DE202016003395U1 - light-curing polymer electrode - Google Patents

light-curing polymer electrode Download PDF

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DE202016003395U1
DE202016003395U1 DE202016003395.7U DE202016003395U DE202016003395U1 DE 202016003395 U1 DE202016003395 U1 DE 202016003395U1 DE 202016003395 U DE202016003395 U DE 202016003395U DE 202016003395 U1 DE202016003395 U1 DE 202016003395U1
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/268—Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/296—Bioelectric electrodes therefor specially adapted for particular uses for electromyography [EMG]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • A61B2562/125—Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/251—Means for maintaining electrode contact with the body
    • A61B5/257—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes
    • A61B5/259—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes using conductive adhesive means, e.g. gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate

Abstract

Zu schützen ist ein lichthärtendes, leitfähiges Polymer, gekennzeichnet durch eine Mischung aus PEDOT und Methylmetacrylat (in dessen reiner Form oder einer darauf basierenden Mischung wie z. B. Zahnzement), die im polymerisierten Zustand fest ist und leitfähig haftet.To protect is a light-curing, conductive polymer, characterized by a mixture of PEDOT and methyl methacrylate (in its pure form or a mixture based thereon, such as dental cement), which is solid in the polymerized state and conductive adheres.

Description

1) Welches technische Problem wird durch die Erfindung gelöst?1) What technical problem is solved by the invention?

Eine leitfähige, langfristig stabile, nicht polarisierende und nicht flüssige Haftung auf biologischen Oberflächen wie Haut u. a. zur Messung von EEG, EKG und anderen Biosignalen. Ferner hervorragend geeignet um leitfähige Strukturen im 3D Druck Verfahren herzustellen.A conductive, long-term stable, non-polarizing and non-liquid adhesion on biological surfaces such as skin u. a. for measuring EEG, ECG and other biosignals. Furthermore excellently suited to produce conductive structures in the 3D printing process.

2) In welcher Weise wurde das Problem bisher gelöst? Stand der Technik.2) In what way has the problem been solved so far? State of the art.

Für EEG Ableitungen als der elektrophysiologischen Messmethode bei der die höchste Leitfähigkeit der Elektroden benötigt wird, werden haftende Elektrolytgele in Kombination mit Silber/Silberchlorid Elektroden eingesetzt. Silber/Silberchloridelektroden in Kombination mit einem Chlorid-haltigen Leitgel sind als einzige nicht polarisierende EEG Elektrode der derzeitige Stand der Technik (Tallgren et al., 2005)( Tallgren et al., 2005 ).For EEG discharges as the electrophysiological measuring method in which the highest conductivity of the electrodes is required, adhesive electrolyte gels are used in combination with silver / silver chloride electrodes. Silver / silver chloride electrodes in combination with a chloride-containing conductive gel are the current state of the art as the only non-polarizing EEG electrode (Tallgren et al., 2005) ( Tallgren et al., 2005 ).

3) Welche Nachteile besitzen die bekannten Lösungen (Kritik des Standes der Technik)?3) What disadvantages do the known solutions (criticism of the prior art)?

Ein Schwachpunkt dieses Systems ist die fehlende Langzeitstabilität der Messung durch Austrocknung des Elektrolytgels und mögliche Kurzschlüsse durch verlaufendes Gel, besonders bei der Applikation einer hohen Anzahl von Elektroden. ( Ferree et al., 2001 , Chen et al., 2014 ). Hydrogelelektroden sind relativ großflächig und erlauben daher keine Ableitungen mit einer hohen Anzahl an Elektroden (wie es für medizinische Montagen empfohlen wird) bei Frühgeborenen.A weak point of this system is the lack of long-term stability of the measurement due to drying out of the electrolyte gel and possible short circuits due to running gel, especially when applying a large number of electrodes. ( Ferree et al., 2001 . Chen et al., 2014 ). Hydrogel electrodes are relatively large and therefore do not allow discharges with a high number of electrodes (as recommended for medical mounting) in premature babies.

