Polythiophenes in organic solvents

Abstract

The invention relates to polythiophenes in organic solvents. The present invention relates to a composition comprising i) at least one polythiophene comprising a monomer unit of the structure (Ia) or (Ib) wherein a bond to an adjacent monomer unit is indicated, X, Z represent O or S, R1-R6 independently of each other represent a hydrogen atom or an organic residue R, with the proviso that at least one of the residues R1 to R4 and one of the residues R5 and R6 represent an organic residue R; ii) at least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups; iii) at least one organic solvent. The invention also relates to a method for producing a composition, to a composition obtainable by this method, to a layer structure, to a method for producing a layer structure, to a layer structure obtainable by this method, to an electronic component, and to the use of a composition according to the invention.

Description

[0001] This application is a divisional application of the invention patent application filed on September 29, 2020, with application number "202080069431.7" and invention title "Polythiophene in Organic Solvents". Technical Field

[0002] This invention relates to compositions comprising at least one polythiophene. The invention also relates to methods for preparing compositions, compositions obtainable by such methods, layer structures, methods for preparing layer structures, layer structures obtainable by such methods, electronic components, and uses of compositions according to the invention. Background Technology

[0003] Polythiophene is widely used as an intrinsically conductive polymer. Specifically, poly(3,4-ethylenedioxythiophene) (PEDOT) has been found in many industrial applications, such as solid electrolyte capacitors, antistatic coatings, electroluminescent lamps, organic light-emitting diodes, organic solar cells, and many other applications. For many of these applications, PEDOT is used in the form of a polymer complex with polystyrene-sulfonic acid as the opposing ion, the polymer complex being dispersed in water or a mixture of water and other solvents (also known as "PEDOT / PSS").

[0004] Efforts have been made to supply aprotic solvents containing PEDOT to expand its applications. WO-A-2012 / 059215 A1 discloses the use of block copolymers as the relative ions to make the dispersion soluble in organic, aprotic solvents. The solubility parameters of the block copolymers dominate and limit the solubility characteristics of the resulting PEDOT complex. Therefore, the dispersion becomes unstable upon the addition of solvents such as PGMEA or ethanol.

[0005] 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 redispersibility methods are expensive and undesirable.

[0006] McCullough et al. "A method for preparing head-to-tail coupled regio-regular polymers using Grinner metathesis" A Simple Method to Prepare Head-to-Tail Coupled (3-alkylthiophene) Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis)” (Advanced Materials, 1999, 11, 250) describes the synthesis of site-regular copolymers that can be dispersed in a variety of solvents. However, coupling via organometallic compounds is expensive, and the resulting polymers exhibit only limited conductivity. Therefore, their applications are limited to hole transport layers, where only conductivity across the layer is required. Summary of the Invention

[0007] The objective of this invention is to overcome the shortcomings of the prior art related to conductive polymers, which are based on thiophene monomers, preferably based on 3,4-ethylenedioxythiophene monomers.

[0008] Specifically, one object of the present invention is to provide a composition comprising polythiophene, said composition being based on an organic solvent, preferably an organic aprotic solvent, and dispersible in a wide range of solvents. The composition should also be characterized in that the conductive layer prepared by such a composition is highly conductive and highly transparent. Furthermore, the composition should be able to achieve low sheet resistance when blended with inert polymers such as polyacrylates. Additionally, the composition should be characterized in that it is readily dilutable with organic solvents.

[0009] Another object of the present invention is to provide a method that allows the preparation of such advantageous compositions in as few process steps as possible.

[0010] An independent technical solution contributes to at least partially solving one, and preferably more than one, objective. An auxiliary technical solution provides a preferred embodiment that facilitates at least partial solving of one of the objectives.

[0011] Example 1 of composition 1 contributes to solving at least one objective according to the invention, said composition comprising:

[0012] i) At least one polythiophene comprising a monomeric unit of structure (Ia) or (Ib), preferably at least one cationic polythiophene.

[0013]

[0014] in

[0015] Indicates the bond with adjacent unit cells.

[0016] X and Z represent O or S,

[0017] R 1 -R 6 Each can be represented independently by a hydrogen atom or an organic residue R.

[0018] Its limiting condition is residue R 1 To R 4 At least one of them and residue R 5 and R 6 One of them represents an organic residue R;

[0019] ii) At least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, preferably less than 900 g / mol, more preferably less than 800 g / mol, even more preferably less than 700 g / mol, even more preferably less than 600 g / mol and even more preferably less than 500 g / mol;

[0020] iii) At least one organic solvent. Attached Figure Description

[0021] Figure 1 The layer structure 100 according to the invention is shown in its general form. Detailed Implementation

[0022] Surprisingly, it has been found that polythiophenes comprising monomeric units of the structures (Ia) or (Ib) described above can be dispersed in a wide range of solvents, said polythiophenes being, for example, copolymers of 3,4-ethylenedioxythiophene and derivatives of 3,4-ethylenedioxythiophene, wherein at least one hydrogen atom of the ethylene is substituted with an organic residue R, said copolymers using organic compounds as relative ions that carry one or two inorganic acid groups, such as sulfonic acid (-SO2OH), sulfate (-O-SO2OH), phosphonic acid (-PO(OH)2), phosphate (-O-PO(OH)2), or a salt of at least one of these groups, and have a molecular weight of less than 1,000 g / mol, preferably monovalent sulfonic acid anions. If the organic residue R corresponds to an alkyl group, especially one having the formula -C n H 2n+1 Straight-chain or branched-chain alkyl groups, wherein n is an integer in the range of 1 to 20, preferably corresponding to a branched-chain alkyl group, wherein n is an integer in the range of 3 to 15 and more preferably in the range of 3 to 10, or if the organic residue R corresponds to a branched-chain ether group, such polythiophene and the above-mentioned organic compounds carrying one or two inorganic acid groups are particularly advantageous to form compositions, preferably dispersions, wherein these compositions are dispersed in protic or aprotic solvents, and a large amount of non-conductive binders, especially poly(meth)acrylates, (meth)acrylate resins and polysilicon, can be added without excessively reducing the conductivity of these compositions.

[0023] In Example 2 of Composition 1 according to the invention, Composition 1 was designed according to Example 1, wherein the composition exists in the form of a dispersion or solution (and wherein an organic solvent iii), preferably an aprotic solvent iii), thus acts as a dispersant or solvent), wherein polythiophene i) and organic compound ii) (which preferably exists in anionic form), preferably copolymer i) and organic compound ii) form a complex that is dispersed or dissolved, preferably uniformly dispersed or dissolved in organic solvent iii). Most preferably, the composition according to the invention is a dispersion in which the complex of polythiophene i) and organic compound ii) is uniformly dispersed in organic solvent iii). 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) and organic solvent iii).

[0024] In Example 3 of Composition 1 according to the invention, Composition 1 was designed according to Example 2 thereof, wherein the polythiophene / organic compound complex i) / ii) is dispersed at a weight content of 30% or less, preferably 20% or less and more preferably 10% or less, in each case based on the total weight of the dispersion.

[0025] In Example 4 of Composition 1 according to the invention, Composition 1 was designed according to any one of Examples 1 to 3, wherein the organic residue R does not carry an anionic group. Preferably, residue R does not carry any sulfonic acid group or a salt of such a group.

[0026] In Example 5 of the composition 1 according to the invention, the composition 1 was designed according to any one of Examples 1 to 4, wherein the organic residue R is selected from the group consisting of alkyl, alkoxy, aryl, ether, and ester.

[0027] In Example 6 of the composition 1 according to the invention, composition 1 is designed according to any one of Examples 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib), wherein X and Z represent O, preferably monomer units of structure (Ia), wherein X and Z represent O, and wherein R is selected from 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue in the group represents a hydrogen atom, and the remaining residues represent an ether group having structural formula (IIa).

[0028]

[0029] in

[0030] R 7For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 7 For H;

[0031] R 8 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 8 For H;

[0032] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0033] R 9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl, more preferably C2-C 25 Alkyl groups, or even more preferably C5-C 20 alkyl.

[0034] In Example 7 of the composition 1 according to the invention, composition 1 is designed according to any one of Examples 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib), wherein X and Z represent O, preferably monomer units of structure (Ia), wherein X and Z represent O, and wherein R is selected from 1 R 2 R 3 and R 4 The group consists of at least two residues and selected from R. 5 and R 6 A residue of the group is preferably selected from R. 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue of the group represents a hydrogen atom, and the remaining residues, preferably one of the remaining residues, represent an alkyl group having formula (IIb):

[0035]

[0036] Wherein n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15, and even more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl, wherein ethyl, n-butyl, and n-decyl are particularly preferred, and n-butyl is the most preferred.

[0037] Suitable examples of monomeric units carrying a branched alkyl or more than one alkyl structure (Ia) include compounds selected from the group consisting of compounds (A), (B), (C), and (D):

[0038]

[0039] In Example 8 of the composition 1 according to the invention, composition 1 was designed according to any one of Examples 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib), wherein X and Z represent O, preferably monomer units of structure (Ia), wherein X and Z represent O, and wherein R is selected from 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue in the group represents a hydrogen atom, and the remaining residues represent branched alkyl or branched ether groups, preferably branched ether groups. In the sense of this invention, a "branched ether group" is preferably an ether group in which at least one of the two organic residues bonded to an oxygen atom is a branched organic residue, i.e., an organic residue containing at least one carbon atom bonded via a single bond to at least three carbon atoms or at least two carbon atoms and an oxygen atom as part of the ether group. More preferably, the remaining residues represent a branched ether group having the structural formula (IIc).

[0040]

[0041] in

[0042] R 10 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 10 For H;

[0043] R 11 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 11 For H;

[0044] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0045] R 12 The residue is a branched organic chain, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain, and even more preferably an organic residue having formula (IId).

[0046]

[0047] in

[0048] m is 1, 2, or 3.

[0049] R 13 For H or C1-C 12 Alkyl groups, preferably C2-C 10 Alkyl, more preferably C3-C8 alkyl, even more preferably butyl, the limiting condition being that there are m structural units -CHR 13 In only one of them, residue R 13 For C1-C 12 alkyl;

[0050] R 14 For C1-C 10 Alkyl, preferably C2-C6 alkyl, or aryl.

[0051] In Example 9 of Composition 1 according to the invention, Composition 1 was designed according to Example 8 thereof, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):

[0052]

[0053] In conjunction with Examples 8 and 9 of Composition 1 according to the present invention, it is also possible to use an organic compound as component ii), said organic compound carrying more than two inorganic acid groups and having a molecular weight greater than 1,000 g / mol, such as polystyrene sulfonic acid (PSS).

[0054] In Example 10 of the composition 1 according to the invention, the composition 1 is designed according to any one of Examples 1 to 9, wherein at least one polythiophene i) is a copolymer of 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene having the structural formula (Ia), wherein X and Z represent O, and wherein at least one organic solvent iii) is preferably an aprotic solvent iii). In this case, the polythiophene i) is therefore a copolymer of 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene, wherein at least one of the hydrogen atoms of the ethylene group is substituted with an organic residue R.

[0055] In Example 11 of the composition 1 according to the invention, composition 1 was designed according to Example 10 thereof, wherein the 3,4-ethylenedioxythiophene derivative has the structural formula (Ia'):

[0056] ,

[0057] R is preferably selected from the group consisting of alkyl, alkoxy, aryl, ether, and ester groups.

[0058] In Example 12 of the composition 1 according to the invention, the composition 1 was designed according to Example 11 thereof, wherein the organic residue R is an ether group.

[0059] In Example 13 of the composition 1 according to the invention, composition 1 was designed according to Example 12, wherein the ether group has the structural formula (IIa).

