invention from Example 1 was filtered (Millipore HV, 0.45 μm). The cleaned ITO coated substrate is placed on a spin coater and the filtered solution is spread on the ITO coated side of the substrate. The excess solution was then centrifuged by rotating the plate for 30 seconds at 500 rpm. Thereafter, the substrate coated in this manner was dried on a heating plate at 200 ° C. for 5 minutes. The layer thickness is about 50 nm (Tencor, Alphastep 500).

3. Application of Light Absorbing Layer (LAL) 50 mg of the above polymer P3HT (BASF, Semipilid P 200) and 50 mg of fullerene PCBM (Solenne [60] PCBM) are dissolved in 5 mL of dichlorobenzene at room temperature. In order to achieve complete dissolution of these materials in the solution, the solution is stirred for about 10 hours using a stirring blade. The solution is then filtered through a syringe filter (Millipore HV, 0.45 μm), then spread over the substrate on the spin coater and the plate is spun at 750 rpm for 30 seconds to centrifuge the excess solution. To separate. Thereafter, the substrate coated in this manner is dried on a heating plate at 130 ° C. for 10 minutes. The layer thickness is 100 nm (Tencor, Alphastep 500). This operation and all the following operations are performed in a glove box system and in a pure nitrogen atmosphere.

4). Application of a metal cathode A metal electrode is vapor deposited as a cathode on a substrate having the layer system ITO // HEL // LAL. A vacuum device (Edwards) with two thermal vaporizers is used for this. This layer system is covered with a shadow mask having holes with diameters of 2.5 mm and 5 mm. The substrate is placed on a rotating sample holder with the mounted shadow mask facing down. The dimension of the sample holder is such that four substrates can be accommodated simultaneously. A 25 nm thick Ca layer and then an 80 nm thick Ag layer are vapor deposited from two ^thermal vaporizers under a pressure of p = 10 ⁻³ Pa. The vapor deposition rate is 10 Å / s for Ba [as is] and 20 Å / s for Ag. Isolated metal electrodes, respectively, having an area of 4.9 mm ² and 28mm ^2.

5. OSC characterization This OSC is similarly characterized in a glove box system filled with nitrogen alone. An artificial solar light source (Atlas, Solar Celltest 575) is inserted at the bottom of the glove box system, and the uniform light is directed upward. Place holder with OSC in light cone. The distance from the sample surface to the bottom is about 10 cm. The light intensity can be weakened using an inserted grating filter. The strength on the sample surface is measured with a pyranometer (Kipp & Zonen, CM10) and is about 500 W / m ² . The temperature of the sample holder is measured using a thermal sensor (PT100) and is a maximum of 40 ° C.

  The OSC is brought into electrical contact by connecting the ITO electrode to the Au contact pin (+ pole) and crimping a thin flexible Au wire to one of the metal electrodes (−pole). Both contacts are connected to a current / voltage source (Keithley 2800) via a cable. First, cover the light source and measure the characteristic curve in the dark. For this purpose, a voltage is applied to the sample and varied in the range of -2 to +2 V and the current is recorded. Next, similarly, a current / voltage characteristic curve is plotted under irradiation. From these data, parameters for this solar cell, such as conversion efficiency, open circuit voltage, short circuit current and fill factor, are measured according to OENORM EN 60904-3.

Example 9: OSC reference cell without HEL The construction of the reference cell without HEL is carried out in the same way as in Example 8 except for the difference of omitting step 2 "application of hole extraction layer".

Example 10: OSC Reference Cell with Alternative HEL In Step 2, an alternative material, namely Clevios® P AI4083 (HC Star Stark Clevios GmbH, Leverkusen (H.C. Stark Clevios GmbH), The construction of a reference cell without HEL is carried out in the same way as in Example 8, except that Leverkusen)) is used instead of the formulation according to the invention. The conditions for step 2 are as follows: About 1 mL of a solution of Clevios® P AI4083 is filtered (Millipore HV, 0.45 μm). The cleaned ITO coated substrate is placed on a spin coater and the filtered solution is spread on the ITO coated side of the substrate. The excess solution was then centrifuged by rotating the plate at 750 rpm for 30 seconds. Thereafter, the substrate coated in this manner is dried on a heating plate at 200 ° C. for 5 minutes. The layer thickness is about 50 nm (Tencor, Alphastep 500).

Example 11: Comparison of results from Examples 8-10:
The OSC current / voltage characteristic curves from Examples 1-3 were plotted under the same experimental conditions. In the results table, parameters related to the evaluation are extracted; cell area (A), irradiance (P0), short circuit current (I _SC ), open circuit voltage (V _oc ), electrical output at the point of action (P _max ). , Fill factor (FF) and conversion efficiency (η).

  From the results table it can be seen that the formulation according to the invention is particularly suitable as an intermediate layer for OSC and improves the resistance of the composition to short circuits. Comparison with the reference Clevios® P AI4083 shows that basically similar OSC characteristics are achieved and open circuit voltage and fill factor are improved.

  A further advantage of the formulation according to the invention compared to Clevios® P AI4083 is that the material has a higher thermal stability, which is expected to be longer Guide the OSC life.

