Curable conductive compositions

Abstract

To provide a composition comprising a conductive polymer based on thiophene monomers, dissolved or dispersed in an organic solvent.SOLUTION: A composition comprises i) a polythiophene comprising monomer units of structure (I) in which * indicates the bond to the neighboring monomer units, x, z represent O or S, R1-R4 represent a hydrogen atom or an organic residue R, or a polythiophene characterized by its compatibility in 1-methoxypropan-2-ol, demonstrated by an RF-value of at least 0.8; iii) at least one ethylenically unsaturated compound; iv) at least one organic solvent; and v) at least one radical initiator.SELECTED DRAWING: Figure 1

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 invention.

[0002] Polythiophenes are widely used intrinsically conductive polymers. In particular, poly(3,4-ethylenedioxythiophene) (PEDOT) has found many industrial applications, including solid-state electrolytic capacitors, antistatic coatings, electroluminescent lamps, organic light-emitting diodes, and organic solar cells. For many of these applications, PEDOT is used as a polymer complex with polystyrene sulfonate as the counterion (also known as "PEDOT / PSS") dispersed in water or a mixture of water and other solvents.

[0003] To expand the range of applications, efforts have been made to provide PEDOT in aprotic solvents. International Publication No. 2012 / 059215 discloses the use of block copolymers as counterions to make dispersions soluble in organic aprotic solvents. The solubility parameter of the block copolymer governs and limits the solubility characteristics of the resulting PEDOT complex. Therefore, when solvents such as PGMEA or ethanol are added, the dispersion becomes unstable.

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

[0005] McCullough et al. ("A Simple Method for Preparing Head-to-Tail Linked Regioregular Poly(3-Alkylthiophenes) Using Grignard Metathesis," Adv. Mater. 1999, 11, 250) describe 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 hole-transport layers, where only through-layer conductivity is required.

[0006] WO 2021 / 063956 discloses an organic solvent-based composition comprising a PEDOT derivative and a monomer anion as a counterion. When blended with an inert polymer such as polyacrylate, the composition still exhibits 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 to form antistatic layers.

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

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

[0009] It was also an object of the present invention to provide stable compositions, preferably storage-stable compositions comprising a conductive polymer based on thiophene monomers dissolved or dispersed in an organic solvent, with which conductive layers characterized by a particularly advantageous hardness can be prepared. The term "storage-stable" as used herein preferably characterizes compositions that do not exhibit the formation of a precipitate after storage in the dark for 15 days, more preferably for 30 days.

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

[0011] A 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, said composition comprising: i) at least one polythiophene comprising monomer units of structure (I)

[0012] [ka] [In the formula, * indicates a bond to an adjacent monomer unit, X and Z represent O or S; R 1 ~R 4 represent, independently of one another, a hydrogen atom or an organic residue R, provided that the residue R 1 ~R 4 at least one of which represents an organic residue R; ii) at least one organic compound or a salt thereof having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol; 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.

[0013] A contribution to solving at least one of the objects according to the present invention is made by a second embodiment of a composition, preferably a curable composition, even more preferably a composition that is curable when exposed to electromagnetic radiation, an electron beam, or heat, said 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 0.6, preferably at least 0.8, more preferably 1.0; ii) optionally at least one organic compound or a salt thereof having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol; 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.

[0014] Surprisingly, certain polythiophenes, e.g., those having residues R 1 ~R 4It has been found that polythiophenes comprising monomer units of structure (I) above, in which at least one of the groups represents a branched alkyl group or a branched ether group, are particularly suitable for use as conductive polymers in organic solvent-based curable compositions containing at least one ethylenically unsaturated compound polymerizable by a radical chain reaction. Curing such compositions by polymerizing the polymerizable compound in the presence of the polythiophene to form a polymer matrix in which the polythiophene is embedded can yield conductive layers characterized not only by high conductivity and transparency but also by a sufficiently high hardness. Furthermore, it has been observed that these compositions are characterized by outstanding storage stability.

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

[0016] In a further preferred embodiment of the first embodiment of the composition according to the invention, the polythiophene i) has the formula: X and Z denote O, R 1 , R 2 , R 3 and R 4wherein three of the residues selected from the group consisting of represent hydrogen atoms and the remaining residues represent ether groups having structural formula (Ia).

[0017] [ka] [In the formula, R 7 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 7 is most preferably H, R 8 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 8 is most preferably H, n is an integer ranging from 0 to 10, preferably from 1 to 6, more preferably from 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 C1 to C 30 Alkyl groups, more preferably C2 to C 25 -Alkyl group, even more preferably C5-C 20 -alkyl group]

[0018] This preferred embodiment is a fourth embodiment of the composition according to the invention, which 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, the polythiophene i) is 1 , R 2 , R 3 and R4 and a homopolymer or copolymer comprising monomer units of structure (I), wherein three of the residues selected from the group consisting of: represent hydrogen atoms, and the remaining residues represent branched alkyl or branched ether groups. In this regard, it is also particularly preferred that the remaining residues do not have sulfonic acid groups or salts of such groups. This preferred embodiment is a fifth embodiment of the composition according to the present invention, and is preferably subordinate to any of the first, third, and fourth embodiments. As used herein, the term "branched ether group" preferably defines an ether group in which at least one of the two organic residues bonded to the oxygen atom is a branched organic residue, i.e., an organic residue containing at least three carbon atoms, or at least two carbon atoms and at least one carbon atom bonded to an oxygen atom that is part of the ether group, via a single bond.

