# Patent

## Title
Layer configuration with improved stability to sunlight exposure

## Abstract

Disclosed are a light-emitting diode, a photovoltaic device, a transistor, and an electroluminescent device, each comprising a layer disposed on a support, the layer comprising a [A] composition exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.

## Background
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This application claims priority to and the benefit of U.S. Provisional Application No. 61/012,111 filed Dec. 7, 2007, the entirety of which is herein incorporated by reference.


FIELD OF THE INVENTION
The present invention relates to a composition and layer configuration with improved stability to visible and UV light exposure at high surface conductivity.
BACKGROUND OF THE INVENTION
Polythiophenes have been studied extensively due to their interesting electrical and/or optical properties. Polythiophenes become electrically conducting upon chemical or electrochemical oxidation or reduction.
EP-A 339 340 discloses a polythiophene containing structural units of the formula:




in which A denotes an optionally substituted C1-4-alkylene radical and its preparation by oxidative polymerization of the corresponding thiophene.

EP-A 440 957 discloses dispersions of polythiophenes, constructed from structural units of formula (I):




in which R1 and R2 independently of one another represent hydrogen or a C1-4-alkyl group or together form an optionally substituted C1-4-alkylene residue, in the presence of polyanions.

EP-A 686 662 discloses mixtures of A) neutral polythiophenes with the repeating structural unit of formula (I),




in which R1 and R2 independently of one another represent hydrogen or a C1-C4 alkyl group or together represent an optionally substituted C1-C4 alkylene residue, preferably an optionally with alkyl group substituted methylene, an optionally with C1-C12-alkyl or phenyl group substituted 1,2-ethylene residue or a 1,2-cyclohexene residue, and B) a di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound; and conductive coatings therefrom which are tempered to increase their resistance preferably to <300 ohm/square. Examples of di- and polyhydroxy organic compounds disclosed in EP-A 0 686 662 are: sugar and sugar derivatives, such as saccharose, glucose, fructose, lactose, sugar alcohols, such as sorbitol and mannitol, and alcohols such as ethylene glycol, glycerine, diethylene glycol and triethylene glycol.

U.S. Pat. No. 5,427,841 discloses a laminated structure comprising an electrically insulating substrate carrying a polymer layer consisting essentially of a polymer selected from the group of poly-3,4-ethylene dioxythiophene, poly(3,4-ethylene dioxythiophene) wherein the ethylene group is substituted with a C1-C12 alkyl group, poly(3,4-ethylene dioxythiophene) wherein the ethylene group is substituted with an alkoxy group, and oligomers of ethylene dioxythiophene, said layer having first electrically conductive portions having a sheet resistance of maximally 1000 Ω/square, and a pattern of second substantially non-conductive portions whose sheet resistance is at least a factor of 106 higher than that of the conductive polymer in said first portions, a metal layer being deposited into the electrically conductive first portions of said polymer layer. U.S. Pat. No. 5,427,841 also discloses a room temperature stable spin coating solution which comprises a substance selected from the group of monomers, oligomers and polymers selectively polymerizable (a) to an electrically conductive polymer having a sheet resistance of maximally 1000 Ω/square; (b) to an electrically non-conductive polymer; and (c) to a polymer having conductive and non-conductive areas; said solution further including an oxidation agent; a base (e.g. imidazole); and a solvent.
U.S. Pat. No. 5,447,824 discloses a method of manufacturing a pattern of an electrically conductive polymer on a substrate surface, said method comprising: a) forming a liquid layer on a surface of said substrate from a solution containing a material capable of forming said electrically conductive polymer upon being heated, an oxidizing agent and a base (e.g. imidazole), b) exposing said liquid layer to patterned radiation, and c) heating said layer thereby forming a pattern of an electrically conductive polymer, said conductive polymer being formed in unexposed areas and a non-conductive polymer being formed in the exposed areas of the layer.
U.S. Pat. No. 5,620,800 discloses a method of manufacturing a laminated structure having an electrically insulating substrate carrying a polymer layer comprising first electrically conductive portions having a sheet resistance of maximally 1000 Ω/square and a pattern of second relatively substantially non-conductive portions when the sheet resistance of the polymer in the first portions is compared to the sheet resistance of the polymer in the second portions, a metal layer being electrodeposited onto the electrically conductive first portions of said polymer layer, said method comprising the steps of: providing a layer of a solution comprising 3,4-ethylene dioxythiophene monomers, an oxidation agent, a base (e.g. imidazole) and a solvent on the substrate, exposing the layer to patterned radiation, heating said exposed layer thereby forming conductive polymer areas in the unexposed areas and said substantially non-conductive polymer areas in the exposed areas, and thereafter electrodepositing a metal layer selectively onto the conductive polymer from a metal salt solution.
US 2006/0076541A discloses a conductive composition comprising: a π-conjugated conductive polymer, a polyanion, and a hydroxy group-containing aromatic compound containing two or more hydroxy groups. In a preferred embodiment the polyhydroxyl group-containing aromatic compound is represented by formula (1):




wherein R represents a group selected from a linear or branched alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, or an aralkyl group, each having 1 to 15 carbon atoms. In a further preferred embodiment the hydroxy group-containing aromatic compound contains a sulfo group and/or a carboxy group. The invention examples of US 2006/0076541A demonstrate conductivity enhancement upon addition of a hydroxy group-containing aromatic compound containing two or more hydroxy groups and enhanced heat stability and humidity stability of the electrical conductivity.

JP 2006-291133A1 discloses a conductive polymeric coating material contains a π-conjugated conductive polymer, a polyanion, an ester compound, and a solvent, the ester compound being a dehydration reaction product of a carboxylic acid compound having at least two carboxyl groups and a polyhydric alcohol compound having at least two hydroxyl groups. The method for producing the coating material comprises an ester compound synthesis process for synthesizing the ester compound by the dehydration reaction of the carboxylic acid compound having at least two carboxyl groups and the polyhydric alcohol compound having at least two hydroxyl groups and an ester compound addition process for adding the ester compound to a solution or dispersion containing the π-conjugated conductive polymer, the polyanion, and the solvent.
JP 2006-321840A discloses an electrically conductive polymer solution comprising a π-conjugated conductive polymer, a polyanion, a nitrogen-containing compound and a solvent, the nitrogen-containing compound having one or more nitrogen-containing functional groups selected from urea group, urethane group, allophanate group, biuret group, imide group and amide group, wherein the nitrogen atom of the nitrogen-containing functional group has the form of quaternarized salt, the nitrogen-containing compound of the conductive polymer solution preferably having one or more unsaturated double bonds. The conductive coating film is produced by coating the conductive polymer solution.
JP 2006-328276A1 discloses an electrically conductive polymer solution comprises a π-conjugated electrically conductive polymer, a solubilizing polymer, an amide compound and a solvent. The electrically conductive coating film is such as to be formed by coating the above polymer solution.
A general drawback of electroconductive layers containing poly(3,4-dialkoxythiophene) polymers, a polyanion and a hydroxy group-containing aromatic compound containing two or more hydroxy groups is the low electrical conductivity and the prohibitive increase in their surface resistance upon exposure to visible and UV light.
A general drawback of electroconductive layers containing poly(3,4-dialkoxythiophene) polymers and a polyanion with conductivity enhanced by contact with high boiling point liquids such as di- or polyhydroxy- and/or carboxy groups or amide or lactam group containing organic compound optionally followed by heating at elevated temperature is the rapid increase in their surface resistance upon exposure to visible and UV light.
ASPECTS OF THE INVENTION
It is therefore an aspect of the present invention to provide electroconductive layers containing poly(3,4-dialkoxythiophene) polymers, a polyanion and a hydroxy group-containing aromatic compound containing two or more hydroxy groups with increased electrical conductivity which do not undergo a rapid increase in their surface resistance upon exposure to visible and ultraviolet light or to a combination of heat and high humidity.
It is therefore further aspect of the present invention to provide electroconductive layers containing poly(3,4-dialkoxythiophene) polymers in the presence of a polyanion with conductivity enhanced by contact with high boiling point liquids which do not undergo a rapid increase in their surface resistance upon exposure to visible and ultraviolet light or to a combination of heat and high humidity.
Further aspects and advantages of the invention will become apparent from the description hereinafter.
SUMMARY OF THE INVENTION
It has been surprisingly found that the combined addition of at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and a polyhydroxy group-containing aromatic compound to conductive compositions comprising a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion whose conductivity has been enhanced by contact with high boiling point liquids provide layers and prints result in a dramatic increase in the stability of the surface resistance upon exposure to visible and UV-light and to a combination of heating and high humidity.
It has been also surprisingly been found that the addition of at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and contact with high boiling point liquids which reduce the surface resistance to conductive compositions comprising a polymer comprising (3,4-dialkoxythiophene) monomer units, a polyanion and a polyhydroxy group-containing aromatic compound provides layers and prints result in a dramatic increase in the stability of the surface resistance upon exposure to visible and UV-light and to a combination of heating and high humidity.
Aspects of the present invention have been realized by a composition exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by a process for producing a layer, according to the present invention, said process comprising the step of: providing a coating of a composition according to the present invention on a support optionally provided with one or more layers; and drying the coating.
Aspects of the present invention are also realized by a layer configuration on a support, the layer configuration comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by a light emitting diode comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by a photovoltaic device comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by a transistor comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by an electroluminescent device comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Preferred embodiments are disclosed in the dependent claims.
DEFINITIONS
The term alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
The term aqueous for the purposes of the present invention means containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
The term polyanion, as used in disclosing the present invention, means a polymeric or non-polymeric polyanionic substance present as an acid, a salt or partially as an acid and partially as a salt.
The term amine, as used in disclosing the present invention, includes ammonia, ammonium hydroxide, and primary, secondary and tertiary amino-compounds.
The term heterocyclic compound with at least one ring nitrogen atom, as used in disclosing the present invention, includes all ring-systems comprising at least one ring nitrogen atom i.e. includes all such saturated, unsaturated and heteroaromatic compounds.
The term carboxy, as used in disclosing the present invention, is a carboxylic acid group or a salt thereof.
The term sulfo, as used in disclosing the present invention, is a sulphonic acid group or a salt thereof.
Conductivity enhancement refers to a process in which contact results in conductivity increase. Alternatively in the case of aprotic compounds with a dielectric constant ≧15, e.g. N-methyl-pyrrolidinone, temperatures below 100° C. can be used. Such conductivity enhancement is observed with polythiophenes and can take place during the preparation of a layer or subsequently. Particularly preferred liquids for such treatment are formamide, 2-pyrrolidone and diethylene glycol such as disclosed in EP-A 686 662 and EP-A 1 003 179.
The abbreviation PEDOT represents poly(3,4-ethylenedioxy-thiophene).
The abbreviation PSS represents poly(styrenesulphonic acid) or poly(styrenesulphonate).
The term e-paper as used in disclosing the present invention is a portable, reusable storage and display medium that looks like paper but can be repeatedly written on (refreshed)—by electronic means—thousands or millions of times. E-paper will be used for applications such as e-books, electronic newspapers, portable signs, and foldable, rollable displays. Information to be displayed is downloaded through a connection to a computer or a cell phone, or created with mechanical tools such as an electronic “pencil”. There are a number of different technologies being developed: Xerox, in partnership with 3M, has created an e-paper called Gyricon and Lucent, in partnership with a company called E Ink, is working on a device (also called E Ink) that is expected to be available within the next few years. Both of these technologies enable a black (or other color) and white display. The Gyricon version consists of a single sheet of transparent plastic, containing millions of tiny bichromal (two color) beads in oil-filled pockets. Lucent's E Ink device uses electronic ink and combines thin, plastic, flexible transistors with polymer LEDs (light-emitting diodes) to create what are called smart pixels.
The term touch screen as used in disclosing the present invention is a computer display screen that is sensitive to human touch, allowing a user to interact with the computer by touching pictures or words on the screen. Touch screens are used with information kiosks, computer-based training devices, and systems designed to help individuals who have difficulty manipulating a mouse or keyboard. There are three types of touch screen technology: resistive, surface wave and capacitive.
Composition
Aspects of the present invention have been realized by a composition exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
According to a first embodiment of the composition, according to the present invention, the composition further contains a dispersion medium.
According to a second embodiment of the composition, according to the present invention, the composition further contains an organic liquid as dispersion medium.
According to a third embodiment of the composition, according to the present invention, the composition further contains water as dispersion medium.
According to a fourth embodiment of the composition, according to the present invention, the composition further contains an aqueous medium.
According to a fifth embodiment of the composition, according to the present invention, the composition further contains an aqueous medium with a pH of at least 3.5, preferably of at least 4.0 and particularly preferably of at least 4.5.
According to a sixth embodiment of the composition, according to the present invention, the composition further contains a surfactant.
According to a seventh embodiment of the composition, according to the present invention, the composition further contains a binder.
According to an eighth embodiment of the composition, according to the present invention, the composition further contains a cross-linking agent.
According to a ninth embodiment of the composition, according to the present invention, the composition is exclusive of an ester compound produced by the dehydration of a polycarboxylic acid compound with at least two carboxy groups and a polyhydric alcohol with at least two hydroxyl-groups.
According to a tenth embodiment of the composition, according to the present invention, the composition is exclusive of imide compound.
According to an eleventh embodiment of the composition, according to the present invention, the composition is exclusive of tertiary ammonium compounds.
According to a twelfth embodiment of the composition, according to the present invention, the composition is exclusive of aromatic or heteroaromatic amide compounds.
According to a thirteenth embodiment of the composition, according to the present invention, the polyanion and the at least one polymer comprising (3,4-dialkoxythiophene) monomer units are present in a latex and the weight ratio of the polyanion to the polymer comprising (3,4-dialkoxythiophene) monomer units in the latex is at least 4.0.
According to a fourteenth embodiment of the composition, according to the present invention, the composition is a printing ink e.g. a screen-printing ink, an offset ink. a flexographic ink, an ink-jet ink or a gravure ink.
According to a fifteenth embodiment of the composition, according to the present invention, the composition is a coating composition.
Polymer Containing Optionally Substituted 3,4-alkylenedioxythiophene Monomer Units
The polymer, according to the present invention, contains optionally substituted 3,4-alkylenedioxythiophene monomer units in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge.
According to a sixteenth embodiment of the composition, according to the present invention, the polymer is selected from the group consisting of: poly(3,4-methylenedioxy-thiophene), poly(3,4-methylenedioxythiophene) derivatives, poly(3,4-ethylene-dioxythiophene), poly(3,4-ethylenedioxy-thiophene) derivatives, poly(3,4-propylenedioxythiophene), poly(3,4-propylenedioxy-thiophene) derivatives, poly(3,4-butylenedioxythiophene), poly(3,4-butylenedioxythiophene) derivatives and copolymers therewith. The term derivatives used in disclosing the ninth embodiment of the composition, according to the present invention, means that the monomers are substituted.
According to a seventeenth embodiment of the composition, according to the present invention, the substituents for the oxy-alkylene-oxy bridge are alkyl, alkoxy, alkyloxyalkyl, alkyloxyalkylenecarboxy, alkyloxyalkylenesulfo, carboxy, alkylsulphonato and carboxy ester groups.
According to an eighteenth embodiment of the composition, according to the present invention, the optionally substituted oxy-alkylene-oxy bridge is a 1,2-ethylene group, an optionally alkyl-substituted methylene group, an optionally C1-12-alkyl- or phenyl-substituted 1,2-ethylene group, a 1,3-propylene group or a 1,2-cyclohexylene group.
According to a nineteenth embodiment of the composition, according to the present invention, the optionally substituted 3,4-alkylenedioxythiophene structural units are represented by formula (I):




in which X and Y are O, Z is —(CH2)m—CR3R4—(CH2)n—; R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3−M+; R4 is —(CH2)s—O—(CH2)p—SO3−M+; M+ is a cation; m and n are independently a whole number from 0 to 3; s is a whole number from 0 to 10; and p is a whole number from 1 to 18.