[0060]

[0061] in

[0062] R 7 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 7 For H;

[0063] R 8 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 8 For H;

[0064] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0065] R9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl, more preferably C2-C 25 Alkyl groups, or even more preferably C5-C 20 alkyl.

[0066] In Example 14 of Composition 1 according to the present invention, Composition 1 was designed according to Example 13 thereof, wherein the 3,4-ethylenedioxythiophene derivative has the general formula (III).

[0067]

[0068] Where R 9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl, more preferably C2-C 25 Alkyl groups, or even more preferably C5-C 20 alkyl.

[0069] In Example 15 of the composition 1 according to the invention, composition 1 was designed according to Example 14, wherein the 3,4-ethylenedioxythiophene derivative has the general formula (IV).

[0070]

[0071] Where m is an integer in the range of 0 to 24, preferably in the range of 1 to 19, and more preferably in the range of 4 to 14, wherein most preferably m is 9.

[0072] In Example 16 of the composition 1 according to the invention, composition 1 was designed according to Example 11 thereof, wherein the organic residue R is an alkyl group.

[0073] In Example 17 of Composition 1 according to the invention, Composition 1 was designed according to Example 16, wherein the alkyl group has the formula (IIb).

[0074]

[0075] Wherein n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15, and even more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl, wherein ethyl, n-butyl, and n-decyl are particularly preferred, and n-butyl is the most preferred.

[0076] In Example 18 of Composition 1 according to the present invention, Composition 1 was designed according to Example 17 thereof, wherein the 3,4-ethylenedioxythiophene derivative has the general formula (V).

[0077]

[0078] Wherein n is in the range of 0 to 19, preferably in the range of 1 to 14, and more preferably in the range of 2 to 9. Particularly preferred is that n is 2, 3, or 4, with n=3 being the most preferred.

[0079] In Example 19 of the composition 1 according to the invention, composition 1 was designed according to Example 11 thereof, wherein the organic residue R is a branched alkyl or branched ether group, preferably a branched ether group, more preferably a branched ether group having the structural formula (IIc).

[0080]

[0081] in

[0082] R 10 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 10 For H;

[0083] R 11 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 11 For H;

[0084] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0085] R 12 The residue is a branched organic chain, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain, and even more preferably an organic residue having formula (IId).

[0086]

[0087] in

[0088] m is 1, 2, or 3.

[0089] R 13 For H or C1-C 12 Alkyl groups, preferably C2-C 10 Alkyl, more preferably C3-C8 alkyl, even more preferably butyl, the limiting condition being that there are m structural units -CHR 13 In only one of them, residue R13 For C1-C 12 alkyl;

[0090] R 14 For C1-C 10 Alkyl, preferably C2-C6 alkyl, or aryl.

[0091] In Example 20 of Composition 1 according to the invention, Composition 1 was designed according to Example 19 thereof, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):

[0092]

[0093] In Example 21 of the composition 1 according to the invention, the composition 1 was designed according to any one of Examples 1 to 20, wherein the copolymer i) comprises 5 to 95% monomer units, preferably 10 to 80% and more preferably 20 to 60% monomer units, based on the derivative of 3,4-ethylenedioxythiophene, in each case based on the total number of monomer units (i.e., based on the total number of 3,4-ethylenedioxythiophene monomer units and monomer units based on the derivative of 3,4-ethylenedioxythiophene).

[0094] In Example 22 of Composition 1 according to the invention, Composition 1 is designed according to any one of Examples 1 to 21, wherein copolymer i) comprises at least 30% by weight, preferably at least 40% by weight and more preferably at least 70% by weight of monomer units based on the derivative of 3,4-ethylenedioxythiophene, in each case based on the total number of monomer units (i.e., based on the total weight of 3,4-ethylenedioxythiophene monomer units and monomer units based on the derivative of 3,4-ethylenedioxythiophene).

[0095] In Example 23 of Composition 1 according to the present invention, Composition 1 was designed according to Example 8 thereof, wherein at least one polythiophene (i) is a copolymer of the following:

[0096] α) At least one derivative of 3,4-ethylenedioxythiophene having the structural formula (Ia')

[0097] ,

[0098] Wherein R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group having the structural formula (IIc) as defined above.

[0099] β) At least one derivative of 3,4-ethylenedioxythiophene having the structural formula (Ia').

[0100] ,

[0101] Wherein R is an alkyl group having the structural formula (IIb) as defined above, and thiophene derivatives selected from the group consisting of: 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-propyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxanediene, and 2-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxanediene, with 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene (Butyl-EDOT) being particularly preferred.

[0102] and optional

[0103] γ) 3,4-ethylenedioxythiophene.

[0104] In Example 24 of Composition 1 according to the invention, Composition 1 was designed according to Example 23 thereof, wherein copolymer i) comprises 5 to 99 mol%, preferably 15 to 70 mol%, and more preferably 30 to 50 mol%, of monomer units based on monomer α), 5 to 95 mol%, preferably 30 to 90 mol%, and more preferably 50 to 70 mol%, of monomer units based on monomer β), and 0 to 50 mol%, preferably 0 to 35 mol%, and more preferably 0 to 20 mol%, of monomer units based on monomer γ), wherein in each case the total amount of monomers α), β), and γ) in the copolymer is 100 mol%. According to the particularly preferred copolymer i), the copolymer does not contain 3,4-ethylenedioxythiophene as a comonomer.

[0105] In Example 25 of the composition 1 according to the invention, the composition 1 was designed according to any one of Examples 1 to 24, wherein the inorganic acid group is a sulfonic acid group (-SO2OH), a sulfate group (-O-SO2OH), a phosphonic acid group (-PO(OH)2) or a phosphate group (-O-PO(OH)2), preferably a sulfonic acid group (-SO2OH).

[0106] In Example 26 of the composition 1 according to the invention, the composition 1 was designed according to any one of Examples 1 to 25, wherein the organic compound ii) is an anionic surfactant.

[0107] In Example 27 of Composition 1 according to the invention, Composition 1 was designed according to Example 26 thereof, wherein the anionic surfactant is a sulfonic acid (R-SO2OH), an ester of sulfuric acid (RO-SO2OH), or a salt of one of these esters, preferably a sulfonic acid. In this case, it is particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (i.e., a compound carrying only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.

[0108] In Example 28 of Composition 1 according to the invention, Composition 1 was designed according to Example 27 thereof, wherein the anionic surfactant is dodecylbenzenesulfonic acid or a salt thereof. As used herein, the term "..." dodecyl sulfonic acid "It also includes a mixture of alkylbenzene sulfonic acids, which, in addition to dodecylbenzene sulfonic acid, further contain alkylbenzene sulfonic acids having alkyl chains that are longer or shorter than dodecyl.

[0109] In Example 29 of Composition 1 according to the invention, Composition 1 is designed according to any one of Examples 1 to 28, wherein the weight ratio of polythiophene i) to organic compound ii) or salt thereof, preferably copolymer i) to organic compound ii) or salt thereof, is in the range of 1:30 to 1:0.1, more preferably in the range of 1:20 to 1:0.2, and more preferably in the range of 1:5 to 1:0.5.

[0110] In Example 30 of Composition 1 according to the present invention, Composition 1 is designed according to any one of Examples 1 to 29 thereof, wherein the boiling point (measured at a pressure of 1013 mbar) of at least one organic solvent (iii), preferably at least one aprotic solvent (iii), is in the range of 50 to 300°C, preferably in the range of 60 to 250°C and more preferably in the range of 70 to 220°C.

[0111] In Example 31 of the composition 1 according to the invention, the composition 1 is designed according to any one of Examples 1 to 30, wherein at least one organic solvent is an aprotic solvent (iii), more preferably a polar aprotic solvent.

[0112] In Example 32 of Composition 1 according to the present invention, Composition 1 was designed according to Example 31 thereof, wherein the dielectric constant of the polar aprotic solvent (iii) is less than 20, preferably less than 10 and more preferably less than 7.

[0113] In Example 33 of Composition 1 according to the present invention, Composition 1 was designed according to Example 31 or 32, wherein the dipole moment of the polar aprotic solvent (iii) is less than 4 D, preferably less than 2 D and more preferably less than 1.5 D.

[0114] In Example 34 of Composition 1 according to the invention, Composition 1 was designed according to any one of Examples 1 to 33, wherein at least one organic solvent iii) is selected from the group consisting of: aromatic hydrocarbons, esters, ethers, alcohols and mixtures thereof.

[0115] In Example 35 of Composition 1 according to the invention, Composition 1 was designed according to Example 34 thereof, wherein at least one organic solvent iii) is selected from the group consisting of: 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 with one or two other solvents. In the case of a mixture of two or more organic solvents, it is particularly preferred that at least one of these solvents is an aprotic solvent iii).

[0116] In Example 36 of the composition 1 according to the invention, composition 1 is designed according to any one of Examples 1 to 35, wherein the composition comprises

[0117] i) 0.01 to 20% by weight, preferably 0.02 to 10% by weight, and more preferably 0.1 to 5% by weight of the polymer;

[0118] ii) 0.01 to 15% by weight, preferably 0.02 to 10% by weight, and more preferably 0.1 to 5% by weight of organic compounds;

[0119] iii) 50 to 99.98% by weight, preferably 70 to 99.86% by weight and more preferably 85 to 99.3% by weight of a solvent or solvent mixture, preferably an aprotic solvent or solvent mixture;

[0120] iv) 0 to 15% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, of additives different from components i) to iii).

[0121] The total weight of components i) to iv) is 100 by weight.

[0122] In Example 37 of Composition 1 according to the invention, Composition 1 is designed according to any of Examples 1 to 36, wherein the composition comprises a non-conductive oligomer or polymer, preferably a non-conductive oligomer or polymeric binder as another component (iv) different from components (i) to (iii). Non-conductive oligomeric or polymeric adhesives "In the context of this invention, an oligomer layer or a polymer layer is preferred, having an electrical conductivity of less than 10." -6 S / cm, preferably less than 10 -8S / cm and the optimal value is less than 10. -10 S / cm. In contrast, the composition according to the invention contains " conductive polymer (Polythiophene i) or polythiophene-polymer i) is preferably a polymer layer in the sense of the present invention, having an electrical conductivity of at least 10. -6 S / cm, preferably at least 10 -5 S / cm and the optimal value is 10. -4 S / cm.

[0123] In Example 38 of Composition 1 according to the invention, Composition 1 was designed according to Example 37 thereof, wherein the non-conductive polymeric adhesive is selected from the group consisting of: polyolefins, polyvinyl acetate, polycarbonate, poly(meth)acrylate, polyvinyl butyral, poly(meth)acrylamide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, polysulfone, polysilicon, epoxy resin, styrene-acrylate, vinyl acetate / acrylate or ethylene / vinyl acetate copolymer, polyvinyl alcohol, cellulose derivatives or mixtures comprising at least two of these polymers, wherein poly(meth)acrylate and polysilicon are particularly preferred non-conductive polymeric adhesives. Multifunctional (meth)acrylates, such as diisopentanetetramethylolpentade / hexaacrylate, are also suitable as non-conductive polymeric adhesives.

[0124] In Example 39 of Composition 1 according to the invention, Composition 1 was designed according to Example 38 thereof, wherein the poly(meth)acrylate is selected from the group consisting of: poly(methyl acrylate), poly(methyl methacrylate), poly(ethyl acrylate), poly(ethyl methacrylate), poly(n-propyl acrylate), poly(n-propyl methacrylate), poly(isopropyl acrylate), poly(isopropyl methacrylate), poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(isobutyl acrylate), poly(isobutyl methacrylate), poly(tert-butyl acrylate), poly(tert-butyl methacrylate), poly(2-ethylhexyl acrylate), poly(2-ethylhexyl methacrylate), poly(cyclohexyl acrylate), poly(cyclohexyl methacrylate), poly(phenyl acrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), and copolymers of these polyacrylates or polymethacrylates.