4) Welche Aufgabe liegt der Erfindung zu Grunde?4) What is the purpose of the invention?

Im Rahmen des vom BMBF geförderten Projektes TENECOR (Telemetric Neonatal CORtex Monitoring) werden schonende Verfahren entwickelt um Langzeit EEGs als Routineuntersuchung für Frühgeborene Kinder durchführen zu können. Ziel ist es dabei langfristig, die Gefahr für häufig auftretende kognitive Spätschäden ( Nosarti et al., 2014 ) diagnostizieren und behandeln zu können. Spätschäden durch den Risikofaktor Frühgeburt stellen einen erheblichen Kostenfaktor für die Krankenkassensysteme dar, da die Inzidenz von Frühgeburten deutlich gestiegen ist, mit anhaltendem Trend ( Howson et al., 2013 ).As part of the BMBF-funded TENECOR project (Telemetric Neonatal CORtex Monitoring), gentle procedures are being developed to perform long-term EEGs as a routine check-up for premature babies. The aim in the long term is to reduce the risk of frequent cognitive late damage ( Nosarti et al., 2014 ) diagnose and treat. Late damage due to the risk factor premature birth represents a considerable cost factor for the health insurance systems, as the incidence of premature births has increased significantly, with a continuing trend ( Howson et al., 2013 ).

5a) Wie wird diese Aufgabe durch die Erfindung gelöst? Beschreibung der Erfindung.5a) How is this problem solved by the invention? Description of the invention.

Die hier vorgestellten Polymerelektroden bieten eine niederohmige, biokompatible und langfristig stabile Hauthaftung in einem Arbeitsgang. Die Anbringung ist einfach, die Materialien sind kostengünstig. Die Flexibilität der Polymerelektroden ermöglicht eine Einbindung in andere Monitoringsysteme, wie z. B. bereits verwendete Hauben zur Befestigung von Beatmungsgeräten etc..The polymer electrodes presented here offer low-resistance, biocompatible and long-term stable skin adhesion in one operation. The attachment is simple, the materials are inexpensive. The flexibility of the polymer electrodes allows integration into other monitoring systems, such. B. already used hoods for attaching ventilators etc.

Beschreibung: Eine durchsichtige, hautfreundliche Folie (Abb. 1a) mit einer Dicke von etwa 200 μm (hier Elastosil von Wacker) wird mit einem medizinisch geprüften, vulkanisierenden Haftsilikon beschichtet, der atmungsaktiv sowie transparent ist und auf der Haut haftet (hier: Silpuran von Wacker, Abb. 1b). Die transparente Silpuran Schicht wird mit einer dünnen Schicht des leitfähigen Polymers bestrichen, so dass die Ränder frei bleiben (Abb. 1c). Das Pflaster mit dem leitfähigen, gelartigen Polymer wird als dünner Film auf die Haut geklebt. Eine Bestrahlung des Polymers durch das Pflaster hindurch führt zur Polymerisation des leitfähigen Polymers und damit zu einem haftenden und zugleich leitfähigen Hautkontakt. Als Bestrahlungsquelle wird eine handelsübliche Blaulichtquelle aus der Zahnarztpraxis genutzt. Das leitfähige Polymer besteht aus einer 1:1 Mischung aus PEDOT (Heraeus) und einem auf Methylmetacrylat basierenden Zahnzement. Die Impedanzmessung ist in Abb. 2 zu sehen. 5 kOhm sind ein hervorragender Wert für herkömmliche EEG Elektroden, der jedoch real selten erreicht wird.Description: A transparent, skin-friendly foil (Fig. 1a) with a thickness of approximately 200 μm (here Elastosil from Wacker) is coated with a medically tested, vulcanizing adhesive silicone, which is breathable as well as transparent and adheres to the skin (here: Silpuran von Wacker, Fig. 1b). The transparent Silpuran layer is coated with a thin layer of the conductive polymer so that the edges remain free (Figure 1c). The patch with the conductive, gel-like polymer is stuck as a thin film on the skin. Irradiation of the polymer through the patch leads to the polymerization of the conductive polymer and thus to an adhesive and at the same time conductive skin contact. The radiation source used is a commercially available blue light source from the dental practice. The conductive polymer consists of a 1: 1 mixture of PEDOT (Heraeus) and a methyl methacrylate-based dental cement. The impedance measurement is shown in Fig. 2. 5 kohms are an excellent value for conventional EEG electrodes, but rarely achieved.

