CA2343444C - Printed conductors made of polyalkylene dioxythiophene - Google Patents
Printed conductors made of polyalkylene dioxythiophene Download PDFInfo
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- CA2343444C CA2343444C CA002343444A CA2343444A CA2343444C CA 2343444 C CA2343444 C CA 2343444C CA 002343444 A CA002343444 A CA 002343444A CA 2343444 A CA2343444 A CA 2343444A CA 2343444 C CA2343444 C CA 2343444C
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- alkyloxy
- polyalkylenedioxythiophene
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a process for coating substrates, such as paper or plastic films, with open, electrically conductive structures, by ink-jet printing. A polymer solution made from water-dispersible polyalkylenedioxythiophenes is used for the printing process.
Description
PRINTED CONDIJCTORS MADE OF POLY ALKYLENE DIOXYTHIOPHENE
Tlle invention relates to a process for coating substrates, such as paper or plastic films, with open, electrically conductive structures, by ink-jet printing or using X,Y plotters. A polymer solution made from ,vater-dispersible polvalkylenedioxy-tlvophenes is used for the printing process.
Printed circtiit boards used for electrical eircuitry are' ~vell known substrates which have an electrically conductive structure_ Printed circuit boards are composed of a rigid or flexible plastic substrate to which conductor tracks made from copper have been applied. The copper tracks are applied by photogr-aphic printing or by sereen printing.
In photo~raphic printin~ by the positive process the first step isfull-surface 1 S application of copper to the substrate. Photoresist is distributed over the full surface of the copper. The photoresist is irradiated throu2h a masl: at those locations where conductor tracks are to run. The irradiation cures the photoresist.
Subseqtient development removes the uncured photoresist areas. T'he copper which is now uncovered is removed by etching in the next step. Once the cured photoresist has been removed (strippecl) it is only the desired copper conductor tracks which renlain.
In the screen printing process an iinage of the desired coriductor structure is prirlted as an etch resist, onto a substrate with a full-surface covering of copper. jn the etching which follows the copper between the desired conductor tracks is removed by etching, and then the etch resist is removed.
In the direct coating of a nietal deposit onto nonconducting substrates ther e can be probleins with the adhesion of the nletal to the substrate. In this case a screen-printed paste based on an electrically conductive polymer can produce a good bond between substrate and superimposed layer. The conductor track structures made from the polynler are, for example, printed using screen printirig onto a nonc.onducting substrate and then coppered chernically (DE 36 25 5S7, DE 36 27 256).
T}Ze use of electrically conductive polymers as an electrically conductive structure on substrates is also l:.no-,vn in connection with polymer-based electroluminescence indicators (Science, 17 October 1997, p. 383). To apply the electrically conductive polti-:ncrs, a solution oFthe polyni:;rs wa~ introduced into tlie cartrid~~e of an ink-jet printer, and printed onto the substrate by the printer. A
major problem with this process was that the organic solvent for the polymers, generally a halogenated hydrocarbon or tetrahydrofuran, attacked the plastic of the printer cartridge by salvation or swelling.
To avoid this disadvantage Y. Yang and J. Bharathan (Science, Vol. 279, 20 February 1998) used a water-soluble polymer from the polythiophene class of compounds. These water-soluble polymers did not attack the printer cartridges.
Since structures of water-soluble polymers are also altered by atmospheric moisture, they are suitable only if they have no further contact with water after the water has been removed in an annealing step. In polymer-based luminescence indicators this condition poses no problem, since, after the water has been removed and after any further operations which may be required, conductive structures are encapsulated under inert conditions excluding water completely. However, the water-soluble polythiophenes are unsuitable for open conductor track structures, i.e. those exposed to the atmosphere.
The object of the invention was to find a process for producing open electrically conductive structures on substrates which is simpler and faster to carry out than the known processes of structuring using copper conductor tracks, and gives stable conductor track structures under normal conditions.
Thus, the present invention provides such a process by printing, onto a substrate, the conductive structures using an ink-jet printer or X,Y plotter in the cartridge of which there is an aqueous dispersion of polyalkylenedioxythiophenes with a suitable polyanion as a counter anion.
- 2a -The substrate used may be paper or plastic film.
The polyalkylenedioxythiophenes have been cationically charged and are composed of structural units of the formula (I) Le A 33 106-Foreign Countries I 1 {I) s in which A' and A2, independently of one another, represent substituted or unsubstituted CI-C4-alkyl or together form a substituted or unsubstituted Cl-C4-alkylene group, and n represents an integer from 2 to 10,000, preferably from 5 to 5000, in the presence of polyanions.