According to a twentieth embodiment of the composition, according to the present invention, the polymer containing optionally substituted 3,4-alkylenedioxythiophene structural units is a polythiophene according to formula (IV)




in which X and Y are O, Z is —(CH2)m—CR3R4—(CH2)n—; R3 is hydrogen or —(CH2)s—O—(CH2)p—SO3−M+; R4 is —(CH2)s—O—(CH2)p—SO3−M+; M+ is a cation; m and n are independently a whole number from 0 to 3; s is a whole number from 0 to 10; and p is a whole number from 1 to 18; and q is a whole number from 2 to 10,000.

According to a twenty-first embodiment of the composition, according to the present invention, the polymer containing optionally substituted 3,4-alkylenedioxythiophene structural units is poly[4-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-ylmethoxy)-butane-1-sulphonic acid].
According to a twenty-second embodiment of the composition, according to the present invention, the polymer containing optionally substituted 3,4-alkylenedioxythiophene structural units is poly(3,4-ethylenedioxythiophene).
Polymers, according to the present invention, can be polymerized chemically or electrochemically. Chemical polymerization can be carried out oxidatively or reductively. The oxidation agents used for the oxidative polymerisation of pyrrole, as described, for example, in Journal of the American Chemical Society, volume 85, pages 454-458 (1963) and J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988), can be utilized for the oxidative polymerization of such polymers.
Inexpensive and easily accessible oxidation agents such as iron (III) salts such as FeCl3, the iron (III) salts of organic acids, e.g. Fe(OTs)3, H2O2, K2Cr2O7, alkali and ammonium persulphates, alkali perborates and potassium permanganate can be used in the oxidative polymerization.
Theoretically the oxidative polymerization of thiophenes requires 2.25 equivalents of oxidation agent per mole thiophene of formula (III) [see e.g. J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988)]. In practice an excess of 0.1 to 2 equivalents of oxidation agent is used per polymerizable unit. The use of persulphates and iron (III) salts has the great technical advantage that they do not act corrosively. Furthermore, in the presence of particular additives oxidative polymerization to the polymers, according to the present invention, proceeds so slowly that the thiophenes and oxidation agent can be brought together as a solution or paste and applied to the substrate to be treated. After application of such solutions or pastes the oxidative polymerization can be accelerated by heating the coated substrate as disclosed in U.S. Pat. No. 6,001,281 and WO 00/14139 herein incorporated by reference.
Reductive polymerization can be performed using the Stille (organotin) or Suzuki (organoboron) routes described in 2002 by Appperloo et al. in Chem. Eur. Journal, volume 8, pages 2384-2396, and as disclosed in 2001 in Tetrahedron Letters, volume 42, pages 155-157 and in 1998 in Macromolecules, volume 31, pages 2047-2056 respectively or with nickel complexes as disclosed in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621 and in 1998 in Advanced Materials, volume 10, pages 93-116.
Optionally substituted 3,4-dialkoxythiophene monomer units, according to the present invention, can be chemically or electrochemically copolymerized with other thiophene monomer or polymerizable heterocyclic compounds such as pyrrole.
Polyanion
The polyanion compounds for use in the layer configuration, according to the present invention, are disclosed in EP-A 440 957 herein incorporated by reference and include polymeric carboxylic acids, e.g. polyacrylic acids, polymethacrylic acids, or polymaleic acids and polysulphonic acids, e.g. poly(styrene sulphonic acid). These polycarboxylic acids and polysulphonic acids can also be copolymers of vinylcarboxylic acids and vinylsulphonic acids with other polymerizable monomers, e.g. acrylic acid esters, methacrylic acid esters and styrene.
According to a twenty-third embodiment of the composition, according to the present invention, the at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom is present in a molar ratio of at least 0.4 with respect to the monomer units of polyanion, with a molar ratio of at least 0.6 with respect to the monomer units of polyanion being preferred and a molar ratio of at least 0.8 with respect to the monomer units of polyanion being particularly preferred.
According to a twenty-fourth embodiment of the composition, according to the present invention, the polyanion is poly(styrene sulphonate).
Polyhydroxy Group-Containing Aromatic Compound
Aspects of the present invention have been realized by a composition comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
According to a twenty-fifth embodiment of the composition, according to the present invention, the polyhydroxy group-containing aromatic compound is an optionally substituted polyhydroxy benzene e.g. pyrogallol, catechol, resorcinol, 1,2-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, gallic acid, gallic acid esters, 3,4-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid esters.
Suitable polyhydroxy group-containing aromatic compounds include:












com-

Melting point


pound

[° C.]

















1
pyrogallol (1,2,3-trihydroxybenzene)
133


2
catechol (1,2-dihydroxybenzene)
105


3
resorcinol (1,3-dihydroxybenzene)
110


4
gallic acid (3,4,5-trihydroxybenzoic acid)
253 (decomp.)


5
methyl gallate (methyl 3,4,5-
201-203



trihydroxybenzoate)


6
ethyl gallate (ethyl 3,4,5-trihydroxybenzoate)


7
propyl gallate (propyl 3,4,5-
148-150



trihydroxybenzoate)


8
2,3,4-trihydroxybenzoic acid
228 (decomp.)


9
2,3,4-trihydroxybenzoic acid methyl eater


10
2,3,4-trihydroxybenzoic acid ethyl ester


11
2,3,4-trihydroxybenzoic acid propyl ester


12
3,4-dihydroxybenzoic acid
200-202


13
3,4-dihydroxybenzoic acid methyl ester


14
3,4-dihydroxybenzoic acid ethyl ester


15
3,4-dihydroxybenzoic acid propyl ester


16
2,5-dihydroxybenzoic acid
205 (decomp.)


17
2,5-dihydroxybenzoic acid methyl ester


18
2,5-dihydroxybenzoic acid ethyl ester


19
2,5-dihydroxybenzoic acid propyl ester


20
1,2-dihydroxynaphthalene
101-103


21
1,5-dihydroxynaphthalene
259-261(decomp)


22
2,6-dihydroxynaphthalene
223-225


23
1,2,4-trihydroxybenzene
140


24
3,5-dihydroxybenzoic acid
236-238(decomp)


25
2,3-dihydroxybenzoic acid
207-210


26
2,4-dihydroxybenzoic acid
225-227(decomp)


27
2,6-dihydroxybenzoic acid
165 (decomp.)


28
2,3-dihydroxy-1-pentadecylbenzene


29
2,5-dihydroxyacetophenone
204-206


30
2,4-dihydroxybenzophenone
144.5-147


31
2,6-dihydroxybenzophenone


32
3,4-dihydroxybenzophenone


33
3,5-dihydroxybenzophenone


34
2,4′-dihydroxydiphenylsulfone


35
2,2′,5,5′-tetrahydroxydiphenylsulfone


36
3,3′,5,5′-tetramethyl-4,4′-



dihydoxydiphenylsulfone


37
1,6-dihydroxynaphthalene
138-140


38
2,7-dihydroxynaphthalene
187 (decomp.)


39
2,3-dihydroxynaphthalene
162-164


40
1,5-dihydroxynaphthalene-2,6-



dicarboxylic acid


41
1,6-dihydroxynaphthalene-2,5-



dicarboxylic acid


42
1,5-dihydroxynaphthoic acid


43
1,4-dihydroxy-2-phenyl naphthoate


44
5-methyl-1,2,3-trihydroxybenzene


45
5-ethyl-1,2,3-trihydroxybenzene


46
5-propyl-1,2,3-trihydroxybenzene


47
trihydroxy benzoic acid


48
trihydroxyacetophenone


49
trihydroxybenzophenone


50
trihydroxybenzaldehyde


51
trihydroxyanthraquinone


52
2,4,6-trihydroxybenzene
205 (decomp.)


53
tetrahydroxy-p-benzoquinone


54
tetrahydroxyanthraquinone









Amino-Compounds and Heterocyclic Compounds with at Least One Ring Nitrogen Atom
The at least one amino-compound used in the composition or the layer configuration, according to the present invention, may be ammonia, ammonium hydroxide, or a primary, secondary or tertiary amino-compound. The substituents of the primary or secondary amino-compound are selected from the group consisting of aliphatic, aromatic, heterocyclic and heteroaromatic groups.
According to a twenty-sixth embodiment of the composition, according to the present invention, the at least one amino-compound is an aliphatic secondary amino-compound. Suitable aliphatic secondary amino-compounds include: 2-diethylamino-ethanol, 2-dimethylamino-ethanol and dicyclohexylamine.
Suitable tertiary amino-compounds include triethylamine and trimethylamine.
According to a twenty-seventh embodiment of the composition, according to the present invention, the at least one heterocyclic compounds with at least one ring nitrogen atom is a saturated compound.
According to a twenty-eighth embodiment of the composition, according to the present invention, the at least one heterocyclic compounds with at least one ring nitrogen atom is an unsaturated compound e.g. imidazole, imidazole derivatives e.g. benzimidazole, triazoles, triazole derivatives e.g. benztriazole, tetrazole and tetrazole derivatives e.g. 1-phenyl-5-mercaptotetrazole.
According to a twenty-ninth embodiment of the composition, according to the present invention, the at least one heterocyclic compounds with at least one ring nitrogen atom is a heteroaromatic compound e.g. benzimidazole, benztriazole, imidazole, pyridine, pyridine derivatives which may be substituted.
Suitable heterocyclic compounds with at least one ring nitrogen atom include imidazole, imidazole derivatives, pyrimidine, pyrimidine derivatives, piperidine, piperidine derivatives, pyrrolidine, pyrrolidine derivatives, pyridine, pyridine derivatives, quinoline, quinoline derivatives, isoquinoline, isoquinoline derivatives and 1,8-diazabicyclo[5.4.0]undec-7-ene:




Suitable amino-compounds and heterocyclic compounds with at least one ring nitrogen atom with pKa's less than 4.9 include:













pKa



















pyrrole
−0.27



pyrazine
0.60



pyrimidine
1.30



benztriazole
1.60



1,2,4-triazole
2.19



1-phenyl-5-mercaptotetrazole
2.30



pyrazole
2.53



aniline
4.63



tetrazole
4.89










According to a thirtieth embodiment of the composition, according to the present invention, the at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom has a pKa of at least 4.9. Amino-compounds and heterocyclic compounds with at least one ring nitrogen atom with a pKa of at least 4.9 include:













pKa



















quninoline
4.94



isoquinoline
5.2



pyridine
5.21



acridine
5.6



benzimidazole
6.00



2-methylbenzimidazole
6.96



imidazole
7.03



4-methyl-imidazole
7.45



triethanolamine
7.77



triallylamine
8.31



2-(dimethylamino)ethanol
8.88



furfurylamine
8.89



benzylamine
9.33



allylamine
9.49



ethanolamine
9.50



trimethylamine
9.81



ethylene diamine
9.98



N-methyl-piperidine
10.08



N-ethyl-piperidine
10.40



piperidine
10.4



t-butylamine
10.45



N-methylpyrrolidine
10.46



n-propylamine
10.58



n-butylamine
10.61



methylamine
10.62



isopropylamine
10.63



ethylamine
10.63



n-pentylamine
10.63



triethylamine
10.7



dimethylamine
10.77



diethylamine
10.93



di-n-propylamine
11.00



piperidine
11.22



pyrrolidine (pyrolidine)
11.3



(1,8-diazabicyclo[5.4.0]undec-7-ene)
11.6










Polyhydroxy- and/or Carboxy Group or Amide or Lactam Group Containing Aliphatic Compound
According to a thirty-first embodiment of the composition, according to the present invention, the at least one polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compound and/or at least one aprotic compound with a dielectric constant ≧15 is a polyhydroxy aliphatic compound with at least two hydroxy groups.
According to a thirty-second embodiment of the composition, according to the present invention, the at least one polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compound is selected from the group consisting of diethylene glycol, 1,2-propandiol, glycerol, hexylene glycol, propylene glycol, di(ethylene glycol)ethyl ether acetate (CarbitolTM acetate), N-methylacetamide, N-methyl pyrrolidinone and sugar alcohols, such as sorbitol, mannitol, 2,4-dihydroxyacetophenone, saccharose and fructose.
According to a thirty-third embodiment of the composition, according to the present invention, the at least one polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compound is an aprotic compound with a dielectric constant ≧15, such as N-methyl pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidone, N,N,N′,N′-tetramethylurea, formamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylene sulphone, dimethyl sulphoxide and hexamethylphosphoramide.
According to a thirty-fourth embodiment of the composition, according to the present invention, the at least one polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compound is selected from the group consisting of 1,2-propandiol, propylene glycol, diethylene glycol, N-methyl pyrrolidinone and di(ethylene glycol)ethyl ether acetate (CarbitolTM acetate).
Surfactants
According to a thirty-fifth embodiment of the composition, according to the present invention, the layer further contains a non-ionic surfactant e.g. ethoxylated/fluororalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluro-alkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants.
Suitable non-ionic surfactants include:

    Surfactant no. 01=ZONYLTMFSN, a 40% by weight solution of F(CF2CF2)1-9CH2CH2O)xH in a 50% by weight solution of isopropanol in water where x=0 to about 25, from DuPont;
    Surfactant no. 02=ZONYLTM FSN-100: F(CF2CF2)1-9CH2CH2O(CH2CH2O)xH where x=0 to about 25, from DuPont;
    Surfactant no. 03=ZONYLTM FS300, a 40% by weight aqueous solution of a fluorinated surfactant, from DuPont;
    Surfactant no. 04=ZONYLTM FSO, a 50% by weight solution of a mixture of ethoxylated non-ionic fluoro-surfactant with the formula: F(CF2CF2)1-7CH2CH2O(CH2CH2O)yH where y=0 to ca. 15 in a 50% by weight solution of ethylene glycol in water, from DuPont;
    Surfactant no. 05=ZONYLTM FSO-100, a mixture of ethoxylated non-ionic fluoro-surfactant from DuPont with the formula: F(CF2CF2)1-7CH2CH2O(CH2CH2O)yH where y=0 to ca. 15 from DuPont;
    Surfactant no. 06=TegoglideTM 410, a polysiloxane-polymer copolymer surfactant, from Goldschmidt;
    Surfactant no. 07=TegowetTM, a polysiloxane-polyester copolymer surfactant, from Goldschmidt;
    Surfactant no. 08=FLUORADTM FC431: CF3(CF2)7SO2(C2H5)N—CH2CO—(OCH2CH2)nOH from 3M;
    Surfactant no. 09=FLUORADTMFC126, a mixture of the ammonium salts of perfluorocarboxylic acids, from 3M;
    Surfactant no. 10=Polyoxyethylene-10-lauryl ether
    Surfactant no. 11=FLUORADTMFC430, a 98.5% active fluoroaliphatic ester from 3M;
    Surfactant no. 12=Synperonic A7, a C11-13-fatty alcohol condensed with an average of 7 ethylene oxide groups, from ICI


According to a thirty-sixth embodiment of the composition, according to the present invention, the layer further contains an anionic surfactant.
Suitable anionic surfactants include:

    Surfactant no. 13=ZONYLTM 7950, a fluorinated surfactant, from DuPont;
    Surfactant no. 14=ZONYLTM FSA, 25% by weight solution of F(CF2CF2)1-9CH2CH2SCH2CH2COOLi in a 50% by weight solution of isopropanol in water, from DuPont;
    Surfactant no. 15=ZONYLTM FSE, a 14% by weight solution of [F(CF2CF2)1-7CH2CH2O]xP(O) (ONH4)y where x=1 or 2; y=2 or 1; and x+y=3 in a 70% by weight solution of ethylene glycol in water, from DuPont;
    Surfactant no. 16=ZONYLTM FSJ, a 40% by weight solution of a blend of F(CF2CF2)1-7CH2CH2O]xP(O) (ONH4)y where x=1 or 2; y=2 or 1; and x+y=3 with a hydrocarbon surfactant in a 25% by weight solution of isopropanol in water, from DuPont;
    Surfactant no. 17=ZONYLTM FSP, a 35% by weight solution of [F(CF2CF2)1-7CH2CH2O]xP(O) (ONH4)y where x=1 or 2; y=2 or 1 and x+y=3 in 69.2% by weight solution of isopropanol in water, from DuPont;
    Surfactant no. 18=ZONYLTM UR: [F(CF2CF2)1-7CH2CH2O]xP(O) (OH)y where x=1 or 2; y=2 or 1 and x+y=3, from DuPont;
    Surfactant no. 19=ZONYLTM TBS: a 33% by weight solution of F(CF2CF2)3-8CH2CH2SO3H in a 4.5% by weight solution of acetic acid in water, from DuPont;
    Surfactant no. 20=ammonium salt of perfluoro-octanoic acid from 3M.


Layer Configuration
Aspects of the present invention are also realized by a layer configuration on a support, the layer configuration comprising a layer exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
According to a first embodiment of the layer configuration, according to the present invention, the polymer is selected from the group consisting of: poly(3,4-methylenedioxy-thiophene), poly(3,4-methylenedioxythiophene) derivatives, poly(3,4-ethylenedioxy-thiophene), poly(3,4-ethylenedioxy-thiophene) derivatives, poly(3,4-propylenedioxythiophene), poly(3,4-propylenedioxythiophene) derivatives, poly(3,4-butylenedioxythiophene), poly(3,4-butylenedioxythiophene) derivatives and copolymers therewith.
According to a second embodiment of the layer configuration, according to the present invention, the polymer contains optionally substituted 3,4-alkylenedioxythiophene structural units is poly(3,4-ethylenedioxythiophene).
According to a third embodiment of the layer configuration, according to the present invention, the polyanion is poly(styrene sulphonate).
According to a fourth embodiment of the layer configuration, according to the present invention, the layer configuration is a light emitting diode.
According to a fifth embodiment of the layer configuration, according to the present invention, the layer configuration is a solar cell.
According to a sixth embodiment of the layer configuration, according to the present invention, the layer configuration is a touch screen.
According to a seventh embodiment of the layer configuration, according to the present invention, the layer configuration is an e-paper configuration.
According to an eighth embodiment of the layer configuration, according to the present invention, the layer is a between a positive electrode and a material capable of hole transport and capable of reducing hole-electron recombination at the positive electrode.
Electroluminescent Phosphors
According to a ninth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor.
According to a tenth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor belongs to the class of II-VI semiconductors e.g. ZnS, or is a combination of group II elements with oxidic anions, the most common being silicates, phosphates, carbonates, germanates, stannates, borates, vanadates, tungstates and oxysulphates. Typical dopants are metals and all the rare earths e.g. Cu, Ag, Mn, Eu, Sm, Tb and Ce.
According to an eleventh embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is encapsulated with a transparent barrier layer against moisture e.g. Al2O3 and AlN. Such phosphors are available from Sylvania, Shinetsu polymer KK, Durel, Acheson and Toshiba. An example of coatings with such phosphors is 72X, available from Sylvania/GTE, and coatings disclosed in U.S. Pat. No. 4,855,189.
According to a twelfth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with manganese, copper or terbium, CaGa2S4 doped with cerium, electroluminescent phosphor pastes supplied by DuPont e.g.: LUXPRINTTM type 7138J, a white phosphor; LUXPRINTTM type 7151J, a green-blue phosphor; and LUXPRINTTM type 7174J, a yellow-green phosphor; and ELECTRODAGTM EL-035A supplied by Acheson.
According to a thirteenth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is a zinc sulphide phosphor doped with manganese and encapsulated with AlN.
Dielectric layer
According to a fourteenth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a dielectric layer.
Any dielectric material may be used in the dielectric layer, with yttria and barium titanate being preferred e.g. the barium titanate paste LUXPRINTTM type 7153E high K dielectric insulator supplied by DuPont and the barium titanate paste ELECTRODAGTM EL-040 supplied by Acheson. A positive ion exchanger may be incorporated into the dielectric layer to capture any ions escaping from the phosphor of the light-emitting layer. The amount of ion exchanger in the dielectric layer has to be optimized so that it has a maximum effectiveness in reducing black spots while not reducing the initial brightness level. It is therefore preferred to add 0.5 to 50 parts by weight of ion exchanger to 100 parts by weight of the total amount of resin and dielectric material in the dielectric layer. The ion exchanger may be organic or inorganic.
Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, salts of phosphoric acid and silicic acid and zeolite.
Support
According to a fifteenth embodiment of the layer configuration, according to the present invention, the support is transparent or translucent.
According to a sixteenth embodiment of the layer configuration, according to the present invention, the support is paper, polymer film, glass or ceramic.
According to a seventeenth embodiment of the layer configuration, according to the present invention, the support is a transparent or translucent polymer film.
A transparent or translucent support suitable for use with the electroconductive or antistatic layers, according to the present invention, may be rigid or flexible and consist of a glass, a glass-polymer laminate, a polymer laminate, a thermoplastic polymer or a duroplastic polymer. Examples of thin flexible supports are those made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, with poly(ethylene terephthalate) or poly(ethylene naphthalene-1,4-dicarboxylate) being particularly preferred.
Process
Aspects of the present invention are realized by a process for producing a composition with a pH of at least 3.0, said process comprising the steps of:

    i) providing an aqueous dispersion comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, and a polyanion; and
    ii) adding at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups; and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15, wherein the pH of said aqueous dispersion is increased to a pH of at least 3 with at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom at any time during said process.


According to a first embodiment of the process for producing a composition, according to the present invention, the pH of the aqueous dispersion comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, and a polyanion is adjusted to a value of at least 3.0 before addition of at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups; and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15.
Aspects of the present invention are also realized by a composition obtainable by the process for producing a composition a composition with a pH of at least 3.0, said process comprising the steps of: i) providing an aqueous dispersion comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, and a polyanion; and ii) adding at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups; and at least one compound selected from the group consisting of polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15, wherein the pH of said aqueous dispersion is increased to a pH of at least 3 with at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom at any time during said process.
Electroluminescent Devices
According to an eighteenth embodiment of the layer configuration, according to the present invention, the layer configuration is an electroluminescent device.
According to a nineteenth embodiment of the layer configuration, according to the present invention, the layer configuration is a light emitting diode.
Thin film electroluminescent devices (ELDs) are all characterized by one (or more) electroluminescent active layer(s) sandwiched between two electrodes. Optionally a dielectric layer may also be part of the sandwich.
Thin film ELDs can be subdivided into organic and inorganic based ELDs. Organic-based thin film ELDs can be subdivided into low molecular weight organic devices including oligomers (Organic Light Emitting Diodes (OLEDs)) and high molecular weight organic devices (Polymer Light Emitting Diodes (PLEDs). The inorganic ELDs on the other hand can be further subdivided into the High Voltage Alternating Current (HV-AC) ELDs and the Low Voltage Direct Current (LV-DC) ELDs. The LV-DC ELDs include Powder ELDs (DC-PEL Devices or DC-PELDs) and thin film DC-ELDs, hereinafter called Inorganic Light Emitting Diodes (ILEDs).
The basic construction of organic ELDs (PLED and OLED) comprises following layer arrangement: a transparent substrate (glass or flexible plastic), a transparent conductor, e.g. Indium Tin Oxide (ITO), a hole transporting layer, a luminescent layer, and a second electrode, e.g. a Ca, Mg/Ag or Al/Li electrode. For OLEDs the hole transporting layer and the luminescent layer are 10-50 nm thick and applied by vacuum deposition, whereas for PLEDs the hole transporting layer is usually about 40 nm thick and the luminescent layer is usually about 100 nm thick and applied by spin coating or other non-vacuum coating techniques. A direct voltage of 5-10 V is applied between both electrodes and light emission results from holes and electrons being injected from the positive and negative electrodes respectively combining in the luminescent layer thereby producing the energy to excite the luminescent species to emit light.
In OLEDs the hole transporting layer and electroluminescent layer consist of low molecular organic compounds, N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (TPD) can, for example be used as the hole transporter and aluminium (III) 8-hydroxyquinoline complex (Alq3), polyaromatics (anthracene derivatives, perylene derivatives and stilbene derivatives) and polyhetero-aromatics (oxazoles, oxadiazoles, thiazoles etc.) can be used as electroluminescent compounds.
In PLEDs electroluminescent compounds that can be used are polymers like the non-conjugated polyvinylcarbazole derivatives (PVK) or conjugated polymers like poly(p-phenylene vinylenes) (PPV), polyfluorenes, poly(3-alkylthiophene), poly(p-phenylene ethynylenes) etc. These high-molecular-weight materials allow for the easy preparation of thin films by casting, and show a high resistance to crystallization.
Low voltage DC PEL Devices generally comprise a transparent substrate, a transparent conductor (ITO), a doped ZnS phosphor layer (20 μm), and a top electrode of evaporated aluminium. The phosphor layer is applied by means of the doctor blade technique or screen printing on an ITO conducting layer. Subsequently an aluminium electrode is applied by evaporation. Upon applying a direct current voltage of several volts (ITO positive), holes start moving towards the aluminium electrode, thereby creating an insulating region (about 1 μm in thickness) next to the ITO layer within one minute or so. This results in a current drop which is associated with the onset of light emission. This process has been called the forming process. In the thin high resistive phosphor layer thereby formed, high electric fields occur and electroluminescence is already possible at low voltages (typically between 10 and 30 V). Que et al. [see Appl. Phys. Lett., volume 73, pages 2727-2729 (1998)] using ZnS:Cu nano crystals achieved turn on voltages of below 5 V.
In hybrid LEDs, inorganic emitting so-called quantum dots are used in combination with organic polymers with charge transporting properties and in some cases also emitting properties. Hybrid LEDs with CdSe nano particles have been reported by Colvin et al. [see Nature, volume 370, pages 354-357, (1994)], Dabbousi et al. [see Appl. Phys. Lett., volume 66, pages 1316-1318 (1995), and Gao et al. [see J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)]; and with ZnS:Cu nano-crystals have been reported by Huang et al. [see Appl. Phys. Lett., volume 70, pages 2335-2337 (1997)] all included herein by reference.
Photovoltaic Devices
According to a twentieth embodiment of the layer configuration, according to the present invention, the layer configuration is a photovoltaic device.
According to a twenty-first embodiment of the layer configuration, according to the present invention, the layer configuration is a solar cell.
According to a twenty-second embodiment of the layer configuration, according to the present invention, the layer configuration further comprises at least one photovoltaic layer. The photovoltaic layer may be an organic layer, a hybrid inorganic and organic layer or an inorganic layer.
Photovoltaic devices incorporating the layer configuration, according to the present invention, can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode. In the case of the regenerative type of photovoltaic cell, as exemplified by the Graetzel cell, the hole transporting medium may be a liquid electrolyte supporting a redox reaction, a gel electrolyte supporting a redox reaction, an organic hole transporting material, which may be a low molecular weight material such as 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9′-spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, poly(N-vinylcarbazole) etc., or inorganic semiconductors such as CuI, CuSCN etc. The charge transporting process can be ionic as in the case of a liquid electrolyte or gel electrolyte or electronic as in the case of organic or inorganic hole transporting materials.
Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types: structures which receive light from both sides and those which receive light from one side. An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer. Such devices preferably have their sides sealed with a polymer, an adhesive or other means to prevent deterioration or volatilization of the inside substances. The external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known.
Organic photovoltaic layers of the layer configuration, according to the present invention are, for example, mixtures of fullerene molecules (as electron acceptor and electron transporter) with conjugated polymers (e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter)[see Brabec et al., Adv. Funct. Mater., volume 11(1), pages 15-26 (2001)]. In 1995 Halls et al. reported in Nature, volume 376, page 498 the successful use of acceptor-type conjugated polymers instead of fullerenes.
Alternatively the layer configuration, according to the present invention, can be incorporated in hybrid photovoltaic compositions such as described in 1991 by Graetzel et al. in Nature, volume 353, pages 737-740, in 1998 by U. Bach et al. [see Nature, volume 395, pages 583-585 (1998)] and in 2002 by W. U. Huynh et al. [see Science, volume 295, pages 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transporter or hole transporter) is inorganic (e.g. nano-TiO2 as electron transporter, CdSe as light absorber and electron transporter) and at least one of the components is organic (e.g. triphenylamine as hole transporter or poly(3-hexylthiophene) as hole transporter).
Inorganic photovoltaic layers which can be used in the layer configuration according to this invention are described in EP-A 1 176 646.
Transistors
According to a twenty-third embodiment of the layer configuration, according to the present invention, the layer configuration is a transistor.
According to a twenty-fourth embodiment of the layer configuration, according to the present invention, the layer configuration further comprises a layer with one or more of the electron transporting or hole transporting components described above, but within such a configuration that it can be used as a transistor. The semiconductor can be n-type, p-type or both (ambipolar transistor) and can be either organic or inorganic.
INDUSTRIAL APPLICATION
Compositions, according to the present invention, can be used as coating compositions and printing inks e.g. in flexographic printing, in offset printing, in screen printing, in ink-jet printing and in gravure printing.
Layer configurations, according to the present invention, can also be used in a wide range of electronic devices such as photovoltaic devices, solar cells, batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, sensors for organic and bio-organic materials and field effect transistors, touch screens and e-paper configurations [see also chapter 10 of the Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, Weinheim (1999)].
The invention is illustrated hereinafter by way of comparative and invention examples. The percentages and ratios given in these examples are by weight unless otherwise indicated.
Subbing layer Nr. 01 used in the LAYER CONFIGURATIONS exemplified below has the composition:













copolymer of 88% vinylidene chloride, 10% methyl acrylate
79.1%


and 2% itaconic acid


Kieselsol ® 100F, a colloidal silica from BAYER
18.6%


Mersolat ® H, a surfactant from BAYER
0.4%


Ultravon ® W, a surfactant from CIBA-GEIGY
1.9%









Ingredients used in the COMPARATIVE and REFERENCE LAYER CONFIGURATIONS:
Polyhydroxy-Compounds:
DEG=diethylene glycol (disclosed in EP-A 686 662);
TEG=triethylene glycol (disclosed in EP-A 686 662).
Aprotic Compound with a Dielectric Constant ≧15:
formamide
2-pyrrolidone
DMSO=dimethyl sulphoxide
NMP=N-methyl pyrrolidone