[0125] In Example 40 of Composition 1 according to the invention, Composition 1 is designed according to any one of Examples 37 to 39, wherein the composition comprises a non-conductive polymeric adhesive (iv), preferably poly(meth)acrylate and / or polysiloxane, and a polythiophene / organic compound complex (i) / ii), in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

[0126] In Example 41 of Composition 1 according to the present invention, Composition 1 is designed according to any one of Examples 37 to 40, wherein the sheet resistance of the conductive layer prepared by the composition is at most 1 × 10⁻⁶. 10 Ohm / sq, preferably up to 5×10 9 Ohm / sq and more preferably up to 1×10 8 Ohm / sq.

[0127] In Example 42 of the composition 1 according to the invention, the composition 1 is designed according to any one of Examples 1 to 41, wherein the composition contains less than 2% by weight, preferably less than 1% by weight and most preferably less than 0.1% by weight of water, in each case based on the total weight of the composition.

[0128] In Example 43 of Composition 1 according to the invention, Composition 1 was designed according to any of Examples 1 to 42, wherein the total metal content of the composition is less than 30 ppm, preferably less than 15 ppm and more preferably less than 5 ppm, in each case based on the total weight of the composition. The metals particularly include sodium, potassium, and iron. Most preferably, the iron content of the composition is less than 30 ppm, preferably less than 15 ppm and more preferably less than 5 ppm, in each case based on the total weight of the composition.

[0129] In Example 44 of the composition 1 according to the invention, the composition 1 is designed according to any one of Examples 1 to 43, wherein the conductivity of the conductive layer prepared by the composition is greater than 1 S / cm, preferably greater than 2 S / cm and most preferably greater than 5 S / cm.

[0130] Example 1, which describes a method for preparing a composition, preferably a dispersion, also contributes to solving at least one of the objectives according to the invention, the method comprising the following steps:

[0131] I) Provide a reaction mixture comprising the following:

[0132] i) Thiophene monomer units of structure (VIa) or (VIb)

[0133]

[0134] in

[0135] X and Z represent O or S,

[0136] R 1 -R 6 Each can be represented independently by a hydrogen atom or an organic residue R.

[0137] Its limiting condition is residue R 1 To R4 At least one of them and residue R 5 and R 6 One of them represents an organic residue R.

[0138] ii) At least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, preferably less than 900 g / mol, more preferably less than 800 g / mol, even more preferably less than 700 g / mol, even more preferably less than 600 g / mol and even more preferably less than 500 g / mol;

[0139] iii) at least one organic solvent, and

[0140] iv) At least one oxidizing agent, preferably at least one organic, metal-free oxidizing agent, more preferably at least one organic peroxide;

[0141] II) Oxidative polymerization of the thiophene monomer to form polythiophene, preferably cationic polythiophene, more preferably a complex of polythiophene and an organic compound ii) (which is preferably present in anionic form).

[0142] In Example 2 of Method 1 according to the present invention, Method 1 is designed according to Example 1, wherein the organic residue R does not carry an anionic group. Preferably, residue R does not carry any sulfonic acid group or a salt of such a group.

[0143] In Example 3 of Method 1 according to the present invention, Method 1 is designed according to Example 1 or 2 thereof, wherein the organic residue R is selected from the group consisting of alkyl, alkoxy, aryl, ether and ester groups.

[0144] In embodiment 4 of method 1 according to the present invention, according to any one of embodiments 1 to 3 of method 1, the reaction mixture provided in step I) comprises a thiophene monomer of structure (VIa) or structure (VIb), wherein X and Z represent O, preferably a thiophene monomer of structure (VIa), wherein X and Z represent O, and wherein R is selected. 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue in the group represents a hydrogen atom, and the remaining residues represent an ether group having structural formula (IIa).

[0145]

[0146] in

[0147] R 7 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 7 For H;

[0148] R 8 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 8 For H;

[0149] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0150] R 9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl, more preferably C2-C 25 Alkyl groups, or even more preferably C5-C 20 alkyl.

[0151] In embodiment 5 of method 1 according to the present invention, according to any one of embodiments 1 to 3 of method 1, the reaction mixture provided in step I) comprises a thiophene monomer of structure (VIa) or structure (VIb), wherein X and Z represent O, preferably a thiophene monomer of structure (VIa), wherein X and Z represent O, and wherein R is selected. 1 R 2 R 3 and R 4 The group consists of at least two residues and selected from R. 5 and R 6 A residue of the group is preferably selected from R. 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue in the group represents a hydrogen atom, and the remaining residues, preferably one of the remaining residues, represent an alkyl group having formula (IIb).

[0152]

[0153] Wherein n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15, and even more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl, wherein ethyl, n-butyl, and n-decyl are particularly preferred, and n-butyl is the most preferred.

[0154] Suitable examples of monomeric units carrying a branched alkyl chain or more than one alkyl group (Ia) include compounds selected from the group consisting of compounds (A), (B), (C), and (D):

[0155]

[0156] In embodiment 6 of method 1 according to the present invention, according to any one of embodiments 1 to 3 of method 1, the reaction mixture provided in step I) comprises a thiophene monomer of structure (VIa) or structure (VIb), wherein X and Z represent O, preferably a thiophene monomer of structure (VIa), wherein X and Z represent O, and wherein R is selected. 1 R 2 R 3 and R 4 The three residues that make up the group and the selection of R 5 and R 6 One residue in the group represents a hydrogen atom, and the remaining residues represent branched alkyl or branched ether groups, preferably branched ether groups, more preferably branched ether groups having the structural formula (IIc).

[0157]

[0158] in

[0159] R 10 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 10 For H;

[0160] R 11 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 11 For H;

[0161] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0162] R 12 The residue is a branched organic chain, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain, and even more preferably an organic residue having formula (IId).

[0163]

[0164] in

[0165] m is 1, 2, or 3.

[0166] R 13 For H or C1-C 12 Alkyl groups, preferably C2-C 10 Alkyl, more preferably C3-C8 alkyl, even more preferably butyl, the limiting condition being that there are m structural units -CHR 13 In only one of them, residue R 13 For C1-C 12 alkyl;

[0167] R 14 For C1-C 10 Alkyl, preferably C2-C6 alkyl, or aryl.

[0168] In Example 7 of Method 1 according to the present invention, Method 1 is designed according to Example 6 thereof, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):

[0169]

[0170] In conjunction with Examples 6 and 7 of the method according to the invention, it is also possible to use an organic compound as component ii), said organic compound carrying more than two inorganic acid groups and having a molecular weight greater than 1,000 g / mol, such as polystyrene sulfonic acid (PSS).

[0171] In Example 8 of Method 1 according to the invention, Method 1 is designed according to Examples 1 to 7 thereof, wherein the reaction mixture comprises 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene having the structural formula (VIa) as component i), wherein X and Z represent O, wherein at least one organic solvent iii) is an aprotic solvent iii), and wherein in step II), 3,4-ethylenedioxythiophene and the derivative of 3,4-ethylenedioxythiophene are oxidatively polymerized to form a copolymer. The reaction mixture provided in step I) therefore comprises 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene as component i), wherein at least one hydrogen atom of the ethylene group is substituted with an organic residue R.

[0172] In Example 9 of Method 1 according to the present invention, Method 1 is designed according to Example 8 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the structural formula (Ia'):

[0173] ,

[0174] R is preferably selected from the group consisting of alkyl, alkoxy, aryl, ether, and ester groups.

[0175] In Example 10 of Method 1 according to the present invention, Method 1 is designed according to Example 9 thereof, wherein the organic residue R is an ether group.

[0176] In Example 11 of Method 1 according to the present invention, Method 1 is designed according to Example 10 thereof, wherein the ether group has the structural formula (IIa).

[0177]

[0178] in

[0179] R 7 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 7 For H;

[0180] R 8 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 8 For H;

[0181] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0182] R 9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl, more preferably C2-C 25 Alkyl, more preferably C5-C 20 alkyl.

[0183] In Example 12 of Method 1 according to the present invention, Method 1 is designed according to Example 11 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (III).

[0184]

[0185] Where R 9 It is an alkyl, alkoxy, aryl, ether, or ester group, preferably C1-C. 30 Alkyl groups, preferably C2-C 25 Alkyl, more preferably C5-C 20 alkyl.

[0186] In Example 13 of Method 1 according to the present invention, Method 1 is designed according to Example 12 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (IV).

[0187]

[0188] Where m is an integer in the range of 0 to 24, preferably in the range of 1 to 19, and more preferably in the range of 4 to 14, wherein most preferably m is 9.

[0189] In Example 14 of Method 1 according to the present invention, Method 1 was designed according to Example 9 thereof, wherein the organic residue R is an alkyl group.

[0190] In Example 15 of Method 1 according to the present invention, Method 1 was designed according to Example 14 thereof, wherein the alkyl group has the formula (IIb).

[0191]

[0192] Wherein n is an integer in the range of 1 to 20, preferably in the range of 2 to 15, more preferably in the range of 3 to 15, and even more preferably in the range of 3 to 10. Particularly preferred alkyl groups are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl, wherein ethyl, n-butyl, and n-decyl are particularly preferred, and n-butyl is the most preferred.

[0193] In Example 16 of Method 1 according to the present invention, Method 1 is designed according to Example 15 thereof, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (V).

[0194]

[0195] Wherein n is in the range of 0 to 19, preferably in the range of 1 to 14, and more preferably in the range of 3 to 9. Particularly preferred is that n is 2, 3, or 4, with n=3 being the most preferred.

[0196] In Example 17 of Method 1 according to the present invention, Method 1 is designed according to Example 9 thereof, wherein the organic residue R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group having the structural formula (IIc).

[0197]

[0198] in

[0199] R 10 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 10 For H;

[0200] R 11 For H, C1-C 10 Alkyl, preferably C1-C5 alkyl, more preferably methyl, or C1-C 10 Alkoxy, preferably C1-C5 alkoxy, more preferably methoxy, and most preferably, R 11 For H;

[0201] n is an integer in the range of 0 to 10, preferably in the range of 1 to 6, and more preferably in the range of 1 to 3, wherein most preferably, n is 1; and

[0202] R 12 The residue is a branched organic chain, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain, and even more preferably an organic residue having formula (IId).

[0203]

[0204] in

[0205] m is 1, 2, or 3.

[0206] R 13 For H or C1-C 12 Alkyl groups, preferably C2-C10 Alkyl, more preferably C3-C8 alkyl, even more preferably butyl, the limiting condition being that there are m structural units -CHR 13 In only one of them, residue R 13 For C1-C 12 alkyl;

[0207] R 14 For C1-C 10 Alkyl, preferably C2-C6 alkyl, or aryl.

[0208] In Example 18 of Method 1 according to the present invention, Method 1 is designed according to Example 17 thereof, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):

[0209]

[0210] In Example 19 of Method 1 according to the present invention, according to any one of Examples 1 to 18 of Method 1, wherein the reaction mixture provided in step I) comprises a relative amount of 5 to 95%, preferably 10 to 80% and more preferably 20 to 60% of a 3,4-ethylenedioxythiophene derivative, in each case based on the total molar amount of 3,4-ethylenedioxythiophene and the 3,4-ethylenedioxythiophene derivative.