Preferred cationic polyalkylenedioxythiophenes are composed of structural units of the formula (Ia) or (Ib) R2Ri O O
(Ia) s n O O
\ {Ib) s n where R, and R2, independently of one another, represent hydrogen, substituted or unsubstituted C1-C18-alkyl, preferably C1-Ci,o-alkyl, in particular CI -C6-alkyl, C2-C]Z-alkenyl, preferably C2-C8-alkenyl;, C3-C7-cycloalkyl, preferably cyclopentyl or cyclohexyl, C7-CI5-aralkyl, preferably phenyl-Cl-C4-alkyl, C6-C10-aryl, preferably phenyl or naphth.yl, Ct-C18-alkyloxy, preferably Le A 33 106-Foreign Countries C1-Clo-alkyloxy, such as methoxy, ethoxy, n-propoxy or isopropoxy, or C2-Clg-alkyloxy esters, and R3 and R4, independently of one another, represent hydrogen, but not both simultaneously, or at least singly siul:phonate-substituted C1-C1%-alkyl, preferably Cl-Clo-alkyl, in particular CI-C6-alkyl, C2-C12-alkenyl, preferably C2-C8-alkenyl, C3-C7-cycloalkyl, preferably cyclopentyl or cyclohexyl, C7-Ci5-aralkyl, preferably phenyl-CI-C4-allcyl, C6-Clo-aryl, preferably phenyl or naphthyl, C1-C18-alkyloxy, preferably Ci-Cto-alkyloxy, such as methoxy, ethoxy, n-propoxy or isopropoxy, or C2-C1 g-alkyloxy esters, and n represents a number from 2 to 10,000, preferably from 5 to 5000.
Particular preference is given to cationic or neutral polyalkylenedioxythiophenes of the formulae (Ia-1) and/or (lb-1) (Ia-1) S
n O O
(Ib-1) s n where R3 is as defined above, and n represents an integer from 2 to 10,000, preferably from 5 to 5000.
The polyanions comprise anions of polymeric carboxylic acids, for example polyacrylic acids, polymethacrylic acids or polymaleic acids, and of polymeric sulphonic acids, such as polystyrenesulphonic acids and polyvinylsulphonic acids.
These polycarboxylic and polysulphonic acids may also be copolymers of Le A 33 106-Foreign Countries vinylcarboxylic and vinylsulphonic acids with other polymerizable monomers, such as acrylates and styrene.
The gegenion particularly preferably comprises tlie anion of polystyrenesuiphonic acid (PSA).
The molecular weight of the polyacids supplying the polyanions is preferably from 1000 to 2,000,000, particularly preferably from 2000'ao 500,000. The polyacids or their alkali metal salts are available commercially, e.g. polystyrenesulphonic acids and polyacrylic acids, or else can be prepared by known processes (see, for example, Houben Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Vol. E 20 Malcromolekulare Stoffe, Part 2, (1987), pp. 1141 et seq.).
Instead of the free polyacids required for forming the dispersions of polyalkylenedioxythiophenes and polyanions, it is also possible to use mixtures of alkali metal salts of the polyacids and appropriate amounts of monoacids.
In the case of formula (Ib-1) the polyalkylenedioxythiophenes carry positive and negative charge in the structural unit.
The preparation of the polyalkylenedioxythiopheries is described, for example, in EP-A 0 440 957 (= US-A 5 300 575). The polyalkylenedioxythiophenes are prepared by oxidative polymerization. This gives them positive charges which are not represented in the formulae, since their number and position cannot be established beyond question.
An advantage of the novel process is that open, electrically conductive structures can be produced on printed circuit boards with quality comparable to that of the known copper conductor tracks, but in a small number of' steps which are easy to carry out.
All that is needed for production is an ink-jet printer with an appropriately prepared printer cartridge and a computer to control the printer. The desired conductor track structure can be designed on the computer screen and immediately printed out on a suitable substrate.
The water-dispersible polyalkylenedioxythiophene is not water-soluble and, even under normal conditions, forms a conductive structure which has long-term stability.
I'.
Le A 33 106-Foreign Countries Fitwes and examples The figures show:
Fig.l Bayer cross symbols printed on paper using poly-(3,4-ethylenedioxy-thiophene) (PEDT) and polystyrene sulphonate (PSS).
Fig. 2 Conductor track system printed onto paper using PEDT/PSS.
Fig. 3 Conductor track system printed onto polyethylene terephthalate (PET) film using PEDT/PSS.
Example 1 Preparation of the 3,4-polyalkylenedioxythiophene dispersion g of free polystyrenesulphonic acid (Mn about 40,000), 21.4 g of potassium 15 peroxodisulphate and 50 mg of iron(III) sulphate were stirred in 2000 ml of water.