[0020] In a further preferred embodiment of the first embodiment of the composition according to the invention, the polythiophene i) has the formula: X and Z denote O, 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 residues represent branched alkyl groups.

[0021] This preferred embodiment is a sixth embodiment of the composition according to the invention, which 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] [ka]

[0023] In a further preferred embodiment of the first embodiment of the composition according to the invention, the polythiophene i) is 1 , R 2 , R 3and R 4 wherein three of the residues selected from the group consisting of represent hydrogen atoms, and the remaining residues represent branched ether groups having structural formula (Ic).

[0024] [ka] [In the formula, R 10 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 10 is most preferably H, R 11 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 11 is most preferably H, n is an integer ranging from 0 to 10, preferably from 1 to 6, more preferably from 1 to 3, and most preferably n is 1; R 12 is 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 that does not have an unsaturated C=C bond in the alkyl chain, even more preferably an organic residue having the formula (Id),

[0025] [ka] During the ceremony, m is 1, 2 or 3; R 13 is H or C1~C 12 Alkyl groups, preferably C2 to C 10alkyl group, more preferably a C3 to C8 alkyl group, and even more preferably a butyl group, provided that m structural units -CHR 13 In only one of the 13 is C1~C 12 is an alkyl group, R 14 is C1~C 10 -alkyl group, preferably a C2-C6 alkyl group, or an aryl group.

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

[0027] [ka]

[0028] In a further preferred embodiment of the first embodiment of the composition according to the invention, the polythiophene i) is a copolymer of monomer units of structure (I) with 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, wherein the copolymer comprises 5 to 95% of monomer units of structure (I), preferably 10 to 80%, and more preferably 20 to 60%, in each case based on the total number of thiophene monomer units. This preferred embodiment is an eighth embodiment of the composition according to the invention, and preferably depends on any one of the first or 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-dioxine, 2-propyl-2,3-dihydro-thieno[3,4-b]-1,4-dioxine, 2-butyl-2,3-dihydro-thieno[3,4-b]-1,4-dioxine and 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxine, the use of 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxine being particularly preferred.

[0029] In a further preferred embodiment of the first embodiment of the composition according to the invention, the polythiophene i) is characterized by its compatibility in PGME (1-methoxypropan-2-ol), as evidenced by an RF value of at least 0.6, preferably at least 0.8, more preferably 1.0. This preferred embodiment is a ninth embodiment of the composition according to the invention, which is preferably dependent on the first or any one of 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 a tenth embodiment of the composition according to the invention and is preferably dependent 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 comprising monomer units of structure (I).

[0032] [ka] [In the formula, * indicates a bond to an adjacent monomer unit, X and Z represent O or S; R 1 ~R 4 represent, independently of one another, a hydrogen atom or an organic residue R, provided that the residue R 1 ~R 4 at least one of which represents an organic residue R]

[0033] This preferred embodiment is an eleventh embodiment of the composition according to the invention, which is preferably dependent 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, the 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, which are a sulfonic acid group (-SO2OH), a sulfate group (-O-SO2OH), a phosphonic acid group (-PO(OH)2), a phosphate group (-O-PO(OH)2 or a salt thereof, preferably a sulfonic acid group (-SO2OH) or a salt thereof. This preferred embodiment is a twelfth embodiment of the composition according to the invention, which preferably depends from 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 invention, the organic compound ii) having at least one acid group is an anionic surfactant. This preferred embodiment is a thirteenth embodiment of the composition according to the invention, which is preferably dependent on any one of the first to twelfth embodiments.

[0036] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the 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, with the use of dodecylbenzenesulfonic acid being particularly preferred. As used herein, the term "dodecylbenzenesulfonic acid" also encompasses mixtures of alkylbenzenesulfonic acids, including, in addition to dodecylbenzenesulfonic acid, alkylbenzenesulfonic acids with alkyl chains longer or shorter than the dodecyl group. This preferred embodiment is a 14th embodiment of the composition according to the invention, preferably subordinate to any one of the first to 13th embodiments.

[0037] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the weight ratio of polythiophene i) to at least one organic compound having at least one acid group in the composition ii) 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 a twelfth embodiment of the composition according to the invention, which is preferably dependent on any one of the first to eleventh embodiments.

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

[0039] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the 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 a 16th embodiment of the composition according to the invention, which is preferably dependent on any one of the first to fifteenth embodiments. The term "(meth)acrylic acid", as used herein, refers to both acrylic acid derivatives as well as 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 invention, the composition comprises at least one ethylenically unsaturated compound iii) polymerizable in a radical chain reaction in an amount in the range of 30 to 99.99% by weight, more preferably in an amount in the range of 50 to 98% by weight, and most preferably in an amount in the range of 80 to 95% by weight, in each case based on the solids content of the composition. This preferred embodiment is a 17th embodiment of the composition according to the invention, which preferably depends from any one of the 1 to 16 embodiments.

