Patent Application
20220348712
The present invention relates to a composition comprising at least one polythiophene. The present invention also relates to a process for preparing a composition, to a composition obtainable by this process, to a layer structure, to a process for the preparation of a layer structure, to a layer structure obtainable by this process, to an electronic component and to the use of composition according to the present invention.
Polythiophenes are widely used as intrinsically conductive polymers. In particular poly(3,4-ethylenedioxythiophene) (PEDOT) has found many industrial applications such as solid electrolyte capacitors, antistatic coatings, electroluminescent lamps, organic light emitting diodes, organic solar cells and many others. For a large number or these applications PEDOT is used as a polymer complex with polystyrene-sulfonic acid as counter-ion dispersed in water or mixtures of water and other solvents (also referred to as “PEDOT/PSS”).
Efforts have been made to supply PEDOT in aprotic solvents in order to extend the range of applications. WO-A-2012/059215 A1 discloses the use of block-copolymers as counter-ions rendering the dispersion soluble in organic, aprotic solvents. The solubility parameters of the block-copolymer dominate and limit the solubility properties of the resulting PEDOT complex. Hence the dispersion becomes unstable once solvents such as PGMEA or ethanol are added.
KR-A-100945056 describes the polymerization of 3,4-ethylenedioxythiophene in water in the presence of surfactants. Subsequently the solvent is removed and is replaced by organic solvents. Such a re-dispersing process, however, is expensive and undesirable.
McCullough et al. (“A Simple Method to Prepare Head-to-Tail Coupled, Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis”; Adv. Mater. 1999, 11, 250) describe the synthesis of regioregular copolymers that can be dispersed in a number of solvents. However, the coupling through metal-organic compounds is expensive and the resulting polymers show only limited conductivity. Hence their application is limited to hole-transport layers, where only conductivity through the layer is required.
The object of the present invention was to overcome the disadvantages of the prior art relating to electrically conductive polymers that are based on thiophene-monomers, preferably on 3,4-ethylenedioxythiophene-monomers.
Particularly, it was an object of the present invention to provide a composition comprising polythiophenes that is based on organic solvents, preferably on organic aprotic solvents, and that can be dispersed in a wide range of solvents. The composition should also be characterized in that conductive layers prepared with such a composition should be highly conductive and highly transparent. Furthermore, the composition should be able to achieve low sheet resistance when blended with inert polymers such as polyacrylates. Furthermore, the composition should be characterized in that they can easily be diluted with organic solvents.
It was also an object of the present invention to provide a process that allows the preparation of such advantageous compositions in as few process steps as possible.
A contribution to at least partly solving at least one, preferably more than one, of the above objects is made by the independent claims. The dependent claims provide preferred embodiments which contribute to at least partly solving at least one of the objects.
A contribution to solving at least one of the objects according to the invention is made by an embodiment 1 of a composition 1 comprising
Surprisingly it was found that polythiophenes comprising monomer units of structure (Ia) or (Ib) as described above, for example copolymers of 3,4-ethylenedioxythiophene and derivatives of 3,4-ethylenedioxythiophene in which at least one of the hydrogen atoms of the ethylene group is substituted by an organic residue R, which use organic compounds carrying one or two inorganic acid group(s), such as a sulfonic acid group (—SO2OH), a sulfuric acid group (—O—SO2OH), a phosphonic acid group (—PO(OH)2), a phosphoric acid group (—O—PO(OH)2), or a salt of at least one of these groups and having a molecular weight of less than 1,000 g/mol, preferably monovalent sulfonic acid anions, as counter-ions can be dispersed in wide range of solvents. If organic residue R corresponds to an alkyl group, particularly to a linear or branched alkyl group having formula —CnH2n+1 in which n is an integer in the range from 1 to 20, preferably to a branched alkyl group in which n is an integer in the range from 3 to 15 and more preferably in the range from 3 to 10, or if organic residue R corresponds to a branched ether group, complexes of such polythiophenes and the above described organic compounds carrying one or two inorganic acid groups(s) are particularly advantageous as into compositions, preferably dispersions, in which these complexes are dispersed in protic or aprotic solvents, large amounts of non-conductive binders, particular poly(meth)acrylates, (meth)acrylic resins, and polysilicones, can be added without unduly reducing the conductivity of these compositions.
In an embodiment 2 of composition 1 according to the invention, composition 1 is designed according to its embodiment 1, wherein the composition is present in the form of a dispersion or solution (and wherein the organic solvent iii), preferably the aprotic solvent iii), thus serves as the dispersant or solvent), wherein the polythiophene i) and the organic compound ii) (which is preferably present in the form of an anion), preferably the copolymer i) and the organic compound ii), form a complex that is dispersed or dissolved, preferably homogeneously dispersed or solved, in the organic solvent iii). Most preferably, the compositions according to the present invention are dispersions in which the complex of the polythiophene i) and the organic compound ii) is homogeneously dispersed in the organic solvent iii). However, in the compositions according to the present invention the transitions between a “dispersion” and a “solution” can be fluid depending on the actual nature of the polythiophene i), the organic compound ii) and the organic solvent iii).
In an embodiment 3 of composition 1 according to the invention, composition 1 is designed according to its embodiment 2, 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.
In an embodiment 4 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 3, wherein the organic residue R does not carry anionic groups. Preferably, residue R does not carry any sulfonic acid groups or salts of this group.
In an embodiment 5 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 4, wherein the organic residue R is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.
In an embodiment 6 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib) in which X and Z represent O, preferably monomer units of structure (Ia) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residue represents an ether group having the structural formula (IIa)
—(CR7R8)n—O—R9 (IIa)
wherein
In an embodiment 7 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib) in which X and Z represent O, preferably monomer units of structure (Ia) in which X and Z represent O, and wherein at least two of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6, preferably three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residues, preferably the remaining residue represent/s an alkyl group having formula (IIb)
—CnH2n+1 (IIb)
wherein n is an integer in the range from 1 to 20, preferably in the range from 2 to 15, more preferably in the range from 3 to 15 and even more preferably in the range from 3 to 10. A particularly preferred alkyl group is an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group or a n-decyl group, wherein an ethyl group, a n-butyl group and a n-decyl group are particularly preferred and wherein a n-butyl group is most preferred.