Claims (20)

  A complex comprising at least one optionally substituted conductive polymer and at least one functionalized polyketone, wherein the polyketone is a polymer comprising (—CO—) groups in repeating units, and A complex characterized in that in the repeating unit, the (—CO—) group is bonded to two aromatic groups. The functionalized polyketone is a repeating unit of the general formula (I)

(Where
Ar ₁ and Ar ₂ may be the same or different and are optionally substituted aromatics;
R ₁ is an optionally substituted organic radical having ₁ to 80 carbon atoms, a (—CO—) group or an oxygen atom,
n is an integer of 5 to 5,000)
The complex according to claim 1, comprising: The functionalized polyketone is a repeating unit of the general formula (II)

(Where
Ar ₁ and Ar ₂ may be the same or different and each represents an aromatic group,
X ₁ and X ₂ may be the same or different and each represents a sulfonic acid, sulfonate, phosphonic acid, phosphonate, carboxylic acid or carboxylate group,
a and b may be the same or different, and each independently represents an integer or non-integer in the range of 0 to 2, and the non-integer represents that the acid appears for each repeating unit Rather, it means that it only appears in the corresponding proportion of the repeating unit,
R ₂ has the same meaning as R ₁ in claim 2,
n is an integer of 5 to 5,000)
The complex according to claim 1 or 2, comprising: The functionalized polyketone is a repeating unit of the general formula (IIa)

(Where
a, b and R ₂ have the meaning given in claim 3;
M represents a metal cation or H)
The complex according to any one of claims 1 to 3, comprising: The functionalized polyketone is a repeating unit of the general formula (III)

A repeating unit of the general formula (IV),

A repeating unit of the general formula (V),

Or a repeating unit of the general formula (VI),

(Where
a, b, c and d may be the same or different, and each represents an integer or non-integer in the range of 0 to 2, wherein the non-integer appears for each repeating unit. Rather, it means that it only appears in the corresponding proportion of the repeating unit,
M represents a metal cation or H;
n is an integer of 5 to 5,000)
The complex according to any one of claims 1 to 4, comprising: The conductive polymer is an optionally substituted polythiophene comprising a repeating unit of general formula (VII)

(Where
R ₄ and R ₅ each independently of one another represent H, an optionally substituted C ₁ -C ₁₈ -alkyl radical or an optionally substituted C ₁ -C ₁₈ -alkoxy radical, or R ₄ and R ₅ Together are optionally substituted C ₁ -C ₈ -alkylene radicals (in the optionally substituted C ₁ -C ₈ -alkylene radical, one or more C atoms are one or more identical or different, Or may be replaced by a heteroatom selected from S), preferably a C ₁ -C ₈ -dioxyalkylene radical, an optionally substituted C ₁ -C ₈ -oxythiaalkylene radical or an optionally substituted C ₁ -C 8 _- or represents a di thiaalkylene radical or an optionally substituted C ₁ -C 8, _- alkylidene radical (wherein optionally is substituted And C ₁ -C 8 _- In alkylidene radical, represents at least one C atom is replaced by a heteroatom selected from O or S) optionally)
The complex according to any one of claims 1 to 5, comprising: The polythiophene is a repeating unit of the general formula (VII-a) and / or (VII-b)

(Where
A represents an optionally substituted C ₁ -C ₅ -alkylene radical, preferably an optionally substituted C ₂ -C ₃ -alkylene radical;
Y represents O or S;
R ₆ is a linear or branched, optionally substituted C ₁ -C ₁₈ -alkyl radical, preferably a linear or branched, optionally substituted C ₁ -C ₁₄ -alkyl. substituted aralkyl radical, optionally - radical, optionally substituted _C 5 _{-C 12} - cycloalkyl radical, optionally _{-C 14 C} 6 substituted - aryl radicals, _C 7 _{-C 18} optionally substituted Represents a C ₇ -C ₁₈ -alkaryl radical, an optionally substituted C ₁ -C ₄ -hydroxyalkyl radical or a hydroxyl radical;
y represents an integer of 0 to 8, preferably 0, 1 or 2, particularly preferably 0 or 1;
If several radicals R ₆ are attached to A, these may be the same or different)
The complex according to claim 6, comprising:   The complex according to claim 7, wherein the polythiophene is poly (3,4-ethylenedioxythiophene).   The complex according to any one of claims 1 to 8, wherein the complex is dispersed or dissolved in one or more dispersants.   The complex according to claim 9, wherein the dispersion has a pH in the range of 1-8.   A process for the preparation of a complex from an electrically conductive polymer according to any one of claims 6 to 8 and a functionalized polyketone according to any one of claims 2 to 5. A process wherein a precursor for the preparation of the electrically conductive polymer is polymerized in the presence of the sulfonated polyketone.   A complex obtainable by the process according to claim 11.   Use of a complex according to any one of claims 1 to 10 and claim 12 for the production of a transparent conductive coating.   Use of the complex according to any one of claims 1 to 10 and claim 12 for the production of a hole injection layer or a hole transport layer in an organic light emitting diode or an organic solar cell.   Use of a sulfonated polyketone according to any one of claims 2 to 5 as a polyanion in a complex with an electrically conductive polymer according to any one of claims 6 to 8.   A coated substrate provided with a coating comprising a complex according to any one of claims 1 to 10 and claim 12. A process for the manufacture of a coated substrate,
i) preparing a substrate;
ii) coating the substrate with a composition comprising the complex of any one of claims 1 to 10 and claim 12.   A coated substrate obtainable by the process of claim 17.   An electronic component comprising the coated substrate of claim 16 or claim 18.   The electronic component according to claim 19, wherein the electronic component is an organic light emitting diode or an organic solar cell.