8.0 g of 3,4-ethylenedioxythiophene were added, with stirring. The dispersion was stirred for 24 h at room temperature. 100 g of anion exchanger (commercially available product Lewatit MP 62 from Bayer AG) and 100 g of cation exchanger (commercially available product Lewatit S 100 from Bayer AG) were added, both in 20 moistened form, followed by stirring for 8 hours.
The ion exchangers were removed by filtering tl:n-ough a polyacrylonitrile fabric of pore size 50 m. This gave a ready-to-use dispersion of 3,4-polyalkylenedioxy-thiophenes (PEDT) with polystyrenesulphonate (PSS) as gegenanion (see Il) with a solids content of about 1.2% by weight.
The dispersion could easily be filtered through a 0.45 m filter and was used after filtration to prepare the colours for the ink-jet printer.
a o a o O o s S
s H s 0 o c) o Le A 33 106-Foreign Countries Tn m SO~ S 3 H
Example 2 The aqueous dispersion of the PEDT/PSS as in (I][) from Example 1 was introduced into an empty ink-jet printer cartridge for an HP-]Desk-Jet PLUS (Hewlett-Packard) ink-jet printer. The cartridge had been cut open and thoroughly cleaned and after the PEDT/PSS dispersion as in (II) had been introduced it was sealed again using a polyethylene hot-melt adhesive from Henkel. An ink-jet printer cartridge prepared in this way was inserted into the HP-Desk-Jet PLI;rS ink j et printer and served as a reservoir for the printing liquid for applying the PEDT/PSS dispersion using the printer under computer control. The pattern to be printed was designed on the computer using a conventional software progran;i. An image of three Bayer cross symbols placed under one another (Fig. 1) was selected. This image was printed onto paper using computer control. The result was a;print on paper of the three Bayer cross symbols placed one underneath the other and composed of conductive PEDT/PSS, which had a blue intrinsic colour.
Example 3 The procedure followed was similar to that of Exzunple 2, except that a polyethylene terephthalic (PET) film of 0.1 mm thickness was used instead of the paper and printed with the Bayer cross symbols.
Example 4 The procedure followed was similar to that of Example 2, except that the pattern was a section for a printed circuit board designed using EAGLE layout software (Fig. 2).
This conductor track pattern was printed onto paper using PEDT/PSS as in Example 3.
Le A 33 106-Foreign Countries Example 5 In a manner similar to that of Example 4, the conductor track system of Fig. 3 was printed onto a PET film of 0,1 nun thickness. The electrical conductivity of the printed conductor tracks was demonstrated using a continuity tester.
Tlle invention relates to a process for coating substrates, such as paper or plastic films, with open, electrically conductive structures, by ink-jet printing or using X,Y plotters. A polymer solution made from ,vater-dispersible polvalkylenedioxy-tlvophenes is used for the printing process.
Printed circtiit boards used for electrical eircuitry are' ~vell known substrates which have an electrically conductive structure_ Printed circuit boards are composed of a rigid or flexible plastic substrate to which conductor tracks made from copper have been applied. The copper tracks are applied by photogr-aphic printing or by sereen printing.
In photo~raphic printin~ by the positive process the first step isfull-surface 1 S application of copper to the substrate. Photoresist is distributed over the full surface of the copper. The photoresist is irradiated throu2h a masl: at those locations where conductor tracks are to run. The irradiation cures the photoresist.
Subseqtient development removes the uncured photoresist areas. T'he copper which is now uncovered is removed by etching in the next step. Once the cured photoresist has been removed (strippecl) it is only the desired copper conductor tracks which renlain.
In the screen printing process an iinage of the desired coriductor structure is prirlted as an etch resist, onto a substrate with a full-surface covering of copper. jn the etching which follows the copper between the desired conductor tracks is removed by etching, and then the etch resist is removed.
In the direct coating of a nietal deposit onto nonconducting substrates ther e can be probleins with the adhesion of the nletal to the substrate. In this case a screen-printed paste based on an electrically conductive polymer can produce a good bond between substrate and superimposed layer. The conductor track structures made from the polynler are, for example, printed using screen printirig onto a nonc.onducting substrate and then coppered chernically (DE 36 25 5S7, DE 36 27 256).
T}Ze use of electrically conductive polymers as an electrically conductive structure on substrates is also l:.no-,vn in connection with polymer-based electroluminescence indicators (Science, 17 October 1997, p. 383). To apply the electrically conductive polti-:ncrs, a solution oFthe polyni:;rs wa~ introduced into tlie cartrid~~e of an ink-jet printer, and printed onto the substrate by the printer. A
major problem with this process was that the organic solvent for the polymers, generally a halogenated hydrocarbon or tetrahydrofuran, attacked the plastic of the printer cartridge by salvation or swelling.