Suitable examples of monomer units of structure (Ia) carrying a branched alkyl group or more than one alkyl group comprise a compound selected from the group consisting of compounds (A), (B), (C) and (D):
In an embodiment 8 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 5, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) or structure (Ib) in which X and Z represent O, preferably monomer units of structure (Ia) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residue represents a branched alkyl group or a branched ether group, preferably a branched ether group, wherein a “branched ether group” in the sense of the present invention is preferably an ether group in which at least one of the two organic residues that are bonded to the oxygen atom are branched organic residues, i. e. organic residues comprising at least one carbon atom that is bonded via a single bond to at least three carbon atoms or to at least two carbon atoms and to the oxygen atom that is part of the ether group. More preferably, the remaining residue represents a branched ether group having the structural formula (IIc)
—(CR10R11)n—O—R12 (IIc)
wherein
—(CHR13)m—R14 (IId)
In an embodiment 9 of composition 1 according to the invention, composition 1 is designed according to its embodiment 8, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):
In connection with embodiment 8 and 9 of composition 1 according to the present invention it may also be possible to use organic compounds as component ii) that carry more than two inorganic acid groups and the molecular weight of which is larger than 1,000 g/mol, such as polystyrene sulfonic acid (PSS).
In an embodiment 10 of composition 1 according to the invention, composition 1 is designed according to anyone if its embodiments 1 to 9, wherein the 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) in which X and Z represent O, wherein the at least one organic solvent iii) preferably is an aprotic solvent iii). In this case, the polythiophene i) is thus copolymer of 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene in which at least one of the hydrogen atoms of the ethylene group is substituted by an organic residue R.
In an embodiment 11 of composition 1 according to the invention, composition 1 is designed according to its embodiment 10, wherein the derivative of 3,4-ethylenedioxythiophene has the structural formula (Ia′):
in which R is preferably selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.
In an embodiment 12 of composition 1 according to the invention, composition 1 is designed according to its embodiment 11, wherein the organic residue R is an ether group.
In an embodiment 13 of composition 1 according to the invention, composition 1 is designed according to its embodiment 12, wherein the ether group has the structural formula (IIa)
—(CR7R8)n—O—R9 (IIa)
wherein
In an embodiment 14 of composition 1 according to the invention, composition 1 is designed according to its embodiment 13, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (III)
in which R9 is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C1-C30 alkyl group, more preferably a C2-C25-alkyl group, even more preferably a C5-C20-alkyl group.
In an embodiment 15 of composition 1 according to the invention, composition 1 is designed according to its embodiment 14, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (IV)
wherein m is an integer in the range from 0 to 24, preferably in the range from 1 to 19 and more preferably in the range from 4 to 14, wherein it is most preferred that m is 9.
In an embodiment 16 of composition 1 according to the invention, composition 1 is designed according to its embodiment 11, wherein the organic residue R is an alkyl group.
In an embodiment 17 of composition 1 according to the invention, composition 1 is designed according to its embodiment 16, wherein the alkyl group has formula (IIb)
—CnH2n+1 (IIb)
wherein n is an integer in the range from 1 to 20, preferably in the range from 2 to 15, more preferably in the range from 3 to 15 and even more preferably in the range from 3 to 10. A particularly preferred alkyl group is an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group or a n-decyl group, wherein an ethyl group, a n-butyl group and a n-decyl group are particularly preferred and wherein a n-butyl group is most preferred.
In an embodiment 18 of composition 1 according to the invention, composition 1 is designed according to its embodiment 17, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (V)
wherein n is in the range from 0 to 19, preferably in the range from 1 to 14 and more preferably in the range from 2 to 9. It is particularly preferred that n is 2, 3 or 4, wherein n=3 is most preferred.
In an embodiment 19 of composition 1 according to the invention, composition 1 is designed according to its embodiment 11, 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)
−(CR10R11)n—O—R12 (IIc)
wherein
—(CHR13)m—R14 (IId)
In an embodiment 20 of composition 1 according to the invention, composition 1 is designed according to its embodiment 19, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):
In an embodiment 21 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 20, wherein the copolymer i) comprises 5 to 95% monomer units, preferably 10 to 80% monomer units and more preferably 20 to 60% monomer units that are 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).
In an embodiment 22 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 21, wherein the copolymer i) comprises at least 30 wt.-%, preferably at least 40 wt.-% and more preferably at least 70 wt.-% monomer units that are 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).
In an embodiment 23 of composition 1 according to the invention, composition 1 is designed according its embodiment 8, wherein the at least one polythiophene i) is a copolymer of
In an embodiment 24 of composition 1 according to the invention, composition 1 is designed according to its embodiment 23, wherein the copolymer i) comprises 5 to 99 mol.-%, preferably 15 to 70 mol-% and more preferably 30 to 50 mol-% monomer units that are based on monomers α), 5 to 95 mol-%, preferably 30 to 90 mol-% and more preferably 50 to 70 mol-% monomer units that are based on monomers β) and 0 to 50 mol-%, preferably 0 to 35 mol-% and more preferably 0 to 20 mol-% monomer units that are based on monomers γ), in each case based on the total amount of monomers α), β) and γ) in the copolymer, wherein the amounts of monomers α), β) and γ) sum up to 100 mol-%. According to a particularly preferred copolymer i) the copolymer does not comprise 3,4-ethylenedioxythiophene as a comonomer.
In an embodiment 25 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 24, wherein the inorganic acid group is a sulfonic acid group (—SO2OH), a sulfuric acid group (—O—SO2OH), a phosphonic acid group (—PO(OH)2) or a phosphoric acid group (—O—PO(OH)2), preferably a sulfonic acid group (—SO2OH).
In an embodiment 26 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 25, wherein the organic compound ii) is an anionic surfactant.
In an embodiment 27 of composition 1 according to the invention, composition 1 is designed according to its embodiment 26, wherein the anionic surfactant is a sulfonic acid (R—SO2OH), an ester of sulfuric acid (R—O—SO2OH) or a salt of one of these esters, preferably a sulfonic acid. In this context it is particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (i.e. a compound that carries only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.
In an embodiment 28 of composition 1 according to the invention, composition 1 is designed according to its embodiment 27, wherein the anionic surfactant is dodecylbenzene sulfonic acid or a salt thereof. The term “dodecyl sulfonic acid” as used herein also encompassed mixtures of alkylbenzene sulfonic acids which, in addition to dodecylbenzene sulfonic acid, further comprises alkylbenzene sulfonic acids with alkyl chains that are longer or shorter than the dodecyl-group.
In an embodiment 29 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 28, wherein the weight ratio of polythiophene i) to organic compound ii) or the salt thereof, preferably the weight ratio of copolymer i) to organic compound ii) or the salt thereof, is in the range from 1:30 to 1:0.1, preferably in the range from 1:20 to 1:0.2 and more preferably in the range from 1:5 to 1:0.5.
In an embodiment 30 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 29, wherein the at least one organic solvent iii), preferably the at least one aprotic solvent iii), has a boiling point (determined at a pressure of 1013 mbar) in the range from 50 to 300° C., preferably in the range from 60 to 250° C. and more preferably in the range from 70 to 220° C.
In an embodiment 31 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 30, wherein the at least one organic solvent is an aprotic solvent iii), more preferably is a polar aprotic solvent.
In an embodiment 32 of composition 1 according to the invention, composition 1 is designed according to its embodiment 31, wherein the dielectric constant of the polar aprotic solvent iii) is less than 20, preferably less than 10 and more preferably less than 7.