[0041] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the weight ratio of the total weight of the polythiophene i) and the organic compound having at least one acid group ii) 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 an 18th embodiment of the composition according to the invention, which preferably depends from any one of the 1 to 17th embodiments.

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

[0043] In a further preferred embodiment of the first and second embodiments of the composition according to the 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 a 20th embodiment of the composition according to the invention, which is preferably dependent on any one of the first to nineteenth embodiments.

[0044] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the 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 mixtures of one or two of these aprotic solvents with one or two further solvents. This preferred embodiment is a 21st embodiment of the composition according to the invention, which is preferably subordinate to any one of the first 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 invention, the at least one radical initiator is a photoradical initiator capable of forming radicals upon irradiation with light, more preferably a UV photoradical initiator capable of forming radicals upon irradiation with UV light.

[0046] This preferred embodiment is a 22nd embodiment of the composition according to the invention, which preferably depends from any one of the 1st to 21st embodiments.

[0047] Suitable examples of the radical initiator v) include Type 1 initiators, which generate radicals by molecular decomposition due to differences in chemical structure or molecular bond energy, and Type 2 initiators, which cause hydrogen abstraction in the presence of a tertiary amine. The Type 1 initiator may 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, and 1-hydroxycyclohexylphenyl ketone; benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzyl dimethyl ketal; phosphine oxides; and titanocene compounds. The type 2 initiator may 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, and 3'-methyl-4-methoxybenzophenone, and thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and isopropylthioxanthone. These photoinitiators may be used alone or in combination, or a mixture of type 1 and type 2 photoinitiators may be used.

[0048] In a further preferred embodiment of the first and second embodiments of the composition according to the invention, the composition comprises 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 a 23rd embodiment of the composition according to the invention, which is preferably dependent on any one of the 1st to 22nd embodiments.

[0049] In a further preferred embodiment of the first and second embodiment of the composition according to the invention, the composition comprises: vi) further comprising 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 a 24th embodiment of the composition according to the invention, preferably dependent 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 invention, the composition comprises an additive vi) 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, in each case based on the solids content of the composition. This preferred embodiment is a 25th embodiment of the composition according to the invention, which is preferably dependent 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 invention, the composition has a water content of less than 2 wt.-%, preferably less than 1 wt.-%, even more preferably less than 0.5 wt.-%, in each case based on the total weight of the composition. This preferred embodiment is a 26th embodiment of the composition according to the invention, which is preferably dependent 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 invention, the composition has an iron content of less than 10 ppm, preferably less than 1 ppm, more preferably less than 0.1 ppm, in each case based on the total weight of the composition. This preferred embodiment is a 27th embodiment of the composition according to the invention, which is preferably dependent from any one of the 1st to 26th embodiments.

[0054] In a further preferred embodiment of the first and second embodiment of the composition according to the invention, the conductive layer prepared using the composition has a maximum of 1×10 10 Ω / sq, preferably up to 5×10 9 Ω / sq, preferably up to 1×10 8 This preferred embodiment is a 28th embodiment of the composition according to the present invention, which preferably depends from 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 invention, a 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 a 29th embodiment of the composition according to the invention, which preferably depends from any one of the 1st to 28th embodiments.

[0056] A contribution to solving at least one of the objects according to the invention can also be made by a first embodiment of a process for the preparation of a layer structure, which process comprises: A) preparing a substrate; B) coating the substrate with a composition according to the present invention; C) optionally 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 the at least one ethylenically unsaturated compound iii) in 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-transmitting. Transparent substrates 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-naphthalenedicarboxylate), copolycarbonate, polysulfone, polyethersulfone (PES), polyimide, polyethylene, polypropylene, or cyclic polyolefins or cyclic olefin copolymers (COC), hydrogenated styrene polymers or copolymers. Rigid or flexible substrates can be used. This preferred embodiment is a second embodiment of the method according to the invention, preferably subordinate to the first embodiment.

[0058] In a further preferred embodiment of the method according to the invention, coating the substrate with the composition according to the invention in method step B) is achieved by immersion, dipping, pouring, dripping, 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, which is preferably subordinate to the first or second embodiment.

[0059] A contribution to solving at least one of the objects according to the invention is also made by the layer structure obtainable 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] A contribution to solving at least one of the objects according to the invention is also made by a first embodiment of the following layer structure. a) a substrate; b) a conductive layer coated on the substrate, the conductive layer comprising: At least one polythiophene containing monomer units of structure (I):

[0061] [ka] [In the formula, * indicates a bond to an adjacent monomer unit, X and Z represent O or S; R 1 ~R 4 represent, independently of one another, a hydrogen atom or an organic residue R, provided that the residue R 1 ~R 4 at least one of which represents an organic residue R; at least one organic compound or a salt thereof having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, a polymer matrix based on polymerized ethylenically unsaturated compounds 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, and more preferably at least 3H.

[0062] A contribution to solving at least one of the objects according to the invention is also made by a second embodiment of the layer structure below. a) a substrate; b) a conductive layer coated on the substrate, the conductive layer comprising: 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; optionally at least one organic compound or a salt thereof having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, wherein the molecular weight of the organic compound or the salt thereof is less than 1,000 g / mol, a polymer matrix based on polymerized ethylenically unsaturated compounds 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, and more preferably at least 3H.