To avoid this disadvantage Y. Yang and J. Bharathan (Science, Vol. 279, 20 February 1998) used a water-soluble polymer from the polythiophene class of compounds. These water-soluble polymers did not attack the printer cartridges.
Since structures of water-soluble polymers are also altered by atmospheric moisture, they are suitable only if they have no further contact with water after the water has been removed in an annealing step. In polymer-based luminescence indicators this condition poses no problem, since, after the water has been removed and after any further operations which may be required, conductive structures are encapsulated under inert conditions excluding water completely. However, the water-soluble polythiophenes are unsuitable for open conductor track structures, i.e. those exposed to the atmosphere.
The object of the invention was to find a process for producing open electrically conductive structures on substrates which is simpler and faster to carry out than the known processes of structuring using copper conductor tracks, and gives stable conductor track structures under normal conditions.
Thus, the present invention provides such a process by printing, onto a substrate, the conductive structures using an ink-jet printer or X,Y plotter in the cartridge of which there is an aqueous dispersion of polyalkylenedioxythiophenes with a suitable polyanion as a counter anion.
- 2a -The substrate used may be paper or plastic film.
The polyalkylenedioxythiophenes have been cationically charged and are composed of structural units of the formula (I) Le A 33 106-Foreign Countries I 1 {I) s in which A' and A2, independently of one another, represent substituted or unsubstituted CI-C4-alkyl or together form a substituted or unsubstituted Cl-C4-alkylene group, and n represents an integer from 2 to 10,000, preferably from 5 to 5000, in the presence of polyanions.
Preferred cationic polyalkylenedioxythiophenes are composed of structural units of the formula (Ia) or (Ib) R2Ri O O
(Ia) s n O O
\ {Ib) s n where R, and R2, independently of one another, represent hydrogen, substituted or unsubstituted C1-C18-alkyl, preferably C1-Ci,o-alkyl, in particular CI -C6-alkyl, C2-C]Z-alkenyl, preferably C2-C8-alkenyl;, C3-C7-cycloalkyl, preferably cyclopentyl or cyclohexyl, C7-CI5-aralkyl, preferably phenyl-Cl-C4-alkyl, C6-C10-aryl, preferably phenyl or naphth.yl, Ct-C18-alkyloxy, preferably Le A 33 106-Foreign Countries C1-Clo-alkyloxy, such as methoxy, ethoxy, n-propoxy or isopropoxy, or C2-Clg-alkyloxy esters, and R3 and R4, independently of one another, represent hydrogen, but not both simultaneously, or at least singly siul:phonate-substituted C1-C1%-alkyl, preferably Cl-Clo-alkyl, in particular CI-C6-alkyl, C2-C12-alkenyl, preferably C2-C8-alkenyl, C3-C7-cycloalkyl, preferably cyclopentyl or cyclohexyl, C7-Ci5-aralkyl, preferably phenyl-CI-C4-allcyl, C6-Clo-aryl, preferably phenyl or naphthyl, C1-C18-alkyloxy, preferably Ci-Cto-alkyloxy, such as methoxy, ethoxy, n-propoxy or isopropoxy, or C2-C1 g-alkyloxy esters, and n represents a number from 2 to 10,000, preferably from 5 to 5000.
Particular preference is given to cationic or neutral polyalkylenedioxythiophenes of the formulae (Ia-1) and/or (lb-1) (Ia-1) S
n O O
(Ib-1) s n where R3 is as defined above, and n represents an integer from 2 to 10,000, preferably from 5 to 5000.
The polyanions comprise anions of polymeric carboxylic acids, for example polyacrylic acids, polymethacrylic acids or polymaleic acids, and of polymeric sulphonic acids, such as polystyrenesulphonic acids and polyvinylsulphonic acids.
These polycarboxylic and polysulphonic acids may also be copolymers of Le A 33 106-Foreign Countries vinylcarboxylic and vinylsulphonic acids with other polymerizable monomers, such as acrylates and styrene.
The gegenion particularly preferably comprises tlie anion of polystyrenesuiphonic acid (PSA).
The molecular weight of the polyacids supplying the polyanions is preferably from 1000 to 2,000,000, particularly preferably from 2000'ao 500,000. The polyacids or their alkali metal salts are available commercially, e.g. polystyrenesulphonic acids and polyacrylic acids, or else can be prepared by known processes (see, for example, Houben Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Vol. E 20 Malcromolekulare Stoffe, Part 2, (1987), pp. 1141 et seq.).