In an embodiment 33 of composition 1 according to the invention, composition 1 is designed according to its embodiment 31 or 32, wherein the polar aprotic solvent iii) has a dipole moment of less than 4 D, preferably less than2 D and more preferably less than 1.5 D.
In an embodiment 34 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 33, wherein the at least one organic solvent iii) is selected from the group consisting of aromatic hydrocarbons, esters, ethers, alcohols and mixtures thereof.
In an embodiment 35 of composition 1 according to the invention, composition 1 is designed according to its embodiment 34, 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-propylacetat, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or mixtures of one or two of these aprotic solvents with one or two further solvents. In 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).
In an embodiment 36 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 35, wherein the composition comprises
In an embodiment 37 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 36, wherein the composition comprises, as a further component iv) being different from components i) to iii), a non-conductive oligomer or polymer, preferably a non-conductive oligomeric or polymeric binder. A “non-conductive oligomeric or polymeric binder” in the sense of the present invention is preferably a layer of an oligomer or a polymer a layer which has an electrical conductivity of less than 10−6 S/cm, preferably less than 10−8 S/cm and most preferably less than 10−10 S/cm. In contrast, “a conductive polymer” (the polythiophene i) or the polythiophene-copolymer i) in the composition according to the present invention in the sense of the present invention is preferably a polymer a layer of which has an electrical conductivity of at least 10−6 S/cm, preferably at least 10−5 S/cm and most preferably 10−4 S/cm.
In an embodiment 38 of composition 1 according to the invention, composition 1 is designed according to its embodiment 37, wherein the non-conductive polymeric binder is selected from the group consisting of a polyolefin, a polyvinyl acetate, a polycarbonate, a poly(meth)acrylate, a polyvinyl butyral, a poly(meth)acrylic acid amide, a polystyrene, a polyacrylonitrile, a polyvinyl chloride, a polyvinyl pyrrolidone, a polybutadiene, a polyisoprene, a polyether, a polyester, a polyurethane, a polyamide, a polyimide, a polysulphone, a polysilicone, an epoxy resin, a styrene-acrylate, a vinyl acetate/acrylate or an ethylene/vinyl acetate copolymer, a polyvinyl alcohol, a cellulose derivative or a mixture comprising at least two of these polymers, wherein a poly(meth)acrylate and a polysilicone are particularly preferred non-conductive polymeric binders. Also suitable as non-conductive polymeric binders are multifunctional (meth)acrylates such as dipentaerythritol penta-/hexaacrylate.
In an embodiment 39 of composition 1 according to the invention, composition 1 is designed according to its embodiment 38, 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(benzyl acrylate), poly(benzyl methacrylate) and copolymers of these polyacrylates or polymethacrylates.
In an embodiment 40 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 37 to 39, wherein the composition comprises the non-conductive polymeric binder iv), preferably the poly(meth)acrylate and/or the polysilicone, and the 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.
In an embodiment 41 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 37 to 40, wherein a conductive layer prepared with the composition has a sheet resistance of at most 1×1010 Ohm/sq, preferably at most 5×109 Ohm/sq and more preferably of at most 1×108 Ohm/sq.
In an embodiment 42 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 41, wherein the composition comprises less than 2 wt.-%, preferably less than 1 wt.-% and most preferably less than 0.1 wt.-% water, in each case based on the total weight of the composition.
In an embodiment 43 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 42, wherein the composition has a total metal content of 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. Metals particularly include sodium, potassium and iron. Most preferably, the composition has an iron content of 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
In an embodiment 44 of composition 1 according to the invention, composition 1 is designed according to anyone of its embodiments 1 to 43, wherein a conductive layer prepared with the composition has a conductivity of more than 1 S/cm, preferably more than 2 S/cm and most preferably more than 5 S/cm.
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of a process 1 for preparing a composition, preferably a dispersion, the process comprising the steps of
In an embodiment 2 of process 1 according to the invention, process 1 is designed according to its embodiment 1, wherein the organic residue R does not carry anionic groups. Preferably, residue R does not carry any sulfonic acid groups or salts of this group.
In an embodiment 3 of process 1 according to the invention, process 1 is designed according to its embodiment 1 or 2, wherein the organic residue R is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.
In an embodiment 4 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 3, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) or structure (VIb) in which X and Z represent O, preferably thiophene monomers of structure (VIa) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residue represents an ether group having the structural formula (IIa)
—(CR7R8)n—O—R9 (IIa)
wherein
In an embodiment 5 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 3, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) or structure (VIb) in which X and Z represent O, preferably thiophene monomers of structure (VIa) in which X and Z represent O, and wherein at least two of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6, preferably three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residues, preferably the remaining residue represent/s an alkyl group having formula (IIb)
—CnH2n+1 (IIb)
wherein n is an integer in the range from 1 to 20, preferably in the range from 2 to 15, more preferably in the range from 3 to 15 and even more preferably in the range from 3 to 10. A particularly preferred alkyl group is an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group or a n-decyl group, wherein an ethyl group, a n-butyl group and a n-decyl group are particularly preferred and wherein a n-butyl group is most preferred.
Suitable examples of monomer units of structure (Ia) carrying a branched alkyl group or more than one alkyl groups comprise a compound selected from the group consisting of compounds (A), (B), (C) and (D):
In an embodiment 6 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 3, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) or structure (VIb) in which X and Z represent O, preferably thiophene monomers of structure (VIa) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R1, R2, R3 and R4 and one of the residues selected from the group consisting of R5 and R6 represent a hydrogen atom and the remaining residue represents a branched alkyl group or branched ether group, preferer ably a branched ether group, more preferably a branched ether group having the structural formula (IIc)
—(CR10R11)n—O—R12 (IIc)
wherein
—(CHR13)m—R14 (IId)
In an embodiment 7 of the process 1 according to the invention, process 1 is designed according to its embodiment 6, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):
In connection with embodiment 6 and 7 of the process according to the present invention it may also be possible to use organic compounds as component ii) that carry more than two inorganic acid groups and the molecular weight of which is larger than 1,000 g/mol, such as polystyrene sulfonic acid (PSS).
In an embodiment 8 of process 1 according to the invention, process 1 is designed according to its embodiment 1 to 7, wherein the reaction mixture comprises as component i) 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene having structural formula (VIa) in which X and Z represent O, wherein the at least one organic solvent iii) is an aprotic solvent iii) and wherein in process step II) the 3,4-ethylenedioxythiophene and the derivative of 3,4-ethylenedioxythiophenethiophene are oxidatively polymerized for the formation a copolymer. The reaction mixture provided in process step I) thus comprises as component i) 3,4-ethylenedioxythiophene and at least one derivative of 3,4-ethylenedioxythiophene in which at least one of the hydrogen atoms of the ethylene group is substituted by an organic residue R.