[0063] In a further preferred embodiment of the first embodiment of the layer structure according to the invention, the polythiophene i) is 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 residues represent ether groups having structural formula (Ia).

[0064] [ka] [In the formula, R 7 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 7 is most preferably H, R 8 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 8 is most preferably H, n is an integer ranging from 0 to 10, preferably from 1 to 6, more preferably from 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 C1 to C 30 Alkyl groups, more preferably C2 to C 25 -Alkyl group, even more preferably C5-C 20 -alkyl group]

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

[0066] In a further preferred embodiment of the first embodiment of the layer structure according to the invention, the polythiophene i) is 1 , R 2 , R 3 , and R 4 and a homopolymer or copolymer comprising monomer units of structure (I), wherein three of the residues selected from the group consisting of are hydrogen atoms, and the remaining residues are branched alkyl or branched ether groups. In this regard, it is also particularly preferred that the remaining residues do not have a sulfonic acid group or a salt of this group. This preferred embodiment is a fourth embodiment of the layer structure according to the invention, and is preferably subordinate to the first or third embodiment.

[0067] In a further preferred embodiment of the first embodiment of the layer structure according to the invention, the polythiophene i) is 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 residues represent branched alkyl groups.

[0068] This preferred embodiment is a fifth embodiment of the layer structure according to the present invention, which is preferably dependent on the fourth 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).

[0069] [ka]

[0070] In a further preferred embodiment of the first embodiment of the layer structure according to the invention, the polythiophene i) is 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 residues represent branched ether groups having structural formula (Ic).

[0071] [ka] [In the formula, R 10 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 10 is most preferably H, R 11 H, C1~C 10 -alkyl group, preferably a C1-C5-alkyl group, more preferably a methyl group, or a C1-C 10 -alkoxy group, preferably C1-C5-alkoxy group, more preferably methoxy group, and R 11 is most preferably H, n is an integer ranging from 0 to 10, preferably from 1 to 6, more preferably from 1 to 3, and most preferably n is 1; R12 is 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 that does not have an unsaturated C=C bond in the alkyl chain, even more preferably an organic residue having the formula (Id),

[0072] [ka] During the ceremony, m is 1, 2, or 3; R 13 is H or C1~C 12 Alkyl groups, preferably C2 to C 10 alkyl group, more preferably a C3 to C8 alkyl group, and even more preferably a butyl group, provided that m structural units -CHR 13 In only one of the 13 is C1~C 12 is an alkyl group, R 14 is C1~C 10 -alkyl group, preferably a C2-C6 alkyl group, or an aryl group.

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

[0074] [ka]

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

[0076] In a preferred embodiment of the second embodiment of the layer structure 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 an eighth embodiment of the layer structure according to the invention, which is preferably dependent on the second embodiment.

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

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

[0079] This preferred embodiment is a ninth embodiment of the composition according to the invention, which is preferably dependent 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 invention, the 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, which are a sulfonic acid group (-SOOH), a sulfate group (-O-SOOH), a phosphonic acid group (-PO(OH)), a phosphoric acid group (-O-PO(OH)) or a salt thereof, preferably a sulfonic acid group (-SOOH) or a salt thereof. This preferred embodiment is a tenth embodiment of the layer structure according to the invention, which preferably depends from 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 invention, the organic compound ii) having at least one acid group is an anionic surfactant. This preferred embodiment is an eleventh embodiment of the layer structure according to the invention, which preferably depends from any one of the first to tenth embodiments.

[0082] In a further preferred embodiment of the first and second embodiments of the layer structure according to the present invention, the 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, with dodecylbenzenesulfonic acid being particularly preferred. As used herein, the term "dodecylbenzenesulfonic acid" also encompasses mixtures of alkylbenzenesulfonic acids, including, in addition to dodecylbenzenesulfonic acid, alkylbenzenesulfonic acids with alkyl chains longer or shorter than the dodecyl group. This preferred embodiment is a twelfth embodiment of the layer structure according to the present invention, which preferably depends on any one of the first to eleventh embodiments.

[0083] In a further preferred embodiment of the first and second embodiments of the layer structure according to the invention, the weight ratio of polythiophene i) to at least one organic compound having at least one acid group ii) 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 a thirteenth embodiment of the layer structure according to the invention, which preferably depends from any one of the first to twelfth embodiments.

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

[0085] In a further preferred embodiment of the first and second embodiments of the layer structure according to the invention, the at least one ethylenically unsaturated compound iii) on which the polymer matrix is ​​based (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 a 15th embodiment of the layer structure according to the invention, which preferably depends from any one of the first to fourteenth embodiments.

[0086] In a further preferred embodiment of the first and second embodiments of the layer structure according to the invention, the layer structure comprises the polymer forming the polymer matrix in an amount in the range of 30 to 99.99 wt. %, more preferably in an amount in the range of 50 to 98 wt. %, most preferably in an amount in the range of 80 to 95 wt. %, in each case based on the total weight of the conductive layer. This preferred embodiment is a 16th embodiment of the layer structure according to the invention, which is preferably dependent on any one of the 1 to 15 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 organic compound having at least one acid group ii) 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 a 17th embodiment of the layer structure according to the present invention, which preferably depends from any one of the first to sixteenth embodiments.