[0211] In Example 20 of Method 1 according to the present invention, according to any one of Examples 1 to 18 of Method 1, wherein the reaction mixture provided in step I) comprises at least 30% by weight, preferably at least 40% by weight and more preferably at least 70% by weight of monomer units based on the derivative of 3,4-ethylenedioxythiophene, in each case based on the total number of monomer units (i.e., based on the total weight of 3,4-ethylenedioxythiophene monomer units and monomer units based on the derivative of 3,4-ethylenedioxythiophene).

[0212] In Example 21 of the composition 1 according to the invention, the composition 1 was designed according to Example 6 thereof, wherein the reaction mixture comprises the following as components i):

[0213] α) At least one derivative of 3,4-ethylenedioxythiophene having the structural formula (Ia')

[0214] ,

[0215] Wherein R is a branched alkyl group or a branched ether group, preferably a branched ether group, more preferably a branched ether group having the structural formula (IIc) as defined above.

[0216] β) At least one derivative of 3,4-ethylenedioxythiophene having the structural formula (Ia').

[0217] ,

[0218] Wherein R is an alkyl group having the structural formula (IIb) as defined above, and thiophene derivatives selected from the group consisting of: 2-ethyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-propyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene, 2-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxanediene, and 2-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxanediene, with 2-butyl-2,3-dihydrothieno[3,4-b]-1,4-dioxanediene (Butyl-EDOT) being particularly preferred.

[0219] and optional

[0220] γ) 3,4-ethylenedioxythiophene.

[0221] In Example 22 of Method 1 according to the invention, Method 1 is designed according to Example 21 thereof, wherein the reaction mixture comprises 5 to 99 mol%, preferably 15 to 70 mol%, and more preferably 30 to 50 mol%, of monomer units based on monomer α), 5 to 95 mol%, preferably 30 to 90 mol%, and more preferably 50 to 70 mol%, of monomer units based on monomer β), and 0 to 50 mol%, preferably 0 to 35 mol%, and more preferably 0 to 20 mol%, of monomer units based on monomer γ), wherein in each case the total amount of monomers α), β), and γ) in the reaction mixture is 100 mol%. According to a particularly preferred embodiment of Method 1, the reaction mixture does not contain 3,4-ethylenedioxythiophene as a comonomer.

[0222] In Example 23 of Method 1 according to the present invention, according to any one of Examples 1 to 22 of Method 1, wherein in Method Step I), the organic compound ii) is present in the form of a free acid, or in both Method Steps.

[0223] In Example 24 of Method 1 according to the present invention, according to any one of Examples 1 to 23 of Method 1, the inorganic acid group is a sulfonic acid group (-SO2OH), a sulfate group (-O-SO2OH), a phosphonic acid group (-PO(OH)2) or a phosphate group (-O-PO(OH)2), preferably a sulfonic acid group (-SO2OH).

[0224] In Example 25 of Method 1 according to the present invention, according to any one of the design methods 1 of Examples 1 to 24 thereto, wherein the organic compound ii) is an anionic surfactant.

[0225] In Example 26 of Method 1 according to the invention, according to any one of Examples 1 to 25 of Method 1, the anionic surfactant is a sulfonic acid (R-SO2OH), an ester of sulfuric acid (RO-SO2OH), or a salt of one of these anionic surfactants, preferably a salt of sulfonic acid. In this case, it is also particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (i.e., a compound carrying only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.

[0226] In Example 27 of Method 1 according to the present invention, Method 1 is designed according to Example 26 thereof, wherein the anionic surfactant is dodecylbenzenesulfonic acid or a salt thereof.

[0227] In Example 28 of Method 1 according to the present invention, according to any one of Examples 1 to 27 of Method 1, wherein the total amount of thiophene monomer (component i) in the reaction mixture provided in step I) of method, preferably the total amount of 3,4-ethylenedioxythiophene and its derivatives (component i) to organic compound ii) is in the weight ratio of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2 and more preferably in the range of 1:5 to 1:0.5.

[0228] In Example 29 of Method 1 according to the present invention, according to any one of the design methods 1 in Examples 1 to 28 thereto, the boiling point (measured at a pressure of 1013 mbar) of at least one organic solvent (iii), preferably at least one aprotic solvent (iii), is in the range of 50 to 300°C, preferably in the range of 60 to 250°C and more preferably in the range of 70 to 220°C.

[0229] In Example 30 of Method 1 according to the present invention, according to any one of the design methods 1 in Examples 1 to 29 thereto, at least one organic solvent is an aprotic solvent (iii), more preferably a polar aprotic solvent.

[0230] In Example 31 of Method 1 according to the present invention, Method 1 is designed according to Example 30 thereof, wherein the dielectric constant of the polar aprotic solvent (iii) is less than 20, preferably less than 10 and more preferably less than 7.

[0231] In embodiment 32 of method 1 according to the present invention, method 1 is designed according to embodiment 30 or 31, wherein the dipole moment of the polar aprotic solvent (iii) is less than 4 D, preferably less than 2 D and more preferably less than 1.5 D.

[0232] In Example 33 of Method 1 according to the present invention, according to any one of Examples 1 to 32 of Method 1, wherein at least one organic solvent iii) is selected from the group consisting of: aromatic hydrocarbons, esters, ethers, alcohols and mixtures thereof.

[0233] In Example 34 of Method 1 according to the present invention, Method 1 is designed according to Example 33 thereof, wherein at least one organic solvent iii) is selected from the group consisting of: 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 with one or two other solvents. In the case of a mixture of two or more organic solvents, it is particularly preferred that at least one of these solvents is an aprotic solvent iii).

[0234] In embodiment 35 of the method according to the invention, according to any one of embodiments 1 to 34 of design method 1, wherein method 1 includes the following additional steps:

[0235] III) Add an additive v) that is different from monomer i), anion ii), aprotic solvent iii) and oxidant iv) to the reaction mixture provided in step I).

[0236] In embodiment 36 of the method according to the invention, according to any one of embodiments 1 to 35 of design method 1, wherein method 1 includes the following additional steps:

[0237] IV) Dilute the composition obtained after step II) with an organic solvent vi) other than solvent iii) to a solution obtained after step III) or after step IV).

[0238] In Example 37 of the method according to the invention, method 1 was designed according to Example 36 thereof, wherein the weight ratio of the composition to another solvent (vi) is in the range of 50:1 to 0.02:1.

[0239] In Example 38 of the method according to the invention, Method 1 is designed according to Example 36 or 37 thereof, wherein the additional organic solvent (vi) is an organic solvent as defined in any of Examples 31 to 37 of Method 1, preferably an aprotic solvent.

[0240] In embodiment 39 of method 1 according to the present invention, according to any one of embodiments 1 to 38 of design method 1, wherein the composition provided in method step I) comprises

[0241] i) A total of 0.01 to 20% by weight, preferably 0.02 to 10% by weight and more preferably 0.1 to 5% by weight of thiophene monomers having structure (VIa) or (VIb), preferably a total amount of 3,4-ethylenedioxythiophene and its derivatives in these ranges (these amounts therefore correspond to the total weight of 3,4-ethylenedioxythiophene and its derivatives).

[0242] ii) 0.01 to 15% by weight, preferably 0.02 to 10% by weight, and more preferably 0.1 to 5% by weight of organic compounds;

[0243] iii) 50 to 99.98% by weight, preferably 70 to 99.86% by weight and more preferably 85 to 99.3% by weight of a solvent or solvent mixture, preferably an aprotic solvent or solvent mixture;

[0244] iv) 0.01 to 15% by weight, preferably 0.1 to 10% by weight and more preferably 0.5 to 5% by weight of additives different from components i) to iv);

[0245] The total weight of components i) to v) is 100 by weight.

[0246] In embodiment 40 of method 1 according to the present invention, according to any one of embodiments 1 to 39 of design method 1, wherein method 1 includes the following additional steps:

[0247] V) Add a non-conductive oligomer or polymer, preferably a non-conductive oligomer or polymeric adhesive, to the product obtained in step II), III) or IV) of the method.

[0248] In Example 41 of Method 1 according to the invention, Method 1 is designed according to Example 40 thereof, wherein the non-conductive polymeric adhesive is selected from the group consisting of: polyolefins, polyvinyl acetate, polycarbonate, poly(meth)acrylate, polyvinyl butyral, poly(meth)acrylamide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, polysulfone, polysilicon, epoxy resin, styrene-acrylate, vinyl acetate / acrylate or ethylene / vinyl acetate copolymer, polyvinyl alcohol, cellulose derivatives, or mixtures comprising at least two of these polymers, wherein poly(meth)acrylate and polysilicon are particularly preferred non-conductive polymeric adhesives. Multifunctional (meth)acrylates, such as diisopentanetetramethylolpropane / hexaacrylate, are also suitable as non-conductive polymeric adhesives.

[0249] In Example 42 of Method 1 according to the present invention, Method 1 is designed according to Example 41 thereof, wherein the poly(meth)acrylate is selected from the group consisting of: poly(methyl acrylate), poly(methyl methacrylate), poly(ethyl acrylate), poly(ethyl methacrylate), poly(n-propyl acrylate), poly(n-propyl methacrylate), poly(isopropyl acrylate), poly(isopropyl methacrylate), poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly(tert-butyl acrylate), poly(tert-butyl methacrylate), poly(2-ethylhexyl acrylate), poly(2-ethylhexyl methacrylate), poly(cyclohexyl acrylate), poly(cyclohexyl methacrylate), poly(phenyl acrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), poly(phenyl methacrylate), and copolymers of these polyacrylates or polymethacrylates.

[0250] In Example 43 of Method 1 according to the invention, according to any one of the design methods 40 to 42 thereof, the non-conductive polymeric adhesive, preferably poly(meth)acrylate and / or polysilicon, is added in such amounts that the non-conductive polymeric adhesive and the polythiophene / organic compound composite are present in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

[0251] In Example 44 of Method 1 according to the present invention, according to any one of Examples 1 to 43 of Method 1, wherein the reaction mixture provided in step I) contains less than 2% by weight, preferably less than 1% by weight and most preferably less than 0.1% by weight of water based on the total weight of the composition.

[0252] The composition 2, as described in Example 1, also contributes to solving at least one of the objectives according to the invention, which can be obtained by method 1 according to any one of Examples 1 to 44.

[0253] Furthermore, embodiment 1 of layer structure 1 contributes to solving at least one of the objectives according to the invention, the layer structure comprising a substrate and a conductive layer applied to the substrate, wherein the conductive layer comprises...

[0254] i) At least one monomeric unit comprising structure (Ia) or (Ib) of polythiophene

[0255]

[0256] in

[0257] Indicates the bond with adjacent unit cells.

[0258] X and Z represent O or S,

[0259] R 1 -R 6 Each can be represented independently by a hydrogen atom or an organic residue R.

[0260] Its limiting condition is residue R 1 To R 4 At least one of the residues R 5 and R 6 One of them represents an organic residue R, preferably a copolymer of 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene, wherein at least one of the hydrogen atoms of the ethylene group is substituted with an organic residue R.

[0261] ii) At least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups, wherein the molecular weight of the organic compound or its salt is less than 1,000 g / mol, preferably less than 900 g / mol, more preferably less than 800 g / mol, even more preferably less than 700 g / mol, even more preferably less than 600 g / mol and even more preferably less than 500 g / mol.

[0262] Preferred polythiophene or copolymer i) and anionic anion ii) are those polythiophene or copolymer and anion that have been described in combination with composition 1 and method 1 according to the present invention.

[0263] In Embodiment 2 of the layer structure 1 according to the present invention, the layer structure 1 is designed according to Embodiment 1, wherein the weight ratio of polythiophene i), preferably copolymer i), to organic compound ii) or salt thereof in the conductive layer is in the range of 1:30 to 1:0.1, preferably in the range of 1:20 to 1:0.2, and more preferably in the range of 1:5 to 1:0.5.