In an embodiment 9 of process 1 according to the invention, process 1 is designed according to its embodiment 8, wherein the derivative of 3,4-ethylenedioxythiophene has the structural formula (Ia′):
in which R is preferably selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an ether group and an ester group.
In an embodiment 10 of process 1 according to the invention, process 1 is designed according to its embodiment 9, wherein the organic residue R is an ether group.
In an embodiment 11 of process 1 according to the invention, process 1 is designed according to its embodiment 10, wherein the ether group has the structural formula (IIa)
—(CR7R8)n—O—R9 (IIa)
wherein
In an embodiment 12 of process 1 according to the invention, process 1 is designed according to its embodiment 11, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (III)
in which R9 is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably is a C1-C30 alkyl group, preferably a C2-C25-alkyl group, more preferably a C5-C20-alkyl group.
In an embodiment 13 of process 1 according to the invention, process 1 is designed according to its embodiment 12, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (IV)
wherein m is an integer in the range from 0 to 24, preferably in the range from 1 to 19 and more preferably in the range from 4 to 14, wherein it is most preferred that m is 9.
In an embodiment 14 of process 1 according to the invention, process 1 is designed according to its embodiment 9, wherein the organic residue R is an alkyl group.
In an embodiment 15 of process 1 according to the invention, process 1 is designed according to its embodiment 14, wherein the alkyl group has formula (IIb)
—CnH2n+1 (IIb)
wherein n is an integer in the range from 1 to 20, preferably in the range from 2 to 15, more preferably in the range from 3 to 15 and even more preferably in the range from 3 to 10. A particularly preferred alkyl group is an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group or a n-decyl group, wherein an ethyl group, a n-butyl group and a n-decyl group are particularly preferred and wherein a n-butyl group is most preferred.
In an embodiment 16 of process 1 according to the invention, process 1 is designed according to its embodiment 15, wherein the derivative of 3,4-ethylenedioxythiophene has the general formula (V)
wherein n is in the range from 0 to 19, preferably in the range from 1 to 14 and more preferably in the range from 3 to 9. It is particularly preferred that n is 2, 3 or 4, wherein n=3 is most preferred.
In an embodiment 17 of process 1 according to the invention, process 1 is designed according to its embodiment 9, 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)
—(CR10R11)n—O—R12 (IIc)
wherein
—(CHR13)m—R14 (IId)
In an embodiment 18 of process 1 according to the invention, process 1 is designed according to its embodiment 17, wherein the polythiophene is a homopolymer or copolymer comprising monomer units selected from the group consisting of compounds (E), (F) and (G):
In an embodiment 19 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 18, wherein the reaction mixture provided in process step I) comprises the derivative of 3,4-ethylenedioxythiophene in a relative amount of 5 to 95%, preferably 10 to 80% and more preferably 20 to 60%, in each case based on the total molar amount of 3,4-ethylenedioxythiophene and derivative of 3,4-ethylenedioxythiophene.
In an embodiment 20 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 18, wherein the reaction mixture provided in process step I) comprises at least 30 wt.-%, preferably at least 40 wt.-% and more preferably at least 70 wt.-% monomer units that are based on the derivative of 3,4-ethylenedioxythiophene, in each case based on the total weight 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).
In an embodiment 21 of composition 1 according to the invention, composition 1 is designed according its embodiment 6, wherein the reaction mixture comprises as component i)
In an embodiment 22 of process 1 according to the invention, process 1 is designed according to its embodiment 21, wherein the reaction mixture comprises 5 to 99 mol.-%, preferably 15 to 70 mol-% and more preferably 30 to 50 mol-% monomer units that are based on monomers α), 5 to 95 mol-%, preferably 30 to 90 mol-% and more preferably 50 to 70 mol-% monomer units that are based on monomers β) and 0 to 50 mol-%, preferably 0 to 35 mol-% and more preferably 0 to 20 mol-% monomer units that are based on monomers γ), in each case based on the total amount of monomers α), β) and γ) in the reaction mixture, wherein the amounts of monomers α), β) and γ) sum up to 100 mol-%. According to a particularly preferred embodiment of process 1 the reaction mixture does not comprise 3,4-ethylenedioxythiophene as a comonomer.
In an embodiment 23 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 22, wherein in process step I), in process step II) or in both process steps the organic compound ii) is present in the form of the free acid.
In an embodiment 24 of of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 23, wherein the inorganic acid group is a sulfonic acid group (—SO2OH), a sulfuric acid group (—O—SO2OH), a phosphonic acid group (—PO(OH)2) or a phosphoric acid group (—O—PO(OH)2), preferably a sulfonic acid group (—SO2OH).
In an embodiment 25 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 24, wherein the organic compound ii) is an anionic surfactant.
In an embodiment 26 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 25, wherein the anionic surfactant is a sulfonic acid (R—SO2OH), an ester of sulfuric acid (R—O—SO2OH) or a salt of one of these anionic surfactants, preferably a salt of a sulfonic acid. In this context it is again particularly preferred that the anionic surfactant is a monovalent or divalent sulfonic acid (i.e. a compound that carries only a single sulfonic acid group or two sulfonic acid groups), most preferably a monovalent sulfonic acid.
In an embodiment 27 of process 1 according to the invention, process 1 is designed according to its embodiment 26, wherein the anionic surfactant is dodecylbenzene sulfonic acid or a salt thereof.
In an embodiment 28 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 27, wherein the weight ratio of the total amount of thiophene monomers (component i), preferably the total amount of 3,4-ethylenedioxythiophene and derivative of 3,4-ethylenedioxythiophene (component i) to the organic compound ii) in the reaction mixture provided in process step I) is in the range from 1:30 to 1:0.1, preferably in the range from 1:20 to 1:0.2 and more preferably in the range from 1:5 to 1:0.5.
In an embodiment 29 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 28, wherein the at least one organic solvent iii), preferably the at least one aprotic solvent iii), has a boiling point (determined at a pressure of 1013 mbar) in the range from 50 to 300° C., preferably in the range from 60 to 250° C. and more preferably in the range from 70 to 220° C.
In an embodiment 30 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 29, wherein the at least one organic solvent is an aprotic solvent iii), more preferably is a polar aprotic solvent.
In an embodiment 31 of process 1 according to the invention, process 1 is designed according to its embodiment 30, wherein the dielectric constant of the polar aprotic solvent iii) is less than 20, preferably less than 10 and more preferably less than 7.
In an embodiment 32 of process 1 according to the invention, process 1 is designed according to its embodiments 30 or 31, wherein the polar aprotic solvent iii) has a dipole moment of less than 4 D, preferably less than 2 D and more preferably less than 1.5 D.
In an embodiment 33 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 32, wherein the at least one organic solvent iii) is selected from the group consisting of aromatic hydrocarbons, esters, ethers, alcohols and mixtures thereof.