[0088] In a further preferred embodiment of the first and second embodiments of the layer structure according to the invention, 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%. This preferred embodiment is an 18th embodiment of the layer structure according to the invention, which is preferably dependent on any one of the 1 to 17 embodiments.

[0089] A contribution to achieving at least one of the objects according to the invention is also made by an electronic component, in particular an organic light-emitting diode, an organic solar cell or a capacitor, which comprises a layer structure according to the invention.

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

[0091] ii) an organic compound having at least one acid group or a salt thereof; The organic compound ii) having at least one acid group or a salt thereof present in the composition or layer structure according to the invention preferably comprises an anionic surfactant, more preferably selected from the group consisting of organic phosphonic acids, organic phosphoric acids, organic sulfonic acids, such as sulfonic acids, for example 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 with different alkyl chain lengths. Suitable alkyl sulfates include C8 to 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, include, but are not limited to, 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. Suitable alkyl ether sulfates include C8 to C18 Alkyl ether sulfates, including but not limited to, sodium laureth sulfate and sodium myreth sulfate. Suitable alkyl sulfonates include C8-C 18 Alkyl sulfonates, including but not limited to sodium tetradecyl sulfonate, sodium octadecyl sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate and the corresponding sulfonic acids. Suitable aryl sulfonates or sulfonic acids, optionally substituted with alkyl or aryl substituents, include C2-C 18 Alkylbenzenesulfonates or sulfonic acids, such as sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid, ethylbenzenesulfonic acid, and dodecylbenzenesulfonic acid isopropylamine salt; C2-C 18 Examples of suitable alkyl ester sulfonates or sulfonic acids include, but are not limited to, alkyl esters such as sodium butyl naphthalene sulfonate and sodium hexyl naphthalene sulfonate, and in particular sodium dodecyl benzene sulfonate or dodecyl benzene sulfonic acid. When optionally substituted with alkyl substituents, the aryl sulfonate or sulfonic acid may be located at any point along the alkyl chain, for example, on a primary, secondary, or tertiary carbon. Suitable alkyl ester sulfonates or sulfonic acids include C2-C 18 Alkyl methyl ester sulfonates or sulfonic acids, such as, but not limited to, methyl ester sulfonate, sodium dodecyl methyl ester α-sulfonate, sodium tetradecyl methyl ester α-sulfonate, and sodium hexadecyl methyl ester α-sulfonate, can be located on any carbon, e.g., primary, secondary, or tertiary, along the alkyl chain or aryl ring. Surfactants with two sulfonic acid groups, such as C2-C 16 Also suitable are alkyl diphenyl oxide disulfonates or disulfonic acids, such as sodium dodecyl diphenyl oxide disulfonate. 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.

[0092] However, particularly preferably, the anionic surfactant is a monovalent sulfonic acid, particularly preferably dodecylbenzenesulfonic acid or a salt thereof.

[0093] ethylenically unsaturated compounds iii) The 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 include 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-cyclohexane tetra(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 and a polyfunctional (meth)acrylic acid monomer selected from the group consisting of bis(2-hydroxyethyl)isocyanurate di(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, hydroxylethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and isoborneol (meth)acrylate.

[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 (meth)acrylates 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-opened hydroxyacrylate, pentaerythritol tri / tetra(meth)acrylate mixture, and dipentaerythritol penta / hexa(meth)acrylate mixture. Specific examples of compounds having an isocyanate group include 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)cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4- At least one selected from the group consisting of diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenylisocyanate), 4,4'-oxybis(phenylisocyanate), trifunctional isocyanates derived from hexamethylene diisocyanate, and trimethylenepropanol adduct toluene diisocyanate can be used.