[0264] In embodiment 3 of the layer structure 1 according to the present invention, the layer structure 1 is designed according to embodiment 1 or 2, wherein the conductive layer further comprises

[0265] iii) Non-conductive oligomers or polymers, preferably non-conductive oligomeric or polymeric adhesives.

[0266] The preferred non-conductive oligomeric or polymeric adhesives are those mentioned in Examples 37 to 39 of Composition 1 according to the invention.

[0267] In embodiment 4 of the layer structure 1 according to the invention, the layer structure 1 is designed according to embodiment 3, wherein the conductive layer comprises a non-conductive polymeric adhesive iv), preferably poly(meth)acrylate and / or polysilicon, and a polythiophene / organic compound i) / ii), in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.

[0268] In embodiment 5 of the layer structure 1 according to the present invention, layer structure 1 is designed according to embodiment 3 or 4, wherein the sheet resistance of the conductive layer is at most 1 × 10⁻⁶. 10 Ohm / sq, preferably up to 5×10 9 Ohm / sq and more preferably up to 1×10 8 Ohm / sq.

[0269] Example 1 of method 2 for preparing the layered structure also contributes to solving at least one of the objectives according to the invention, the method comprising the following steps:

[0270] A) Provide a substrate;

[0271] B) Coat the substrate with composition 1 according to any one of Examples 1 to 44 or with composition 2 according to Example 1;

[0272] C) At least partially remove organic solvent iii), preferably aprotic solvent iii), to form a conductive layer.

[0273] In embodiment 2 of method 2 according to the present invention, method 2 further includes the following steps:

[0274] D) Apply an intermediate coating, such as an adhesive layer or a base coat, to the substrate before performing step B).

[0275] The layer structure 2, embodiment 1, also contributes to solving at least one of the objectives according to the invention, which can be obtained by method 2 according to the invention.

[0276] In Embodiment 2 of the layer structure 1 or layer structure 2 according to the present invention, the layer structure is designed according to its corresponding Embodiment 1, wherein the conductivity of the conductive layer is at least 1 S / cm, preferably at least 2 S / cm and most preferably at least 5 S / cm.

[0277] The invention also contributes to solving at least one of the objectives of the invention through an electronic component, particularly an organic light-emitting diode, an organic solar cell, or a capacitor, wherein the electronic component comprises a layer structure 1 according to embodiment 1 or 2 or a layer structure 2 according to embodiment 1.

[0278] The invention also contributes to solving at least one of the objectives of the invention by using composition 1 according to any one of its embodiments 1 to 46 or composition 2 according to its embodiment 1 to generate a conductive layer or an antistatic coating in electronic components, particularly organic light-emitting diodes, organic solar cells or capacitors.

[0279] Organic compounds ii)

[0280] The organic compound i) or its salt carrying one or two inorganic acid groups present in the composition or layer structure according to the invention, or in the reaction mixture provided in step I) of the method according to the invention, is preferably an anionic surfactant, wherein, more preferably, the anionic surfactant is selected from the group consisting of: organophosphonic acids, organophosphates, organosulfonic acids, such as sulfonic acids, such as alkyl-aryl-sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and their salts or mixtures. Each of the following anionic surfactants may contain a mixture of compounds with altered alkyl chain lengths:

[0281] Suitable alkyl sulfates include, but are not limited to, C8-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.

[0282] Suitable alkyl ether sulfates include, but are not limited to, C8-C. 18 Alkyl ether sulfates, such as sodium lauryl ether sulfate and sodium myristyl ether sulfate.

[0283] Suitable alkyl sulfonates include, but are not limited to, C8-C 18 Alkyl sulfonates, such as sodium tetradecyl sulfonate, sodium octadecyl sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate, and their corresponding sulfonic acids.

[0284] - Suitable aryl sulfonates or sulfonic acids optionally substituted with alkyl or aryl substituents, including but not limited to C2-C 18 Alkylbenzene sulfonates or sulfonic acids, such as sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid, ethylbenzene sulfonic acid, and isopropylamine dodecylbenzene sulfonic acid; C2-C 18 Alkyl naphthalene sulfonates or sulfonic acids, such as sodium butyl naphthalene sulfonate and sodium hexyl naphthalene sulfonate, especially sodium dodecylbenzene sulfonate or dodecylbenzene sulfonic acid. If optionally substituted with an alkyl substituent, 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, but are not limited to, C2-C... 18Alkyl 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. The sulfate, sulfonate, or sulfonic acid group may be located at any point along the alkyl chain or aromatic ring, such as on a primary, secondary, or tertiary carbon.

[0285] - Also suitable are surfactants carrying two sulfonic acid groups, such as C2-C 16 Alkyl diphenyl oxide disulfonates or disulfonic acids, such as sodium dodecyl diphenyl ether disulfonate.

[0286] Suitable organophosphonic acids include monovalent phosphonic acids such as phenylphosphonic acid, 11-hydroxyundecylphosphonic acid, 2,4-dimethylphosphonic acid, 4-ethylphenylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, p-(diphenylmethyl)phosphonic acid, 11-phosphonoundecanoic acid and p-(1-naphthylmethyl)phosphonic acid, or diphosphonic acids such as (12-phosphonododecyl)phosphonic acid and 1,8-octanediphosphonic acid.

[0287] However, it is particularly preferred that the anionic surfactant is a monovalent sulfonic acid, especially dodecylbenzenesulfonic acid or its salt.

[0288] Additives (iv)

[0289] Suitable additives (iv) that may also be present in the compositions according to the invention include oxidants (preferably in their reduced form), conductivity modifiers, adhesion promoters, adhesives, and crosslinking agents:

[0290] - Additives that enhance conductivity include compounds such as tetrahydrofuran; compounds containing lactone groups such as butyrolactone and valproic acid; compounds containing amide or lactam groups such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide, N-methylformaniline; N-methylpyrrolidone (NMP); N-octylpyrrolidone; pyrrolidone; sulfones and sulfoxides such as sulfolane (tetramethylene sulfone) and 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 and mannitol); furan derivatives such as 2-furanic acid and 3-furanic acid; and / or glycols or polyols such as ethylene glycol, glycerol, or diethylene glycol or triethylene glycol. Tetrahydrofuran, N-methylformamide, N-methylpyrrolidone, ethylene glycol, dimethyl sulfoxide, or sorbitol are particularly preferred as additives to improve conductivity.

[0291] - Suitable adhesion promoters are compounds such as organic functional silanes or their hydrolysis products, for example, 3-glycidoxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane.

[0292] - The adhesive comprises organic adhesives, particularly those soluble in organic solvents, such as polyolefins, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylate, polyacrylamide, polymethacrylate, polymethacrylamide, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylpyrrolidone, polybutadiene, polyisoprene, polyether, polyester, polyurethane, polyamide, polyimide, polysulfone, polysilicon, epoxy resin, styrene-acrylate, vinyl acetate / acrylate and ethylene / vinyl acetate copolymers, polyvinyl alcohol or cellulose derivatives, which may also be added to the composition. Copolymers of the above polymers are also suitable as adhesives. Particularly in the case of polythiophene containing a thiophene monomer carrying an alkyl group as residue R, it is particularly preferred that the composition further comprises a non-conductive oligomeric or polymeric adhesive, especially poly(meth)acrylate and / or polysilicon.

[0293] Suitable crosslinking agents include melamine compounds, end-capped isocyanates, functional silanes (e.g., tetraethoxysilanes), alkoxysilane hydrolysis products (e.g., based on tetraethoxysilanes), or epoxysilanes (e.g., 3-glycidoxypropyltrialkoxysilane).

[0294] Method for producing the composition according to the invention

[0295] In the method according to the invention, the thiophene monomer is oxidatively polymerized in the presence of an organic compound ii) (which is preferably in anionic form) and an aprotic solvent iii). An oxidant iv) suitable for the oxidative polymerization of pyrrole can be used as the oxidant. For practical reasons, inexpensive and readily handleable oxidants can be used, such as iron(III) salts, like FeCl3, Fe(ClO4)3, and iron(III) salts of organic acids and inorganic acids containing organic groups. For example, C1-C... 20 Iron (III) salts of sulfated half-esters of alkanols, such as the Fe(III) salt of lauryl sulfate, are iron (III) salts of inorganic acids containing organic groups. For example, the following are iron (III) salts of organic acids: Fe(III) salts of the following, C1-C 20 Alkyl sulfonic acids, such as methanesulfonic acid and dodecanesulfonic acid; aliphatic C1-C 20 Carboxylic acids, such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids, such as oxalic acid; and optionally C1-C6 fluorocarboxylic acids. 20Alkyl-substituted aromatic sulfonic acids, such as benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid. A significant practical advantage of iron (III) salts of organic acids is their partial or complete solubility in organic solvents, especially water-immiscible organic solvents. The following organic peroxides can also be used as oxidants: tert-butyl peroxide, diisobutyryl peroxide, di-n-propyl peroxydicarbonate, didecyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, and di-tert-pentyl peroxide. Organic azo compounds, such as 2,2'-azobisisobutyronitrile, can also be used. Particularly preferred oxidants are organic, metal-free oxidants, such as organic peroxides, with benzoyl peroxide being the most preferred.

[0296] Theoretically, for the oxidative polymerization of the thiophene monomer, 2.25 equivalents of oxidant are required per mole of thiophene (see, for example, Journal of Polymer Science, Part A, Polymer Chemistry, Vol. 26, p. 1287 (1988)). However, in the prior art, the oxidant is usually used in a certain excess amount, for example, 0.1 to 2 equivalents per mole of thiophene.

[0297] In step II) of the method according to the invention, the thiophene monomer is oxidatively polymerized in the presence of organic compound ii) by reducing the oxidant to a reduction product and oxidizing the thiophene monomer to form a composition preferably comprising cationic polythiophene copolymer i) and the reduction product, wherein the polymerization preferably occurs at a temperature in the range of 0°C to 100°C. In this case, it is particularly preferred that the reaction temperature be in the range of 25°C up to a temperature below the lowest boiling point of the solvent contained in the reaction mixture.

[0298] The anion ii) present in the reaction mixture provided in step I) acts as a relative ion to compensate for the positive charge of the polythiophene i), preferably copolymer i). The anion ii) and polythiophene i) are preferably present in the form of a polythiophene / anionic complex. In this case, it is also preferred that step II) yield a composition comprising polythiophene i) and anion ii) in the form of such a complex, wherein, particularly preferably, the composition is present in the form of a dispersion containing an aprotic solvent iii) in which the complex is dispersed.

[0299] The invention will now be described in more detail with reference to the drawings, test methods and non-limiting embodiments.

[0300] Figure 1 The layer structure 100 according to the invention is shown in a general form, such as the structure of an antistatic film. A conductive layer 102 is formed on the substrate surface of the substrate 101 (typically a PE, PP, or PET layer in the case of an antistatic film), which has been prepared by the composition according to the invention.

[0301] Test methods

[0302] conductivity measurement

[0303] Conductivity refers to the reciprocal of resistivity. Resistivity is calculated as the product of the surface resistance of the conductive polymer layer and the layer thickness. The surface resistance of the conductive polymer was determined according to DIN EN ISO 3915. Specifically, the composition under study was applied as a homogeneous film to a 50 mm × 50 mm glass substrate using a spin coater, which was thoroughly cleaned using the substrate cleaning process described above. In this procedure, the coating composition was applied to the substrate by a dropper to completely cover the area and then directly spin-coated. The spin conditions for the coating composition were approximately 1,000 rpm in air for 20 seconds. Afterward, a drying process was performed on a hot plate (130°C in air for 10 minutes). Silver electrodes, 2.0 cm long and spaced 2.0 cm apart, were vapor-deposited onto the polymer layer via a shadow mask. The square area of ​​the layer between the electrodes was then electrically separated from the remainder of the layer by scraping two lines with a doctor blade. The surface resistance between the Ag electrodes was measured using an ohmmeter (Keithley 614). The thickness of the polymer layer was determined at the scraped location using a stylus profilometer (Dektac 150, Veeco).