In an embodiment 34 of process 1 according to the invention, process 1 is designed according to its embodiment 33, 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-propylacetat, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or mixtures of one or two of these aprotic solvents with one or two further solvents. In 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).
In an embodiment 35 of the process according to the invention, process 1 is designed according to anyone of its embodiments 1 to 34, wherein process 1 comprises the further step of:
In an embodiment 36 of the process according to the invention, process 1 is designed according to anyone of its embodiments 1 to 35, wherein process 1 comprises the further step of:
In an embodiment 37 of the process according to the invention, process 1 is designed according to its embodiment 36, wherein the weight ratio of the composition to the further solvent vi) is in the range from 50:1 to 0.02:1.
In an embodiment 38 of the process according to the invention, process 1 is designed according to its embodiment 36 or 37, wherein the further organic solvent vi) is organic solvent, preferably an aprotic solvent, as defined in anyone of embodiments 31 to 37 of process 1.
In an embodiment 39 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 38, wherein the composition provided in process step I) comprises
In an embodiment 40 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 39, wherein process 1 comprises the further step of:
In an embodiment 41 of process 1 according to the invention, process 1 is designed according to its embodiment 40, wherein the non-conductive polymeric binder is selected from the group consisting of a polyolefin, a polyvinyl acetate, a polycarbonate, a poly(meth)acrylate, a polyvinyl butyral, a poly(meth)acrylic acid amide, a polystyrene, a polyacrylonitrile, a polyvinyl chloride, a polyvinyl pyrrolidone, a polybutadiene, a polyisoprene, a polyether, a polyester, a polyurethane, a polyamide, a polyimide, a polysulphone, a polysilicone, an epoxy resin, a styrene-acrylate, a vinyl acetate/acrylate or an ethylene/vinyl acetate copolymer, a polyvinyl alcohol, a cellulose derivative or a mixture comprising at least two of these polymers, wherein a poly(meth)acrylate and a polysilicone area particularly preferred non-conductive polymeric binders. Also suitable as non-conductive polymeric binders are multifunctional (meth)acrylates such as dipentaerythritol penta-/hexaacrylate.
In an embodiment 42 of process 1 according to the invention, process 1 is designed according to its embodiment 41, 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(benzyl acrylate), poly(benzyl methacrylate) and copolymers of these polyacrylates or polymethacrylates.
In an embodiment 43 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 40 to 42, wherein the non-conductive polymeric binder, preferably the poly(meth)acrylate and/or the polysilicone, is/are added in such an amount that the non-conductive polymeric binder and the polythiophene/organic compound complex are present in a mass ratio of at least 20:1, preferably at least 25:1 and more preferably at least 30:1.
In an embodiment 44 of process 1 according to the invention, process 1 is designed according to anyone of its embodiments 1 to 43, wherein the reaction mixture provided in process step I) comprises less than 2 wt.-%, preferably less than 1 wt.-% and most preferably less than 0.1 wt.-% water, based on the total weight of the composition.
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of a composition 2, obtainable by process 1 according to anyone of its embodiments 1 to 44.
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of a layer structure 1 comprising a substrate and an electrically conductive layer applied onto the substrate, wherein the electrically conductive layer comprises
Preferred polythiophenes or copolymers i) and anions ii) are those polythiophenes or copolymers and anions, that have already been described in connection with composition 1 and process 1 according to the invention.
In an embodiment 2 of layer structure 1 according to the invention, layer structure 1 is designed according its embodiment 1, wherein the weight ratio of polythiophene i), preferably of copolymer i), to organic compound ii) or the salt thereof in the electrically conductive layer is in the range from 1:30 to 1:0.1, preferably in the range from 1:20 to 1:0.2 and more preferably in the range from 1:5 to 1:0.5.
In an embodiment 3 of layer structure 1 according to the invention, layer structure 1 is designed according its embodiment 1 or 2, wherein the electrically conductive layer further comprises
In an embodiment 4 of layer structure 1 according to the invention, layer structure 1 is designed according to its embodiment 3, wherein the electrically conductive layer comprises the non-conductive polymeric binder iv), preferably the poly(meth)acrylate and/or the polysilicone, and the 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.
In an embodiment 5 of layer structure 1 according to the invention, layer structure 1 is designed according to its embodiment 3 or 4, wherein the electrically a conductive layer has a sheet resistance of at most 1×1010 Ohm/sq, preferably at most 5×109 Ohm/sq and more preferably of at most 1×108 Ohm/sq.
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of a process 2 for the preparation of a layer structure, comprising the process steps of
In an embodiment 2 of process 2 according to the invention, process 2 further comprises the step of
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of a layer structure 2, obtainable by process 2 according to the invention.
In an embodiment 2 of layer structure 1 or layer structure 2 according to the invention, the layer structure is designed according its corresponding embodiment 1, wherein the electrically conductive layer has a conductivity of at least 1 S/cm, preferably at least 2 S/cm and most preferably at least 5 S/cm.
A contribution to solving at least one of the objects according to the invention is also made by an embodiment 1 of an electronic component, in particular an organic light-emitting diodes, an organic solar cells or a capacitors, comprising a layer structure 1 according to its embodiment 1 or 2 or a layer structure 2 according to its embodiment 1.
A contribution to solving at least one of the objects according to the invention is also made by the use of composition 1 according to anyone of its embodiments 1 to 46 or of composition 2 according to its embodiment 1 to produce an electrically conductive layer in an electronic component, in particular in organic light-emitting diodes, organic solar cells or capacitors or to produce an antistatic coating.
Organic Compound ii)
The organic compound carrying one or two inorganic acid groups i) or the salt thereof that is present in the composition or the layer structure according to the invention or that is present in the reaction mixture that is provided in process step I) of the process according to the invention preferably is an anionic surfactant, wherein it is furthermore preferred that the anionic surfactant is selected from the group consisting of organic phosphonic acids, organic phosphoric acids, organic sulfonic acids such as sulfonic acids, such as alkyl-aryl-sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, and salts or mixtures thereof. Each of the following anionic surfactants may contain a mixture of compounds varying in the length of the alkyl chain:
It is, however, particularly preferred that the anionic surfactant is a monovalent sulfonic acid, particularly preferred dodecylbenzene sulfonic acid or a salt thereof.