Instead of the free polyacids required for forming the dispersions of polyalkylenedioxythiophenes and polyanions, it is also possible to use mixtures of alkali metal salts of the polyacids and appropriate amounts of monoacids.
In the case of formula (Ib-1) the polyalkylenedioxythiophenes carry positive and negative charge in the structural unit.
The preparation of the polyalkylenedioxythiopheries is described, for example, in EP-A 0 440 957 (= US-A 5 300 575). The polyalkylenedioxythiophenes are prepared by oxidative polymerization. This gives them positive charges which are not represented in the formulae, since their number and position cannot be established beyond question.
An advantage of the novel process is that open, electrically conductive structures can be produced on printed circuit boards with quality comparable to that of the known copper conductor tracks, but in a small number of' steps which are easy to carry out.
All that is needed for production is an ink-jet printer with an appropriately prepared printer cartridge and a computer to control the printer. The desired conductor track structure can be designed on the computer screen and immediately printed out on a suitable substrate.
The water-dispersible polyalkylenedioxythiophene is not water-soluble and, even under normal conditions, forms a conductive structure which has long-term stability.
I'.
Le A 33 106-Foreign Countries Fitwes and examples The figures show:
Fig.l Bayer cross symbols printed on paper using poly-(3,4-ethylenedioxy-thiophene) (PEDT) and polystyrene sulphonate (PSS).
Fig. 2 Conductor track system printed onto paper using PEDT/PSS.
Fig. 3 Conductor track system printed onto polyethylene terephthalate (PET) film using PEDT/PSS.
Example 1 Preparation of the 3,4-polyalkylenedioxythiophene dispersion g of free polystyrenesulphonic acid (Mn about 40,000), 21.4 g of potassium 15 peroxodisulphate and 50 mg of iron(III) sulphate were stirred in 2000 ml of water.
8.0 g of 3,4-ethylenedioxythiophene were added, with stirring. The dispersion was stirred for 24 h at room temperature. 100 g of anion exchanger (commercially available product Lewatit MP 62 from Bayer AG) and 100 g of cation exchanger (commercially available product Lewatit S 100 from Bayer AG) were added, both in 20 moistened form, followed by stirring for 8 hours.
The ion exchangers were removed by filtering tl:n-ough a polyacrylonitrile fabric of pore size 50 m. This gave a ready-to-use dispersion of 3,4-polyalkylenedioxy-thiophenes (PEDT) with polystyrenesulphonate (PSS) as gegenanion (see Il) with a solids content of about 1.2% by weight.
The dispersion could easily be filtered through a 0.45 m filter and was used after filtration to prepare the colours for the ink-jet printer.
a o a o O o s S
s H s 0 o c) o Le A 33 106-Foreign Countries Tn m SO~ S 3 H
Example 2 The aqueous dispersion of the PEDT/PSS as in (I][) from Example 1 was introduced into an empty ink-jet printer cartridge for an HP-]Desk-Jet PLUS (Hewlett-Packard) ink-jet printer. The cartridge had been cut open and thoroughly cleaned and after the PEDT/PSS dispersion as in (II) had been introduced it was sealed again using a polyethylene hot-melt adhesive from Henkel. An ink-jet printer cartridge prepared in this way was inserted into the HP-Desk-Jet PLI;rS ink j et printer and served as a reservoir for the printing liquid for applying the PEDT/PSS dispersion using the printer under computer control. The pattern to be printed was designed on the computer using a conventional software progran;i. An image of three Bayer cross symbols placed under one another (Fig. 1) was selected. This image was printed onto paper using computer control. The result was a;print on paper of the three Bayer cross symbols placed one underneath the other and composed of conductive PEDT/PSS, which had a blue intrinsic colour.
Example 3 The procedure followed was similar to that of Exzunple 2, except that a polyethylene terephthalic (PET) film of 0.1 mm thickness was used instead of the paper and printed with the Bayer cross symbols.
Example 4 The procedure followed was similar to that of Example 2, except that the pattern was a section for a printed circuit board designed using EAGLE layout software (Fig. 2).
This conductor track pattern was printed onto paper using PEDT/PSS as in Example 3.
Le A 33 106-Foreign Countries Example 5 In a manner similar to that of Example 4, the conductor track system of Fig. 3 was printed onto a PET film of 0,1 nun thickness. The electrical conductivity of the printed conductor tracks was demonstrated using a continuity tester.
Claims (10)
1. A process for preparing an open electrically conductive structure on a substrate, which comprises printing the open electrically conductive structure onto the substrate using an ink-jet printer or X,Y plotter in the cartridge of which there is an aqueous dispersion of a polyalkylenedioxythiophene having a suitable polyanion as a counter anion.
