EP0044844B1 - Elektroempfindliches aufzeichnungspapier - Google Patents

Elektroempfindliches aufzeichnungspapier Download PDF

Info

Publication number
EP0044844B1
EP0044844B1 EP81900302A EP81900302A EP0044844B1 EP 0044844 B1 EP0044844 B1 EP 0044844B1 EP 81900302 A EP81900302 A EP 81900302A EP 81900302 A EP81900302 A EP 81900302A EP 0044844 B1 EP0044844 B1 EP 0044844B1
Authority
EP
European Patent Office
Prior art keywords
layer
paper according
electrosensitive
paper
bismuth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81900302A
Other languages
English (en)
French (fr)
Other versions
EP0044844A1 (de
Inventor
Claude Raymond Riou
Christian Henri Gabriel Nodin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aussedat Rey SA
KDP Keller Dorian Papiers SA
Original Assignee
Aussedat Rey SA
KDP Keller Dorian Papiers SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aussedat Rey SA, KDP Keller Dorian Papiers SA filed Critical Aussedat Rey SA
Priority to AT81900302T priority Critical patent/ATE7584T1/de
Publication of EP0044844A1 publication Critical patent/EP0044844A1/de
Application granted granted Critical
Publication of EP0044844B1 publication Critical patent/EP0044844B1/de
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • the present invention relates to a chemical system capable of irreversibly changing color when subjected to the passage of an electrical signal.
  • the invention also relates to the electro-sensitive recording paper corresponding to this chemical system.
  • electrographic recording means an electrical recording by the direct route by means of an electrode in the form of a stylus.
  • Electrolytic papers are also known in which a chromogenic chemical reaction occurs during the passage of the current corresponding to the electrical signal. Such electrolytic papers can operate at a relatively low voltage, but the intensity of the current must be high and the degree of humidity must remain high, which leads to storage constraints. In addition, the above two types of paper have a limited recording speed.
  • Dielectric papers are also known in which an electrostatic process takes place.
  • the implementation of these papers is complicated and the tension must be high.
  • the machines which use them are more bulky and expensive.
  • thermographic in the sense that a colored trace results from the application of heat due to the passage of an electric current to metallic chlorides included in an electro-sensitive layer.
  • the present invention aims to remedy the drawbacks of the prior art by proposing a new recording paper involving the complexation of a bismuth or antimony halide with a divalent metal halide in order to form a more reactive stable species.
  • a permanent trace is formed in an electrographic recording paper by the local injection of electrons using at least one marking electrode brought to a negative potential, in an electro-sensitive layer.
  • the grain size of the abovementioned oxides may be chosen between 0.1 and 5 ⁇ , and preferably around 0.3 ⁇ .
  • the electro-sensitive layer described above must naturally have sufficient electrical conductivity to allow the passage of an electric current between the marking electrode and the layer which is a good conductor of electricity.
  • a satisfactory electrical conductivity can be chosen between 1,000 and 10,000 ohms / cm 2 .
  • the grain size can be chosen there between 0.1 and 3 ⁇ m, and preferably around 0.3 ⁇ m.
  • the electro-sensitive layer it has been discovered that it is necessary to establish a ratio, by dry weight, of approximately 0.5 to 3/1, preferably approximately 1/1, as regards the ratio of the oxide (or oxides when used as a mixture) to the layer binder.
  • the various constituents are passed through a ball mill, the mixture of bismuth (or antimony) halide and a divalent metal halide being however dissolved beforehand ethanol; the mixture leaving the ball mill is coated on the good electrically conductive layer, which may consist, as indicated above, in an aluminum support, at a rate of approximately 7 to 25 g / m 2 . Drying is then carried out.
  • the implementation of the paper according to the invention consists in applying to the stylus electrode a certain current whose voltage and intensity correspond to the signal to be reproduced.
  • the end of the electrode is brought into substantial contact with the upper face of the electro-sensitive layer according to the invention, which is coated on the layer which conducts electricity well, which is itself deposited on a substrate (paper).
  • paper a substrate
  • the threshold of response to an electrical pulse is as low as possible, and that the system works for applied voltages also as low as possible, as will easily understand the tradesman.
  • currently known systems have a pulse threshold of the order of 1 ms and operate at voltages which are at least 50 V and often higher.
  • the pulse threshold is lowered to at least 100 ⁇ s, and one works under a voltage which can be of the order of 10 V and an intensity between 75 and 200 ⁇ A.