[0304] Determining water content

[0305] The water content of the compositions according to the invention can be determined by Karl Fischer titration. A Metrohm 787 KF Titrino with a 703 titration rack was used for this purpose. The titration vessel was filled with analytical grade methanol so that approximately 1 cm of platinum electrode was immersed. Then, approximately 5 ml of Hydranal buffer acid was drawn in. The titration cell was automatically dried by starting the KFT program. Preparation was complete when the message "KFT conditioned" appeared. Then, approximately 5 ml of the composition to be analyzed was introduced into the titration vessel using a syringe, and the precise mass of the dispersion used was determined by weighing the syringe. Titration was then started. The measurements were determined as the average of three individual measurements.

[0306] Solid content

[0307] The solids content was determined using a precision balance (Mettler AE 240) via gravimetric analysis. First, the empty weighing bottle, including the cap, was weighed (weight A). Then, approximately 3 g of the dispersion to be analyzed was rapidly filled into the bottle, sealed with the cap, and weighed again to determine the precise total weight B. The bottle was then placed in a fume hood for approximately 3 hours to allow the volatile solvent to evaporate at room temperature. In the 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, it was important to immediately cap it due to the hygroscopic nature of the drying dispersion material. After a 10–15 minute cooling period, the bottle, including the cap, was weighed again to determine the weight C.

[0308] Calculation of solid content: Solid content wt.% = 100 × (CA) / (BA)

[0309] The result is the average of the two measurements.

[0310] Film fabrication on PET substrate

[0311] The dispersion was applied to a PET substrate at room temperature using a manual doctor blade from Erichsen, the blade having a 12 μm gap. In this context, the gap spacing of the manual doctor blade determines the thickness of the formed wet film, also known as the wet film thickness. The coating or film formed in this manner was then dried in a drying oven at 130°C for 5 minutes. The coated PET substrate was cooled to room temperature before any further processing.

[0312] Surface resistivity measurement

[0313] Surface resistivity was measured using a Staticide ACL 800 Digital Megohmmeter at a setting of 100 V. Two measurements were taken at different locations on the thin film, and the lowest value was considered the result. The highest measurable surface resistivity was 2 × 10⁻⁶. 11 Ω / sq. Values ​​at or above the threshold are considered outside the range, but will still be displayed in 2×10. 11 At Ω / sq.

[0314] Determination of the stability of dispersions in organic solvents

[0315] The stability of the dispersion was determined by slowly adding the mentioned amount of solvent to the initial dispersion over a 5-minute timeframe. The mixture was slowly stirred during the solvent addition process and for an additional 15 minutes. The mixture was stored at room temperature for 24 hours without any mechanical disturbance. After visual evaluation, the resulting mixtures were classified into three categories:

[0316] + Stable, homogeneous dispersion, free of any particles

[0317] 0 small particles visible

[0318] - Large particles and / or significant gelation and / or phase separation

[0319] Example

[0320] Example 1:

[0321] (Reference example for the synthesis of 2-[(decoxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxane)

[0322]

[0323] The synthesis was carried out under dry and inert conditions.

[0324] THF (6.6 L) and 18-crown ether-6 (22.0 g, 88 mmol) were added to the reaction vessel. NaH (166.4 g, 4.15 mol) in the form of a 60% suspension in oil was added with stirring, and the mixture was stirred at room temperature. A solution of EDOT-MeOH (551 g, 3.2 mol) in THF was added to the NaH solution at 0 °C. After the addition of the solution, the reaction mixture was stirred at room temperature for 1.5 h, followed by stirring at 50 °C for 1 h. The reaction mixture was cooled to 0 °C, and a solution of 1-bromo-decane (936.7 g, 4.2 mol) was stirred at room temperature for 1 h and then at 50 °C for 15 h. The reaction mixture was cooled to room temperature and quenched with a 70:30 (v / v) mixture of isopropanol / water. The crude product was purified by column chromatography.

[0325] The reaction product (2-[(decoxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxane, CAS: 210476-55-4), which is a yellow oil, was obtained in a yield of 74-80%.

[0326] Example 2 :

[0327] (Comparative example based on the teachings of WO-A-2012 / 059215)

[0328] 294 g of anisole (Aldrich), 9.4 g of benzoyl peroxide (39 mmol; Aldrich), and 8.25 g of sulfonated block copolymer (Kraton Nexar) were added to a 1 L three-necked round-bottom flask equipped with a mechanical stirrer. ®MD) and 7.2 g of p-toluenesulfonic acid (38 mmol, Aldrich). After heating to 60°C, 4.95 g of 3,4-ethylenedioxythiophene (35 mmol; Clevios MV2; Heraeus Deutschland GmbH & Co KG, Germany) dissolved in 20 g of anisole was added over 40 minutes. The dispersion was then stirred at 60°C for 3 hours and then cooled to room temperature. This dispersion is called dispersion 2A.

[0329] 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 sonication for 2 minutes (Hielscher UP 200 S, period 1, amplitude 100%). This sample is referred to as dispersion 2B.

[0330] Analysis of dispersion 2B:

[0331] Solid content: 2.5% (by weight)

[0332] Using a wire spindle, a 12 µm wet film of dispersion 2B was deposited on the substrate and dried in an oven at 130 °C for 15 minutes. The conductive layer was characterized by the following properties:

[0333] Electrical conductivity (on glass): 7.7 S / cm

[0334] Thin-film resistivity (12 µm on PET): 17,000 Ohm / sq

[0335] Example 3 (According to the present invention)

[0336] In Example 3, the following complex was prepared:

[0337]

[0338] Dispersion A:

[0339] 29.7 g of anisole (Aldrich), 2.7 g of benzoyl peroxide (11.1 mmol; Aldrich), and 3.7 g of dodecylbenzenesulfonic acid (11.5 mmol; Aldrich) were added to a 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet. After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios MV2; Heraeus AG, Germany) and 1.55 g of the EDOT derivative obtained in Example 1 (5 mmol) were added. The dispersion was then stirred at 60 °C under nitrogen for 3 hours. Next, 35 g of anisole was added. After cooling to room temperature, the dispersion was allowed to stand overnight. This dispersion is referred to as Dispersion 3A.

[0340] Dispersion 3B:

[0341] Mix 5 g of dispersion 3A and 5 g of butyl acetate in a 20 ml glass bottle and sonicate for 1 minute (Hilcher UP 200 S, period 1, amplitude 100%). This substance is called dispersion 3B.

[0342] Analysis of dispersion 3B:

[0343] Solid content: 2.4% (by weight)

[0344] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film was characterized by the following properties:

[0345] Thin-film resistivity (12 µm on PET): 20,000 Ohm / sq

[0346] Dispersion 3C:

[0347] Mix 2.5 g of dispersion 3A, 2.5 g of anisole, and 5 g of butyl acetate in a 20 ml glass vial and subject to sonication for 1 minute (Hilcher UP 200 S, period 1, amplitude 100%). This substance is called dispersion 3C.

[0348] Analysis of 3Cs in the dispersion:

[0349] Solid content: 1.2% (by weight)

[0350] Water content: 0.04%

[0351] Ion content was measured using inductively coupled plasma optical emission spectroscopy.

[0352] Na content: 24 ppm

[0353] Ca content: 0.6 ppm

[0354] Mg content: 0.06 ppm

[0355] The detection limits for K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn, and Cd are below 0.025 ppm.

[0356] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film was characterized by the following properties:

[0357] Thin-film resistivity (12 µm on PET): 16,000 Ohm / sq

[0358] Transmittance (including PET): 83.3%

[0359] Haze (including PET): 0.58

[0360] The 3C dispersion was deposited onto glass by spin coating and dried on a hot plate at 130°C for 10 minutes. Conductivity was measured according to the test method described above.

[0361] The membrane is characterized by the following properties:

[0362] Conductivity 9.4 S / cm

[0363] Example 4 (According to the present invention)

[0364] (In Example 4, the concentration of dodecylbenzenesulfonic acid was reduced.)

[0365] 29.7 g of anisole (Aldrich), 2.7 g of benzoyl peroxide (11.1 mmol; Aldrich), and 3.08 g of dodecylbenzenesulfonic acid (9.6 mmol; Aldrich) were added to a 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet. After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios MV2; Heraeus AG, Germany) and 1.55 g of the EDOT derivative obtained in Example 1 (5 mmol) were added. The dispersion was then stirred at 60 °C under nitrogen for 3 hours. Then, 35 g of anisole was added. After cooling to room temperature, the dispersion was allowed to stand overnight. This dispersion is referred to as Dispersion 4A.

[0366] Mix 5 g of dispersion 4A and 5 g of butyl acetate in a 20 ml glass bottle and sonicate for 1 minute (Hilcher UP 200 S, period 1, amplitude 100%). This substance is called dispersion 4C.

[0367] Analysis of 4C in the dispersion:

[0368] Solid content: 2.1% (by weight)

[0369] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film was characterized by the following properties:

[0370] Thin-film resistivity (12 µm on PET): 12,000 Ohm / sq

[0371] Example 5 (According to the present invention)

[0372] (In Example 5, the concentration of dodecylbenzenesulfonic acid was further reduced.)

[0373] 29.7 g of anisole (Aldrich), 2.7 g of benzoyl peroxide (11.1 mmol; Aldrich), and 2.2 g of dodecylbenzenesulfonic acid (6.8 mmol; Aldrich) were added to a 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet. After heating to 60 °C, 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios MV2; Heraeus AG, Germany) and 1.55 g of the EDOT derivative obtained in Example 1 (5 mmol) were added. The dispersion was then stirred at 60 °C under nitrogen for 3 hours. Next, 35 g of anisole was added. After cooling to room temperature, the dispersion was allowed to stand overnight. This dispersion is referred to as Dispersion 5A.

[0374] Example 6

[0375] Dispersions 2A and 5A were compared in terms of their solvent compatibility. The samples were mixed with additional solvents as shown in Table 1 and then subjected to sonication for 1 minute.

[0376] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film resistivity was then measured.

[0377]

[0378] Table 1: Thin film resistance of dispersion 5A and reference dispersion 2A diluted with different solvents and corresponding films.

[0379] Table 1 shows that the dispersion 5A of the present invention yields less than 1.5 × 10⁻⁶ ppm in various solvents. 5 Low thin-film resistivity of Ohm / sq, while dispersion 2A gives at most 10 11 The value of Ohm / sq.

[0380] Example 7

[0381] A 2.5% solution of poly(isobutyl methacrylate) in a mixture of anisole / butyl acetate (50% / 50% w / w) was prepared. This solution was mixed with dispersion 2B at different ratios. Since both solutions had the same solids content, the solution / dispersion ratio corresponded to the solids ratio in the resulting film.

[0382] Additionally, a 2.4% solution of poly(isobutyl methacrylate) in a mixture of anisole / butyl acetate (50% / 50% w / w) was prepared. This solution was mixed with dispersion 3B at different ratios. Since both solutions have the same solids content, the solution / dispersion ratio corresponds to the solids ratio in the resulting film.

[0383] Using a wire spindle, 12 µm wet films of all eight mixtures were deposited on a PET substrate and dried in an oven at 130 °C for 15 minutes.

