Hardened conductive composition

Abstract

The present invention further provides a composition comprising: i) * represents a bond to an adjacent monomer unit, x and z represent O or S, and R 1 ~R 4 each independently represents a hydrogen atom or an organic residue R, provided that the residue R 1 ~R 4 at least one polythiophene selected from the group consisting of polythiophenes comprising monomer units of structure (I), at least one of which represents an organic residue R, characterized by its compatibility in PGME (1-methoxypropan-2-ol), as indicated by an RF value of at least 0.8; iii) at least one ethylenically unsaturated compound; iv) at least one organic solvent; v) at least one radical initiator. The present invention also relates to a process for preparing the layer structure, a layer structure obtainable by this process, a layer structure, an electronic component and the use of the composition according to the invention. [Formula 1] JPEG2024526121000031.jpg41128

Description

Technical Field

[0001] The present invention relates to a curable composition comprising at least one polythiophene and at least one ethylenically unsaturated compound polymerizable by a radical chain reaction. The present invention also relates to a method for preparing a layer structure, a layer structure obtainable by this method, a layer structure, an electronic component, and the use of the composition according to the present invention.

Summary of the Invention

Problems to be Solved by the Invention

[0002] Polythiophenes are widely used as essentially conductive polymers. In particular, poly(3,4-ethylenedioxythiophene) (PEDOT) has found many industrial applications such as solid electrolytic capacitors, antistatic coatings, electroluminescent lamps, organic light emitting diodes, and organic solar cells. For many or these applications, PEDOT is used as a polymer complex having polystyrene sulfonic acid as a counter ion dispersed in water or a mixture of water and other solvents (also called "PEDOT / PSS").

[0003] In order to expand the scope of application, efforts have been made to provide PEDOT in an aprotic solvent. WO 2012 / 059215 discloses the use of block copolymers as counter ions to make the dispersion soluble in organic aprotic solvents. The solubility parameters of the block copolymer govern and limit the solubility characteristics of the resulting PEDOT complex. Thus, when a solvent such as PGMEA or ethanol is added, the dispersion becomes unstable.

[0004] KR-A-100945056 describes the polymerization of 3,4-ethylenedioxythiophene in water in the presence of a surfactant. Subsequently, the solvent is removed and replaced with an organic solvent. However, such a redispersion process is costly and undesirable.

[0005] McCullough et al. ("A Simple Method for the Preparation of Head-to-Tail Regular Poly(3-alkylthiophene) Using Grignard Metathesis", Adv. Mater. 1999, 11, 250) described the synthesis of regioregular copolymers that can be dispersed in a number of solvents. However, coupling with organometallic compounds is expensive, and the resulting polymers exhibit only limited conductivity. Therefore, their use is limited to the hole transport layer, where only conductivity through the layer is required.

[0006] WO 2021 / 063956 discloses a composition based on an organic solvent, comprising a PEDOT derivative and a monomer anion as a counterion. When blended with an inert polymer such as polyacrylate, the composition still features a low sheet resistance. However, the drawback of such blends can be seen in the fact that the hardness of the conductive layer obtained using such blends can still be improved, especially when these blends are used for the formation of an antistatic layer.

[0007] The object of the present invention was to overcome the drawbacks of the prior art regarding conductive polymers based on thiophene monomers that are dissolved or dispersed in an organic solvent.

[0008] In particular, the object of the present invention is to provide a composition comprising a conductive polymer based on thiophene monomers that is dissolved or dispersed in an organic solvent, the composition enabling the formation of a conductive layer that is not only highly conductive and highly transparent compared to similar conductive layers known from the prior art, but also characterized by a sufficiently high hardness.

[0009] Furthermore, an object of the present invention is a stable composition, preferably a storage-stable composition containing a conductive polymer dissolved or dispersed in an organic solvent and based on a thiophene monomer, and by means of these compositions, it was also an object to provide a composition capable of preparing a conductive layer characterized by particularly advantageous hardness. As used herein, the term "storage-stable" preferably characterizes a composition that does not show the formation of a precipitate after storage for 15 days, more preferably 30 days, in the dark.

[0010] The contribution to solving at least one, preferably two or more, of the above objects is made by the independent claims. The dependent claims provide preferred embodiments that contribute to solving at least one of the objects at least in part.

[0011] The contribution to solving at least one of the objects according to the present invention is made by a first embodiment of the present invention, preferably a curable composition, even more preferably a composition that is curable when exposed to electromagnetic radiation, an electron beam, or heat, and the composition is i) at least one polythiophene containing monomer units of structure (I)

[0012]

Chemical formula

[0013] The contribution to solving at least one of the objects according to the present invention is made by a second embodiment of the composition, preferably a curable composition, more preferably a composition curable when exposed to electromagnetic radiation, an electron beam, or heat, and the composition is i) at least one polythiophene, characterized by its compatibility in PGME (1-methoxypropan-2-ol), indicated by an RF value of at least 0.6, preferably at least 0.8, more preferably 1.0, at least one polythiophene, ii) optionally, at least one organic compound having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfuric acid groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, or a salt of the organic compound, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, the organic compound or its salt, iii) at least one ethylenically unsaturated compound, preferably at least one ethylenically unsaturated compound polymerizable in a radical chain reaction, iv) at least one organic solvent, v) at least one radical initiator, and comprises.

[0014] Surprisingly, certain polythiophenes, such as residues R 1 ~R 4Among them, at least one of the monomer units of the above-mentioned structure (I) representing a branched alkyl group or a branched ether group, the polythiophene is particularly suitable for use as a conductive polymer in a curable composition containing at least one ethylenically unsaturated compound polymerizable by a radical chain reaction based on an organic solvent. It has been found that when such a composition is cured by polymerizing a polymerizable compound in the presence of polythiophene to form a polymer matrix in which the polythiophene is embedded, a conductive layer having not only high conductivity and high transparency but also sufficiently high hardness can be obtained. Furthermore, it has also been observed that these compositions are characterized by remarkable storage stability.

[0015] In a preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition exists in the form of a dispersion or a solution (organic solvent iv) serves as a dispersant or a solvent), and polythiophene i) and at least one organic compound ii) having at least one acid group (preferably present in the form of an anion) form a complex with at least one ethylenically unsaturated compound iii) and are dispersed or dissolved in the organic solvent iv), preferably uniformly dispersed or dissolved. Most preferably, the composition according to the present invention is a dispersion in which the complex of polythiophene i) and the organic compound ii) having at least one acid group is uniformly dispersed in the organic solvent iv). However, in the composition according to the present invention, the transition between "dispersion" and "solution" can be fluid depending on the actual properties of polythiophene i), the organic compound ii) having at least one acid group, and the organic solvent iv). This preferred embodiment is the third embodiment of the composition according to the present invention and preferably depends on the first and second embodiments.

[0016] In a further preferred embodiment of the first embodiment of the composition according to the present invention, for polythiophene i), X and Z represent O, and R 1 , R 2 , R 3 and R 4A homopolymer or copolymer containing the monomer unit of structure (I), wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent ether groups having the structural formula (Ia).

[0017]

Chemical formula

[0018] This preferred embodiment is a fourth embodiment of the composition according to the invention and is preferably dependent on the first or third embodiment.

[0019] In a further preferred embodiment of the first embodiment of the composition according to the invention, polythiophene i) is such that X and Z represent O, and R 1 , R 2 , R 3 and R 4 where three of the residues selected from the group consisting of are hydrogen atoms, and the remaining residue represents a branched alkyl group or a branched ether group, and is a homopolymer or copolymer containing a monomer unit of structure (I). In this context, it is also particularly preferred that the remaining residue does not have a sulfonic acid group or a salt of this group. This preferred embodiment is a fifth embodiment of the composition according to the invention and is preferably dependent on any of the first, third, and fourth embodiments. As used herein, the term "branched ether group" preferably means that at least one of the two organic residues bonded to the oxygen atom is a branched organic residue, i.e., an organic residue bonded to at least three carbon atoms via a single bond, or an organic residue containing at least one carbon atom bonded to at least two carbon atoms and an oxygen atom that is part of an ether group.

[0020] In a further preferred embodiment of the first embodiment of the composition according to the invention, polythiophene i) is such that X and Z represent O, and R 1 , R 2 , R 3 and R 4 where three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residue represents a branched alkyl group, and is a homopolymer or copolymer containing a monomer unit of structure (I).