    Z6040=3-glycidoxypropyltri-methoxy-silane from Dow Chemical

PEDOT/PSS Dispersion A0:



a 1.11% by weight aqueous dispersion of PEDOT/PSS with a PEDOT:PSS weight ratio of 1:2.46, which was produced under an inert atmosphere such that when said initiator is added less than 3 mg of oxygen per litre of said reaction medium is present in said reaction medium as disclosed in WO 03/048227A.
PEDOT/PSS Dispersion A1:
7.1 g [0.1043 moles] of imidazole was added to 350 g of PEDOT/PSS dispersion A0 [0.01492 moles PSS] whereby the initial pH of 2.0 was increased to 7.85.
PEDOT/PSS Dispersion A2:
680.6 g of PEDOT/PSS dispersion A0 [0.02901 moles PSS] was added to 100 g of PEDOT/PSS dispersion A1 [0.004178 moles PSS; 0.029207 moles imidazole] whereby the initial pH of 7.85 was reduced to 7.0 [1:0.88 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A3:
905.1 g of PEDOT/PSS dispersion A0 [0.03858 moles PSS] was added to 100 g of PEDOT/PSS dispersion A1 [0.004178 moles PSS; 0.029207 moles imidazole] whereby the initial pH of 7.85 was reduced to 4.5 [1:0.683 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A4:
10.20 g of 1M aqueous imidazole solution [0.01020 moles] was added to 350 g of PEDOT/PSS dispersion A0 [0.01492 moles PSS] whereby the initial pH of 2.11 was increased to 4.5 [1:0.684 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A5:
1.26 g of PEDOT/PSS dispersion A0 [0.00005355 moles] was added to 100 g of PEDOT/PSS dispersion A4 [0.004142 moles PSS; 0.002832 moles imidazole] whereby the initial pH of 4.5 was reduced to 4.0 [1:0.675 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A6:
2.29 g of PEDOT/PSS dispersion A0 [0.0000975 moles PSS] was added to 100 g of PEDOT/PSS dispersion A4 [0.004142 moles PSS; 0.002832 moles imidazole] whereby the initial pH of 4.5 was reduced to 3.5 [1:0.668 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A7:
10.68 g of PEDOT/PSS dispersion A0 [0.000455 moles PSS] was added to 100 g of PEDOT/PSS dispersion A4 [0.004142 moles PSS; 0.002832 moles imidazole] whereby the initial pH of 4.5 was reduced to 3.0 [1:0.616 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion A8:
51.79 g of PEDOT/PSS dispersion A0 [0.002208 moles PSS] was added to 100 g of PEDOT/PSS dispersion A4 [0.004142 moles PSS; 0.002832 moles imidazole] whereby the initial pH of 4.5 was reduced to 2.5 [1:0.446 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion B0:
a 1.14% by weight aqueous dispersion of PEDOT/PSS with a PEDOT:PSS weight ratio of 1:2.46, which was produced under an inert atmosphere such that when said initiator is added less than 3 mg of oxygen per litre of said reaction medium is present in said reaction medium as disclosed in WO 03/048227A.
PEDOT/PSS Dispersion C0:
a 1.13% by weight aqueous dispersion of PEDOT/PSS with a PEDOT:PSS weight ratio of 1:2.46, which was produced as described in EP 0 440 957A i.e. in the presence of air.
PEDOT/PSS Dispersion C1:
2.67 g [0.00267 moles] of a 1M aqueous solution of imidazole was added to 100 g of PEDOT/PSS dispersion C0 [0.004341 moles PSS] whereby the initial pH of 2.0 was increased to 3.0 [1:0.616 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion C2:
3.01 g [0.00301 moles] of 1M imidazole was added to 100 g of PEDOT/PSS dispersion C0 [0.004341 moles PSS] whereby the initial pH of 2.0 was increased to 5.0 [1:0.693 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion C3:
3.81 g [0.00381 moles] of 1M imidazole was added to 100 g of PEDOT/PSS dispersion C0 [0.004341 moles PSS] whereby the initial pH of 2.0 was increased to 7.0 [1:0.877 PSS/imidazole molar ratio].
PEDOT/PSS Dispersion D0:
a 1.15% by weight aqueous dispersion of PEDOT/PSS with a PEDOT:PSS weight ratio of 1:2.46, which was produced under an inert atmosphere such that when said initiator is added less than 3 mg of oxygen per litre of said reaction medium is present in said reaction medium as disclosed in WO 03/048227A.
PEDOT/PSS Dispersion E0:
a 1.15% by weight aqueous dispersion of PEDOT/PSS with a PEDOT:PSS weight ratio of 1:2.46, which was produced under an inert atmosphere such that when said initiator is added less than 3 mg of oxygen per litre of said reaction medium is present in said reaction medium as disclosed in WO 03/048227A.
Effect of imidazole, 2-(dimethylamino)ethanol and Pyridine Upon the pH of PEDOT/PSS-Dispersion AO












added imidazole
added 2-(dimethylamino)ethanol



[g/100 g AO]
[g/100 g AO]
pH

















0   
0   
2.11


0.132
0.163
2.5


0.198
0.256
3.5


0.203; 0.196
0.265
4.5


0.255; 0.262
0.270; 0.277
7.0









Effect of Pyridine Upon the pH of PEDOT/PSS-Dispersion EO














added pyridine [g/100 g EO]
pH



















0
2.11



0.11
2.26



0.22
2.6



0.31
3.45



0.38
5.26



0.78
5.84



1.33
6.17



2.22
6.42



4.0
6.66



6.67
6.85



11.11
7.02












COMPARATIVE EXAMPLES 1 TO 7
The compositions of COMPARATIVE EXAMPLES 1 to 7 were produced by adding the ingredients given in Table 1 to the PEDOT/PSS dispersions specified in Table 1.









TABLE 1









Comparative Example















1
2
3
4
5
6
7


















solid PEDOT/PSS
(0.268}
(0.268}
(0.268}
(0.268}
(0.268}
(0.268}
(0.268}


diethylene glycol
2.9
2.9
2.9
2.9
2.9
2.9
2.9


isopropanol
2.1
2.1
2.1
2.1
2.1
2.1
2.1


PEDOT/PSS
23.31
23.31
23.31
23.31-
23.31
23.31
23.31


dispersion B0


deionized water
31.04
31.04
31.04
31.04
31.04
31.04
31.17


Z6040
0.13
0.13
0.13
0.13
0.13
0.13
—


1M aq. 2-dimethyl-
—
to pH
—
—
—
—
to pH


aminoethanol

7.52




7.74


1M aq. imidazole
—
—
to pH
—
—
—
—





7.02


1M aqueous NH4OH
—
—
—
to pH
—
—
—






7.43


1M aqueous NaOH
—
—
—
—
to pH
—
—







8.71


1M aqueous KOH
—
—
—
—
—
to pH
—








8.16


pH (initial)
2.4
7.52
7.02
7.43
8.71
8.16
7.74


pH (after 2 h)
2.53
4.73
7.05
6.74
7.18
6.77
7.28


pH (after 34 h)
2.43
6.41
6.94
6.17
6.46
6.32
605


pH (after 90 h)
2.4
5.69
6.89
5.7
6.03
5.81
6.02


pH (after 168 h)
2.52
5.56
6.84
5.7
6.07
5.25
5.78


pH (after 336 h)
2.47
5.48
6.94
5.54
5.77
5.64
5.6


pH (after 1 month)
2.48
5.33
6.8
5.39
5.66
5.5
5.38


pH (after 2 months)
2.52
5.37
6.86
5.29
5.42
5.43
5.23









The compositions of COMPARATIVE EXAMPLES 1 to 7 after different standing times were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. A strip 45 mm wide was cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of the fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 2 for each strip together with the appropriate standing time of the dispersion prior to coating.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 2.








TABLE 2







Comparative
Standing time













Example 
fresh
2 h
34 h
90 h
168 h
336 h



















nr
OD
SER
OD
SER
OD
SER
OD
SER
OD
SER
OD
SER






















1
0.043
389
0.047
376
0.052
349
0.052
326
0.054
319
0.047
352


2
0.060
368
0.055
400
0.060
374
0.062
355
0.066
347
0.058
405


3
0.067
390
0.064
425
0.069
424
0.070
414
0.072
435
0.071
456


4
0.055
357
0.059
338
0.057
377
0.062
352
0.061
392
0.057
373


5
0.078
798
0.084
790
0.061
858
0.089
760
0.076
831
0.080
892


6
0.075
1102
0.081
1110
0.085
1094
0.088
1083
0.090
1015
0.070
1021


7
0.055
342
0.056
353
0.070
324
0.064
332
0.064
341
0.054
313





SER = Surface resistance in Ω/square






The results with the layers of COMPARATIVE EXAMPLES 5 and 6 show that the presence of sodium or potassium hydroxide resulted in a prohibitive increase in surface resistance over the layers of COMPARATIVE EXAMPLE 1 without sodium or potassium hydroxide. The results with the layers of COMPARATIVE EXAMPLES 2, 3 and 4 show that layers with 2-N,N-dimethylamino-ethanol, imidazole and ammonium hydroxide exhibited comparable surface resistances to the layers of COMPARATIVE EXAMPLE 1 without 2-N,N-dimethylamino-ethanol, imidazole or ammonium hydroxide. A comparison of the results with the layers of COMPARATIVE EXAMPLES 2 and 7 show that the presence of 3-glycidoxypropyl-trimethoxysilane slightly increased the surface resistance of layers with 2-N,N-dimethylamino-ethanol.
COMPARATIVE EXAMPLES 8 TO 11 AND INVENTION EXAMPLES 1 AND 2
The compositions of COMPARATIVE EXAMPLES 8 to 11 and INVENTION EXAMPLES 1 and 2 were produced by adding the ingredients given in Table 3 to the PEDOT/PSS dispersions specified in Table 3.










TABLE 3









Comparative Example
Invention Example














8
9
10
11
1
2

















solid PEDOT/PSS
(3.565)
(3.565)
(3.565)
(3.565)
(3.565)
(3.565)


diethylene glycol
28.0
28.0
28.0
28.0
28.0
28.0


isopropanol
20.0
20.0
20.0
20.0
20.0
20.0


compound 7
—
—
—
1.8
1.8
1.8


PEDOT/PSS disp B0
225
225
225
225
225
225


deionized water
220.6
220.6
220.6
218.8
218.8
218.8


Z6040
1.4
1.4
1.4
1.4
1.4
1.4


5 wt % aq. Zonyl ®
5.0
5.0
5.0
5.0
5.0
5.0


FSO100


1M aq. imidazole
—
ca. 12 (to
—
—
13.62 (to




pH = 7.0)


pH = 7.0)


1M aq. 2-dimethyl-
—
—
6.85 (to
—

8.13 (to


amino-ethanol


pH = 7.0)


pH = 7.0)



500
ca. 512
506.85
500
513.62
508.13


pH (initial)
2.45
7.27
7.09
2.44
7.02
7.20


pH (after 2 h)
2.44
7.28
6.44
2.48
7.17
7.09


pH (after 24 h)
2.46
7.16
5.52
2.50
6.91
7.04


pH (after 168 h)
2.42
7.21
4.24
2.45
7.10
6.54


pH (after 336 h)
2.42
7.17
4.03
2.40
7.04
6.29


pH (after 720 h)
2.44
7.13
3.92
2.43
6.93
6.04


pH (after 1440 h)
2.37
7.25
3.84
2.36
6.88
5.98









The compositions of COMPARATIVE EXAMPLES 8 to 11 and INVENTION EXAMPLES 1 and 2 after different standing times were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. A strip 45 mm wide was cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of the fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 4 for each strip together with the appropriate standing time of the dispersion prior to coating.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 4.









TABLE 4









Standing time















fresh
2 h
24 h
168 h
336 h
720 h
1440 h






















OD
SER*
OD
SER*
OD
SER
OD
SER*
OD
SER*
OD
SER*
OD
SER*

























Comparative
















Example


nr


 8
0.055
273
0.048
318
0.055
265
0.053
250
0.055
261
0.060
218
0.053
260


 9
0.063
318
0.062
384
0.068
321
0.073
285
0.072
348
0.075
298
0.070
341


10
0.062
292
0.060
224
0.062
289
0.067
271
0.063
321
0.070
268
0.063
315


11
0.048
302
0.047
317
0.052
275
0.052
264
0.052
265
0.057
223
0.048
264


Invention


example


nr.


 1
0.067
462
0.063
516
0.070
461
0.063
423
0.070
508
0.080
468
0.068
537


 2
0.063
452
0.063
495
0.067
447
0.060
439
0.070
418
0.078
332
0.062
426





*SER = surface resistance in Ω/square






A comparison of the results for the layers of COMPARATIVE EXAMPLES 8 and 11 show that the additional presence of propyl gallate has no effect on the surface resistance observed. However, a comparison of the results for the layers of COMPARATIVE EXAMPLES 9 and 10 with those for COMPARATIVE EXAMPLE 8 shows that in the absence of propyl gallate the surface resistance of the layers is slightly increased upon addition of imidazole or 2-dimethylamino-ethanol. A comparison of the results for the layers of INVENTION EXAMPLES 1 and 2 with those for the layer of COMPARATIVE EXAMPLE 11 shows that this effect is more pronounced in the presence of propyl gallate.