2. The process according to claim 1, wherein the polyalkylenedioxythiophene is cationically charged and is composed of a structural unit of the formula (I):
in which:
A1 and A2, independently of one another, represent a substituted or unsubstituted C1-C4-alkyl, or together form a substituted or unsubstituted C1-C4-alkylene group, and n represents an integer from 2 to 10,000, in the presence of the polyanion.
in which:
A1 and A2, independently of one another, represent a substituted or unsubstituted C1-C4-alkyl, or together form a substituted or unsubstituted C1-C4-alkylene group, and n represents an integer from 2 to 10,000, in the presence of the polyanion.
3. The process according to claim 2, wherein n represents an integer of from 5 to 5000.
4. The process according to claim 1, wherein the cationic polyalkylenedioxythiophene is composed of a structural unit of the formula (Ia) or (Ib):
where:
R1 and R2, independently of one another, represent hydrogen, substituted or unsubstituted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy, or C2-C18-alkyloxy esters, and R3 and R4, independently of one another, represent hydrogen, or at least singly sulphonate-substiuted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy, or C2-C18-alkyloxy ester, provided that R3 and R4 do not simultaneously represent hydrogen, and n represents a number from 2 to 10,000.
where:
R1 and R2, independently of one another, represent hydrogen, substituted or unsubstituted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy, or C2-C18-alkyloxy esters, and R3 and R4, independently of one another, represent hydrogen, or at least singly sulphonate-substiuted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy, or C2-C18-alkyloxy ester, provided that R3 and R4 do not simultaneously represent hydrogen, and n represents a number from 2 to 10,000.
5. The process according to claim 4, wherein the structural unit has the formula (Ia) where R1 and R2, independently of one another, represent hydrogen, C1-C10-alkyl, C2-C8-alkenyl, cyclopentyl, cyclohexyl, phenyl-C1-C4-alkyl, phenyl, naphthyl, or C1-C10-alkyloxy; and n represents a number from 5 to 5000.
6. The process according to claim 4, wherein the structural unit has the formula (Ib) where R3 and R4, independently of one another, represent hydrogen or at least singly sulfonate-substituted C1-C10-alkyl, C2-C8-alkenyl, cyclopentyl, cyclohexyl, phenyl-C1-C4-alkyl, phenyl, naphthyl or C1-C10-alkoxy, provided that R3 and R4 do not simultaneously represent hydrogen; and n represents a number from 5 to 5000.
7. The process according to claim 1, wherein the cationic polyalkylenedioxythiophene is composed of at least one of structural units of the formulae (Ia-1) and (Ib-1) where:
R3 is hydrogen or at least singly sulfone-substituted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy or C2-C18-alkyloxy ester, and n represents an integer from 2 to 10,000, and the polyanion comprises an anion of a polymeric carboxylic acid or a polymeric sulphonic acid.
R3 is hydrogen or at least singly sulfone-substituted C1-C18-alkyl, C2-C12-alkenyl, C3-C7-cycloalkyl, C7-C15-aralkyl, C6-C10-aryl, C1-C18-alkyloxy or C2-C18-alkyloxy ester, and n represents an integer from 2 to 10,000, and the polyanion comprises an anion of a polymeric carboxylic acid or a polymeric sulphonic acid.
8. The process according to claim 7, wherein the cationic polyalkylenedioxythiophene is composed of the structural unit of the formula (Ia-1).
9. The process according to claim 7, wherein the cationic polyalkylenedioxythiophene is composed of the structural unit of the formula (Ib-1).