[0021] This preferred embodiment is a sixth embodiment of the composition according to the invention and is preferably dependent on the fifth embodiment. Suitable examples of monomer units of structure (Ia) having a branched alkyl group or two or more alkyl groups include compounds selected from the group consisting of compounds (A), (B), (C), and (D).

[0022] [Chemical formula]

[0023] In a further preferred embodiment of the first embodiment of the composition according to the present invention, polythiophene i) is such that X and Z represent O, and three of the residues selected from the group consisting of R 1 , R 2 , R 3 and R 4 represent hydrogen atoms, and the remaining residue represents a branched ether group having the structural formula (Ic), which is a homopolymer or copolymer containing the monomer unit of structure (I).

[0024] [Chemical formula] [In the formula, R 10 is H, a C 1 ~C 10 -alkyl group, preferably a C 1 ~C 5 -alkyl group, more preferably a methyl group, or a C 1 ~C 10 -alkoxy group, preferably a C 1 ~C 5 -alkoxy group, more preferably a methoxy group, R 10 is most preferably H, R 11 is H, a C 1 ~C 10 -alkyl group, preferably a C 1 ~C 5 -alkyl group, more preferably a methyl group, or a C 1 ~C 10 -alkoxy group, preferably a C 1 ~C 5 -alkoxy group, more preferably a methoxy group, R 11 is most preferably H, n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, more preferably in the range of 1 to 3, and most preferably n is 1. R 12is a branched organic residue, preferably a branched alkyl group or a branched arylalkyl group, more preferably a branched alkyl group or a branched arylalkyl group having no unsaturated C═C-bond in the alkyl chain, and even more preferably an organic residue having the formula (Id),

[0025]

Chemical formula

[0026] This preferred embodiment is the seventh embodiment of the composition according to the present invention and preferably depends on the fifth embodiment. Suitable examples of such polythiophenes are homopolymers or copolymers containing monomer units selected from the group consisting of compounds (E), (F), and (G).

[0027]

Chemical formula

[0028] In a further preferred embodiment of the first embodiment of the composition according to the invention, polythiophene (i) is a copolymer of monomer units of structure (I) and at least one further thiophene monomer selected from the group consisting of 3,4-ethylenedioxythiophene, 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-propyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin and 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, the copolymer containing, in each case based on the total number of thiophene monomer units, 5 to 95%, preferably 10 to 80%, more preferably 20 to 60% of the monomer units of structure (I). This preferred embodiment is the eighth embodiment of the composition according to the invention and preferably depends on any one of the first or the third to seventh embodiments. According to a particularly preferred variant of this preferred embodiment of the composition according to the invention, the at least one further thiophene monomer is a thiophene monomer selected from the group consisting of 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-propyl-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, 2-butyl-2,3-dihydro-thieno[3,4-b]-1,4-dioxin and 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, and the use of 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin is particularly preferred.

[0029] In a further preferred embodiment of the first embodiment of the first composition of the composition according to the invention, polythiophene (i) is characterized by its compatibility in PGME (1-methoxypropan-2-ol), demonstrated by an RF value of at least 0.6, preferably at least 0.8, more preferably 1.0. This preferred embodiment is the ninth embodiment of the composition according to the invention and preferably depends on any one of the first or the third to eighth embodiments.

[0030] In a preferred embodiment of the second embodiment of the composition according to the invention, the polythiophene i) is characterized by a contact angle of more than 40, preferably more than 50, more preferably more than 60. This preferred embodiment is the tenth embodiment of the composition according to the invention and preferably depends on the second embodiment.

[0031] In a further preferred embodiment of the second embodiment of the composition according to the invention, the polythiophene i) is a polythiophene containing monomer units of structure (I).

[0032] [Chemical formula] [wherein, * represents a bond to an adjacent monomer unit, X and Z represent O or S, R 1 ~R 4 each independently represents a hydrogen atom or an organic residue R, provided that at least one of the residues R 1 ~R 4 represents an organic residue R]

[0033] This preferred embodiment is the eleventh embodiment of the composition according to the invention and preferably depends on the second and tenth embodiments.

[0034] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, at least one organic compound ii) having at least one acid group is an organic compound having at least one inorganic acid group, preferably one or two inorganic acid groups, and the inorganic acid group is a sulfonic acid group (-SO 2 OH), a sulfuric acid group (-O-SO 2 OH), a phosphonic acid group (-PO(OH) 2 ), a phosphoric acid group (-O-PO(OH) 2 or a salt thereof, preferably a sulfonic acid group (-SO 2 OH) or a salt thereof. This preferred embodiment is the twelfth embodiment of the composition according to the invention and preferably depends on any one of the first to eleventh embodiments.

[0035] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the organic compound (ii) having at least one acid group is an anionic surfactant. This preferred embodiment is the 13th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 12th embodiments.

[0036] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, at least one organic compound (ii) having at least one acid group is a monovalent sulfonic acid or a salt thereof. Suitable monovalent sulfonic acids are, for example, benzenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid or mixtures or salts thereof, and the use of dodecylbenzenesulfonic acid is particularly preferred. As used herein, the term "dodecylbenzenesulfonic acid" includes, in addition to dodecylbenzenesulfonic acid, mixtures of alkylbenzenesulfonic acids further containing alkylbenzenesulfonic acids having an alkyl chain longer or shorter than the dodecyl group. This preferred embodiment is the 14th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 13th embodiments.

[0037] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the weight ratio of polythiophene (i) to at least one organic compound (ii) having at least one acid group in the composition is in the range of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2, more preferably in the range of 1:5 to 1:0.5. This preferred embodiment is the 12th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 11th embodiments.

[0038] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition comprises polythiophene i) and an organic compound ii) having at least one acid group, in each case in an amount in the range of 0.01 to 10% by weight, more preferably in the range of 0.2 to 6% by weight, most preferably in the range of 0.5 to 4% by weight, based on the total solids of the composition. This preferred embodiment is the 15th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 14th embodiments.

[0039] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, at least one ethylenically unsaturated compound iii) is a compound having one or more (alk)acrylic acid groups, preferably one or more (meth)acrylic acid groups, a compound having one or more allyl groups, a compound having one or more vinyl groups, or a compound having a combination of at least two of these ethylenically unsaturated groups. This preferred embodiment is the 16th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 15th embodiments. The term "(meth)acrylic acid" as used herein refers to both acrylic acid derivatives and methacrylic acid derivatives of the corresponding compounds having "(meth)acrylic acid groups".

[0040] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition comprises at least one ethylenically unsaturated compound iii) polymerizable by a radical chain reaction, in each case in an amount in the range of 30 to 99.99% by weight, more preferably in the range of 50 to 98% by weight, most preferably in the range of 80 to 95% by weight, based on the solids of the composition. This preferred embodiment is the 17th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 16th embodiments.

[0041] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the weight ratio of the total weight of polythiophene i) and the organic compound ii) having at least one acid group to the weight of the ethylenically unsaturated compound iii) is in the range of 0.1:99.99 to 1:10, preferably in the range of 0.2:99.8 to 5:95, more preferably in the range of 0.5:99.5 to 4:96. This preferred embodiment is the 18th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 17th embodiments.

[0042] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, at least one organic solvent iv) is a protic solvent. This preferred embodiment is the 19th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 18th embodiments.

[0043] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the organic solvent iv) is selected from the group consisting of aromatic hydrocarbons, ketones, esters, ethers, alcohols, and mixtures thereof. This preferred embodiment is the 20th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 19th embodiments.

[0044] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the organic solvent iv) is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, anisole, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or a mixture of one or two of these aprotic solvents and one or two further solvents selected from the group consisting of. This preferred embodiment is the 21st embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 20th embodiments. A particularly preferred solvent is 1-methoxy-2-propanol (PGME).

[0045] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, at least one radical initiator is a photo radical initiator capable of forming radicals upon irradiation with light, more preferably a UV photo radical initiator capable of forming radicals upon irradiation with UV light.

[0046] This preferred embodiment is the 22nd embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 21st embodiments.