Additives iv)
Suitable additives iv) which can also be present in the composition according to the present invention include oxidizing agents (preferably in their reduced form), conductivity-improving agent, adhesion promoters, binders and crosslinking agents:
Process for Producing the Composition According to the Present Invention
In the process according to the invention the thiophene monomers are oxidatively polymerised in the presence of the organic compound ii) (which is preferably present in the form of an anion) and the aprotic solvent iii). The oxidising agents iv) that are suitable for the oxidative polymerisation of pyrrole can be used as oxidising agents. For practical reasons, inexpensive and easy-to-handle oxidising agents can be used, for example iron(III) salts such as FeCl3, Fe(ClO4)3 and the iron(III) salts of organic acids and of inorganic acids comprising organic radicals. The iron(III) salts of sulphuric acid hemiesters of C1-C20 alkanols, for example the Fe(III) salt of lauryl sulphate, are cited by way of example as iron(III) salts of inorganic acids comprising organic radicals. The following are cited by way of example as iron(III) salts of organic acids: the Fe(III) salts of C1-C20 alkyl sulphonic acids, such as methane- and dodecane-sulphonic acid; aliphatic C1-C20 carboxylic acids such as 2-ethylhexyl carboxylic acid; aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as oxalic acid and above all of aromatic sulphonic acids optionally substituted with C1-C20 alkyl groups, such as benzenesulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic acid. The iron(III) salts of organic acid have the big applicational advantage that they are partially or completely soluble in organic solvents and in particular in water-immiscible organic solvents. Organic peroxides such as for example tert-butyl peroxide, diisobutyryl peroxide, di-n-propyl peroxydicarbonate, didecanoyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-amyl peroxide can also be used as oxidising agents. Organic azo compounds such as for example 2,2′-azodiisobutyronitrile can also be used. Particularly preferred oxidizing agents are organic, metal-free oxidizing agents such as organic peroxides, wherein dibenzoyl peroxide is most preferred.
Theoretically, for the oxidative polymerization of the thiophene monomers, per mole of thiophene, 2.25 equivalents of oxidizing agent are needed (see e.g. J. Polym. Sc., Part A, Polymer Chemistry, vol. 26, p. 1287 (1988)). However, in the prior art, the oxidising agent is normally used in a certain excess amount, e.g. an excess of 0.1 to 2 equivalents per mole of thiophene.
In process step II) of the process according to the invention, the thiophene monomers are oxidatively polymerized—in the presence of the organic compound ii)—by reduction of the oxidising agent to a reduction product and oxidation of the thiophene monomer, to form a composition preferably comprising cationic polythiophene-copolymers i) and the reduction product, wherein said polymerization preferably takes place at a temperature in the range from 0° C. to 100° C. In this context it is particularly preferred that the reaction temperature is in a range from 25° C. up to a temperature that is below the lowest boiling point of the solvents comprised in the reaction mixture.
The anions ii) that are present in the reaction mixture provided in process step I) serve as counterions to compensate that positive charge of the polythiophenes i), preferably of the copolymers i). Anions ii) and polythiophenes i) are preferably present in the form of a polythiophene/anion-complex. In this context it is also preferred that in process step II) a composition is obtained that comprises the polythiophene i) and the anions ii) in the form of such a complex, wherein it is particularly preferred that the composition is present in the form of a dispersion comprising the aprotic solvent iii) in which this complex is dispersed.
The invention is now described in more detail by reference to figures, test methods and non-limiting examples.
Test Methods
Determination of the Conductivity
The electrical conductivity means the inverse of the specific resistance. The specific resistance is calculated from the product of surface resistance and layer thickness of the conductive polymer layer. The surface resistance is determined for conductive polymers in accordance with DIN EN ISO 3915. In concrete terms, the composition to be investigated is applied as a homogeneous film by means of a spin coater to a glass substrate 50 mm×50 mm in size thoroughly cleaned by the above-mentioned substrate cleaning process. In this procedure, the coating composition is applied to the substrate by means of a pipette to completely cover the area and spun off directly by spin coating. The spin conditions for coating compositions were 20 s at approx. 1,000 rpm in air. Thereafter, a drying process on a hot-plate was carried out (10 min at 130° C. in air). Silver electrodes of 2.0 cm length at a distance of 2.0 cm are vapour-deposited on to the polymer layer via a shadow mask. The square region of the layer between the electrodes is then separated electrically from the remainder of the layer by scratching two lines with a scalpel. The surface resistance is measured between the Ag electrodes with the aid of an ohmmeter (Keithley 614). The thickness of the polymer layer is determined with the aid of a Stylus Profilometer (Dektac 150, Veeco) at the places scratched away.
Determination of the Water Content
The water content of the composition according to the present invention can be determined by means of a Karl Fischer titration. A Metrohm 787 KF Titrino with a 703 titration stand is used to this end. The titration vessel is filled with analytical-grade methanol so that about 1 cm of the platinum electrode is submerged. Then approximately 5 ml of Hydranal buffer acid is pipetted in. The titration cell is automatically dried by starting the KFT program. Preparation is complete when the message “KFT conditioned” appears. Approximately 5 ml of the composition to be analysed is then introduced into the titration vessel using a syringe and the exact mass of the dispersion used is determined by back-weighing the syringe. The titration is then started. The measured value is determined as the mean of three individual measurements.
Solids Content
The solid content was determined by gravimetry using a precision scale (Mettler AE 240). First the empty weighing bottle including lid is weight in (Weight A). Then ca. 3 g of dispersion to be analysed is filled quickly into the bottle, closed by the lid and weighed again to determine the exact total weight B. The bottle is then placed in a fume hood without a lit for ca. 3 hours to allow the evaporation of volatile solvents at room temperature. In a second step the bottle is placed in a drying oven with ventilation (Memmert UNB200) at 160° C. for 16-17 hours. When the sample bottle is removed from the oven, immediate coverage by the glass lid is important due to the hygroscopic nature of the dry dispersion material. After 10-15 min of cooling down period the bottle is weighed again including lid to determine weight C.
Calculation of the solid contents: wt. % solids content=100×(C−A)/(B−A)
The result is the average of two measurement.
Preparation of Films on PET Substrates
The dispersion was applied to a PET substrate at room temperature using manual doctor blades from Erichsen which had a gap separation of 12 μm. The gap separation of the manual doctor blade in this context determines the thickness of the wet film formed, which is also called the wet film thickness. The coatings or films formed in this way were then dried in a drying oven at 130° C. for 5 min. Before any further processing, the coated PET substrate was cooled to room temperature.
Determination of the Surface Resistivity
The surface resistivity was measured with a Staticide ACL 800 Digital Megohmmeter at the 100 V setting. Two measurements on different positions on the sheet were conducted and the lowest value was taken as the result. The highest measurable surface resistivity is 2×1011 Ω/sq. Values at or above that threshold are considered out of range but will still be displayed at 2×1011 Ω/sq.
Determination of the dispersion's stability in organic solvents
The dispersion's stability was determined by slowly adding the mentioned amount of solvent to the initial dispersion over the course of 5 minutes. The mixture was stirred slowly during the process of the solvent addition and for an additional 15 minutes. The mixture was stored at room temperature for 24 h without any mechanical disturbance. The resulting mixtures were classified into three categories after visual assessment:
+ stable, homogenous dispersion without any particles
0 small particles visible
− large particles and/or significant gelation and/or phase separation
The synthesis is conducted under dry and inert conditions.