[0384]

[0385] Table 2: Thin film resistivity and haze of polythiophene / poly(isobutyl methacrylate) coating on PET film

[0386] Table 2 shows that, compared to reference dispersion 2B, dispersion 3B of the present invention produces lower sheet resistance and lower haze when blended with poly(isobutyl methacrylate).

[0387] Example 8 (According to the present invention)

[0388] In Example 8, the following complex was prepared:

[0389]

[0390] Dispersion 8A:

[0391] 29.7 g of anisole (Aldrich), 2.7 g of benzoyl peroxide (11.1 mmol; Aldrich), and 3.0 g of dodecylbenzenesulfonic acid (9.3 mmol; DBSA; Aldrich) were added to a 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet. After heating to 60 °C, 0.42 g of 3,4-ethylenedioxythiophene (3 mmol; Clevios M V2; Heraeus AG, Germany) and 1.38 g of 2-butyl-2,3-dihydrothiophene[3,4b][1,4]dioxanediene (7 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) were added. The dispersion was then stirred at 60 °C under nitrogen for 3 hours. Then, 35 g of anisole was added. After cooling to room temperature, allow the dispersion to stand overnight. This dispersion is called dispersion 8A.

[0392] Dispersion 8B:

[0393] Mix 5 g of dispersion 6A, 3 g of anisole, and 2 g of butanol in a 20 ml glass vial and subject to sonication for 1 minute (Hilcher UP 200 S, period 1, amplitude 100%). This substance is called dispersion 8B.

[0394] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film was characterized by the following properties:

[0395] Thin-film resistivity (12 µm on PET): 17,400 Ohm / sq

[0396] Haze (12 µm on PET): 0.7

[0397] Example 9 (According to the present invention)

[0398] The synthesis of Example 8 was repeated using 0.846 g of 3,4-ethylenedioxythiophene (6 mmol) and 0.79 g of 2-butyl-2,3-dihydrothiophene[3,4b][1,4]dioxanediene (4 mmol). All other parameters remained constant. The final substance obtained after sonication was designated dispersion 9B.

[0399] Example 10 (According to the present invention)

[0400] The synthesis of Example 8 was repeated using 0.705 g of 3,4-ethylenedioxythiophene (5 mmol) and 0.98 g of 2-butyl-2,3-dihydrothiophene[3,4b][1,4]dioxanediene (5 mmol). All other parameters remained constant. The final product obtained after sonication was called dispersion 10B.

[0401] Example 11 (According to the present invention)

[0402] The synthesis of Example 8 was repeated using 0.56 g of 3,4-ethylenedioxythiophene (4 mmol) and 1.18 g of 2-butyl-2,3-dihydrothiophene[3,4b][1,4]dioxanediene (6 mmol). All other parameters remained constant. The final substance obtained after sonication was called dispersion 11B.

[0403] Example 12 (According to the present invention)

[0404] The synthesis of Example 8 was repeated using 10 mmol of 2-butyl-2,3-dihydrothiophene-[3,4b][1,4]dioxanediene. 3,4-ethylenedioxythiophene was not used. All other parameters remained constant. The dispersion obtained after cooling to room temperature and standing overnight was designated dispersion 12A. The final substance obtained after sonication was designated dispersion 12B.

[0405] Using a wire spindle, 12 µm wet films from dispersions 9B to 12B according to Example 8 were deposited on a PET substrate and dried in an oven at 130°C for 15 minutes. The films were characterized by their sheet resistance and haze.

[0406] The ion content of 12B was measured by inductively coupled plasma optical emission spectroscopy.

[0407] Na content: 1.4 ppm

[0408] Ca content: 2.8 ppm

[0409] Mg content: 0.02 ppm

[0410] The detection limits for K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn, and Cd are below 0.025 ppm.

[0411] Table 3 summarizes the results for thin-film resistivity and haze of dispersions 2B and 8B to 12B.

[0412]

[0413] Table 3: Thin film resistivity and haze of films prepared by dispersions 2B and 8B-12B

[0414] Example 13 (According to the present invention)

[0415] A solution of poly(isobutyl methacrylate) (PIBM) was prepared. For the purpose described, 13.6 g of poly(isobutyl methacrylate) was dissolved in a mixture of 220 g anisole, 132 g butyl acetate and 88 g butanol.

[0416] Blend Series 1:

[0417] A series of blends of PIBM solution with dispersions 2B and 8B-12B were prepared. 9 g of PIBM solution was mixed with 0.34 g of dispersion 12B, 0.55 g of anisole, 0.33 g of butyl acetate, and 0.22 g of butanol. The mass ratio of non-conductive PIBM to the polythiophene / DBSA composite was 36:1. Similarly, 0.34 g of dispersions 2B and 8B-11B were blended with 9 g of PIBM solution and additional solvent.

[0418] Blend Series 2:

[0419] A second series of blends were prepared. 4 g of PIBM solution was mixed with 0.29 g of dispersion 12B, 0.35 g of anisole, 0.21 g of butyl acetate, and 0.14 g of butanol. The mass ratio of non-conductive PIBM to the polythiophene / DBSA composite was 19:1. Similarly, 0.29 g of dispersions 2B and 8B through 11B were blended with 4 g of PIBM solution and additional solvent.

[0420] Using a wire spindle, 12 µm wet films of the dispersions from Series 1 and 2 were deposited on PET substrates and dried in an oven at 130 °C for 15 minutes. The films were characterized by their sheet resistance. Table 4 summarizes the results.

[0421]

[0422] Table 4: Thin film resistance of films prepared by dispersants 2B and 8B-12B with added PIBM ( 1) (Not based on the present invention)

[0423] Table 4 clearly demonstrates the advantages of polythiophene containing alkyl-EDOT.

[0424] Example 14 (According to the present invention)

[0425] The dispersion obtained in Example 12A was diluted with a series of solvents.

[0426] Table 5 shows the solvent mixtures.

[0427] Example 14B:

[0428] 5 g of dispersion 12 B was mixed with 3 g of anisole and 2 g of n-butanol. The resulting solvent mixture contained 80% anisole (w / w) and 20% n-butanol (w / w). A 12 µm wet film of the dispersion was deposited onto a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The solids content was 2.2%. The film resistivity was 8 × 10⁻⁶. 4 Ohm / sq.

[0429] Example 14C:

[0430] 5 g of the dispersion was mixed with 10 g of anisole and 5 g of n-butanol. The resulting solvent mixture contained 75% anisole and 25% n-butanol. The solids content was 1.1%. A 12 µm wet film of the dispersion was deposited onto a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film resistivity was 16 × 10⁻⁶. 4 Ohm / sq.

[0431] Accordingly, Examples 14D, 14E, 14F and 14G were prepared.

[0432] Table 5 shows the composition and the resulting thin-film resistance:

[0433]

[0434] Table 5: Blends of Dispersion 12A with Various Solvents

[0435] In all six cases, uniform dispersions without particle formation or precipitation were obtained. Table 5 also clearly demonstrates the advantages of polythiophenes containing alkyl-EDOT.

[0436] Example 15 (According to the present invention)

[0437] 29.7 g of anisole (Aldrich), 2.7 g of benzoyl peroxide (11.1 mmol; Aldrich), and 3.0 g of dodecylbenzenesulfonic acid (9.3 mmol; DBSA; Aldrich) were added to a 100 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet. After heating to 60 °C, 0.56 g of 2-decyl-2,3-dihydrothieno[3,4b][1,4]dioxanediene (2 mmol; DecylEDOT; CAS 126213-55-6) and 1.58 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxanediene (8 mmol; ButylEDOT; CAS 552857-06-4) were added. The dispersion was then stirred at 60 °C under nitrogen for 3 hours. Next, add 35 g of anisole. After cooling to room temperature, allow the dispersion to stand overnight. This dispersion is called dispersion 15A.

[0438] Dispersion 15B:

[0439] Mix 5 g of dispersion 15A, 3 g of anisole, and 2 g of butanol in a 20 ml glass vial and sonicate for 1 minute (Hilcher UP 200 S, period 1, amplitude 100%). This substance is called dispersion 15B.

[0440] Solid content: 2.4%

[0441] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The film was characterized by the following properties:

[0442] Thin-film resistivity (12 µm on PET): 64,000 Ohm / sq

[0443] Haze (12 µm on PET): 0.8

[0444] Example 16 (According to the present invention)

[0445] Poly(n-butyl acrylate) is an example of a polyacrylate with a low glass transition temperature (Tg = -54°C). Toluene (CAS 9003-49-0; 25% by weight) containing poly(n-butyl acrylate) is added to toluene, M w 99000 g / mol; Sigma Aldrich product 181404 was blended with dispersion 15B. Table 6 shows the blending ratios of the three mixtures.

[0446] Using a wire spindle, 12 µm wet films of each mixture were deposited on PET substrates and dried in an oven at 130 °C for 15 minutes. The film resistivity was measured.

[0447]

[0448] Table 6: Blends of Dispersion 15 B with Poly(n-butyl acrylate) and their Thin-Layer Resistance

[0449] Example 17

[0450] (Reference example for the synthesis of 3-(2-ethylhexyloxymethyl)-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene)

[0451]

[0452] The synthesis was carried out under dry and inert conditions.

[0453] THF (60 mL) and 18-crown ether-6 (0.200 g, 0.8 mmol) were added to the reaction vessel. NaH (1.512 g, 37.8 mol) in the form of a 60% suspension in oil was added with stirring, and the mixture was stirred at room temperature. A solution of EDOT-MeOH (5.00 g, 29.0 mmol) in 20 mL of THF was added to the NaH solution at 0 °C. After the addition of the solution, the reaction mixture was stirred at room temperature for 2.5 h, followed by stirring at 55 °C for 0.5 h. The reaction mixture was cooled to 0 °C and a solution of 2-ethylhexyl bromide (7.300 g, 37.8 mmol) in 20 mL of THF was added. The reaction mixture was stirred at room temperature for 1 h and then at 50 °C for 40 h. The reaction mixture was cooled to room temperature and quenched with a mixture of isopropanol / water 70:30 (v / v). The crude product was purified by column chromatography.

[0454] The reaction product (3-(2-ethylhexyloxymethyl)-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene) was obtained as a yellow oil in a yield of 15%.

[0455] Example 18

[0456] (Reference example for the synthesis of 3-(1-phenylethoxymethyl)-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene)

[0457]

[0458] The synthesis was carried out under dry and inert conditions.

[0459] DMSO (50 mL), KOH (3.254 g, 58 mmol), (1-bromoethyl)benzene (6.700 g, 37.8 mmol), and EDOT-MeOH (5.00 g, 29.0 mmol) were added to the reaction vessel. The resulting reaction mixture was stirred at 20 °C for 24 hours. After the reaction was complete, the reaction mixture was poured into deionized water (1000 mL) and stirred for 1 hour. The volume of the resulting mixture was reduced by half by vacuum distillation. The mixture was extracted three times with ethyl acetate (150 mL), and the combined organic phases were washed with brine (150 mL), dried over MgSO4, and the solvent was removed under vacuum. The crude product was purified by column chromatography.

[0460] The reaction product 3-(1-phenylethoxymethyl)-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene, which was yellow and oily, was obtained in a yield of 49%.

[0461] Example 19

[0462] 65 g of anisole (Aldrich), 2.699 g of benzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol; Aldrich) were added to a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. After heating to 60 °C, 1.185 g of 3-butyl-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene (6 mmol; ButylEDOT; CAS 552857-06-4, Junhan Biochemical Co., Ltd., Taiwan) and 1.134 g of the product obtained from the reaction in Example 17 (4 mmol) were added after 40 minutes. The dispersion was then stirred at 60 °C for 3 hours and then cooled to room temperature.