[0047] Preferable examples of the radical initiator (v) include type 1 initiators in which molecules decompose due to differences in chemical structure and molecular bond energy to generate radicals, and type 2 initiators that cause hydrogen abstraction in the coexistence of a tertiary amine. The type 1 initiator can be selected from the group consisting of acetophenones such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone or 1-hydroxycyclohexylphenylketone, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether or benzyl dimethyl ketal, phosphine oxides and titanocene compounds. The type 2 initiator can be selected from the group consisting of benzophenones such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide or 3'-methyl-4-methoxybenzophenone, and thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone or isopropylthioxanthone. These photoinitiators may be used alone, in combination of two or more, or in combination of type 1 and type 2 photoinitiators.

[0048] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition contains the radical initiator (v) in an amount in the range of 0.01 to 20% by weight, preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, in each case based on the solids content of the composition. This preferred embodiment is the 23rd embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 22nd embodiments.

[0049] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition is vi) at least one additive different from components i) to v), preferably selected from the group consisting of a UV stabilizer, a heat stabilizer, an antioxidant, a UV absorber, a conductivity improver, an adhesion promoter, a polymer binder, or a combination of at least two of these additives.

[0050] This preferred embodiment is the 24th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 23rd embodiments.

[0051] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition contains additive vi), which is different from components i) to v), in an amount in the range of 0.01 to 25% by weight, preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 10% by weight, based on the solid content of the composition in each case. This preferred embodiment is the 25th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 24th embodiments.

[0052] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition has a water content of less than 2% by weight, preferably less than 1% by weight, even more preferably less than 0.5% by weight, based on the total weight of the composition in each case. This preferred embodiment is the 26th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 25th embodiments.

[0053] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the composition has an iron content of less than 10 ppm, preferably less than 1 ppm, more preferably less than 0.1 ppm, based on the total weight of the composition in each case. This preferred embodiment is the 27th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 26th embodiments.

[0054] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the conductive layer prepared using the composition has a sheet resistance of at most 1×10 10 Ω / sq, preferably at most 5×10 9 Ω / sq, more preferably at most 1×10 8 Ω / sq. This preferred embodiment is the 28th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 27th embodiments.

[0055] In a further preferred embodiment of the first and second embodiments of the composition according to the present invention, the conductive layer prepared using the composition has a pencil hardness of at least 1H, preferably at least 2H, more preferably at least 3H. This preferred embodiment is the 29th embodiment of the composition according to the present invention and preferably depends on any one of the 1st to 28th embodiments.

[0056] The contribution to solving at least one of the objects according to the present invention can also be made by a first embodiment of a process for the preparation of a layer structure, which process comprises A) a step of preparing a substrate, B) a step of coating the substrate with the composition according to the present invention, C) optionally, a step of at least partially removing the organic solvent iv), D) exposing the coated substrate (101) to electromagnetic radiation, preferably UV radiation, an electron beam, heat, or a combination of at least two of these, in order to cure the composition by polymerizing at least one ethylenically unsaturated compound iii) by a radical chain reaction.

[0057] In a preferred embodiment of the method according to the invention, the substrate provided in method step A) is selected from the group consisting of paper, polymer, glass or ceramic. For optical applications, the substrate is preferably transparent or light-transmissive. The transparent substrate can be made of glass, very thin glass (flexible glass), or plastic. Particularly suitable plastics are polycarbonate, polyester, such as PET and PEN (polyethylene terephthalate or polyethylene-naphthalene dicarboxylate), copolycarbonate, polysulfone, polyethersulfone (PES), polyimide, polyethylene, polypropylene or cyclic polyolefin or cyclic olefin copolymer (COC), hydrogenated styrene polymer or hydrogenated styrene copolymer. Rigid or flexible substrates can be used. This preferred embodiment is a second embodiment of the method according to the invention and is preferably dependent on the first embodiment.

[0058] In a further preferred embodiment of the method according to the invention, the coating of the substrate with the composition according to the invention in method step B) is achieved by dipping, dipping, injection, dropping, spraying, misting, knife coating, brushing, or printing, such as inkjet, screen or tampon printing. This preferred embodiment is a third embodiment of the method according to the invention and is preferably dependent on the first or second embodiment.

[0059] The contribution to solving at least one of the objects according to the invention is also made by the layer structure obtained by the process according to the invention. The layer structure preferably has a pencil hardness of at least 1H, preferably at least 2H, more preferably at least 2H. Furthermore, the layer structure preferably has a transmittance (including the substrate) of at least 80%, preferably at least 85%, more preferably at least 87%, most preferably at least 89%.

[0060] The contribution to solving at least one of the objects according to the invention is also made by the first embodiment of the following layer structure. a) a substrate, b) a conductive layer coated on the substrate, and the conductive layer at least one polythiophene containing monomer units of structure (I)

[0061] [Chemical formula] [wherein, * represents a bond to an adjacent monomer unit, X and Z represent O or S, R 1 ~R 4 each independently represents a hydrogen atom or an organic residue R, provided that at least one of the residues R 1 ~R 4 represents an organic residue R], at least one organic compound having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfuric acid groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, or a salt of the organic compound, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, the organic compound or its salt a polymer matrix based on a polymerized ethylenically unsaturated compound iii) in which at least one polythiophene is embedded, The conductive polymer layer has a pencil hardness of at least 1H, preferably at least 2H, more preferably at least 3H.

[0062] The contribution to solving at least one of the objects according to the present invention is also made by a second embodiment of the following layer structure. a) a substrate, b) a conductive layer coated on the substrate, and the conductive layer at least one polythiophene, characterized by its compatibility in PGME (1-methoxypropan-2-ol) as indicated by an RF value of at least 0.6, preferably at least 0.8, more preferably 1.0, at least one polythiophene Optionally, at least one organic compound having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfuric acid groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, or a salt of the organic compound, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, the organic compound or its salt, A polymer matrix based on a polymerized ethylenically unsaturated compound iii) in which at least one polythiophene is embedded, The conductive polymer layer has a pencil hardness of at least 1H, preferably at least 2H, more preferably at least 3H.

[0063] In a further preferred embodiment of the first embodiment of the layer structure according to the invention, for polythiophene i), X and Z represent O, and R 1 , R 2 , R 3 and R 4 Three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent ether groups having the structural formula (Ia), a homopolymer or copolymer containing the monomer unit of structure (I).

[0064] [In the formula, R is H, a C 7 ~C 1 -alkyl group, preferably a C 10 ~C 1 -alkyl group, more preferably a methyl group, or a C 5 ~C 1 -alkoxy group, preferably a C 10 ~C 1 -alkoxy group, more preferably a methoxy group, and R 5 is most preferably H, R 7 is H, a C 8 ~C 1 ~C 10 -alkyl group, preferably a C 1 ~C 5- an alkyl group, more preferably a methyl group, or C 1 ~C 10 - an alkoxy group, preferably C 1 ~C 5 - an alkoxy group, more preferably a methoxy group, and R 8 is most preferably H, n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, more preferably in the range of 1 to 3, and most preferably n is 1, R 9 is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C 1 ~C 30 alkyl group, more preferably a C 2 ~C 25 - alkyl group, even more preferably a C 5 ~C 20 - alkyl group)

[0065] This preferred embodiment is the third embodiment of the layer structure according to the present invention and preferably depends on the first embodiment.

[0066] In a further preferred embodiment of the first embodiment of the layer structure according to the present invention, polythiophene i) is such that X and Z represent O, and three of the residues selected from the group consisting of R 1 , R 2 , R 3 , and R 4 represent hydrogen atoms, and the remaining residue represents a branched alkyl group or a branched ether group, and is a homopolymer or copolymer containing a monomer unit of structure (I). In this connection, it is also particularly preferred that the remaining residue does not have a sulfonic acid group or a salt of this group. This preferred embodiment is the fourth embodiment of the layer structure according to the present invention and preferably depends on the first or third embodiment.

[0067] In a further preferred embodiment of the first embodiment of the layer structure according to the present invention, polythiophene i) is such that X and Z represent O, and R 1 , R 2 , R 3 , and R 4A homopolymer or copolymer containing a monomer unit of structure (I), wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent a branched alkyl group.