THF (6.6 L) and 18-Crown-6 (22.0 g, 88 mmol) are added to the reaction vessel. NaH (166.4 g, 4.15 mol) as 60% suspension in oil is added under stirring, the mixture is stirred at room temperature. At 0° C. a EDOT-MeOH (551 g, 3.2 mol) solution in THF are added to the NaH solution. After addition of the solution the reaction mixture is stirred for 1.5 h at room temperature, subsequently 1 h at 50° C. Reaction mixture is cooled to 0° C. and a 1-bromo-decane (936.7 g, 4.2 mol) solution, stirred for 1 h at room temperature and 15 h at 50° C. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product was purified by column chromatography.
The reaction product (2-[(decyloxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, CAS: 210476-55-4) is obtained as a yellow oil in a yield of 74-80%.
A 1 L three-necked round-bottom flask equipped with mechanical stirrer was charged with 294 g anisole (Aldrich), 9.4 g of dibenzoyl peroxide (39 mmol; Aldrich), 8.25 g of a sulfonated block-copolymer (Kraton Nexar® MD) and 7.2 g of para-toluene sulfonic acid (38 mmol, Aldrich). After heating to 60° C. 4.95 g of 3,4-ethylenedioxythiophene (35 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature. This dispersion is called dispersion 2A.
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 2 min or ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This sample is called dispersion 2B.
Analysis of Dispersion 2B:
Solids content: 2.5% (gravimetric)
Using a wire-bar a 12 μm wet film was deposited of dispersion 2B on a substrate and dried for 15 min at 130° C. in an oven. The conductive layer was characterized by the following properties:
Conductivity (on glass): 7.7 S/cm
Sheet resistance (12 μm on PET): 17,000 Ohm/sq
In Example 3 the following complex is prepared:
Dispersion A:
A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.7 g dodecylbenzene sulfonic acid (11.5 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1(5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 3A.
Dispersion 3B:
5 g of dispersion 3A and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 3B.
Analysis of Dispersion 3B:
Solids content: 2.4% (gravimetric)
Using a wire-bar a 12 um wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:
Sheet resistance (12 μm on PET) 20,000 Ohm/sq
Dispersion 3C:
2.5 g of dispersion+3A, 2.5 g anisole and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 3C.
Analysis of Dispersion 3C:
Solids content: 1.2% (gravimetric)
Water content: 0.04%
Ion-content was measured by inductively coupled plasma optical emission spectrometry:
Na content: 24 ppm
Ca content: 0.6 ppm
Mg content: 0.06 ppm
K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd were below the detection limit of 0.025 ppm.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:
Sheet resistance (12 μm on PET) 16,000 Ohm/sq
Transmission (including PET) 83.3%
Haze (including PET) 0.58
Dispersion 3C was deposited on glass by spin-coating and dried for 10 min at 130° C. on a hot plat. The conductivity was measured according to the Test method described above.
The film was characterized by the following property
Conductivity 9.4 S/cm
(in Example 4 the concentration of dodecylbenzenesulfonic acid is reduced)
A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.08 g dodecylbenzene sulfonic acid (9.6 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1 (5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 4A.
5 g of dispersion 4A, and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 4C.
Analysis of dispersion 4C:
Solids content: 2.1% (gravimetric)
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:
Sheet resistance (12 μm on PET): 12,000 Ohm/sq
(in Example 5 the concentration of dodecylbenzenesulfonic acid is reduced further)
A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 2.2 g dodecylbenzene sulfonic acid (6.8 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1 (5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 5A.
Dispersion 2A and dispersion 5A were compared with respect to their solvent compatibility. Samples were mixed with additional solvent as shown in Table 1 and then subjected to ultrasound for 1 min.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The sheet resistance was determined.
Table 1 shows that the inventive dispersion 5A gives low sheet resistance values of less 1.5×105 Ohm/sq with various solvents whilst dispersion 2A gives values of up to 1011 Ohm/sq.
A 2.5% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) was prepared. This solution was mixed in different ratios with dispersion 2B. Since both solutions have the same solids content, the ratio of the solution/dispersion corresponds to the ratio of solids in the resulting film.
Additionally, a 2.4% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) was prepared. This solution was mixed in different ratios with dispersion 3B. Since both solutions have the same solids content, the ratio of the solution/dispersion corresponds to the ratio of solids in the resulting film.
Using a wire-bar 12 μm wet films of all eight mixtures were deposited on PET substrates and dried for 15 min at 130° C. in an oven.
Table 2 shows that the inventive dispersion 3B results in lower sheet resistance and lower haze when blended with poly(isobutyl methacrylate) compared to reference dispersion 2B.
In Example 8 the following complex is prepared:
Dispersion 8A:
A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g dodecylbenzene sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C. 0.42 g of 3,4-ethylenedioxythiophene (3 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.38 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (7 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) are added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 8A.
Dispersion 8B:
5 g of dispersion 6A, 3 g anisole and 2 g butanol were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 8B.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:
Sheet resistance (12 μm on PET) 17,400 Ohm/sq
Haze (12 μm on PET) 0.7
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-dihydrothieno[3,4b][1,4]dioxine (4 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 9B.
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-dihydrothieno[3,4b][1,4]dioxine (5 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 10B.
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-dihydrothieno[3,4b][1,4]dioxine (6 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 11B.
The synthesis of example 8 was repeated using 2-butyl-2,3-dihydrothieno-[3,4b][1,4]dioxine in an amount of 10 mmol. No 3,4-ethylenedioxythiophene was used. All other parameters remained unchanged. The dispersion that is obtained after cooling to room temperature and standing overnight is called dispersion 12A. The final material obtained after ultrasound treatment is called dispersion 12B.
Using a wire-bar 12 μm wet films were deposited from dispersions 9B to 12B pursuant to Example 8 on a PET substrate and dried for 15 min at 130° C. in an oven. The films were characterized by their sheet resistance and haze.
Ion-content of 12 B was measured by inductively coupled plasma optical emission spectrometry:
K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd were below the detection limit of 0.025 ppm.
Table 3 summarizes the results of Dispersions 2B and 8B to 12B with respect to sheet resistance and haze.
A solution of poly(isobutylmethacrylate) (PIBM) was prepared. For that purpose, 13.6 g poly(isobutyl methacrylate) were dissolved in a mixture of 220 g anisole, 132 g butyl acetate and 88 g butanol.
Using a wire-bar a 12 um wet film of the dispersions in series 1 and 2 was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The films were characterized by their sheet resistance. Table 4 summarizes the results.
2B1)
Table 4 clearly shows the advantage of polythiophenes comprising alkyl-EDOT.
The dispersion obtained in Example 12A was diluted with a range of solvents. Table 5 shows solvent mixtures.