COMPARATIVE EXAMPLES 12 TO 14 AND INVENTION EXAMPLES 3 TO 5
The compositions of COMPARATIVE EXAMPLES 12 to 14 and INVENTION EXAMPLES 3 to 5 were produced by adding the ingredients given in Table 5 to the PEDOT/PSS dispersions specified in Table 5.










TABLE 5









Comparative Example
Invention Example














12
13
14
3
4
5

















solid PEDOT/PSS
1.12
1.12
(0.400}
(0.392)
(0.623)
(0.624)


diethylene glycol
12.89
—
4.5
4.5
7.0
7.0


isopropanol
9.11
9.11
3.2
3.2
5.0
5.0


compound 7
—
—
0.3
0.3
0.5
0.5


PEDOT/PSS disp A0
—
—
36.0
—
—
—


PEDOT/PSS disp A1
—
—
—
36.0
—
—


PEDOT/PSS disp A2
—
—
—
—
56.3


PEDOT/PSS disp A3
—
—
—
—
—
56.3


deionized water
99.57
112.46
35.0
35.0
54.7
54.7


Z6040
0.62
0.62
0.2
0.2
0.3
0.3


5 wt % aq. Zonyl ® FSO100
2.34
2.34
0.8
0.8
1.3
1.3



125.65
125.65
80.0
80.0
125.1
125.1


wt % PEDOT/PSS latex
0.89
0.89
0.50
0.49
0.5
0.5


wt % diethylene glycol
10.26
—
5.6
5.6
5.6
5.6


wt % compound 7
—
—
0.375
0.375
0.400
0.400


wt % imidazole
—
—
—
0.89
0.11
0.086


wt % Z6040
0.49
0.49
0.25
0.25
0.24
0.24









The compositions of COMPARATIVE EXAMPLES 12 to 14 and INVENTION EXAMPLES 3 to 5 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 6 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 6.













TABLE 6









pH by


Surface resistance (SER) [Ω/square]
SER × OD


















adding


strip
strip
strip
strip
strip

[Ω/



imidazole
OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]





















Comparative












Example


nr


12
—
—
—
222
217
216
—
—
218
—


13
—
—
—
12790
15830
10770
—
—
13130
—


14
—
0.048
89.47
294
300
312
312
339
311
14.9


Invention


Example


nr.


 3
7.85
0.068
85.44
604
586
592
592
632
601
40.9


 4
7.00
0.063
86.43
472
461
448
466
496
469
29.5


 5
4.50
0.055
88.10
389
376
372
375
398
382
21.0









The more imidazole that was added the more the surface resistance of the layers was increased.
The layers of COMPARATIVE EXAMPLES 12 to 14 and INVENTION EXAMPLES 3 to 5 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times, for 250 hours at a temperature of 60° C. at 95% relative humidity, or for 250 h at a temperature of 100° C. at ambient humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 7 together with the average surface resistances from Table 6 for the layers of COMPARATIVE 12 to 14 and INVENTION EXAMPLES 3 to 5 are summarized in Table 7 below.









TABLE 7









Surface resistance [Ω/square]














increase
increase
increase factor
increase




factor after
factor after
after 250 h
factor after



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
250 h 100° C.
















Comparative







Example


nr


12
218
1.80
3.44
1.50*
—


13
13130
2.68
5.19
0.03*
—


14
311
1.48
1.40
1.28
1.25


Invention


Example


nr


 3
601
0.97
1.08
0.75
0.77


 4
469
1.01
1.04
0.91
0.82


 5
382
1.14
1.12
0.94
0.92





*336 h instead of 250 h






The Suntest results for the layer of COMPARATIVE EXAMPLE 14 containing a polymer comprising (3,4-dialkoxythiophene) monomer units with both diethylene glycol and propyl gallate shows an increase in stability over the layers of COMPARATIVE EXAMPLE 12 or COMPARATIVE EXAMPLE 13 containing a polymer comprising (3,4-dialkoxythiophene) monomer units and diethylene glycol or propyl gellate respectively.
However, the results obtained in Suntest and the other stability tests carried out show that the layers of INVENTION EXAMPLES 3 to 5 show a surprising further strong improvement in stability for layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units upon the further addition of the base imidazole over and above that attained by the incorporation of diethylene glycol and propyl gallate. Although, as noted above, this is accompanied by a slight reduction in surface resistance, this slight reduction in surface resistance is considerably outweighed by the very strong improvement in Suntest stability and long term stability to heating at 100° C. and exposure to a relative humidity of 95% at 60° C.
INVENTION EXAMPLES 6
The composition of INVENTION EXAMPLE 6 was produced by adding the ingredients given in Table 8 to the PEDOT/PSS dispersions specified in Table 8.










TABLE 8







Comparative Example
Invention Example



14
6


















solid PEDOT/PSS
(0.400}
(0.308)


5 wt % aq. Zonyl ®
0.8
0.15


FSO100


5 wt % aq. Synperonic A7
—
1.19


isopropanol
3.2
2.4


diethylene glycol
4.5
3.39


Z6040
0.2
0.16


compound 7
0.3
0.24


PEDOT/PSS disp A0
36.0
—


PEDOT/PSS disp B0
—
27.0


50 wt % aq. imidazole

0.8


deionized water
35.0
24.77



80.0
60.1


wt % PEDOT/PSS latex
0.50
0.512


wt % diethylene glycol
5.6
5.64


wt % compound 7
0.375
0.40


wt % imidazole
—
1.09


wt % Z6040
0.25
0.25









The composition of INVENTION EXAMPLES 6 was coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 20 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 9 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 9.










TABLE 9









Surface resistance (SER) [Ω/square]
SER × OD



















strip
strip
strip
strip
strip

[Ω/



OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]




















Comparative











Example


nr


14
0.048
89.47
294
300
312
312
339
311
14.9


Invention


Example


nr


 6
0.030
93.33
717
738
729
748
743
735
22.0









The results of Table 9 showed that the addition of imidazole to the layer increased the surface resistance of the layers.
The layer of INVENTION EXAMPLE 6 was subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times, or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 10 with those for COMPARATIVE EXAMPLE 14 together with the average surface resistances from Table 9 are summarized in Table 10 below.









TABLE 10









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h at
after 500 h at



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example


nr


14
311
1.48
1.40
1.28
—


Invention


Example


nr


 6
735
1.09
1.31
1.00
1.11









The results in Table 10 show that the excellent stability for layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units upon the further addition of the base imidazole over and above that attained by the incorporation of diethylene glycol and propyl gallate reported in Table 8 for INVENTION EXAMPLES 3 to 5 for a PEDOT/PSS-latex with a PEDOT:PSS weight ratio of 1:2.46.
COMPARATIVE EXAMPLE 15 AND INVENTION EXAMPLES 7 TO 11
The compositions of COMPARATIVE EXAMPLE 15 and INVENTION EXAMPLES 7 to 11 were produced by adding the ingredients given in Table 11 to the PEDOT/PSS dispersions specified in Table 11.










TABLE 11









Comparative




Example
Invention Example















14
15
7
8
9
10
11

















solid PEDOT/PSS
(0.400)
(0.400)
(0.388)
(0.388)
(0.388)
(0.389)
(0.392)


[g]


imidazole [g]
—
—
(0.0690)
(0.0681)
(0.0674)
(0.0623)
(0.0454)


diethylene glycol
4.5
4.5
4.5
4.5
4.5
4.5
4.5


isopropanol
3.2
3.2
3.2
3.2
3.2
3.2
3.2


compound 7
0.3
0.3
0.3
0.3
0.3
0.3
0.3


PEDOT/PSS disp A0
36.0
36.0
—
—
—
—
—


PEDOT/PSS disp A4
—
—
36.0
—
—
—
—


pH = 4.5


PEDOT/PSS disp A5
—
—
—
36.0
—
—
—


pH = 4.0


PEDOT/PSS disp A6
—
—
—
—
36.0
—
—


pH = 3.5


PEDOT/PSS disp A7
—
—
—
—
—
36.0
—


pH = 3.0


PEDOT/PSS disp A8
—
—
—
—
—
—
36.0


pH = 2.5


deionized water
35.0
35.0
35.0
35.0
35.0
35.0
35.0


Z6040
0.2
0.2
0.2
0.2
0.2
0.2
0.2


5 wt % aq. Zonyl ®
0.8
0.8
0.8
0.8
0.8
0.8
0.8


FSO100




80.0
80.0
80.0
80.0
80.0
80.0
80.0


wt % PEDOT/PSS
0.50
0.50
0.48
0.48
0.48
0.49
0.49


wt % DEG
5.6
5.6
5.6
5.6
5.6
5.6
5.6


wt % compound 7
0.375
0.375
0.375
0.375
0.375
0.375
0.375


wt % imidazole
—
—
0.086
0.085
0.084
0.078
0.057


wt % Z6040
0.25
0.25
0.25
0.25
0.25
0.25
0.25


pH
2.11
2.11
4.55
4.2
3.47
3.02
2.48









The compositions of COMPARATIVE EXAMPLE 15 and INVENTION EXAMPLES 7 to 11 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 12 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 12.












TABLE 12









pH by

Surface resistance (SER) [Ω/square]
SER × OD


















adding


strip
strip
strip
strip
strip

[Ω/



imidazole
OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]





















Comparative












Example


nr.


14
—
0.048 
89.47
294
300
312
312
339
311
14.9


15
—
0.0566
87.77
242
243
241
254
248
246
13.9


Invention


Example


nr


 7
4.55
0.0666
85.77
324
318
318
323
344
325
21.6


 8
4.2 
0.0650
86.10
323
313
316
324
339
323
21.0


 9
3.47
0.0666
85.77
323
320
325
336
350
331
22.0


10
3.02
0.0666
85.77
347
335
334
341
353
342
22.8


11
2.48
0.0617
86.76
439
433
422
433
455
436
26.9









The increase in surface resistance upon addition of imidazole to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and propyl gallate appears to be a minimum upon addition of imidazole to give a pH of 4.2.
The layers of COMPARATIVE EXAMPLE 15 and INVENTION EXAMPLES 7 to 11 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times, or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 13 together with the average surface resistances from Table 6 for the layers of COMPARATIVE EXAMPLES 14 and 15 and INVENTION EXAMPLES 7 to 11 are summarized in Table 13 below.









TABLE 13









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h
after 500 h



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example nr.


14
311
1.48
1.40
1.28
1.25


15
246
1.18
1.32
1.26
1.26


Invention


Example nr


 7
325
0.97
1.03
0.94
0.94


 8
323
0.98
1.06
0.91
0.94


 9
331
0.95
1.08
0.92
0.90


10
342
0.98
1.00
0.91
0.94


11
436
0.98
1.11
0.92
0.91









There is no significant difference in stability between the layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol, propyl gallate and imidazole of INVENTION EXAMPLES 7 to 11 with concentrations of imidazole in the coating dispersions of 0.057 to 0.086 wt % or 0.446 to 0.684 moles of imidazole/mole PSS.
COMPARATIVE EXAMPLES 16 AND 17 AND INVENTION EXAMPLES 12 TO 14
The compositions of COMPARATIVE EXAMPLES 16 and 17 and INVENTION EXAMPLES 12 to 14 were produced by adding the ingredients given in Table 14 to the PEDOT/PSS dispersions specified in Table 14.










TABLE 14









Comparative




Example
Invention Example













16
17
12
13
14
















solid PEDOT/PSS [g]
(0.195)
(0.195)
(0.190)
(0.189)
(0.188)


imidazole [g]
—
—
(0.0306)
(0.0344)
(0.0432)


2-pyrrolidone
0.9
0.9
0.9
0.9
0.9


5 wt % aq. Zonyl ® FSO100
2.0
2.0
2.0
2.0
2.0


compound 7
—
0.2
0.2
0.2
0.2


PEDOT/PSS disp C0
17.28
17.28
—
—
—


PEDOT/PSS disp C1 pH = 3.0
—
—
17.28
—
—


PEDOT/PSS disp C2 pH = 5.0
—
—
—
17.28
—


PEDOT/PSS disp C3 pH = 7.0
—
—
—
—
17.28


deionized water
179.82
179.62
179.62
179.62
179.62



200.00
200.00
200.00
200.00
200.00


wt % PEDOT/PSS latex
0.097
0.097
0.095
0.095
0.094


wt % 2-pyrrolidone
0.45
0.45
0.45
0.45
0.45


wt % compound 7
—
0.1
0.1
0.1
0.1


wt % imidazole
—
—
0.0153
0.0172
0.0216


pH


3.0
5.0
7.0









The compositions of COMPARATIVE EXAMPLES 16 and 17 and INVENTION EXAMPLES 12 to 14 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 12 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 15 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 15.











TABLE 15









imidazole

Surface resistance (SER) [Ω/square]

















added


strip
strip
strip
strip
strip




pH
OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average




















Comparative











Example nr.


16
—
0.003
99.24
66825
67650
71700
70500
57450
66825


17
—
0.003
99.24
35063
34700
34850
36000
34700
35063


Invention


Example nr


12
3.0
0.003
99.24
53538
82800
50550
42600
38200
53538


13
5.0
0.003
99.24
229313
323000
241500
185150
167600
229313


14
7.0
0.003
99.24
749375
1033000
652500
494000
818000
749375









The surface resistance upon addition of imidazole to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and propyl gallate increases strongly above a pH of 3.0. Lower surface resistances were obtained upon coating the same dispersions at higher wet layer thicknesses that 12 μm as shown in Table 16 below.











TABLE 16









20 μm wet layer
30 μm wet layer
40 μm wet layer



thickness
thickness
thickness

















OD
SER*
SER* × OD
OD
SER*
SER* × OD
OD
SER*
SER* × OD




















Comparative











Example nr.


16
0.0050
12090
60.4
0.010
4900
49.0
0.0117
2305
27.0


17
0.0067
8520
57.1
0.010
3700
37.0
0.0117
2320
27.1


Invention


Example nr


12
0.0083
14285
118.6
0.0117
9400
110.0
0.0117
4805
56.2


13
0.0083
33000
273.9
0.0133
12650
168.2
0.0133
7600
101.1


14
0.0063
57100
359.7
0.0117
18850
220.5
0.0133
7765
103.3





*SER = surface resistance in Ω/square






The layers of COMPARATIVE EXAMPLES 16 and 17 and INVENTION EXAMPLES 12 to 14 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times, or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 17 together with the average surface resistances from Table 15 for the layers of COMPARATIVE EXAMPLES 16 and 17 and INVENTION EXAMPLES 12 to 14 are summarized in Table 17 below.









TABLE 17









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h
after 500 h



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example nr.