[0068] This preferred embodiment is the fifth embodiment of the layer structure according to the present invention and preferably depends on the fourth embodiment. Suitable examples of the monomer unit of structure (Ia) having a branched alkyl group or two or more alkyl groups include compounds selected from the group consisting of compounds (A), (B), (C), and (D).

[0069]

Chemical formula

[0070] In a further preferred embodiment of the first embodiment of the layer structure according to the present invention, polythiophene i) has X and Z representing O, and R 1 , R 2 , R 3 , and R 4 A homopolymer or copolymer containing a monomer unit of structure (I), wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent a branched ether group having the structural formula (Ic).

[0071]

Chemical formula

[0072]

Chemical formula

[0073] This preferred embodiment is the sixth embodiment of the layer structure according to the present invention and preferably depends on the fourth embodiment. Suitable examples of such polythiophenes are homopolymers or copolymers containing monomer units selected from the group consisting of compounds (E), (F), and (G).

[0074]

Chemical formula

[0075] In a further preferred embodiment of the first embodiment of the layer structure according to the present invention, the polythiophene i) is a copolymer of a monomer unit of structure (I) and at least one thiophene monomer selected from the group consisting of 3,4-ethylenedioxythiophene, 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-propyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin and 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, and in each case, based on the total number of thiophene monomer units, a copolymer containing 5 to 95% of the monomer units of structure (I), preferably 10 to 80% of the monomer units, more preferably 20 to 60% of the monomer units. This preferred embodiment is the seventh embodiment of the layer structure according to the present invention and preferably depends on any one of the first and third to fifth embodiments of the present invention. According to a particularly preferred variant of this preferred embodiment of the layer structure according to the present invention, the at least one further thiophene monomer is a thiophene monomer selected from the group consisting of 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-propyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin and 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxin, and the use of 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxin is particularly preferred.

[0076] In a preferred embodiment of the second embodiment of the layer structure according to the present invention, polythiophene i) is characterized by a contact angle of more than 40, preferably more than 50, more preferably more than 60. This preferred embodiment is the eighth embodiment of the layer structure according to the present invention and preferably depends on the second embodiment.

[0077] In a further preferred embodiment of the second embodiment of the layer structure according to the present invention, the composition polythiophene i) according to the present invention is a polythiophene containing monomer units of structure (I).

[0078] [Chemical formula] [In the formula, * represents a bond to an adjacent monomer unit, X and Z represent O or S, R 1 ~R 4 each independently represents a hydrogen atom or an organic residue R, provided that at least one of the residues R 1 ~R 4 represents an organic residue R]

[0079] This preferred embodiment is the ninth embodiment of the composition according to the present invention and preferably depends on the second and eighth embodiments.

[0080] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, at least one organic compound ii) having at least one acid group is an organic compound having at least one inorganic acid group, preferably one or two inorganic acid groups, and the inorganic acid group is a sulfonic acid group (-SO 2 OH), a sulfuric acid group (-O-SO 2 OH), a phosphonic acid group (-PO(OH) 2 ), a phosphoric acid group (-O-PO(OH) 2 or a salt thereof, preferably a sulfonic acid group (-SO 2 OH) or a salt thereof. This preferred embodiment is the tenth embodiment of the layer structure according to the present invention and preferably depends on any one of the first to ninth embodiments.

[0081] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, the organic compound (ii) having at least one acid group is an anionic surfactant. This preferred embodiment is the 11th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 10th embodiments.

[0082] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, at least one organic compound (ii) having at least one acid group is a monovalent sulfonic acid or a salt thereof. Suitable monovalent sulfonic acids are, for example, benzenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid or mixtures or salts thereof, and the use of dodecylbenzenesulfonic acid is particularly preferred. As used herein, the term "dodecylbenzenesulfonic acid" includes, in addition to dodecylbenzenesulfonic acid, mixtures of alkylbenzenesulfonic acids further containing alkylbenzenesulfonic acids having an alkyl chain longer or shorter than the dodecyl group. This preferred embodiment is the 12th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 11th embodiments.

[0083] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, the weight ratio of polythiophene (i) to at least one organic compound (ii) having at least one acid group in the layer structure is in the range of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2, more preferably in the range of 1:5 to 1:0.5. This preferred embodiment is the 13th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 12th embodiments.

[0084] In a further preferred embodiment of the layer structure according to the first and second embodiments of the present invention, the layer structure comprises polythiophene i) and an organic compound ii) having at least one acid group, in a total amount in the range of 0.01 to 10% by weight, more preferably in the range of 0.2 to 6% by weight, and most preferably in the range of 0.5 to 4% by weight, based on the total weight of the conductive layer in each case. This preferred embodiment is the 14th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 13th embodiments.

[0085] In a further preferred embodiment of the layer structure according to the first and second embodiments of the present invention, at least one ethylenically unsaturated compound iii) that forms the basis of the polymer matrix (i.e., the polymer matrix is obtained by radical polymerization) is a compound having one or more (meth)acrylic acid groups, a compound having one or more allyl groups, a compound having one or more vinyl groups, or a compound having a combination of at least two of these ethylenically unsaturated groups. This preferred embodiment is the 15th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 14th embodiments.

[0086] In a further preferred embodiment of the layer structure according to the first and second embodiments of the present invention, the layer structure contains a polymer forming the polymer matrix in an amount in the range of 30 to 99.99% by weight, more preferably in the range of 50 to 98% by weight, and most preferably in the range of 80 to 95% by weight, based on the total weight of the conductive layer in each case. This preferred embodiment is the 16th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 15th embodiments.

[0087] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, the weight ratio of the total weight of polythiophene i) and the organic compound ii) having at least one acid group to the weight of the polymer forming the polymer matrix is in the range of 0.1:99.99 to 1:10, preferably in the range of 0.2:99.8 to 5:95, more preferably in the range of 0.5:99.5 to 4:96. This preferred embodiment is the 17th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 16th embodiments.

[0088] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, the layer structure preferably has a transmittance (including the substrate) of at least 80%, preferably at least 85%, more preferably at least 87%, and most preferably at least 89%. This preferred embodiment is the 18th embodiment of the layer structure according to the present invention and preferably depends on any one of the 1st to 17th embodiments.

[0089] The contribution to solving at least one of the objects according to the present invention is also made by an electronic component including the layer structure according to the present invention, particularly an organic light emitting diode, an organic solar cell, or a capacitor.

[0090] The contribution to solving at least one of the objects according to the present invention is also made by the use of the composition according to the present invention for manufacturing a conductive layer in an electronic component, particularly an organic light emitting diode, an organic solar cell or a capacitor, or for manufacturing an antistatic coating.

[0091] organic compound ii) having at least one acid group or a salt thereof The organic compound ii) having at least one acid group present in the composition or layer structure according to the present invention, or a salt thereof, preferably contains an anionic surfactant, and the anionic surfactant is more preferably selected from the group consisting of organic phosphonic acids, organic phosphates, organic sulfonic acids, such as sulfonic acids, such as alkyl-aryl-sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and salts or mixtures thereof. Each of the following anionic surfactants may contain a mixture of compounds having different alkyl chain lengths. Suitable alkyl sulfates include C 8 ~C 18 alkyl sulfates such as sodium dodecyl sulfate, lithium dodecyl sulfate, ammonium dodecyl sulfate, sodium tetradecyl sulfate, sodium 7-ethyl-2-methyl-4-undecyl sulfate, and sodium 2-ethylhexyl sulfate, but are not limited thereto. Suitable alkyl ether sulfates include C 8 ~C 18 alkyl ether sulfates such as sodium lauryl sulfate and sodium myreth sulfate, but are not limited thereto. Suitable alkyl sulfonates include C 8 ~C 18 alkyl sulfonates such as sodium tetradecyl sulfonate, sodium octadecyl sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate, and the corresponding sulfonic acids, but are not limited thereto. Suitable aryl sulfonates or sulfonic acids optionally substituted with an alkyl or aryl substituent include C 2 ~C 18 alkylbenzene sulfonates or sulfonic acids such as sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid, ethylbenzene sulfonic acid, and isopropylamine salt of dodecylbenzene sulfonic acid; C 2 ~C 18Alkyl naphthalene sulfonates or sulfonic acids, such as sodium butyl naphthalene sulfonate and sodium hexyl naphthalene sulfonate, and particularly sodium dodecyl benzene sulfonate or dodecyl benzene sulfonic acid, are mentioned, but not limited thereto. When it may be substituted with an alkyl substituent, the aryl sulfonate or sulfonic acid may be located at any point along the alkyl chain, for example, on primary, secondary or tertiary carbon. Suitable alkyl ester sulfonates or sulfonic acids include C 2 ~C 18 alkyl methyl ester sulfonates or sulfonic acids, such as methyl ester sulfonate, sodium dodecyl methyl ester α-sulfonate, sodium tetradecyl methyl ester α-sulfonate, and sodium hexadecyl methyl ester α-sulfonate, are mentioned, but not limited thereto. The sulfate group, sulfonate group, or sulfonic acid group may be located at any, for example, primary, secondary or tertiary carbon along the alkyl chain or aryl ring. Surfactants having two sulfonic acid groups, such as C 2 ~C 16 alkyl diphenyl oxide disulfonates or disulfonic acids, such as sodium dodecyl diphenyl oxide disulfonate, are also suitable. Suitable organic phosphonic acids include monovalent phosphonic acids, such as phenylphosphonic acid, 11-hydroxyundecylphosphonic acid, 2,4-xylylphosphonic acid, 4-ethylphenylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, p-(diphenylmethyl)phosphonic acid, 11-phosphonoundecanoic acid, and p-(1-naphthalenylmethyl)phosphonic acid, or diphosphonic acids, such as (12-phosphonododecyl)phosphonic acid and 1,8-octanediphosphonic acid, etc.