5 g of Dispersion 12 B were mixed with 3 g anisole and 2 g n-butanol. The resulting solvent mixture contained 80% anisole (w/w) and 20% n-butanol (w/w). Using a wire-bar a 12 μm wet films of dispersions was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The solids content was 2.2%. The sheet resistance was 8×104 Ohm/sq
5 g dispersion were mixed with 10 g anisole and 5 g n-butanol. The resulting solvent mixture contained 75% anisole and 25% n-butanol. The solids content was 1.1%. Using a wire-bar a 12 μm wet films of dispersions was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The sheet resistance was 16×104 Ohm/sq.
Examples 14D, 14 E, 14F and 14 G are prepared accordingly.
Table 5 shows the compositions and resulting sheet resistances:
In all six cases uniform dispersions were obtained that do not form particles or precipitates. Table 5 also clearly shows the advantage of polythiophenes comprising alkyl-EDOT.
A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g dodecylbenzene sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C. 0.56 g of 2-decyl-2,3-dihydrothieno[3,4b][1,4]dioxine (2 mmol; DecylEDOT; CAS 126213-55-6) and 1.58 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4) are added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 15A.
Dispersion 15B:
5 g of dispersion 15A, 3 g anisole and 2 g butanol were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 15B.
Solids content: 2.4%
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:
Sheet resistance (12 μm on PET) 64,000 Ohm/sq
Haze (12 μm on PET) 0.8
Poly(n-butylacrylate) is an example of a polyacrylate with a low glass-transition temperature (Tg=−54° C.). Poly(n-butylacrylate) in toluene (CAS 9003-49-0; 25 wt % in toluene, Mw 99000 g/mol; Sigma Aldrich product 181404) was blended with Dispersion 15B. Table 6 shows the blending ratio of three mixtures.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate for each mixture and dried for 15 min at 130° C. in an oven. The sheet resistance was measured.
The synthesis is conducted under dry and inert conditions.
THF (60 mL) and 18-Crown-6 (0.200 g, 0.8 mmol) are added to the reaction vessel. NaH (1.512 g, 37.8 mmol) as 60% suspension in oil is added under stirring, the mixture is stirred at room temperature. At 0° C. a EDOT-MeOH (5.00 g, 29.0 mmol) solution in 20 mL THF is added to the NaH solution. After addition of the solution the reaction mixture is stirred for 2.5 h at room temperature, subsequently 0.5 h at 55° C. Reaction mixture is cooled to 0° C. and a 2-ethylhexyl bromide (7.300 g, 37.8 mmol) solution in 20 mL THF is added. The reaction mixture is stirred for 1 h at room temperature and 40 h at 50° C. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product was purified by column chromatography.
The reaction product (3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in a yield of 15%.
The synthesis is conducted under dry and inert conditions.
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) are added to the reaction vessel. The resulting reaction mixture is stirred at 20° C. for 24 h. After the reaction is completed, the reaction mixture is poured into deionized water (1000 mL) and stirred for 1 h. The volume of the resulting mixture is halved by vacuum distillation. The mixture is extracted three times with ethyl acetate (150 ml), the combined organic phases are washed with brine (150 ml), dried over MgSO4 and the solvent is removed in vacuo. The crude product is purified by column chromatography.
The reaction product 3-(1-phenylethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in a yield of 49%.
A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (6 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g product obtained from the reaction in Example 17 (4 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.
50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.
This is called dispersion 19.
Analysis of dispersion 19:
Solids content: 2.4% (gravimetric)
Sheet resistance (12 μm on PET): 210000 Ohm/sq
The ion-content of dispersion 19 was measured by inductively coupled plasma optical emission spectrometry:
Na 0.324 ppm
Fe 0.043 ppm
Cu 0.000 ppm
Pb 0.000 ppm
B 0.010 ppm
Mo 0.370 ppm
Al 0.000 ppm
Cr 0.028 ppm
Co 0.000 ppm
Mn 0.000 ppm
Ni 0.000 ppm
V 0.000 ppm
Zn 0.514 ppm
Ca 0.172 ppm
K 0.000 ppm
Mg 0.077 ppm
Cd 0.012 ppm
A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (10 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.
50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.
This is called dispersion 20.
Analysis of dispersion 20:
Solids content: 2.2% (gravimetric)
Sheet resistance (12 μm on PET): 70000 Ohm/sq
Dispersion 19 and dispersion 20 were tested with respect to their solvent compatibility. 1 g of the named dispersion is mixed by gentle stirring and shaking with 9 g of the additional solvent as shown in Table 7.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.
A blank PET substrate yields the following baseline values upon measurement:
Surface resistivity: 1.8×1011 Ohm/sq
Transmission: 91%
Table 7 shows that the dispersion from the inventive example 19 and 20 are demonstrating a good surface resistivity and forms stable dispersions in a variety of common organic solvents.
A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.565 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.565 g of 3-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (2 mmol; CAS: 210476-55-4) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.
50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.
This is called dispersion 22.
Analysis of dispersion 22:
Solids content: 2.3% (gravimetric)
Sheet resistance (12 μm on PET): 63000 Ohm/sq
Dispersion 19 and dispersion 22 were tested with respect to their compatibility with acrylic resins. Table 8 shows the amounts of used dispersions, solvents, and dipentaerythritol penta-/hexa-acrylate (CAS 60506-81-2, Sigma Aldrich).
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.
Table 8 shows the compatibility of dispersions 19 and 22 with acrylic resins as demonstrated in the achieved surface resistivity values.
Dispersion 19 and dispersion 2B were compared with respect to their compatibility with silicon release resins. Table shows the amounts of used dispersions, solvents, and KS 847-H (CAS: 63148-53-8; Shin-Etsu Silicone). As a solvent, a mixture of toluene, alkanes and ketones is used.
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.
Table 9 shows the superior compatibility of dispersion 19 with silicone release resins as demonstrated in the achieved surface resistivity values.
Dispersion 19 and dispersion 22 were tested with respect to their compatibility with polyacrylic resins. Table 10 shows the amounts of used dispersions, solvents, and polybutylacrylate (CAS 9003-49-0, Sigma Aldrich).
Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.
Table 10 shows the compatibility of the dispersion 19 and 22 with poly(meth)acrylate binders as demonstrated in the achieved surface resistivity.
A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.584 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.553 g product obtained from the reaction in Example 18 (2 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.
5 g of the dispersion, 3 g anisole, and 2 g of n-butanol are mixed via gentle stirring and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%) to yield the resulting dispersion.
This is called dispersion 26.
Analysis of dispersion 26:
Solids content: 2.4% (gravimetric)
Sheet resistance (12 μm on PET): 19000 Ohm/sq
100 layer body
101 substrate
102 electrically conductive layer
| Number | Date | Country | Kind |
|---|---|---|---|
| 19200608.8 | Sep 2019 | EP | regional |
| 19219007.2 | Dec 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/077250 | 9/29/2020 | WO |