16
66825
256.95
—
2.78
6.65


17
35063
11.85
220.75
0.94
1.48


Invention


Example nr


12
53538
10.26
 69.08
0.65
1.45


13
229313
26.73
—
0.26
0.61


14
749375
40.49
—
0.14
0.39









The results in Table 17 show that the stability of layers comprising (3,4-dialkoxythiophene) monomer units and a polyanion, 2-pyrrolidone, propyl gallate and imidazole of INVENTION EXAMPLES 12 to 14 is significantly higher than the layer of COMPARATIVE EXAMPLE 17 comprising (3,4-dialkoxythiophene) monomer units and a polyanion, 2-pyrrolidone, and propyl gallate or the layer of COMPARATIVE EXAMPLE 16 comprising (3,4-dialkoxythiophene) monomer units and a polyanion and 2-pyrrolidone.
COMPARATIVE EXAMPLES 18 TO 21 AND INVENTION EXAMPLES 15 AND 16
The compositions of COMPARATIVE EXAMPLES 18 to 21 and INVENTION EXAMPLES 15 and 16 were produced by adding the ingredients given in Table 18 to the PEDOT/PSS dispersions specified in Table 18.










TABLE 18










Invention



Comparative Example
Example














18
19
20
21
15
16

















diethylene glycol
5.70
5.70
5.7
5.7
5.7
5.7


PEDOT/PSS disp A0
45.00
45.00
45.00
45.00
45.00
45.00


5 wt % aq. Zonyl ® FSO100
1.0
1.0
1.0
1.0
1.0
1.0


1M aq. imidazole
—
2.01
—
—
1.95
—


1M aq. 2-dimethyl-
—
—
1.37
—
—
1.38


aminoethanol


compound 5
—
—
—
0.35
0.35
0.35


deionized water
48.30
46.29
46.93
47.95
46.00
46.57



100.00
100.00
100.00
100.00
100.00
100.00


wt % PEDOT/PSS latex
0.50
0.50
0.50
0.50
0.50
0.50


wt % diethylene glycol
5.70
5.70
5.70
5.70
5.70
5.70


wt % compound 5
—
—
—
0.35
0.35
0.35


wt % imidazole
—
0.137
—
—
0.133
—


wt % 2-dimethylamino-ethanol
—
—
0.122
—
—
0.123


pH
2.32
7.22
6.69
2.34
6.84
4.84









The compositions of COMPARATIVE EXAMPLES 18 to 21 and INVENTION EXAMPLES 15 and 16 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 12 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 19 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 19.
A comparison of the surface resistances for the layers of INVENTION EXAMPLE 15 with that of COMPARATIVE EXAMPLE 19 or INVENTION EXAMPLE 16 with that of COMPARATIVE EXAMPLE 20, shows that the surface resistance increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and imidazole or 2-dimethylamino-ethanol. The surface resistance also increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion and diethylene glycol, as can be seen by comparing the surface resistances of the layers of COMPARATIVE EXAMPLES 21 and 18.










TABLE 19









Surface resistance (SER) [Ω/square]
SER × OD



















strip
strip
strip
strip
strip

[Ω/



OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]




















Comparative











Example nr


18
0.058
87.43
225
209
202
202
194
206
11.9


19
0.075
84.14
268
251
250
251
251
254
19.0


20
0.067
85.77
222
227
230
216
205
220
14.7


21
0.060
87.10
210
211
214
215
207
211
12.7


Invention


Example nr


15
0.073
84.46
353
349
355
352
336
349
25.5


16
0.067
85.77
288
288
293
290
293
290
19.4









The layers of COMPARATIVE EXAMPLES 18 to 21 and INVENTION EXAMPLES 15 and 16 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 20 together with the average surface resistances from Table 19 for the layers of COMPARATIVE EXAMPLES 18 to 21 and INVENTION EXAMPLES 15 and 16 are summarized in Table 20 below.









TABLE 20









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h
after 500 h



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example nr


18
206
1.77
4.00
1.35
1.49


19
254
1.60
2.02
1.00
1.15


20
220
1.94
2.40
1.12
1.30


21
211
1.30
1.38
1.20
1.30


Invention


Example nr


15
349
0.90
1.02
0.77
0.80


16
290
1.11
1.08
0.91
0.99









The results in Table 20 show a significant improvement in the stability of the surface resistances of layers surface resistance stability that the excellent stability for layers comprising a polymer comprising (3,4-dialkoxythiophene) monomer units and an anion, diethylene glycol and a base such as imidazole or 2-dimethylamino-ethanol upon addition of methyl gallate.
COMPARATIVE EXAMPLES 22 TO 25 AND INVENTION EXAMPLES 17 AND 18
The compositions of COMPARATIVE EXAMPLES 22 to 25 and INVENTION EXAMPLES 17 and 18 were produced by adding the ingredients given in Table 21 to the PEDOT/PSS dispersions specified in Table 21.










TABLE 21










Invention



Comparative Example
Example














22
23
24
25
17
18

















diethylene glycol
5.70
5.70
5.7
5.7
5.7
5.7


PEDOT/PSS disp A0
45.00
45.00
45.00
45.00
45.00
45.00


5 wt % aq. Zonyl ® FSO100
1.0
1.0
1.0
1.0
1.0
1.0


pyridine
—
3.01
—
—
4.70
—


10 wt % aq. 1,8-di-azabicyclo-
—
—
2.36
—
—
2.35


[5.4.0]undec-7-ene(DBU)


compound 5
—
—
—
0.35
0.35
0.35


deionized water
48.30
44.93
45.94
47.95
43.25
45.60



100.00
100.00
100.00
100.00
100.00
100.00


wt % PEDOT/PSS latex
0.50
0.50
0.50
0.50
0.50
0.50


wt % diethylene glycol
5.70
5.70
5.70
5.70
5.70
5.70


wt % compound 5
—
—
—
0.35
0.35
0.35


wt % pyridine
—
3.01
—
—
4.70
—


wt % DBU
—
—
0.236
—
—
0.235


pH
—
7.00
6.82
2.18
7.00
4.80









The compositions of COMPARATIVE EXAMPLES 22 to 25 and INVENTION EXAMPLES 17 and 18 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 12 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 22 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 22.










TABLE 22









Surface resistance (SER) [Ω/square]
SER × OD



















strip
strip
strip
strip
strip

[Ω/



OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]




















Comparative











Example nr


22
0.058
87.43
218
213
215
212
213
214
12.4


23
0.065
86.10
215
219
219
218
217
218
14.2


24
0.077
83.82
316
309
301
305
314
309
23.8


25
0.058
87.43
221
221
217
213
222
219
12.7


Invention


Example nr


17
0.063
86.43
270
248
249
243
255
253
15.9


18
0.073
84.46
342
348
344
339
345
344
25.1









A comparison of the surface resistances for the layers of INVENTION EXAMPLE 17 with that of COMPARATIVE EXAMPLE 23 or INVENTION EXAMPLE 18 with that of COMPARATIVE EXAMPLE 24, shows that the surface resistance increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and pyridine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The surface resistance also increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion and diethylene glycol, as can be seen by comparing the surface resistances of the layers of COMPARATIVE EXAMPLES 25 and 22. Moreover, with pyridine the increase in surface resistance upon addition of a base is much reduced over the situation with imidazole, 2-dimethylamino-ethanol or DBU.
The layers of COMPARATIVE EXAMPLES 22 to 25 and INVENTION EXAMPLES 17 and 18 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 23 together with the average surface resistances from Table 22 for the layers of COMPARATIVE EXAMPLES 22 to 25 and INVENTION EXAMPLES 17 and 18 are summarized in Table 23 below.









TABLE 23









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h
after 500 h



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example nr.


22
214
1.79
3.20
1.25
1.47


23
218
1.86
2.46
1.21
1.32


24
309
1.86
1.80
1.09
1.24


25
219
1.28
1.40
1.17
1.27


Invention


Example nr


17
253
1.08
—
1.04
1.12


18
344
1.01
1.06
0.82
0.88









The results in Table 23 show a significant improvement in the stability of the surface resistances of layers surface resistance stability that the excellent stability for layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and an anion, diethylene glycol and a base such as pyridine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) upon addition of methyl gallate.
COMPARATIVE EXAMPLES 26 TO 33 AND INVENTION EXAMPLES 19 TO 24
The compositions of COMPARATIVE EXAMPLES 26 to 33 and INVENTION EXAMPLES 19 to 24 were produced by adding the ingredients given in Tables 24 and 25 respectively to the PEDOT/PSS dispersions specified in Tables 24 and 25. The concentration of the different amino-compounds or heterocyclic compounds with at least one ring nitrogen atom with the exception of phenyl mercaptotetrazole were approximately equimolar to the PSS in the PEDOT/PSS-latex.









TABLE 24









Comparative Example
















26
27
28
29
30
31
32
33



















diethylene glycol
5.70
5.7
5.7
5.70
5.7
5.7
5.70
5.7


PEDOT/PSS disp A0
45.00
45.00
45.00
45.00
45.00
45.00
45.00
45.00


5 wt % aq. Zonyl ® FSO100
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


1M aq. imidazole
—
2.01
—
—
—
—
—
—


1M aq 2-dimethylamino-
—
—
2.00
—
—
—
—
—


ethanol (DMAE)


10.4 wt % benztriazole
—
—
—
2.05
—
—
—
—


solution in methanol


0.1 wt % solution of PMT
—
—
—
—
48.30
—
—
—


(phenylmercaptotetrazole)


in aqueous ethanol


pyridine
—
—
—
—
—
0.16
—
—


4.25 wt % aqueous NH4OH
—
—
—
—
—
—
—
0.81


compound 5






0.35


deionized water
48.30
46.29
46.30
46.25
0.00
48.14
47.95
47.49



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50


wt % diethylene glycol
5.70
5.70
5.70
5.70
5.70
5.70
5.70
5.70


wt % compound 5
—
—
—
—
—
—
0.35
—


wt % imidazole
—
0.137
—
—
—
—
—
—


wt % DMAE
—
—
0.178
—
—
—
—
—


wt % benztriazole
—
—
—
0.213
—
—
—
—


wt % PMT
—
—
—
—
0.048
—
—
—


wt % pyridine
—
—
—
—
—
0.16
—
—


wt % NH4OH
—
—
—
—
—
—
—
0.0344


pH
2.11
7.09
9.29
2.13
2.33
5.40
2.16
9.12


















TABLE 25









Invention Example














19
20
21
22
23
24

















diethylene glycol
5.7
5.7
5.70
5.7
5.7
5.7


PEDOT/PSS disp A0
45.00
45.00
45.00
45.00
45.00
45.00


5 wt % aq. Zonyl ® FSO100
1.0
1.0
1.0
1.0
1.0
1.0


1M aq. imidazole
2.01
—
—
—
—
—


1M aq. 2-dimethylamino-ethanol
—
2.00
—
—
—
—


benztriazole
—
—
2.05
—
—
—


phenylmercaptotetrazole
—
—
—
48.30
—
—


pyridine
—
—
—
—
0.16
—


30 wt % aqueous NH4OH
—
—
—
—
—
0.81


compound 5
0.35
0.35
0.35
0.35
0.35
0.35


deionized water
45.94
45.95
45.90
−0.35
47.79
47.14



100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.50
0.50
0.50
0.50
0.50
0.50


wt % DEG
5.70
5.70
5.70
5.70
5.70
5.70


wt % compound 5
0.35
0.35
0.35
0.35
0.35
0.35


wt % imidazole
0.137
—
—
—
—
—


wt % DMAE
—
0.178
—
—
—
—


wt % benztriazole
—
—
0.238
—
—
—


wt % PMT
—
—
—
0.048
—
—


wt % pyridine
—
—
—
—
0.16
—


wt % NH4OH
—
—
—
—
—
0.0344


pH
6.93
7.66
2.21
2.30
5.43
7.28









The compositions of COMPARATIVE EXAMPLES 26 to 33 and INVENTION EXAMPLES 19 to 24 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a Braive coater at coating speed 2 with a barcoater giving a wet-layer thickness of 12 μm and the coatings dried for 3 minutes at 130° C. Five strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each of five fresh untreated strips was performed on two occasions during the measurements and the average recorded in Table 26 for each strip together with the average of these five values.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 26.
A comparison of the surface resistances for the layers of INVENTION EXAMPLES 19, 20 and 23 with those of COMPARATIVE EXAMPLE 27, 28 and 31 respectively shows that the surface resistance increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and imidazole, 2-dimethylamino-ethanol or pyridine. The surface resistance also increased upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion and diethylene glycol, as can be seen by comparing the surface resistances of the layers of COMPARATIVE EXAMPLES 26 and 32. Moreover, with pyridine the increase in surface resistance upon addition of a base is much reduced over the situation with imidazole and 2-dimethylamino-ethanol.










TABLE 26









Surface resistance (SER) [Ω/square]
SER × OD



















strip
strip
strip
strip
strip

[Ω/



OD
% VLT
nr 1
nr 2
nr 3
nr 4
nr 5
average
square]




















Comparative











Example nr.


26
0.060
87.10
217
202
204
201
197
204
12.2


27
0.075
84.14
277
265
267
266
261
267
20.0


28
0.075
84.14
276
266
276
272
264
271
20.3


29
0.062
86.76
222
218
225
221
219
221
13.7


30
0.057
87.77
227
229
227
224
223
226
12.9


31
0.063
86.43
217
208
207
206
207
209
13.2


32
0.060
87.10
222
221
219
219
218
220
13.2


33
0.068
85.44
252
251
238
237
247
245
16.7


Invention


Example nr.


19
0.078
83.50
389
367
371
347
376
370
28.9


20
0.082
82.86
523
504
499
466
486
496
40.7


21
0.058
87.43
235
236
229
231
227
232
13.4


22
0.060
87.10
228
224
225
228
224
226
13.6


23
0.065
86.10
242
238
237
214
229
232
15.1


24
0.073
84.46
380
382
379
363
361
373
27.2









There is no such increase in surface resistance upon the incorporation of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, diethylene glycol and benztriazole or 1-phenyl-mercaptotetrazole, see INVENTION EXAMPLES 21 and 22 and COMPARATIVE EXAMPLES 29 and 30.
The layers of COMPARATIVE EXAMPLES 26 to 33 and INVENTION EXAMPLES 19 to 24 were subjected to a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C for different times or for 240 hours or 500 hours at a temperature of 60° C. at 95% relative humidity respectively. The factor increase in surface resistance resulting from these stability tests are summarized in Table 27 together with the average surface resistances from Table 26 for the layers of COMPARATIVE EXAMPLES 26 to 33 and INVENTION EXAMPLES 19 to 24 are summarized in Table 27 below.









TABLE 27









Surface resistance [Ω/square]
















increase





increase
increase
factor after
increase factor




factor after
factor after
240 h
after 500 h



fresh
48 h Suntest
96 h Suntest
60° C./95% RH
60° C./95% RH
















Comparative







Example nr.