[0092] However, particularly preferably, the anionic surfactant is a monovalent sulfonic acid, particularly preferably dodecyl benzene sulfonic acid or its salt.

[0093] Ethylenically unsaturated compound (iii) At least one ethylenically unsaturated compound (iii) is a compound having one or more (meth)acrylic acid groups, a compound having one or more allyl groups, a compound having one or more vinyl groups, or a compound having a combination of at least two of these ethylenically unsaturated groups.

[0094] Preferred compounds having a (meth)acrylic acid group are neopentyl glycol acrylate, 1,6 - hexanediol (meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4 - cyclohexanetetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexatri(meth)acrylate, bis(2 - hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and isobornyl (meth)acrylate, which are polyfunctional (meth)acrylic acid monomers selected from the group consisting of these.

[0095] As the compound having a (meth)acrylic acid group, photocurable (meth)acrylate oligomers such as epoxy (meth)acrylate, urethane (meth)acrylate, and ester (meth)acrylate are also suitable.

[0096] Urethane (meth)acrylate can be prepared by reacting a polyfunctional (meth)acrylate having a hydroxyl group in the molecule with a compound having an isocyanate group in the presence of a catalyst. Specific examples of the (meth)acrylate having a hydroxyl group in the molecule include at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth)acrylate mixture, and dipentaerythritol penta / hexa (meth)acrylate mixture. Specific examples of the compound having an isocyanate group include at least one selected from the group consisting of 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1,5-diisocyanato-2-methyl-pentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclo-hexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenyl isocyanate), 4,4'-oxybis(phenyl isocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, and trimethylenepropanol adduct toluene diisocyanate.

[0097] Suitable compounds having a vinyl group or an allyl group are styrene and oligomers end-capped with a vinyl ether group, an allyl ether group, or any combination thereof.

[0098] Additive vi) Suitable additive vi) that can also be present in the composition according to the present invention includes a UV stabilizer, a heat stabilizer, an antioxidant, a UV absorber, a conductivity improver, an adhesion promoter, a polymer binder, a surfactant, or a combination of at least two of these additives. Suitable UV stabilizers can include absorbers, quenchers, and hindered amine light stabilizers (HALS) as classified according to their mechanism of action, or can include phenyl salicylate (absorber), benzophenone (absorber), benzotriazole (absorber), nickel derivatives (quencher), and radical scavengers as classified according to their chemical structure. As heat stabilizers, polyphenol primary heat stabilizers, phosphite secondary heat stabilizers, lactone secondary heat stabilizers, etc. are commercially available, and these can be used alone or in combination. Suitable antioxidants can be selected from the group consisting of hindered amine light stabilizers such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, and di(1,2,2,6,6-pentamethylpiperidin-4-yl), tetrakisalkylene (dialkylhydroxyaryl) alkyl ester alkanes such as tetrakis(methylene)(3,3’,5-dibutyl-4’-hydroxyphenyl)propionate methane, reaction products of glycidyl methacrylate with p-aminodiphenylamine or n-hexyl-N’-phenyl-p-phenylenediamine, pentaerythritol tetrakis(thioglycolate), trimethylolpropane tris(thioglycolate), trimethylolethane tris(thioglycolate), N-(4-anilinophenyl)acrylamide, N-(4-anilinophenyl)maleamic acid, N-(4-anilinophenyl)maleimide, alkylhydroxyphenyl groups having a carboalkoxy bond to a heterocyclic nitrogen compound containing an imidodicarbonyl or imidodithiocarbonyl group, 3,5-di-tert-butyl-4-hydroxycinnamitrile, ethyl-di-tert-hexyl-4-hydroxy-cinnamic acid, substituted benzyl ethers of β-substituted hydroxyphenylpropionic acid, bis-(hydroxyphenylalkylene)alkyl isocyanurates, tetrakishydroxybenzylphosphonium halides combined alone or with dialkylthioalkanoates, thiodimethylidinetetrakisphenols combined alone or with dialkylthioalkanoates, phosphites or phosphonates, dihydroxycarbylhydroxyphenylaryl or alkylphosphonites, phosphonates, phosphates, phosphites, phosphinates, phosphinites, phosphorothionates, or phosphinothionates, diphenylbis(3,5-ditert-butyl-4-hydroxyphenoxy)silane, hydrocarbylhydroxyl dihydrocarbyl dithiocarbamates such as 3,5-ditert-butyl-4-hydroxyphenyldimethyldithiocarbamate, and aminobenzylthioethers. Other suitable antioxidants and light stabilizers will be apparent to those skilled in the art.Suitable UV absorbers include dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, sulfonic acid-containing hydroxybenzophenone, 2,4-dihydroxy-3’,5’-di-tert-butylbenzophenone, 2,2’,4’-trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2’,4’-trihydroxy-4’-alkoxybenzophenone, 2-hydroxy-4-methoxy-2’-carboxybenzophenone, lower alkylthiomethylene-containing phenols, substituted benzenes such as 1,3-bis-(2’-hydroxybenzoyl)benzene, metal derivatives of 3,5-di-t-butyl-4-hydroxyphenylpropionic acid, asymmetric oxalic acid diarylamides, alkylhydroxyphenylthioalkanonic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri-pentaerythritol, 4,4’-dioctyloxy, 5,5’-di-tert-butyl-oxanilide, 2,2’-di-dodecyloxy-5,5’-di-tert-butyl-oxanilide, 2-ethoxy-2’-ethyl-oxanilide, N,N’-bis(3-dimethylaminopropyl)-oxanilide, and oxalic acid diamides such as 2-ethoxy-5-tert-butyl-2’-ethyloxanilide, phenyl and naphthalene-substituted oxalic acid diamides, methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, α,α-bis-(2-hydroxyphenol)-di-iso-propyl-benzene, 3,5’-dibromo-2’-hydroxyacetophenone, ester derivatives of 4,4’-bis-(4’-hydroxyphenyl)pentaenoic acid having at least one unsubstituted position ortho to the aromatic hydroxyl group, organic phosphorus sulfides such as bis(diphenylphosphinothioyl) monosulfide and bis(diphenylphosphino-thioyl) disulfide, 4-benzoyl-6-(dialkylhydroxybenzyl)resorcinol, bis(3-hydroxy-4-benzoylphenoxy)diphenylsilane, bis(3-hydroxy-4-benzoylphenoxy)dialkylsilane, 1,8-naphthalimide, α-cyano, β,It may contain compounds such as β-diphenylacrylic acid derivatives, bis-(2-benzoxazolyl)alkanes, bis-(2-naphthooxazolyl)alkanes, methylene malonitrile containing aryl and heterocyclic substituents, alkylene-bis-dithiocarbamate, 4-benzoyl-3-hydroxyphenoxyethyl methacrylate, aryl or alkyl substituted acrylonitrile, and 3-methyl-5-isopropylphenyl-6-hydroxycoumarone., Additives for enhancing conductivity include compounds such as tetrahydrofuran, lactone group-containing compounds such as butyrolactone and valerolactone, caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, amide group-containing compounds or lactam group-containing compounds such as N-methylpyrrolidone (NMP), pyrrolidone, sulfones and sulfoxides, such as sulfolane (tetramethylene sulfone), dimethyl sulfoxide (DMSO), sugars or sugar derivatives, such as sucrose, glucose, fructose, lactose, sugar-based surfactants, such as Tween or Span 60, sugar alcohols, such as sorbitol, mannitol, furan derivatives, such as 2-furancarboxylic acid, 3-furancarboxylic acid, and / or di- or polyalcohols, such as ethylene glycol, glycerol or di- or triethylene glycol. Tetrahydrofuran, N-methylformamide, N-methylpyrrolidone, ethylene glycol, dimethyl sulfoxide, or sorbitol is particularly preferably used as the conductivity-improving additive., Suitable adhesion promoters are, for example, organic functional silanes or their hydrolyzates, such as compounds like 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane., Suitable polymer binders are those that are soluble, in particular, in organic solvents, such as polyolefins, polyvinyl acetate, polycarbonates, polyvinyl butyral, polyacrylic esters, polyacrylamides, polymethacrylic esters, polymethacrylamides, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinyl pyrrolidone, polybutadiene, polyisoprene, polyethers, polyesters, polyurethanes, polyamides, polyimides, polysulfones, polysilicons, epoxy resins, styrene-acrylates, vinyl acetate / acrylates, and ethylene / vinyl acetate copolymers, polyvinyl alcohol, or cellulose derivatives can also be added to the composition. Copolymers of the above polymers are also suitable as polymer binders. Suitable surfactants are all amphiphilic compounds having a hydrophilic head group and a hydrophobic moiety. The hydrophilic group can be essentially both ionic and non-ionic. Due to their molecular structure and tendency to adhere to interfaces, substances of this class lower the interfacial tension and provide improved wetting properties. Suitable surfactants are, in particular, anionic surfactants such as paraffin sulfonates, alcohol sulfonates, ether sulfonates, sulfosuccinates, phosphate esters, alkyl ether carboxylic acids or carboxylates, cationic surfactants such as quaternary alkyl ammonium salts, and non-ionic surfactants such as linear alcohol ethoxylates, oxo alcohol ethoxylates, alkylphenol ethoxylates or alkyl polyglucosides.