10. The process according to any one of claims 7 to 9, wherein n is an integer from 5 to 5000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19841804A DE19841804A1 (en) | 1998-09-12 | 1998-09-12 | Preparation of an electrically conducting structure on a substrate for computer-controlled ink jet printing involves using an aqueous dispersion of polyalkylene dioxythiophenes with a polyanion as counter ion |
| DE19841804.3 | 1998-09-12 | ||
| PCT/EP1999/006385 WO2000016595A1 (en) | 1998-09-12 | 1999-08-31 | Printed conductors made of polyalkylene dioxythiophene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2343444A1 CA2343444A1 (en) | 2000-03-23 |
| CA2343444C true CA2343444C (en) | 2009-04-07 |
Family
ID=7880756
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002343444A Expired - Fee Related CA2343444C (en) | 1998-09-12 | 1999-08-31 | Printed conductors made of polyalkylene dioxythiophene |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1112673B1 (en) |
| JP (2) | JP5088989B2 (en) |
| KR (1) | KR100594550B1 (en) |
| AT (1) | ATE287199T1 (en) |
| CA (1) | CA2343444C (en) |
| DE (2) | DE19841804A1 (en) |
| ES (1) | ES2237148T3 (en) |
| MY (1) | MY129793A (en) |
| TW (1) | TW434574B (en) |
| WO (1) | WO2000016595A1 (en) |
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| EP1780233B1 (en) * | 2000-06-26 | 2009-06-17 | Agfa-Gevaert | Redispersible latex comprising a polythiophene |
| DE10058116A1 (en) * | 2000-11-22 | 2002-05-23 | Bayer Ag | Production of polythiophene for use in conductive and antistatic coatings involves reacting 3,4-alkylenedioxythiophene with organic sulfonic acid, oxidising agent and phase transfer catalyst in anhydrous solvent |
| DE10103416A1 (en) | 2001-01-26 | 2002-08-01 | Bayer Ag | Electroluminescent devices |
| US6692662B2 (en) * | 2001-02-16 | 2004-02-17 | Elecon, Inc. | Compositions produced by solvent exchange methods and uses thereof |
| US7094865B2 (en) * | 2001-03-29 | 2006-08-22 | Agfa Gevaert | Thiophenes and polymers derived therefrom |
| FR2825228B1 (en) | 2001-05-25 | 2003-09-19 | Framatome Connectors Int | METHOD FOR MANUFACTURING A PRINTED CIRCUIT AND PLANAR ANTENNA MANUFACTURED THEREWITH |
| CN100503683C (en) * | 2001-06-22 | 2009-06-24 | 爱克发-格法特公司 | Flexographic ink containing polymer or copolymer of 3,4-dialkoxythiophene |
| DE10145750A1 (en) | 2001-09-17 | 2003-04-24 | Infineon Technologies Ag | Process for producing a metal layer on a carrier body and carrier body with a metal layer |
| EP1323764A1 (en) * | 2001-12-20 | 2003-07-02 | Agfa-Gevaert | Process for preparing an aqueous solution or dispersion of a polythiophene or thiophene copolymer |
| US7122130B2 (en) | 2001-12-04 | 2006-10-17 | Agfa Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
| EP1453877B1 (en) * | 2001-12-04 | 2007-03-28 | Agfa-Gevaert | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
| EP1780232A1 (en) | 2001-12-04 | 2007-05-02 | Agfa-Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent. |
| US7105620B2 (en) * | 2001-12-20 | 2006-09-12 | Agfa Gevaert | 3,4-alkylenedioxy-thiophene copolymers |
| EP1323763A1 (en) * | 2001-12-20 | 2003-07-02 | Agfa-Gevaert | 3,4-Alkylenedioxy-thiophene copolymers |
| US6995223B2 (en) * | 2001-12-20 | 2006-02-07 | Agfa-Gevaert | 3,4-alkylenedioxy-thiophene copolymers |
| DE10164260A1 (en) * | 2001-12-27 | 2003-07-17 | Bayer Ag | Process for the production of undoped, neutral polyethylene dioxythiophene, and corresponding polyethylene dioxythiophenes |
| US7125479B2 (en) | 2002-07-11 | 2006-10-24 | The University Of Connecticut | Polymeric compositions comprising thieno[3,4-b]thiophene, method of making, and use thereof |
| EP1551847B1 (en) * | 2002-10-07 | 2006-07-05 | Agfa-Gevaert | 3,4-alkylenedioxythiophene compounds and polymers thereof |
| US7321012B2 (en) | 2003-02-28 | 2008-01-22 | The University Of Connecticut | Method of crosslinking intrinsically conductive polymers or intrinsically conductive polymer precursors and the articles obtained therefrom |
| US7105237B2 (en) * | 2003-10-01 | 2006-09-12 | The University Of Connecticut | Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof |
| DE102004006583A1 (en) * | 2004-02-10 | 2005-09-01 | H.C. Starck Gmbh | Polythiophene formulations for improving organic light-emitting diodes |