26
204
2.17
2.80
1.44
1.48


27
267
1.38
1.84
1.00
1.04


28
271
1.47
1.92
1.00
1.04


29
221
1.92
5.40
1.25
1.34


30
226
1.54
2.87
1.26
1.47


31
209
1.66
3.33
1.23
1.36


32
220
1.09
1.50
1.22
1.20


33
245
1.72
2.89
1.11
1.37


Invention


Example nr


19
370
0.89
0.80
0.79
0.72


20
496
0.89
0.83
0.61
0.59


21
232
1.11
1.12
1.09
1.07


22
226
1.22
1.23
1.22
1.20


23
232
1.15
1.12
1.08
1.05


24
373
0.91
0.99
0.78
0.86









The results in Table 27 show a significant improvement in the stability of the surface resistances of layers surface resistance stability that the excellent stability for layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and an anion, diethylene glycol and a base such as imidazole, 2-dimethylamino-ethanol, benztriazole, 1-phenyl-mercaptotetrazole, pyridine or ammonium hydroxide upon addition of methyl gallate.
INVENTION EXAMPLES 25 TO 28 AND COMPARATIVE EXAMPLES 34 TO 38
The 0.53% by weight PEDOT/PSS compositions of COMPARATIVE EXAMPLE INVENTION 34, COMPARATIVE EXAMPLES 35 to 38 and INVENTION EXAMPLES 25 to 28 were produced by adding the ingredients given in Table 28 to the dispersions specified in Table 28.










TABLE 28









Comparative Example
Invention Example

















34
35
36
37
38
25
26
27
28




















PEDOT/PSS disp D0
—
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80


neutralized with


IM aq. imidazole


to pH = 3.5


PEDOT/PSS disp D0
45.80


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


FSO100


compound 5
0.37
—
—
—
—
0.35
0.35
0.35
0.35


diethylene glycol
5.70
5.70

—
—
5.70

—
—


formamide
—
—
5.70
—
—
—
5.70
—
—


2-pyrrolidone
—
—
—
5.70
—
—
—
5.70
—


DMSO
—
—
—
—
5.70
—
—
—
5.70


deionized water
47.50
47.50
47.50
47.50
47.50
47.13
47.13
47.13
47.13



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.527
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511


wt % imidazole
—
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907


wt % compound 5
0.37
—
—
—
—
0.35
0.35
0.35
0.35


wt % DEG
5.70
5.70
—
—
—
5.70
—
—
—


wt % formamide
—
—
5.70
—
—
—
5.70
—
—


wt % 2-pyrrolidone
—
—
—
5.70
—
—
—
5.70
—


wt % DMSO
—
—
—
—
5.70
—
—
—
5.70









The compositions of COMPARATIVE EXAMPLES 34 to 38 and INVENTION EXAMPLES 25 to 28 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a BRAIVE coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Four strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each fresh untreated strip was performed on two occasions during the measurements and the average recorded for each of the strips together with the average value for all five strips for each composition is given in Table 29 below.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 29.











TABLE 29









polyhydroxy- &/or





carboxy group or



amide or lactam



group containing



aliphatic compound
Surface resistance (SER)



or aprotic compound
[Ω/square]

















with dielectric

strip
strip
strip
strip
strip





constant ≧15
OD
nr 1
nr 2
nr 3
nr 4
nr 5
average
SER × OD




















Comparative











Example nr.


34
—
0.068
377
436
448
525
526
462
31.4


35
diethylene glycol
0.073
232
217
207
231
230
223
16.3


36
formamide
0.077
246
227
229
230
222
231
17.8


37
2-pyrrolidone
0.070
292
283
279
281
277
282
19.7


38
dimethyl sulphoxide
0.073
297
258
269
267
262
271
19.8


Invention


Example nr.


25
diethylene glycol
0.068
248
250
251
253
255
251
17.1


26
formamide
0.075
270
260
260
259
261
262
19.6


27
2-pyrrolidone
0.070
316
309
303
303
310
308
21.6


28
dimethyl sulphoxide
0.068
308
303
314
311
313
310
21.1









The surface resistance results in Table 29 showed an increase in surface resistance upon addition of methyl gallate to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15 such as diethylene glycol, formamide, 2-pyrrolidone or dimethyl sulphoxide. Moreover, the increase for diethylene glycol was significantly lower than when propyl gallate was incorporated.
The layers of COMPARATIVE EXAMPLES 34 to 38 and INVENTION EXAMPLES 25 to 28 were subjected to a Suntest-exposure for 48 and 96 hours in a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C and surface resistance measurements carried out on the layers fresh, after 48 and 96 hours exposure in the SUNTEST CPS+ and the results are summarized in Table 30 below:











TABLE 30







Fresh surface





resistance
increase factor
increase factor



[Ω/square]
after 48 h Suntest
after 96 h Suntest



















Comparative





Example nr.


34
462
1.13
1.47


35
223
1.65
2.34


36
231
1.51
2.25


37
282
1.93
2.68


38
271
1.87
2.11


Invention


Example nr.


25
251
1.07
1.11


26
262
1.08
1.08


27
308
1.05
1.18


28
310
1.05
1.15









The SUNTEST-results in Table 30 show a strong increase in stability of the surface resistance values upon incorporation of methyl gallate in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15 such as diethylene glycol, formamide, 2-pyrrolidone or dimethyl sulphoxide.
The surface resistances of the layers of COMPARATIVE EXAMPLES 34 to 38 and INVENTION EXAMPLES 25 to 28 after 240 h and 500 h in 95% relative humidity at 60° C. are summarized in Table 31 below.











TABLE 31









increase



Fresh surface
increase factor after
factor after 500 h



resistance
240 h in 95% relative
in 95% relative



[Ω/square]
humidity at 60° C.
humidity at 60° C.



















Comparative





Example nr.


34
462
0.76
0.75


35
223
1.51
1.34


36
231
1.24
1.17


37
282
1.10
1.15


38
271
1.21
1.19


Invention


Example nr.


25
251
1.07
1.01


26
262
0.98
0.98


27
308
0.89
0.91


28
310
0.89
0.87









The results of the tests at 95% relative humidity and 60° C. in Table 31 show a strong increase in thermal/moisture stability of the surface resistance values upon incorporation of methyl gallate in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and polyhydroxy- and/or carboxy group or amide or lactam group containing aliphatic compounds and aprotic compounds with a dielectric constant ≧15 such as diethylene glycol, formamide, 2-pyrrolidone or dimethyl sulphoxide.
INVENTION EXAMPLES 29 TO 37 AND COMPARATIVE EXAMPLES 39 TO 41
The ca. 0.51% by weight PEDOT/PSS compositions of COMPARATIVE 15 EXAMPLE INVENTION 34, COMPARATIVE EXAMPLES 39 to 41 and INVENTION EXAMPLES 29 to 37 were produced by adding the ingredients given in Tables 32 and 33 to the dispersions specified in Tables 32 and 33 respectively.









TABLE 32









Comparative Example












34
39
40
41















PEDOT/PSS disp D0
—
45.80
45.80
45.80


neutralized with


IM aq. imidazole


to pH = 3.5


PEDOT/PSS disp D0
45.80
—
—
—


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0


FSO100


compound 5
0.37
—
—
—


DEG
5.70
5.70
—
5.70


formamide
—
—
5.70
5.70


deionized water
47.50
47.50
47.50
41.80



100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.527
0.511
0.511
0.511


wt % imidazole
—
0.0907
0.0907
0.0907


wt % compound 5
0.37
—
—
—


wt % DEG
5.70
5.70
—
5.70


wt % formamide
—
—
5.70
5.70


final pH
—
3.63
4.07
3.88


















TABLE 33









Invention Example

















29
30
31
32
33
34
35
36
37




















PEDOT/PSS disp
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80


D0 neutralized


with IM imidazole


to pH = 3.5


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


FSO100


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


deionized water
47.13
47.13
47.13
47.13
47.13
47.13
41.43
41.43
41.43



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511


wt % imidazole
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907
0.0907


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


wt % DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


wt % formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


final pH
3.87
3.55
3.07
3.87
3.89
3.19
3.87
3.83
3.22









The compositions of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 29 to 37 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a BRAIVE coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Four strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each fresh untreated strip was performed on two occasions during the measurements and the average recorded for each of the strips together with the average value for all five strips for each composition is given in Table 34 below.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 34.











TABLE 34









polyhydroxy-





group containing



aliphatic cpd



&/or aprotic
Surface resistance (SER)



cpd with
[Ω/square]


















Compound
dielectric

strip
strip
strip
strip
strip





nr
constant ≧15
OD
nr 1
nr 2
nr 3
nr 4
nr 5
average
SER × OD





















Comparative












Example nr.


34
5
—
0.068
377
436
448
525
526
462
31.4


39
—
DEG
0.067
248
234
244
259
227
242
16.2


40
—
formamide
0.068
265
255
254
251
247
254
17.3


41
—
DEG/formamide
0.068
265
261
260
265
255
261
17.7


Invention


Example nr.


29
5
DEG
0.065
287
276
277
272
269
276
17.9


30
7
DEG
0.062
287
289
291
296
287
290
18.0


31
12
DEG
0.063
279
282
283
284
281
282
17.8


33
5
formamide
0.070
300
314
319
269
284
297
20.8


34
7
formamide
0.067
303
298
295
294
289
296
19.8


34
12
formamide
0.067
301
293
291
291
281
291
19.5


35
5
DEG/formamide
0.067
305
303
305
303
298
303
20.3


36
7
DEG/formamide
0.065
306
312
302
307
304
306
19.9


37
12
DEG/formamide
0.065
301
299
300
296
292
298
19.4









The surface resistance results in Table 34 showed an increase in surface resistance upon addition of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
The layers of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 29 to 37 were subjected to a Suntest-exposure for 48 and 96 hours in a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C and surface resistance measurements carried out on the layers fresh, after 48 and 96 hours exposure in the SUNTEST CPS+ and the results are summarized in Table 35 below:













TABLE 35









Fresh surface
increase
increase



Compound

resistance
factor after
factor after



nr

[Ω/square]
48 h Suntest
96 h Suntest





















Comparative







Example nr.


34
5
—
462
1.13
1.47


39
—
DEG
242
1.77
2.84


40
—
formamide
254
1.55
2.52


41
—
DEG/formamide
261
1.49
2.00


Invention


Example nr.


29
5
DEG
276
1.06
1.04


30
7
DEG
290
1.22
1.07


31
12
DEG
282
1.22
1.04


32
5
formamide
297
1.06
1.05


33
7
formamide
296
1.26
1.01


34
12
formamide
291
1.03
0.99


35
5
DEG/formamide
303
1.12
1.12


36
7
DEG/formamide
306
1.21
1.07


37
12
DEG/formamide
298
1.17
1.06









The SUNTEST-results in Table 35 show a strong increase in stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
The surface resistances of the layers of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 29 to 37 after 240 h and 500 h in 95% relative humidity at 60° C. are summarized in Table 36 below.
The results of the tests at 95% relative humidity and 60° C. in Table 32 show a strong increase in thermal/moisture stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, imidazole and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.













TABLE 36










increase
increase






factor after
factor after





Fresh
240 h in 95%
500 h in 95%





surface
relative
relative



Compound

resistance
humidity at
humidity at



nr

[Ω/square]
60° C.
60° C.





















Comparative







Example nr.


34
5
—
462
0.76
0.75


39
—
DEG
242
1.13
1.34


40
—
formamide
254
1.08
1.24


41
—
DEG/formamide
261
1.13
1.21


Invention


Example nr.


29
5
DEG
276
0.98
1.00


30
7
DEG
290
0.94
0.97


31
12
DEG
282
0.97
1.08


32
5
formamide
297
0.93
0.93


33
7
formamide
296
0.92
0.98


34
12
formamide
291
0.98
1.04


35
5
DEG/formamide
303
0.97
0.96


36
7
DEG/formamide
306
0.91
0.98


37
12
DEG/formamide
298
0.90
1.00









INVENTION EXAMPLES 38 TO 46 AND COMPARATIVE EXAMPLES 34 AND 42 TO 44
The ca. 0.51% by weight PEDOT/PSS compositions of COMPARATIVE EXAMPLE INVENTION 34, COMPARATIVE EXAMPLES 42 to 44 and INVENTION EXAMPLES 38 to 46 were produced by adding the ingredients given in Tables 37 and 38 to the dispersions specified in Tables 37 and 38 respectively.









TABLE 37









Comparative Example












34
42
43
44















PEDOT/PSS disp D0
—
45.80
45.80
45.80


neutralized with


IM DMAE to pH = 3.5


PEDOT/PSS disp D0
45.80
—
—
—


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0


FSO100


compound 5
0.37
—
—
—


DEG
5.70
5.70
—
5.70


formamide
—
—
5.70
5.70


deionized water
47.50
47.50
47.50
41.80



100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.527
0.511
0.511
0.511


wt % DMAE
—
0.118
0.118
0.118


wt % compound 5
0.37
—
—
—


wt % DEG
5.70
5.70
—
5.70


wt % formamide
—
—
5.70
5.70


final pH
—
3.57
3.92
3.94


















TABLE 38









Invention Example

















38
39
40
41
42
43
44
45
46




















PEDOT/PSS disp
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80


D0 neutralized


with IM DMAE to


pH = 3.5


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


FSO100


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


deionized water
47.13
47.13
47.13
47.13
47.13
47.13
41.43
41.43
41.43



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511


wt % DMAE
0.118
0.118
0.118
0.118
0.118
0.118
0.118
0.118
0.118


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


wt % DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


wt % formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


final pH
3.49
3.52
3.08
3.79
3.84
3.26
3.82
3.84
3.30









The compositions of COMPARATIVE EXAMPLES 34 and 42 to 44 and INVENTION EXAMPLES 38 to 46 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a BRAIVE coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Four strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each fresh untreated strip was performed on two occasions during the measurements and the average recorded for each of the strips together with the average value for all five strips for each composition is given in Table 39 below.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 39.











TABLE 39









polyhydroxy-





group containing



aliphatic cpd



&/or aprotic
Surface resistance (SER)



cpd with
[Ω/square]


















Compound
dielectric

strip
strip
strip
strip
strip





nr
constant ≧15
OD
nr 1
nr 2
nr 3
nr 4
nr 5
average
SER × OD





















Comparative












Example nr.


34
5
—
0.068
377
436
448
525
526
462
31.4


42
—
DEG
0.090
223
220
230
221
216
222
20.0


43
—
formamide
0.077
230
231
240
248
223
234
18.0


44
—
DEG/formamide
0.075
236
235
246
238
221
235
17.6


Invention


Example nr.