[0099] Method for producing the composition according to the present invention In a first step for the formation of the composition according to the invention, the thiophene monomer is oxidatively polymerized in the presence of an organic compound ii) and an organic solvent iv). As the oxidizing agent, an oxidizing agent suitable for the oxidative polymerization of pyrrole can be used. Preferred oxidizing agents are organic peroxides such as tert-butyl peroxide, diisobutyryl peroxide, di-n-propyl peroxydicarbonate, didecanoyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, etc., and di-tert-amyl peroxide can also be used as an oxidizing agent. Organic azo compounds such as 2,2'-azodiisobutyronitrile can also be used. Particularly preferred oxidizing agents are organometal-free oxidizing agents such as organic peroxides, and dibenzoyl peroxide is most preferred.

[0100] The thiophene monomer is oxidatively polymerized by the reduction to the reduction product of the oxidizing agent and the oxidation of the thiophene monomer in the presence of the organic compound ii) to form polythiophene i) and a reduction product, and the polymerization is preferably carried out at a temperature in the range of 0 °C to 100 °C. In this regard, it is particularly preferred that the reaction temperature is in the range from 25 °C to a temperature below the lowest boiling point of the solvent contained in the reaction mixture.

[0101] The anion ii) present in the reaction mixture acts as a counter ion to compensate for the positive charge of the polythiophene i). The anion ii) and the polythiophene i) preferably exist in the form of a polythiophene / anion complex. In this regard, it is also preferred to obtain a composition containing the polythiophene i) and the anion ii), and it is particularly preferred that the composition exists in the form of a dispersion containing the organic solvent iv) in which this complex is dispersed.

[0102] In subsequent process steps, further components, in particular at least one ethylenically unsaturated compound iii) polymerizable in a radical chain reaction and other additives such as a radical initiator, etc., can be added to the dispersion thus obtained.

[0103] The present invention will be described in more detail by referring to the present invention, the drawings, the test method, and non-limiting examples.

[0104] Test method Solid content The solid content was determined by weight measurement using a precision scale (Mettler AE240). First, weigh an empty weighing bottle including the lid (weight A). Then, quickly fill the bottle with approximately 3 g of the dispersion to be analyzed, close it with the lid, and weigh it again to determine the exact total weight B. Next, place the bottle in a fume hood without lighting for approximately 3 hours to evaporate the volatile solvent at room temperature. In the second step, place the bottle in a ventilated drying oven (Memmert UNB200) at 160 °C for 16 - 17 hours. When removing the sample bottle from the oven, immediate covering with a glass lid is important due to the hygroscopicity of the dried dispersion material. After a cooling period of 10 - 15 minutes, weigh the bottle again including the lid to determine the weight C. Calculation of solid content: Solid content weight % = 100×(C - A) / (B - A)

[0105] The results are the average of two measured values.

[0106] Determination of solid content / solid content [%] The solid content / solid content [%] is determined by calculating the coated solid content (in grams as the basic unit) of the conductive dispersion by using a given solid content and the coating amount of the dispersion. Then, this value is divided by the total amount of solid content present in the coating mixture, again using grams as the basic unit.

[0107] Preparation of the film on the PET substrate The dispersion was applied to a polyethylene terephthalate substrate (Melinex 506, 175 μm thick) at room temperature using a manual wire bar (a close-wound K bar manufactured by RK PrintCoat Instruments Ltd.) with a gap spacing of either 6 μm or 12 μm. In this regard, the gap separation of the manual doctor blade determines the thickness of the wet film formed, which is also referred to as the wet film thickness. The coating or film thus formed was then dried in a drying oven at a given time and temperature. Before further processing, the coated PET substrate was cooled to room temperature.

[0108] In the experiments, when no other parameters were described, the wet film thickness was selected to be 12 μm and the drying process was carried out at 130 °C for 15 minutes.

[0109] Determination of surface resistivity The surface resistivity was measured at a 100 V setting using a Staticide ACL 800 Digital Megohmmeter. It was measured twice at different positions on the sheet and the lowest value was taken as the result.

[0110] Solvent compatibility determined by the RF value Place 1 g of the conductive dispersion into a 30 mL screw-cap bottle. While gently shaking, slowly add 9 g of a solvent (e.g., PGME) over 2 minutes while continuing to shake. After the addition of the solvent is complete, continue gentle shaking for an additional 3 minutes to ensure a uniform distribution of the dispersion in the solvent. Then, immediately draw a sample of the mixture into a 2 mL plastic pipette (VWR, REF 612-2849). Here, apply one drop of the mixture in the plastic pipette onto a 5×5 cm piece of filter paper (Schleicher & Schuell, 595 Rundfilter, REF.-No.: 311621). Observe the resulting circle in detail to determine the end point of the droplet diffusion in the filter paper. Once the diffusion has completely stopped, mark the boundary of the formed circle with a pencil to prevent changes due to solvent evaporation. The pattern formed results in two circles, namely, one inner circle from the solid content in the mixture and one outer circle from the solvent. The diameter of both circles is determined using a ruler, thereby ensuring the determination of the diameter passing through the common center point of both circles. Figure 1 visualizes the determination of the diameter, where A is the diameter of the outer circle and B is the diameter of the inner circle.

[0111] RF 1 The value is determined according to the following formula.

[0112]

Number

[0113] The second RF value, RF 2 is determined in the same way using the same pattern, but is orthogonal to the first measurement, ensuring again that the determination of the diameter is made through the common center point of both circles.

[0114] Here, the RF value is 1 and RF 2 is calculated by averaging them.

[0115]

Number

[0116] Transparency determination The total transmittance was measured using Haze-Guard Plus, Illum.C (Byk-Gardner GmbH). The coated PET substrate was pressed against the entrance port of the photometer sphere by a spring holder with the coating facing the sphere. The measurement area has a diameter of 18 mm. The reading displays the transmittance of the coated PET substrate. The transmittance of the uncoated PET substrate (Melinex 506, thickness 175 μm) is 90.5%.