[0463] Add 50 g of dispersion, 30 g of anisole and 20 g of n-butanol to a 100 mL flask and mix by gently stirring the resulting dispersion.

[0464] This is called dispersion 19.

[0465] Analysis of dispersion 19:

[0466] Solid content: 2.4% (by weight)

[0467] Thin-film resistivity (12 µm on PET): 210000 Ohm / sq

[0468] The ion content of dispersion 19 was measured by inductively coupled plasma optical emission spectrometry.

[0469]

[0470] Example 20

[0471] 65 g of anisole (Aldrich), 2.699 g of benzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol; Aldrich) were added to a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. After heating to 60 °C, 1.185 g of 3-butyl-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene (10 mmol; ButylEDOT; CAS 552857-06-4, Junhan Biochemical Co., Ltd., Taiwan) dissolved in 20 g of anisole was added over 40 minutes. The dispersion was then stirred at 60 °C for 3 hours and then cooled to room temperature.

[0472] Add 50 g of dispersion, 30 g of anisole and 20 g of n-butanol to a 100 mL flask and mix by gently stirring the resulting dispersion.

[0473] This is called dispersion 20.

[0474] Analysis of dispersion 20:

[0475] Solid content: 2.2% (by weight)

[0476] Thin-film resistivity (12 µm on PET): 70000 Ohm / sq

[0477] Example 21

[0478] Dispersions 19 and 20 were tested for their solvent compatibility. 1 g of the aforementioned dispersion was mixed with 9 g of additional solvent as shown in Table 7 by gentle stirring and shaking.

[0479] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The surface resistivity was then measured.

[0480] The blank PET substrate produces the following baseline values ​​during measurement:

[0481] Surface resistivity: 1.8 × 10⁻⁶ 11 Ohm / sq

[0482] Transmittance: 91%

[0483] Table 7: Dispersion 19 and Dispersion 20 diluted with various solvents.

[0484]

[0485] Table 7 shows that the dispersions from Examples 19 and 20 of this invention exhibit good surface resistivity and form stable dispersions in a variety of commonly used organic solvents.

[0486] Example 22

[0487] 65 g of anisole (Aldrich), 2.699 g of benzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol; Aldrich) were added to a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. After heating to 60 °C, 1.565 g of 3-butyl-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene (8 mmol; ButylEDOT; CAS 552857-06-4, Junhan Biochemical Co., Ltd., Taiwan) and 0.565 g of 3-decyl-2,3-dihydrothiopheno[3,4-b][1,4]dioxanediene (2 mmol; CAS: 210476-55-4) were added over 40 minutes. The dispersion was then stirred at 60°C for 3 hours and then cooled to room temperature.

[0488] Add 50 g of dispersion, 30 g of anisole and 20 g of n-butanol to a 100 mL flask and mix by gently stirring the resulting dispersion.

[0489] This is called dispersion 22.

[0490] Analysis of dispersion 22:

[0491] Solid content: 2.3% (by weight)

[0492] Thin-film resistivity (12 µm on PET): 63000 Ohm / sq

[0493] Example 23

[0494] Dispersions 19 and 22 were tested for their compatibility with acrylic resins. Table 8 shows the amounts of dispersions, solvents, and diisopentanetetraol penta / hexaacrylate (CAS 60506-81-2, Sigma-Aldrich) used.

[0495] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The surface resistivity was then measured.

[0496] Table 8: Surface resistivity of dispersions 19 and 22 in acrylic resin.

[0497]

[0498] Table 8 shows the compatibility of dispersions 19 and 22 with acrylic resins as demonstrated in the achieved surface resistivity values.

[0499] Example 24

[0500] Dispersions 19 and 2B were tested for their compatibility with the silicone release resin. The table shows the amounts of dispersions, solvents, and KS 847-H (CAS: 63148-53-8; Shin-Etsu Silicone) used. A mixture of toluene, alkanes, and ketones was used as the solvent.

[0501] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The surface resistivity was then measured.

[0502] Table 9: Surface resistivity of dispersions 19 and 24 in polysiloxane-releasing resin.

[0503]

[0504] Table 9 shows the excellent compatibility of dispersion 19 with polysiloxane-releasing resin, as demonstrated in the achieved surface resistivity values.

[0505] Example 25

[0506] Dispersions 19 and 22 were tested for their compatibility with polyacrylic resin. Table 10 shows the amounts of dispersions, solvents, and polybutyl acrylate (CAS 9003-49-0, Sigma-Aldrich) used.

[0507] A 12 µm wet film was deposited on a PET substrate using a wire spindle and dried in an oven at 130 °C for 15 minutes. The surface resistivity was then measured.

[0508] Table 10: Surface resistivity of dispersions 19 and 22 in polyacrylic acid adhesives.

[0509]

[0510] Table 10 shows the compatibility of dispersions 19 and 22 with poly(meth)acrylate adhesives, as demonstrated in the achieved surface resistivity values.

[0511] Example 26

[0512] 65 g of anisole (Aldrich), 2.699 g of benzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g of 4-dodecylbenzenesulfonic acid (9.3 mmol; Aldrich) were added to a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. After heating to 60 °C, 1.584 g of 3-butyl-2,3-dihydrothiopheno[3,4-b][1,4]dioxane (8 mmol; ButylEDOT; CAS 552857-06-4, Junhan Biochemical Co., Ltd., Taiwan) and 0.553 g of the product obtained from the reaction in Example 18 (2 mmol) were added over 40 minutes. The dispersion was then stirred at 60 °C for 3 hours and then cooled to room temperature.

[0513] 5 g of dispersion, 3 g of anisole and 2 g of n-butanol were mixed by gentle stirring and subjected to sonication for 1 minute (Hilcher UP 200 S, cycle 1, amplitude 100%) to produce the resulting dispersion.

[0514] This is called dispersion 26.

[0515] Analysis of dispersion 26:

[0516] Solid content: 2.4% (by weight)

[0517] Thin-film resistivity (12 µm on PET): 19000 Ohm / sq

[0518] Component Symbol List

[0519] 100-layer body

[0520] 101 substrate

[0521] 102 Conductive layer.

Claims

1. A composition comprising i) At least one cationic polythiophene comprising a monomeric unit of structure (Ia). in Indicates the bond with adjacent unit cells. X and Z represent O. R 1 -R 4 Each can be represented independently by a hydrogen atom or an organic residue R. Among them, the choice is free from R. 1 R 2 R 3 and R 4 The three residues in the group represent hydrogen atoms and the remaining residues represent branched alkyl or branched ether groups; ii) At least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups, wherein said organic compound or its salt has a molecular weight of less than 1,000 g / mol. iii) At least one organic solvent; The composition is a dispersion, wherein the polythiophene (i) and the organic compound (ii) form a complex uniformly dispersed in the organic solvent (iii).

2. The composition of claim 1, wherein the composition is a stable dispersion, and wherein 9 g of 1-methoxy-2-propanol is added to 1 g of the dispersion over a 5-minute time period while the mixture is stirred during the solvent addition, followed by stirring of the mixture for an additional 15 minutes, and after storage at room temperature for 24 hours without any mechanical disturbance, the dispersion does not form any particles.

3. The composition according to claim 1 or 2, wherein the organic residue R does not carry anionic groups.

4. The composition according to claim 1 or 2, wherein the remaining residues represent a branched ether group having structural formula (IIc). in R 10 For H, C1-C 10 Alkyl or C1-C 10 Alkoxy; R 11 For H, C1-C 10 Alkyl or C1-C 10 Alkoxy; n is an integer in the range of 0 to 10; and R 12 It is a branched organic residue, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain.

5. The composition according to claim 4, wherein R 12 Organic residues having formula (IId) in m is 1, 2, or 3. R 13 For H or C1-C 12 Alkyl groups, with the limitation that they are in the structural unit -CHR 13 In only one of them, residue R 13 For C1-C 12 alkyl; R 14 For C1-C 10 Alkyl or aryl.

6. The composition according to claim 1 or 2, wherein the composition further comprises iv) At least one non-conductive oligomeric or polymeric adhesive, preferably poly(meth)acrylate and / or polysiloxane.

7. The composition according to claim 1 or 2, wherein the organic compound ii) is an anionic surfactant, preferably a monovalent sulfonic acid or a salt thereof.

8. The composition according to claim 1 or 2, wherein the at least one organic solvent iii) is selected from the group consisting of 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 with one or two other solvents.

9. The composition according to claim 1 or 2, wherein the iron content of the composition is less than 30 ppm based on the total weight of the composition.

10. A method for preparing a composition, the method comprising the following steps: I) Provide a reaction mixture comprising the following components: i) Thiophene monomers with structure (VIa) in X and Z represent O. R 1 -R 4 Each can be represented independently by a hydrogen atom or an organic residue R. Among them, the choice is free from R. 1 R 2 R 3 and R 4 The three residues in the group represent hydrogen atoms, and the remaining residues represent branched alkyl or branched ether groups; ii) At least one organic compound or a salt of said organic compound, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups, wherein said organic compound or its salt has a molecular weight of less than 1,000 g / mol. iii) at least one organic solvent; and iv) At least one oxidizing agent, preferably at least one organic peroxide; II) Oxidative polymerization of the thiophene monomer to form cationic polythiophene. The composition obtained in step II) is a dispersion, wherein the cationic polythiophene i) and the organic compound ii) form a complex uniformly dispersed in the organic solvent iii).

11. The method of claim 10, wherein the composition is a stable dispersion, and wherein 9 g of 1-methoxy-2-propanol is added to 1 g of the dispersion over a 5-minute time period while the mixture is stirred during the solvent addition, followed by stirring of the mixture for an additional 15 minutes, and after storage at room temperature for 24 hours without any mechanical disturbance, the dispersion does not form any particles.

12. The method according to claim 10 or 11, wherein the remaining residues represent a branched ether group having structural formula (IIc). in R 10 For H, C1-C 10 Alkyl or C1-C 10 Alkoxy; R 11 For H, C1-C 10 Alkyl or C1-C 10 Alkoxy; n is an integer in the range of 0 to 10; and R 12 It is a branched organic residue, preferably a branched alkyl or branched aralkyl, more preferably a branched alkyl or branched aralkyl that does not carry unsaturated C=C bonds in the alkyl chain.

13. The method of claim 12, wherein R 12 Organic residues having formula (IId) in m is 1, 2, or 3. R 13 For H or C1-C 12 Alkyl groups, with the limitation that they are in the structural unit -CHR 13 In only one of them, residue R 13 For C1-C 12 alkyl; R 14 For C1-C 10 Alkyl or aryl.

14. A layer structure (100) comprising a substrate (101) and a conductive layer (102) applied to the substrate (101), wherein the conductive layer (102) comprises polythiophene (i) as defined in any one of claims 1, 4 and 5 and at least one organic compound (ii) or a salt of said organic compound as defined in claims 1, 3 and 7, said organic compound carrying one or two inorganic acid groups, preferably one or two sulfonic acid groups, one or two sulfate groups, one or two phosphonic acid groups or one or two phosphate groups.

15. A method for preparing a layered structure (100), comprising the following steps: A) Provide a substrate (101); B) Coat the substrate (101) with the composition according to any one of claims 1 to 9 or with a composition that can be obtained by the method according to any one of claims 10 to 13; C) At least partially remove the organic solvent iii) to form a conductive layer (102).

16. An electronic component comprising the layer structure (100) according to claim 14 or a layer structure obtainable by the method according to claim 15.

17. Use of a composition according to any one of claims 1 to 9 or a composition obtainable by the method according to any one of claims 10 to 13 for producing a conductive layer in an electronic component or for producing an antistatic coating.

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