| US8178629B2 (en) | 2005-01-31 | 2012-05-15 | University Of Connecticut | Conjugated polymer fiber, preparation and use thereof |
| US7746533B2 (en) | 2005-07-11 | 2010-06-29 | The University Of Connecticut | Electrochromic devices utilizing very low band gap conjugated counter electrodes: preparation and use |
| WO2007008977A1 (en) | 2005-07-11 | 2007-01-18 | University Of Connecticut | Polymers of thieno[3,4-b]furan, method of making, and use thereof |
| DE102006002798A1 (en) | 2006-01-20 | 2007-08-09 | H. C. Starck Gmbh & Co. Kg | Polythiophene formulations for improving organic light-emitting diodes |
| US8227567B2 (en) | 2006-02-16 | 2012-07-24 | University Of Connecticut | Conductive polymers from precursor polymers, method of making, and use thereof |
| DE102007027473A1 (en) | 2007-06-14 | 2008-12-18 | Manroland Ag | Technically produced functional components |
| DE102007041039A1 (en) * | 2007-08-29 | 2009-03-05 | H.C. Starck Gmbh | Production of conductive coatings by ink jet printing |
| KR101502978B1 (en) | 2007-12-07 | 2015-03-18 | 아그파-게바에르트 엔.브이. | Layer configuration with improved stability to sunlight exposure |
| US8168671B2 (en) | 2008-06-26 | 2012-05-01 | The University Of Connecticut | Synthesis of thieno[3,4-b]thiophene, thieno[3,4-b]furan, related compounds and their derivatives and use thereof |
| JP5991597B2 (en) * | 2011-08-31 | 2016-09-14 | ナガセケムテックス株式会社 | Plating product manufacturing method and plating product |
| JP6146096B2 (en) * | 2012-07-03 | 2017-06-14 | 東ソー株式会社 | Thiophene compound, water-soluble conductive polymer and aqueous solution thereof, and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4566186A (en) * | 1984-06-29 | 1986-01-28 | Tektronix, Inc. | Multilayer interconnect circuitry using photoimageable dielectric |
| DE59010247D1 (en) * | 1990-02-08 | 1996-05-02 | Bayer Ag | New polythiophene dispersions, their preparation and their use |
| JPH06234290A (en) * | 1993-02-12 | 1994-08-23 | Toppan Printing Co Ltd | Card, its production, and card identification method |
| EP0615257B1 (en) * | 1993-03-09 | 1999-06-02 | Koninklijke Philips Electronics N.V. | Method of manufactoring a laminated structure of a metal layer on a conductive polymer layer |
| ATE171560T1 (en) * | 1993-03-09 | 1998-10-15 | Koninkl Philips Electronics Nv | PROCESS FOR PRODUCING A PATTERN OF AN ELECTRICALLY CONDUCTIVE POLYMER ON A SUBSTRATE SURFACE AND METALIZATION OF SUCH A PATTERN |
| JP2725591B2 (en) * | 1994-03-10 | 1998-03-11 | 日本電気株式会社 | Field-effect transistor |
| DE19524132A1 (en) * | 1995-07-03 | 1997-01-09 | Bayer Ag | Scratch-resistant conductive coatings |
| US6087196A (en) * | 1998-01-30 | 2000-07-11 | The Trustees Of Princeton University | Fabrication of organic semiconductor devices using ink jet printing |
-
1998
- 1998-09-12 DE DE19841804A patent/DE19841804A1/en not_active Withdrawn
-
1999
- 1999-08-31 KR KR1020017003112A patent/KR100594550B1/en not_active IP Right Cessation
- 1999-08-31 EP EP99944561A patent/EP1112673B1/en not_active Expired - Lifetime
- 1999-08-31 ES ES99944561T patent/ES2237148T3/en not_active Expired - Lifetime
- 1999-08-31 CA CA002343444A patent/CA2343444C/en not_active Expired - Fee Related
- 1999-08-31 AT AT99944561T patent/ATE287199T1/en active
- 1999-08-31 WO PCT/EP1999/006385 patent/WO2000016595A1/en active IP Right Grant
- 1999-08-31 DE DE59911451T patent/DE59911451D1/en not_active Expired - Lifetime
- 1999-08-31 JP JP2000571008A patent/JP5088989B2/en not_active Expired - Fee Related
- 1999-09-09 MY MYPI99003914A patent/MY129793A/en unknown
- 1999-09-10 TW TW088115601A patent/TW434574B/en not_active IP Right Cessation
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2010
- 2010-12-10 JP JP2010275906A patent/JP2011068909A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP5088989B2 (en) | 2012-12-05 |
| ES2237148T3 (en) | 2005-07-16 |
| TW434574B (en) | 2001-05-16 |
| DE19841804A1 (en) | 2000-03-16 |
| ATE287199T1 (en) | 2005-01-15 |
| DE59911451D1 (en) | 2005-02-17 |
| EP1112673A1 (en) | 2001-07-04 |
| KR20010075030A (en) | 2001-08-09 |
| WO2000016595A1 (en) | 2000-03-23 |
| EP1112673B1 (en) | 2005-01-12 |
| KR100594550B1 (en) | 2006-07-03 |
| JP2002525390A (en) | 2002-08-13 |
| MY129793A (en) | 2007-04-30 |
| CA2343444A1 (en) | 2000-03-23 |
| JP2011068909A (en) | 2011-04-07 |
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