Brief description of the drawings

[0117]

Figure 1

Figure 2

Examples

[0118] Example 1 (Reference example for the synthesis of 3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin)

[0119]

Chemical formula

[0120] The synthesis is carried out under dry and inert conditions.

[0121] THF (60 mL) and 18-crown-6 (0.200 g, 0.8 mmol) are added to a reaction vessel. NaH (1.512 g, 37.8 mmol) as a 60% suspension in oil is added with stirring, and the mixture is stirred at room temperature. At 0 °C, a solution of EDOT-MeOH (5.00 g, 29.0 mmol) in 20 mL of THF is added to the NaH solution. After the addition of the solution, the reaction mixture is stirred at room temperature for 2.5 h and then at 55 °C for 0.5 h. The reaction mixture is cooled to 0 °C, and a solution of 2-ethylhexyl bromide (7.300 g, 37.8 mmol) in 20 mL of THF is added. The reaction mixture is stirred at room temperature for 1 h and at 50 °C for 40 h. The reaction mixture is cooled to room temperature and quenched with a 70:30 (v / v) mixture of isopropanol / water. The crude product is purified by column chromatography.

[0122] The reaction product (3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]-dioxine) is obtained as a yellow oil in 15% yield.

[0123] Example 2 A 250 mL three-necked round-bottom flask equipped with a mechanical stirrer is charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol, Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60 °C, 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (6 mmol, ButylEDOT, CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g of the product (4 mmol) obtained from the reaction of Example 1 dissolved in 20 g of anisole are added over 40 min. The dispersion is stirred at 60 °C for an additional 3 h and then cooled to room temperature.

[0124] 50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed by gently stirring the resulting dispersion.

[0125] This is designated as Dispersion 2.

[0126] Analysis of Dispersion Liquid 2: Solid content: 2.3% (by weight) Sheet resistance (12 μm on PET): 170000 Ω / sq RF (PGME): 1 RF (MTBE): 0.4

[0127] The ion content of Dispersion Liquid 2 was measured by inductively coupled plasma optical emission spectrometry.

[0128]

Table 1

[0129] Example 3 A 250 mL three-necked round-bottom flask equipped with a mechanical stirrer was charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol, Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60 °C, 1.422 g of EDOT (10 mmol, CAS 126213-50-1, Heraeus) dissolved in 20 g of anisole was added over 40 minutes. The dispersion was stirred at 60 °C for an additional 3 hours and then cooled to room temperature.

[0130] 50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol were added to a 100 mL flask and mixed by gently stirring the resulting dispersion.

[0131] This is referred to as Dispersion Liquid 3.

[0132] Analysis of Dispersion Liquid 3 Solid content: 1.8% (by weight) Sheet resistance (12 μm on PET): 5800 Ω / sq RF (PGME): 0.4

[0133] Example 4 A 250 mL three-necked round-bottom flask equipped with a mechanical stirrer was charged with 65 g of anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol, Aldrich), and 1.732 g of ethylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60 °C, 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (6 mmol, ButylEDOT, CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g of the product (4 mmol) obtained from the reaction of Example 1 dissolved in 20 g of anisole were added over 40 minutes. The dispersion was stirred at 60 °C for an additional 3 hours and then cooled to room temperature.

[0134] 50 g of the dispersion, 30 g of anisole, and 20 g of n-butanol were added to a 100 mL flask and mixed by gently stirring the resulting dispersion.

[0135] This is referred to as Dispersion 4.

[0136] Analysis of Dispersion 4 Solid content: 1.2% (by weight) Sheet resistance (on PET, 12 μm): 170000 Ω / sq RF (PGME): 1

[0137] Example 5 (According to the teachings of International Publication No. WO 2012 / 059215). A 1 L three-necked round-bottom flask equipped with a mechanical stirrer was charged with 294 g of anisole (Aldrich), 9.4 g of dibenzoyl peroxide (39 mmol, Aldrich), 8.25 g of sulfonated block copolymer (Kraton Nexar® MD), and 7.2 g of para-toluenesulfonic acid (38 mmol, Aldrich). After heating to 60 °C, a solution of 4.95 g of 3,4-ethylenedioxythiophene (35 mmol, Clevios M V2, Heraeus Deutschland GmbH & Co KG, Germany) dissolved in 20 g of anisole was added over 40 minutes. The dispersion was stirred at 60 °C for an additional 3 hours and then cooled to room temperature.

[0138] 20 g of the dispersion obtained after filtration and 20 g of butyl acetate were mixed in a 50 ml glass bottle and subjected to ultrasonic treatment for 2 minutes (Hielscher UP 200 S, cycle 1, amplitude 100%). This sample is referred to as dispersion 5.

[0139] Analysis of dispersion 5: Solid content: 2.5% (by weight) Sheet resistance (12 μm on PET): 17,000 Ω / sq RF (PGME): 0.4

[0140] Example 6 Dispersion 2, dispersion 3, dispersion 4, dispersion 5, and Clevios PH1000 (aqueous PEDOT:PSS dispersion, Heraeus) were tested for their compatibility with Sartomer's SR 399 (CAS 384855-91-7) and 1-hydroxycyclohexyl phenyl ketone from Sigma Aldrich as a photoinitiator in PGME as a solvent. The amounts of the compounds used are shown in Table 1.

[0141] Starting from the conductive dispersion, followed by PGME, SR399, and finally the photoinitiator, the components were thoroughly mixed by stirring. The mixture was stirred in the dark for 15 minutes.

[0142] A 6 μm wet film was deposited on a PET substrate using a wire bar and dried in an oven at 75 °C for 3 minutes. After drying, the coated sheet was exposed in a UV chamber at 600 mJ / cm 2 and the surface resistivity and transmittance of the PET sheet were determined.

[0143]

Table 2

[0144] Examples 6A, 6B, and 6C demonstrate that dispersions using polyanions do not achieve an acceptable sheet resistance.

[0145] Examples 6D, 6E, 6F, and 6G demonstrate that aqueous dispersions do not achieve sufficient sheet resistance in the low range. At the high range, significant precipitation is observed (Examples 6E, 6F, and 6G).

[0146] Examples 6H, 6I, and 6J demonstrate that dispersions using EDOT and monovalent sulfonic acid treat the excellent sheet resistance of the initial dispersion but do not result in an acceptable sheet resistance in the cured film.

[0147] Examples 6K, 6L, 6M, 6N, and 6O demonstrate the excellent performance of dispersions containing branched EDOT.

[0148] Example 7 This example shows the adverse effect of water in an antistatic solvent-based hard coating formulation.

[0149] Coating Premix A was prepared by combining Dispersion 2 (1,370 g), PGME (1.011 g), SR399 (1 g, Sartomer), and 1-hydroxycyclohexyl phenyl ketone (0.05 g, Sigma Aldrich). These components were thoroughly mixed by stirring. Subsequently, Premix A was mixed with deionized water in the amounts shown in Table 2. The mixture was stirred for 1 hour. Then, the coating was applied as a 6-μm wet film to a Melinex 506 PET substrate, dried at 75°C for 3 minutes, and exposed to UV irradiation at 600 mJ / cm 2 and the surface resistivity was determined.

[0150] [Table 3]

[0151] As shown in Example 7D, a water content of 2% or more causes loss of the antistatic function of the hard coating.

[0152] Example 8 The coating was prepared by mixing the components shown in Table 3. 1-hydroxycyclohexyl phenyl ketone (Sigma Aldrich) was used as a photoinitiator. DPHA was purchased from Sigma Aldrich (dipentaerythritol-penta- / hexaacrylate, CAS 60506-81-2). These components were thoroughly mixed by stirring. The mixture was stirred for 15 minutes. Then, the coating was applied as a 12-μm wet film to a Melinex 506 PET substrate, dried at 75°C for 3 minutes, and exposed to UV irradiation at 600 mJ / cm 2 and the surface resistivity and transmittance were determined.

[0153] [Table 4]

[0154] Example 9 The examples demonstrate the difference in pencil hardness between the cured composition and the uncured composition according to the present invention. Further examples demonstrate the difference between the cured coating from the composition according to the present invention and the coating from a composition containing already polymerized acrylate.