38
5
DEG
0.067
243
251
268
249
237
250
16.7


39
7
DEG
0.068
258
244
247
246
241
247
16.8


40
12
DEG
0.070
249
247
248
246
245
247
17.3


41
5
formamide
0.075
257
261
260
255
259
258
19.3


42
7
formamide
0.075
268
253
259
266
268
263
19.7


43
12
formamide
0.073
265
252
255
256
258
257
18.8


44
5
DEG/formamide
0.072
273
353
300
283
273
296
21.3


45
7
DEG/formamide
0.070
291
283
289
282
279
285
19.9


46
12
DEG/formamide
0.072
273
267
264
268
270
268
19.3









The surface resistance results in Table 39 showed an increase in surface resistance upon addition of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, dimethylaminoethanol and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide. However, the surface resistance values realized in the layers of INVENTION EXAMPLES 38 to 46 were significantly lower than those realized in the respective layers of INVENTION EXAMPLES 29 to 37 which only differed in containing imidazole instead of dimethylaminoethanol.
The layers of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 38 to 46 were subjected to a Suntest-exposure for 48 and 96 hours in a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C and surface resistance measurements carried out on the layers fresh, after 48 and 96 hours exposure in the SUNTEST CPS+ and the results are summarized in Table 40 below:













TABLE 40









Fresh surface
increase
increase



Compound

resistance
factor after
factor after



nr

[Ω/square]
48 h Suntest
96 h Suntest





















Comparative







Example nr.


34
5
—
462
1.13
1.47


42
—
DEG
222
1.78
2.31


43
—
formamide
234
1.82
2.18


44
—
DEG/formamide
235
1.95
2.17


Invention


Example nr.


38
5
DEG
250
1.01
1.10


39
7
DEG
247
1.11
1.77


40
12
DEG
247
1.03
1.14


41
5
formamide
258
0.93
1.02


42
7
formamide
263
1.00
1.69


43
12
formamide
257
0.97
1.04


44
5
DEG/formamide
296
0.90
1.17


45
7
DEG/formamide
285
0.99
1.65


46
12
DEG/formamide
268
0.97
1.18









The SUNTEST-results in Table 40 show a strong increase in stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, dimethylaminoethanol and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
The surface resistances of the layers of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 38 to 46 after 240 h and 500 h in 95% relative humidity at 60° C. are summarized in Table 41 below.













TABLE 41










increase factor
increase factor





Fresh
after 240 h in
after 500 h in





surface
95% relative
95% relative



Compound

resistance
humidity at
humidity at



nr

[Ω/square]
60° C.
60° C.





















Comparative







Example nr.


34
5
—
462
0.76
0.75


42
—
DEG
222
1.13
1.15


43
—
formamide
234
1.11
1.15


44
—
DEG/formamide
235
1.12
1.13


Invention


Example nr.


38
5
DEG
250
0.96
0.95


39
7
DEG
247
1.02
1.02


40
12
DEG
247
1.00
1.02


41
5
formamide
258
0.93
0.97


42
7
formamide
263
0.96
0.96


43
12
formamide
257
0.97
1.03


44
5
DEG/formamide
296
0.74
0.86


45
7
DEG/formamide
285
0.98
0.95


46
12
DEG/formamide
268
1.07
1.02









The results of the tests at 95% relative humidity and 60° C. in Table 32 show a strong increase in thermal/moisture stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, dimethylaminoethanol and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
INVENTION EXAMPLES 47 TO 55 AND COMPARATIVE EXAMPLES 34 AND 45 TO 47
The ca. 0.51% by weight PEDOT/PSS compositions of COMPARATIVE EXAMPLE INVENTION 34, COMPARATIVE EXAMPLES 45 to 47 and INVENTION EXAMPLES 47 to 55 were produced by adding the ingredients given in Tables 42 and 43 to the dispersions specified in Tables 42 and 43 respectively.









TABLE 42









Comparative Example












34
45
46
47















PEDOT/PSS disp D0
—
45.80
45.80
45.80


neutralized with


10 wt % aq pyridine


to pH = 3.5


PEDOT/PSS disp D0
45.80
—
—
—


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0


FSO100


compound 5
0.37
—
—
—


DEG
5.70
5.70
—
5.70


formamide
—
—
5.70
5.70


deionized water
47.50
47.50
47.50
41.80



100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.527
0.511
0.511
0.511


wt % pyridine
—
0.138
0.138
0.138


wt % compound 5
0.37
—
—
—


wt % DEG
5.70
5.70
—
5.70


wt % formamide
—
—
5.70
5.70


final pH
—
3.52
3.73
3.73


















TABLE 43









Invention Example

















47
48
49
50
51
52
53
54
55




















PEDOT/PSS disp
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80
45.80


D0 neutralized


with 10 wt % aq.


pyridine to


pH = 3.5


5 wt % aq. Zonyl ®
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


FSO100


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


deionized water
47.13
47.13
47.13
47.13
47.13
47.13
41.43
41.43
41.43



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0


wt % PEDOT/PSS
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511
0.511


wt % pyridine
0.138
0.138
0.138
0.138
0.138
0.138
0.138
0.138
0.138


wt % compound 5
0.37
—
—
0.37
—
—
0.37
—
—


wt % compound 7
—
0.37
—
—
0.37
—
—
0.37
—


wt % compound 12
—
—
0.37
—
—
0.37
—
—
0.37


wt % DEG
5.70
5.70
5.70
—
—
—
5.70
5.70
5.70


wt % formamide
—
—
—
5.70
5.70
5.70
5.70
5.70
5.70


final pH
3.44
3.51
3.08
3.69
3.73
3.23
3.71
3.72
3.28









The compositions of COMPARATIVE EXAMPLES 34 and 39 to 41 and INVENTION EXAMPLES 29 to 37 were coated on a 175 μm thick transparent PET sheet provided with subbing layer 1 on the side of the PET sheet being coated with a BRAIVE coater at coating speed 2 with a barcoater giving a wet-layer thickness of 40 μm and the coatings dried for 3 minutes at 130° C. Four strips 45 mm wide were cut from the middle of the coated sheet for surface resistance experiments.

The surface resistances at room temperature were determined by contacting the outermost layer with parallel electrodes each 45 mm long and 45 mm apart capable of forming line contacts with copper electrodes via silver-filled rubber, the electrodes being separated by a Teflon insulator. This enables a direct measurement of the surface resistance to be realized. The surface resistance of each fresh untreated strip was performed on two occasions during the measurements and the average recorded for each of the strips together with the average value for all five strips for each composition is given in Table 44 below.
The optical density measurements were carried out in transmission with a MacBeth TR924 densitometer with a visible filter with six strips with coatings and six strips without coatings to take the contribution from the support into consideration and the difference divided by six to provide the optical density for a single strip recorded in Table 44.
The surface resistance results in Table 44 showed a slight increase in surface resistance upon addition of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) to layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, pyridine and diethylene glycol, a polyhydroxy-group containing aliphatic compound, although the difference in surface resistance values was significantly smaller than in the case of the layers of respective INVENTION EXAMPLES 29 to 37 or respective INVENTION EXAMPLES 38 to 46 which only differed in containing imidazole or dimethylaminoethanol instead of pyridine.











TABLE 44









polyhydroxy-





group containing



aliphatic



cpd &/or



aprotic cpd
Surface resistance (SER)



with
[Ω/square]


















Compound
dielectric

strip
strip
strip
strip
strip





nr
constant ≧15
OD
nr 1
nr 2
nr 3
nr 4
nr 5
average
SER × OD





















Comparative












Example nr.


34
5
—
0.068
377
436
448
525
526
462
31.4


45
—
DEG
0.070
209
180
186
183
203
192
13.4


46
—
formamide
0.073
207
186
196
199
192
196
14.3


47
—
DEG/formamide
0.072
227
209
213
211
211
214
15.4


Invention


Example nr.


47
5
DEG
0.067
232
205
210
215
207
214
14.3


48
7
DEG
0.067
232
212
220
213
213
218
14.6


49
12
DEG
0.067
215
216
213
215
211
214
14.3


50
5
formamide
0.068
223
212
207
217
208
213
14.5


51
7
formamide
0.067
217
208
213
209
207
211
14.1


52
12
formamide
0.068
209
205
213
210
203
208
14.1


53
5
DEG/formamide
0.067
238
225
224
231
225
229
15.3


54
7
DEG/formamide
0.067
228
230
225
230
224
227
15.2


55
12
DEG/formamide
0.068
229
225
237
229
236
231
15.7









The product of the surface resistance and optical density gives a more reliable guide to the electrical conductivity of the layer, since the surface resistance is dependent upon the layer thickness which the optical density is dependent upon. In the case of layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, pyridine and formamide, an aprotic compound with a dielectric constant ≧15, or diethylene glycol and pyridine no significant increase in the product of the surface resistance and optical density was observed upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) unlike the case of the layers of INVENTION EXAMPLES 29 to 37 or INVENTION EXAMPLES 38 to 46 which only differed in containing imidazole and dimethylaminoethanol instead of pyridine.
Furthermore, the surface resistance values realized in the layers of INVENTION EXAMPLES 47 to 55 were significantly lower than those realized in the layers of respective INVENTION EXAMPLES 29 to 37 or respective INVENTION EXAMPLES 38 to 46 which only differed in containing imidazole or dimethylaminoethanol instead of pyridine.
The layers of COMPARATIVE EXAMPLES 34 and 45 to 47 and INVENTION EXAMPLES 47 to 55 were subjected to a Suntest-exposure for 48 and 96 hours in a SUNTEST CPS+ from Atlas with a low pressure Xenon lamp producing 765 W/m2 and having a blackstandard T of 50 C and surface resistance measurements carried out on the layers fresh, after 48 and 96 hours exposure in the SUNTEST CPS+ and the results are summarized in Table 45 below:













TABLE 45









Fresh surface
increase
increase



Compound

resistance
factor after
factor after



nr

[Ω/square]
48 h Suntest
96 h Suntest





















Comparative







Example nr.


34
5
—
462
1.13
1.47


45
—
DEG
192
1.87
3.44


46
—
formamide
196
1.65
2.52


47
—
DEG/formamide
214
1.73
2.38


Invention


Example nr.


47
5
DEG
214
1.04
1.15


48
7
DEG
218
1.05
1.12


49
12
DEG
214
1.03
1.15


50
5
formamide
213
1.07
1.08


51
7
formamide
211
1.04
1.18


52
12
formamide
208
1.04
1.11


53
5
DEG/formamide
229
1.07
1.11


54
7
DEG/formamide
227
1.06
1.14


55
12
DEG/formamide
231
1.10
1.09









The SUNTEST-results in Table 45 show a strong increase in stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, pyridine and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
The surface resistances of the layers of COMPARATIVE EXAMPLES 34 and 45 to 47 and INVENTION EXAMPLES 47 to 55 after 240 h and 500 h in 95% relative humidity at 60° C. are summarized in Table 46 below.













TABLE 46










increase
increase






factor after
factor after





Fresh
240 h in 95%
500 h in 95%





surface
relative
relative



Compound

resistance
humidity at
humidity at



nr

[Ω/square]
60° C.
60° C.





















Comparative







Example nr.


34
5
—
462
0.76
0.75


45
—
DEG
192
1.43
1.61


46
—
formamide
196
1.29
1.45


47
—
DEG/formamide
214
1.24
1.60


Invention


Example nr.


47
5
DEG
214
1.12
1.21


48
7
DEG
218
1.16
1.19


49
12
DEG
214
1.05
1.15


50
5
formamide
213
1.13
1.21


51
7
formamide
211
1.20
1.23


52
12
formamide
208
1.12
1.16


53
5
DEG/formamide
229
1.07
1.15


54
7
DEG/formamide
227
1.11
1.19


55
12
DEG/formamide
231
1.06
1.09









The results of the tests at 95% relative humidity and 60° C. in Table 46 show a strong increase in thermal/moisture stability of the surface resistance values upon incorporation of methyl gallate (compound 5), propyl gallate (compound 7) or 3,4-dihydroxybenzoic acid (compound 12) in layers containing a polymer comprising (3,4-dialkoxythiophene) monomer units and a polyanion, pyridine and diethylene glycol, a polyhydroxy-group containing aliphatic compound, formamide, an aprotic compound with a dielectric constant ≧15 or for a combination of equal quantities of diethylene glycol and formamide.
The present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.
Having described in detail preferred embodiments of the current invention, it will now be apparent to those skilled in the art that numerous modifications can be made therein without departing from the scope of the invention as defined in the following claims.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations of those preferred embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

## Claims

1. A composition exclusive of hydroquinone comprising at least one polymer comprising (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of diethylene glycol, 1,2-propanediol, glycerol, hexylene glycol, propylene glycol, N,N,N′,N′-tetramethylurea, tetramethylene sulphone, and dimethyl sulphoxide.

2. The composition according to claim 1, wherein said at least one polymer is selected from the group consisting of: poly(3,4-methylenedioxy-thiophene), poly(3,4-methylenedioxythiophene) derivatives, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxy-thiophene) derivatives, poly(3,4-propylenedioxythiophene), poly(3,4-propylenedioxythiophene) derivatives, poly(3,4-butylenedioxythiophene), poly(3,4-butylenedioxythiophene) derivatives and copolymers therewith.

3. The composition according to claim 1, wherein said polyanion is poly(styrene sulphonate).

4. The composition according to claim 1, wherein said at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups is selected from the group consisting of pyrogallol, gallic acid esters and polyhydroxy-benzoic acids.

5. The composition according to claim 1, wherein the at least one compound is diethylene glycol.

6. A layer configuration on a support, said layer configuration comprising a layer exclusive of hydroquinone comprising at least one polymer comprising optionally substituted (3,4-dialkoxythiophene) monomer units, in which the two alkoxy groups may be the same or different or together represent an optionally substituted oxy-alkylene-oxy bridge, a polyanion, at least one polyhydroxy group-containing aromatic compound exclusive of sulfo groups, at least one amino-compound or heterocyclic compound with at least one ring nitrogen atom, and at least one compound selected from the group consisting of diethylene glycol, 1,2-propanediol, glycerol, hexylene glycol, propylene glycol, N,N,N′,N′-tetramethylurea, tetramethylene sulphone, and dimethyl sulphoxide.

7. The layer configuration according to claim 6, wherein said at least one polymer is selected from the group consisting of: poly(3,4-methylenedioxy-thiophene), poly(3,4-methylenedioxythiophene) derivatives, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxy-thiophene) derivatives, poly(3,4-propylenedioxythiophene), poly(3,4-propylenedioxythiophene) derivatives, poly(3,4-butylenedioxythiophene), poly(3,4-butylenedioxythiophene) derivatives and copolymers therewith.

8. The layer configuration according to claim 6, wherein said polyanion is poly(styrene sulphonate).

9. The layer configuration according to claim 6, wherein said layer configuration is a light emitting diode.

10. The layer configuration according to claim 6, wherein said layer configuration is a photovoltaic device.

11. The layer configuration according to claim 6, wherein said layer configuration is a solar cell.

12. The layer configuration according to claim 6, wherein said layer configuration is a transistor.

13. The layer configuration according to claim 5, wherein said layer configuration is an electroluminescent device.

14. The layer configuration according to claim 6, wherein said layer configuration is a touch screen.

15. The layer configuration according to claim 6, wherein said layer configuration is an e-paper configuration.

16. The layer configuration according to claim 6, wherein the at least one compound is diethylene glycol.