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

[0098] Additives vi) Suitable additives vi) that may also be present in the composition according to the invention include UV stabilizers, heat stabilizers, antioxidants, UV absorbers, conductivity improvers, adhesion promoters, polymeric binders, surfactants, or a combination of at least two of these additives. Suitable UV stabilizers may include absorbers, quenchers, and hindered amine light stabilizers (HALS), which are classified according to their mechanism of action, or may include phenyl salicylate (absorbers), benzophenones (absorbers), benzotriazoles (absorbers), nickel derivatives (quenchers), and radical scavengers, which are classified according to their chemical structure. As heat stabilizers, polyphenol-based primary heat stabilizers, phosphite-based secondary heat stabilizers, lactone-based secondary heat stabilizers, etc. are commercially available, and these may be used alone or in combination. Suitable antioxidants include 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 tetrakismethylene(3,3',5-dibutyl-4'-hydroxyphenyl)propionate methane, glycidyl methacrylate and p-aminodiphenyl acrylate. Reaction products of N-(4-anilinophenyl)-N-methyl-N'-phenyl-p-phenylenediamine with 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, alkylhydroxy groups having a carbalkoxy bond to heterocyclic nitrogen compounds containing an imidodicarbonyl or imidodithiocarbonyl group phenyl group, 3,5-di-tert-butyl-4-hydroxycinnamonitrile, ethyl-di-tert-hexyl-4-hydroxy-cinnamate, substituted benzyl ethers of β-substituted hydroxyphenylpropionic acid, bis-(hydroxyphenylalkylene) alkyl isocyanurates, tetrakishydroxybenzylphosphonium halides alone or in combination with dialkylthioalkanoates, thiodimethylidinetetrakisphenol alone or in combination with dialkylthioalkanoates, phosphites or phosphonates, dihydroxyphenyl esters, bis(hydroxyphenylalkylene) alkyl isocyanurates, tetrakishydroxybenzylphosphonium halides alone or in combination with dialkylthioalkanoates, phosphites or phosphonates, dihydroxyphenyl esters, bis(hydroxyphenylalkylene) alkyl isocyanurates, bis(hydroxyphenylalkylene) alkyl ... The antioxidant and light stabilizer may be selected from the group consisting of hydroxycarbylhydroxyphenylaryl or alkyl phosphonites, phosphonates, phosphates, phosphites, phosphinates, phosphinites, phosphorothioates, or phosphinothionates, diphenylbis(3,5-ditert-butyl-4-hydroxyphenoxy)silane, hydrocarbylhydroxyldihydrocarbyldithiocarbamates, such as 3,5-ditert-butyl-4-hydroxyphenyldimethyldithiocarbamate, and aminobenzyl thioethers. 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 hydroxybenzophenones, 2,4-dihydroxy-3',5'-ditertiarybutylbenzophenone, 2,2',4'-trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2',4'-trihydroxy-4'-alkoxybenzophenones, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, lower alkyl thiazolinone, 2,4-dihydroxybenzophen ... Omethylene-containing phenols, substituted benzenes such as 1,3-bis-(2'-hydroxybenzoyl)benzene, metal derivatives of 3,5-di-t-butyl-4-hydroxyphenylpropionic acid, unsymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic 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 oxalic acid diamides such as oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxanilide, and 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, for aromatic hydroxyl groups Ester derivatives of 4,4'-bis-(4'-hydroxyphenyl)pentanoic acid having at least one unsubstituted position in the ortho position, organophosphorus 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,These may include compounds such as β-diphenylacrylic acid derivatives, bis-(2-benzoxazolyl)alkanes, bis-(2-naphthoxazolyl)alkanes, methylenemalonitriles containing aryl and heterocyclic substituents, alkylene-bis-dithiocarbamate, 4-benzoyl-3-hydroxyphenoxyethyl methacrylate, aryl- or alkyl-substituted acrylonitriles, and 3-methyl-5-isopropylphenyl-6-hydroxycoumarone. Examples of additives that enhance conductivity include compounds such as tetrahydrofuran, lactone group-containing compounds such as butyrolactone and valerolactone, amide group-containing compounds or lactam group-containing compounds such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, 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 are particularly preferably used as the conductivity-enhancing additive. Suitable adhesion promoters are, for example, organofunctional silanes or their hydrolysates, such as compounds such as 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or octyltriethoxysilane. Suitable polymer binders are particularly those soluble in organic solvents, such as polyolefins, polyvinyl acetates, polycarbonates, polyvinyl butyrals, polyacrylic esters, polyacrylic amides, polymethacrylic esters, polymethacrylic amides, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyethers, polyesters, polyurethanes, polyamides, polyimides, polysulfones, polysilicones, epoxy resins, styrene-acrylates, vinyl acetate / acrylates and ethylene / vinyl acetate copolymers, polyvinyl alcohols or cellulose derivatives. Copolymers of the above polymers are also suitable as polymer binders. Suitable surfactants are all amphiphilic compounds with a hydrophilic head group and a hydrophobic portion. The hydrophilic group can be both ionic and nonionic in nature. Due to their molecular structure and tendency to adhere to interfaces, this class of substances reduces interfacial tension and leads to 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 alkylammonium salts, and nonionic surfactants such as linear alcohol ethoxylates, oxoalcohol ethoxylates, alkylphenol ethoxylates or alkyl polyglucosides.

[0099] Method for producing the composition according to the present invention In the first step of forming the composition according to the present invention, thiophene monomers are oxidatively polymerized in the presence of an organic compound (ii) and an organic solvent (iv). 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, and tert-butyl peroxybenzoate. 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 organic metal-free oxidizing agents, such as organic peroxides, with dibenzoyl peroxide being most preferred.

[0100] The thiophene monomers are oxidatively polymerized in the presence of an organic compound ii) by reduction of the oxidizing agent to a reduction product and oxidation of the thiophene monomer to form a polythiophene i) and a reduction product, the polymerization being preferably carried out at a temperature ranging from 0° C. to 100° C. In this context, it is particularly preferred that the reaction temperature ranges 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 serves as a counterion to compensate for the positive charge of the polythiophene i). The anion ii) and the polythiophene i) are preferably present in the form of a polythiophene / anion complex. In this connection, it is also preferred to obtain a composition comprising the polythiophene i) and the anion ii), which composition is particularly preferably present in the form of a dispersion comprising an organic solvent iv) in which the 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 radical initiators, can be added to the dispersion thus obtained.

[0103] The invention will now be described in more detail by reference to the invention, drawings, test methods and non-limiting examples.