[0155] The coating was prepared by mixing the components shown in Table 4. 1-Hydroxycyclohexyl phenyl ketone (Sigma Aldrich) was used as a photoinitiator. SR399 was purchased from Sartomer. These components were thoroughly mixed by stirring. The mixture was stirred for 15 minutes. Thereafter, the coating was applied as a 12 μm wet film to a glass substrate and dried at 75 °C for 3 minutes.

[0156] Example 9A was further exposed to UV irradiation at 600 mJ / cm 2 Thereafter.

[0157] The pencil hardness of the resulting coating was determined according to the Wolf-Wilburn pencil hardness test. In the test, a pencil of hardness H was attached to a 5800 scratch resistance kit manufactured by BYK instruments. Then, the instrument was pressed onto the coated glass substrate. Thereafter, the coating was inspected carefully. If no damage to the coating was observed, a pencil with a hardness point 1H higher was attached to the 5800 scratch resistance kit and the measurement was repeated at another location. The pencil hardness shown in Table 4 is the first pencil hardness that causes visible damage to the coating.

[0158]

Table 5

[0159] Example 10 The examples demonstrate the performance of Dispersion 2 and Dispersion 4 in cured compositions based on various organic solvents. Further, the RF values determined in PGME demonstrate that, generally, independent of the solvent used, they predict the performance of the conductive dispersions in the compositions according to the present invention. RF value of Dispersion 2 in PGME: 1 RF value of dispersion 3 in PGME: 0.4

[0160] The components shown in Table 5 were mixed with 0.05 g of 1-hydroxycyclohexyl phenyl ketone (Sigma Aldrich, photoinitiator) and 0.95 g of DPHA (Sigma Aldrich, dipentaerythritol-penta- / hexaacrylate, CAS 60506-81-2) to prepare a coating. These components were thoroughly mixed by stirring. The mixture was stirred for 15 minutes. Then, the coating was applied as a 12-μm wet film on a Melinex 506 PET substrate, dried at 75 °C for 3 minutes, and exposed to UV irradiation at 600 mJ / cm 2 and the surface resistivity was determined.

[0161]

Table 6

[0162] Example 11 The contact angle of water on the films coated from dispersion 2 and dispersion 3 was determined. One coated PET sheet was produced from each of the dispersions by applying a 12-μm wet film of the dispersion on a Melinex 506 PET sheet and drying the resulting coated sheet at 130 °C for 15 minutes.

[0163] Here, the contact angle of the water droplet was determined using a Kruss FM40 Easy Drop device. To determine the contact angle, a syringe filled with deionized water was attached to the device. Here, a 2-μL droplet was placed on the coated PET sheet. The contact angle was determined 2 seconds after the application of the droplet using the "tangent-2" fitting method. The measurement was repeated using three water droplets at three positions on the PET film. The reported value was obtained by averaging the measurements performed. The results obtained are shown in Figure 6.

[0164]

Table 7

[0165]

Table 8

Claims

1. A composition comprising: i) at least one polythiophene consisting only of monomer units of structure (I) 【Chemical 1】 [wherein, ＊ indicates the bond to adjacent monomer units, X and Z each represent O or S, R １ ~R ４ each independently represents a hydrogen atom or an organic residue R, provided that at least one of the residues R １ ~R ４ represents an organic residue R], ii) at least one organic compound having at least one acid group, or a salt of said organic compound, wherein the molecular weight of said organic compound or its salt is less than 1,000 g / mol, an organic compound or its salt, iii) at least one ethylenically unsaturated compound, iv) at least one organic solvent, v) at least one radical initiator.

2. A composition comprising: i) at least one polythiophene characterized by its compatibility in PGME (1-methoxypropan-2-ol) as indicated by an RF value of at least 0.8, at least one polythiophene, said at least one polythiophene is at least one polythiophene consisting only of monomer units of structure (I), 【Chemical 2】 [wherein, * represents a bond to an adjacent monomer unit, X and Z each represent O or S, R1 to R4 each independently represent a hydrogen atom or an organic residue R, provided that at least one of the residues R1 to R4 represents an organic residue R], iii) at least one ethylenically unsaturated compound, iv) at least one organic solvent, v) at least one radical initiator.

3. The polythiophene i) is such that X and Z represent O, and R １ , R ２ , R ３ , and R ４ wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residue represents an ether group having the structural formula (Ia), and is a homopolymer or copolymer containing the monomer unit of structure (I) 【Chemical Formula 3】 [wherein, R ７ is an H, C １ ~C １０ -alkyl group or C １ ~C １０ -alkoxy group, and R ８ is an H, C １ ~C １０ -alkyl group or C １ ~C １０ -alkoxy group, and n is an integer from 0 to 10, R ９ is an alkyl group, an alkoxy group, an aryl group, an ether group, or an ester group], the composition according to claim 1.

4. wherein polythiophene i represents O for X and Z, and R １ , R ２ , R ３ and R ４ The composition according to claim 1, which is a homopolymer or copolymer containing a monomer unit of structure (I), wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent a branched alkyl group or a branched ether group.

5. The remaining residue represents a branched ether group having structural formula (Ib) 【Chemical 4】 [wherein, R １０ is an H, C １ to C １０ -alkyl group or C １ to C １０ -alkoxy group, and R １１ is an H, C １ to C １０ -alkyl group or C １ to C １０ -alkoxy group, and n is an integer from 0 to 10, R １２ is a branched organic residue], the composition according to claim 4.

6. The composition according to claim 1, wherein said at least one organic compound ii) having one acid group is a monovalent sulfonic acid or a salt thereof.

7. The composition according to claim 1, wherein said at least one ethylenically unsaturated compound iii) is a compound having one or more (alk)acrylic acid groups.

8. The at least one organic solvent iv) is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, anisole, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof, or a mixture of one or two of these aprotic solvents and one or two further solvents, the composition according to claim 1.

9. The at least one radical initiator is a photo radical initiator capable of forming radicals upon light irradiation, the composition according to claim 1.

10. The composition has a water content of less than 2% by weight based on the total weight of the composition, the composition according to claim 1.

11. A method for preparing a layer structure (100), comprising: A) preparing a substrate (101); B) coating the substrate (101) with the composition according to claim 1; C) optionally, at least partially removing the organic solvent iv); D) exposing the coated substrate (101) to electromagnetic radiation, an electron beam, heat, or a combination of at least two of these to cure the composition by polymerizing the at least one ethylenically unsaturated compound iii) by radical chain reaction.

12. A layer structure (100), comprising: a) a substrate (101); b) a conductive layer (102) coated on the substrate (101), the conductive layer (102) comprising at least one polythiophene consisting only of monomer units of structure (I) [Chemical Formula 5] wherein ＊ indicates the bonding to adjacent monomer units, X, Z represent O or S; R １ ~R ４ each independently represents a hydrogen atom or an organic residue R, provided that at least one of the residues R １ ~R ４ represents an organic residue R]. at least one organic compound having at least one acid group, or a salt of the organic compound, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, the organic compound or its salt; a polymer matrix based on a polymerized ethylenically unsaturated compound iii) in which at least one polythiophene is embedded, and the conductive polymer layer has a pencil hardness of at least 1H.

13. A layer structure (100), comprising: a) a substrate (101), b) a conductive layer (102) coated on the substrate (101), and the conductive layer (102) is at least one polythiophene characterized by its compatibility in PGME (1-methoxypropan-2-ol) as indicated by an RF value of at least 0.8, the at least one polythiophene is at least one polythiophene consisting only of monomer units of structure (I), 【Chemical Formula 6】 [wherein, * represents a bond to an adjacent monomer unit, X, Z represent O or S, R1 to R4 each independently represent a hydrogen atom or an organic residue R, provided that at least one of the residues R1 to R4 represents an organic residue R], a polymer matrix based on a polymerizable ethylenically unsaturated compound iii) in which the at least one polythiophene is embedded, the conductive polymer layer has a layer structure having a pencil hardness of at least 1H.

14. An electronic component comprising the layer structure (100) according to claim 12 or 13.

15. Use of the composition according to claim 1 for producing a conductive layer in an electronic component or for producing an antistatic coating.

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