5b) Worin ist das wesentliche Neue der erfindungsgemäßen Lösung zu sehen?5b) What is the essential new feature of the solution according to the invention?

Neu ist, dass die Pedot-Polymer-Elektrode ohne Elektrolyt auskommt, d. h. die elektrophysiologische Ableitung trocken erfolgt, nicht jedoch kapazitiv. Daher können auch Potentiale im unteren Frequenzbereich (delta Band) aufgezeichnet werden. Neu ist zudem, dass eine Elektrode aus der Tube, flexibel applizierbar ist und innerhalb weniger Sekunden mit hoher Präzision ausgehärtet werden kann durch eine LED im Blaulichtbereich. Die Elektrode besteht aus einer Mischung von Pedot Pss und lichthärtenden Methacrylaten, wie sie z. B. in Zahnzement verwendet werden. Die Polymerelektrode ist nicht polarisierbar und daher geeignet zur Messung von full band EEGs (DC).What is new is that the Pedot polymer electrode does not require electrolyte, d. H. the electrophysiological discharge is dry, but not capacitive. Therefore, potentials in the lower frequency range (delta band) can also be recorded. Another new feature is that an electrode from the tube can be applied flexibly and cured within a few seconds with high precision by means of an LED in the blue light range. The electrode consists of a mixture of Pedot Pss and light-curing methacrylates, such as. B. be used in dental cement. The polymer electrode is not polarizable and therefore suitable for measuring full band EEGs (DC).

6) Welche Vorteile werden durch die Erfindung erzielt?6) What advantages are achieved by the invention?

Die Erfindung ermöglicht langzeitstabile Biosignalmessungen (EEG-, EKG- und EMG) auch während der Bewegung durch die mechanisch und elektrisch stabile Verbindung zur Haut. Die Applikation ist einfach, schnell und kostengünstig. Die Flexibilität bezüglich Auftragung und Kombination mit anderen Materialien bzw. Messystemen erlaubt Biosignalmessungen unter schwierigen Bedingungen (Frühgeborene Kinder, Senioren, in der Notfalldiagnostik etc.).The invention enables long-term stable biosignal measurements (EEG, ECG and EMG) even during movement through the mechanically and electrically stable connection to the skin. The application is simple, fast and inexpensive. The flexibility in terms of application and combination with other materials or measuring systems allows Biosignalmessungen under difficult conditions (premature children, seniors, in emergency diagnostics, etc.).

7) Welche Vorteile hat das System in wirtschaftlicher Hinsicht? 7) What are the advantages of the system in economic terms?

Die Anschaffung und Reinigung spezieller Silberelektroden entfällt durch den Einsatz der Pedot-Polymer Elektroden. Die Rohstoffe sind preiswert und die Härtung kann mit einer handelsüblichen Blaulicht LED erfolgen. Des Weiteren ergeben sich vielfältige Anwendungsmöglichkeiten im Bereich 3 D Druck von leitfähigen Strukturen.The purchase and cleaning of special silver electrodes is eliminated by the use of Pedot-Polymer electrodes. The raw materials are inexpensive and the curing can be done with a commercially available blue light LED. Furthermore, there are many possible applications in the field of 3D printing of conductive structures.