[0104] Test Method Solids The solids content was determined gravimetrically using a precision scale (Mettler AE240). First, the empty weighing bottle, including the lid, was weighed (weight A). Approximately 3 g of the dispersion to be analyzed was then quickly filled into the bottle, closed with the lid, and reweighed to determine the exact total weight B. The bottle was then placed in a fume hood without lighting for approximately 3 hours to allow the volatile solvents to evaporate at room temperature. In a second step, the bottle was placed in a ventilated drying oven (Memmert UNB200) at 160 °C for 16-17 hours. When the sample bottle was removed from the oven, immediate covering with a glass lid was important due to the hygroscopic nature of the dried dispersion material. After a 10-15 minute cooling period, the bottle, including the lid, was reweighed to determine weight C. Calculation of solid content: solid content by weight % = 100 × (C × A / (B A)

[0105] The results are the average of two measurements.

[0106] Determination of solid content / solid content [%] Solids / % Solids is determined by calculating the applied solids (grams as base unit) of the conductive dispersion by using a given solids content and the applied amount of the dispersion, and then dividing this value by the total amount of solids present in the coating mixture, again using grams as base unit.

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

[0108] Unless other parameters are stated in the experiments, the wet film thickness was chosen to be 12 μm, and the drying process was carried out at 130° C. for 15 min.

[0109] Determination of surface resistivity Surface resistivity was measured using a Staticide ACL 800 Digital Megohmmeter set at 100 V. Two measurements were taken at different locations on the sheet, with the lowest value being taken as the result.

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

[0111] The RF1 value is determined according to the following formula:

[0112]

number

[0113] A second RF value, RF2, is determined in the same way using the same pattern, but orthogonal to the first measurement, again ensuring that the diameter determination is made through the common center point of both circles.

[0114] Here, the RF value is calculated by averaging RF1 and RF2.

[0115]

number

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

[0117] [Figure 1] The determination of the diameter of the two circles when determining solvent compatibility is shown (see text methods for determining solvent compatibility for details). [Figure 2] A layer structure 100 according to the invention, for example the structure of an antistatic film, is shown in more general form: on the substrate surface of a substrate 101, which in the case of an antistatic film is often a PE, PP or PET layer, there is a conductive layer 102 prepared with a composition according to the invention. [Example]

[0118] Example 1 (Reference Example for the Synthesis of 3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine)

[0119] [ka]

[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 under 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, followed by 0.5 h at 55 °C. 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 mixture of isopropanol / water 70:30 (v / v). The crude product was 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 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, 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxin (6 mmol, ButylEDOT, CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g of the product from the reaction in Example 1 (4 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was 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 were added to a 100 mL flask, and the resulting dispersion was mixed by gentle stirring.

[0125] This is called dispersion 2.

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

[0127] The ionic content of Dispersion 2 was measured by inductively coupled plasma optical emission spectroscopy.

[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 min. The dispersion was stirred at 60 °C for an additional 3 h 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 the resulting dispersion was mixed by gentle stirring.

[0131] This is called dispersion 3.

[0132] Analysis of dispersion 3 Solid content: 1.8% (weight) Sheet resistance (12µm on PET): 5800Ω / 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]dioxin (6 mmol, ButylEDOT, CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g of the product from the reaction in Example 1 (4 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred at 60 °C for an additional 3 h 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 the resulting dispersion was mixed by gentle stirring.

[0135] This is called dispersion 4.

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

[0137] Example 5 (following the teachings of 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, 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 (Hielscher UP 200 S, cycle 1, amplitude 100%) for 2 minutes. This sample is called dispersion 5.

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

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

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

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

[0143] [Table 2] * =This invention

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

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

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

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

[0148] Example 7 This example illustrates the deleterious effect of water in antistatic solvent-based hard coating formulations.

[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 ingredients were thoroughly mixed by stirring. Premix A was then mixed with deionized water in the amounts shown in Table 2. The mixture was stirred for 1 hour. The coating was then applied as a 6 μm wet film to a Melinex 506 PET substrate, dried at 75°C for 3 minutes, and subjected to a fluence of 600 mJ / cm. 2 The samples were exposed to UV radiation at 100°C and the surface resistivity was determined.

[0150] [Table 3]

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

[0152] Example 8 Coatings were prepared by mixing the components shown in Table 3. 1-Hydroxycyclohexylphenylketone (Sigma Aldrich) was used as the 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. The coatings were then applied as 12 μm wet films to Melinex 506 PET substrates, dried at 75°C for 3 minutes, and applied at 600 mJ / cm. 2 The surface resistivity and transmittance were determined.

[0153] [Table 4]

[0154] Example 9 The examples demonstrate the difference in pencil hardness between cured and uncured compositions according to the invention. Further examples demonstrate the difference between cured coatings from compositions according to the invention and coatings from compositions containing already polymerized acrylates.

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

[0156] Example 9A was treated at 600 mJ / cm 2 The solution was further exposed to UV radiation at .

[0157] The pencil hardness of the resulting coatings was determined according to the Wolf-Wilburn pencil hardness test. For the test, a pencil with a hardness of H was attached to a 5800 scratch resistance kit manufactured by BYK instruments. The instrument was then pressed against the coated glass substrate. The coating was then closely inspected. 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 a different location. The pencil hardness listed 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 Dispersions 2 and 4 in various organic solvent-based cured compositions. Furthermore, they demonstrate that RF values ​​determined in PGME generally predict the performance of conductive dispersions in compositions according to the invention, regardless of the solvent used. RF value of dispersion 2 in PGME: 1 RF value of dispersion 3 in PGME: 0.4

[0160] Coatings were prepared by mixing the ingredients shown in Table 5 with 0.05 g of 1-hydroxycyclohexylphenyl ketone (Sigma Aldrich, photoinitiator) and 0.95 g of DPHA (Sigma Aldrich, dipentaerythritol-penta- / hexaacrylate, CAS 60506-81-2). The ingredients were thoroughly mixed by stirring. The mixture was stirred for 15 minutes. The coatings were then applied as 12 μm wet films to Melinex 506 PET substrates, dried at 75° C. for 3 minutes, and irradiated at 600 mJ / cm. 2 The samples were exposed to UV radiation at 100°C and the surface resistivity was determined.

[0161] [Table 6]

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

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

[0164] [Table 7]

[0165]

Table 8

Claims

1. 1. A composition comprising: i) at least one polythiophene comprising monomer units of structure (I): 【Chemical 1】 [In the formula, ＊ indicates a bond to an adjacent monomer unit, X and Z represent O or S; R １ ~R ４ represent, independently of one another, a hydrogen atom or an organic residue R, provided that the residue R １ ~R ４ at least one of which represents an organic residue R; ii) at least one organic compound or a salt thereof having at least one acid group, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, wherein the molecular weight of the organic compound or the salt thereof is less than 1,000 g / mol; 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.

2. 1. 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; 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.

3. The polythiophene i) is a compound in which X and Z represent O, and R １ , R ２ , R ３ , and R ４ and wherein three of the residues selected from the group consisting of: represent hydrogen atoms, and the remaining residues represent ether groups having structural formula (Ia): 【Chemistry 2】 [In the formula, R ７ is H, C １ ~C １０ -Alkyl group or C １ ~C １０ - an alkoxy group, preferably H, R ８ is H, C １ ~C １０ -Alkyl group or C １ ~C １０ - an alkoxy group, preferably H, 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, and is preferably C １ ~C ３０ The composition of claim 1, wherein the alkyl group is an alkyl group.

4. The polythiophene i is a compound in which X and Z represent O, and R １ , R ２ , R ３ and R ４ 10. The composition of claim 1, wherein the polymer is a homopolymer or copolymer comprising monomer units of structure (I), wherein three of the residues selected from the group consisting of:

5. The remaining residue represents a branched ether group having the structural formula (Ib) 【Chemistry 3】 [In the formula, R １０ is H, C １ ~C １０ -Alkyl group or C １ ~C １０ - is an alkoxy group, R １１ is H, C １ ~C １０ -Alkyl group or C １ ~C １０ - is an alkoxy group, n is an integer from 0 to 10, R １２ is 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 that does not have an unsaturated C═C bond in the alkyl chain.

6. 6. The composition according to any one of claims 1 and 3 to 5, wherein the at least one organic compound ii) having one acid group is a monovalent sulfonic acid or a salt thereof.

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

8. 8. The composition according to any one of claims 1 to 7, wherein 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 mixtures of one or two of these aprotic solvents with one or two further solvents.

9. The composition according to any one of claims 1 to 8, wherein the at least one radical initiator is a photoradical initiator capable of forming radicals upon irradiation with light.

10. The composition of any one of claims 1 to 9, wherein the composition has a water content of less than 2 wt. %, based on the total weight of the composition.

11. A method for preparing a layered structure (100), comprising: A) preparing a substrate (101); B) coating the substrate (101) with a composition according to any one of claims 1 to 10; 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) in a radical chain reaction.

12. A layer structure (100), a) base material (101), b) a conductive layer (102) coated on the substrate (101), wherein the conductive layer (102) At least one polythiophene comprising monomer units of structure (I): 【Chemistry 4】 [In the formula, ＊ indicates a bond to an adjacent monomer unit, X and Z represent O or S; R １ ~R ４ represent, independently of one another, a hydrogen atom or an organic residue R, provided that the residue R １ ~R ４ at least one of which 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 sulfate groups, one or two phosphonic acid groups, or one or two phosphoric acid groups, or a salt of said organic compound, wherein the molecular weight of said organic compound or salt thereof is less than 1,000 g / mol, a polymer matrix based on polymerized ethylenically unsaturated compounds iii) in which at least one polythiophene is embedded, The conductive polymer layer has a pencil hardness of at least 1H.

13. A layer structure (100), a) base material (101), b) a conductive layer (102) coated on the substrate (101), wherein the conductive layer (102) 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; a polymer matrix based on polymerized ethylenically unsaturated compounds iii) in which the at least one polythiophene is embedded, The conductive polymer layer has a pencil hardness of at least 1H.

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

15. Use of a composition according to any one of claims 1 to 10 for producing an electrically conductive layer in an electronic component or for producing an antistatic coating.

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