Anlagen: ImpedanzmessungEquipment: Impedance measurement

Literatur:Literature:

  • Chen et al. ”Soft, Comfortable Polymer Dry Electrodes for High Quality ECG and EEG Recording.” Sensors 14(2014): 23758–23780 . Chen et al. "Soft, Comfortable Polymer Dry Electrodes for High Quality ECG and EEG Recording." Sensors 14 (2014): 23758-23780 ,
  • Ferree, et al. ”Scalp electrode impedance, infection risk, and EEG data quality” Clinical Neurophysiology 112(2001): 536–544 . Ferree, et al. "Scalp electrode impedance, infection risk, and EEG data quality" Clinical Neurophysiology 112 (2001): 536-544 ,
  • Howson et al. ”Born Too Soon: Preterm birth matters” Reproductive Health 10(2013): S1Howson et al. "Born Too Soon: Preterm birth matters" Reproductive Health 10 (2013): S1
  • Nosarti et al., ”Preterm birth and structural brain alterations in early adulthood” Neorolmage: Clinical 6(2014): 180–191 . Nosarti et al., "Preterm birth and structural brain alterations in early adulthood" Neorolmage: Clinical 6 (2014): 180-191 ,

Reference ListReference List

  • 1. Tallgren, P., Vanhatalo, S., Kaila, K., and Voipio, J. (2005). Evaluation of commercially available electrodes and gels for recording of slow EEG potentials. Clinical Neurophysiology 116, 799–806 .1. Tallgren, P., Vanhatalo, S., Kaila, K., and Voipio, J. (2005). Evaluation of available electrodes and gels for recording of slow EEG potentials. Clinical Neurophysiology 116, 799-806 ,

ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Zitierte Nicht-PatentliteraturCited non-patent literature

  • Tallgren et al., 2005 [0002] Tallgren et al., 2005 [0002]
  • Ferree et al., 2001 [0003] Ferree et al., 2001 [0003]
  • Chen et al., 2014 [0003] Chen et al., 2014 [0003]
  • Nosarti et al., 2014 [0004] Nosarti et al., 2014 [0004]
  • Howson et al., 2013 [0004] Howson et al., 2013 [0004]

Claims (2)

Zu schützen ist ein lichthärtendes, leitfähiges Polymer, gekennzeichnet durch eine Mischung aus PEDOT und Methylmetacrylat (in dessen reiner Form oder einer darauf basierenden Mischung wie z. B. Zahnzement), die im polymerisierten Zustand fest ist und leitfähig haftet.To protect is a light-curing, conductive polymer, characterized by a mixture of PEDOT and methyl methacrylate (in its pure form or a mixture based thereon, such as dental cement), which is solid in the polymerized state and conductive adheres. Zu schützenden ist eine lichthärtende Polymerelektrode, gekennzeichnet durch eine Schichtung von einer transparenten Trägerfolie, darauf einem transparenten, haftenden Silikon und darauf einer dünnen Schicht der unter 1. zu schützenden leitfähigen Polymermischung.To be protected is a light-curing polymer electrode, characterized by a layering of a transparent carrier film, thereon a transparent, adhering silicone and thereon a thin layer of the below 1. protective conductive polymer mixture.
DE202016003395.7U 2016-05-28 2016-05-28 light-curing polymer electrode Active DE202016003395U1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020020741A1 (en) 2018-07-21 2020-01-30 De Camp Nora Light-curing polymer electrode for deriving biosignals

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Chen et al. "Soft, Comfortable Polymer Dry Electrodes for High Quality ECG and EEG Recording." Sensors 14(2014): 23758–23780
Chen et al., 2014
Ferree, et al. "Scalp electrode impedance, infection risk, and EEG data quality" Clinical Neurophysiology 112(2001): 536–544
Howson et al. "Born Too Soon: Preterm birth matters" Reproductive Health 10(2013): S1
Howson et al., 2013
Nosarti et al., "Preterm birth and structural brain alterations in early adulthood" Neorolmage: Clinical 6(2014): 180–191
Nosarti et al., 2014
Tallgren et al., 2005
Tallgren, P., Vanhatalo, S., Kaila, K., and Voipio, J. (2005). Evaluation of commercially available electrodes and gels for recording of slow EEG potentials. Clinical Neurophysiology 116, 799–806

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020020741A1 (en) 2018-07-21 2020-01-30 De Camp Nora Light-curing polymer electrode for deriving biosignals

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