Landscapes

  • Paper (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (14)

1. Elektrografisches Registrierpapier, bestehend aus einem unteren Substrat, auf dem eine elektrisch gut leitende Schicht aufgebracht ist, die wiederum mit einer elektrisch empfindlichen oberen Schicht versehen ist, wobei die elektrisch leitende Schicht fähig ist, positive lonen zu liefern, um einen in der elektrisch empfindlichen Schicht auftretenden Mangel an positiven Ladungen auszugleichen, und die Leitfähigkeit der elektrisch empfindlichen Schicht ausreicht, um den Durchgang von Strom zwischen einer im wesentlichen auf ihrer oberen Fläche angebrachten Elektrodenspitze und der elektrisch gut leitenden Schicht zu ermöglichen, dadurch gekennzeichnet, daß die obere, elektrisch empfindliche Schicht ein Wismut- oder Antimonhalogenid und ein Halogenid eines bivalenten Metalles enthält, welches das Wismut- oder Antimonhalogenid komplexieren kann.
. 2. Papier nach Anspruch 1, dadurch gekennzeichnet, daß das Wismut- oder Antimonhalogenid aus BiCl3 oder SbCl3 besteht und daß gegebenenfalls eine geringe Menge Salzsäure zum Ausgleich der fehlenden Reinheit des Wismutsalzes beigefügt ist.
3. Papier nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Halogenid des divalenten Metalles ausgewählt ist aus den Halogeniden von Magnesium, Calcium, Barium, Strontium, Mangan, Eisen, Kobalt oder Nickel, insbesondere den Chloriden.
4. Papier nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die elektrisch empfindliche Schicht neben dem Wismut oder Antimonhalogenid und dem Halogenid des divalenten Metalles,
- ein oder mehrere Halbleiteroxide in Pigmentform,
- ein polymeres Bindemittel,
- und ein Plastifizierungsmittel enthält.
5. Papier nach Anspruch 4, dadurch gekennzeichnet, daß das Oxid ausgewählt ist aus TiO2, SnO2, ZnO, A1203 und Kaolin und Mischungen derselben, und daß dieses Oxid gegebenenfalls oberflächenbehandelt ist.
6. Papier nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß das Bindemittel ausgewählt ist aus Polyvinyl-, Polyacrylbindern und halogenierten Polymeren.
7. Papier nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß das Plastifizierungsmittel ausgewählt ist aus Phthalaten und Adipaten.
8. Papier nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Trockengewichtsverhältnis von Oxid zu Bindemittel in der elektrisch empfindlichen Schicht zwischen 0,5 und 3/1, vorzugsweise nahe 1/1, liegt.
9. Papier nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die elektrisch gut leitende Schicht aus einer gegengeklebten Aluminiumschicht besteht.
10. Papier nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die elektrisch gut leitende Schicht aus Aluminiumpulver und aus Kohlenstoffpulver in einem Bindemittel besteht.
11. Papier nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die elektrisch empfindliche Schicht auf der elektrisch gut leitenden Schicht in einer Menge von etwa 7 bis 25 g/m2 vor dem Trocknen aufgestrichen ist.
12. Elektrisch empfindliche Zusammensetzung für elektrografisches Registrierpapier, wie in irgendeinem der Ansprüche 1 bis 8 definiert.
13. Papier nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die elektrisch empfindliche Schicht insbesondere:
― TiO2, BiCl3 und MgCl2, 6 H2O, oder
― TiO2, BiCl3 und NiCl2, 6 H2O, oder
― TiO2, BiCl3 und MnCl2, 4 H2O, oder
― TiO2, BiCl3 und CaCl2, oder
― TiO2/Kaolin, BiCl3 und CaCl2 enthält.
14. Elektrisch empfindliche Zusammensetzung für elektrografisches Registrierpapier, wie in Anspruch 13 definiert.
EP81900302A 1980-01-30 1981-01-30 Elektroempfindliches aufzeichnungspapier Expired EP0044844B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81900302T ATE7584T1 (de) 1980-01-30 1981-01-30 Elektroempfindliches aufzeichnungspapier.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8002315A FR2474739A1 (fr) 1980-01-30 1980-01-30 Systeme et papier d'enregistrement electrosensible
FR8002315 1980-01-30

Publications (2)

Publication Number Publication Date
EP0044844A1 EP0044844A1 (de) 1982-02-03
EP0044844B1 true EP0044844B1 (de) 1984-05-23

Family

ID=9238149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81900302A Expired EP0044844B1 (de) 1980-01-30 1981-01-30 Elektroempfindliches aufzeichnungspapier

Country Status (5)

Country Link
EP (1) EP0044844B1 (de)
JP (1) JPS57500234A (de)
DE (1) DE3163695D1 (de)
FR (1) FR2474739A1 (de)
WO (1) WO1981002139A1 (de)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916510B1 (de) * 1970-12-14 1974-04-23

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2281013A (en) * 1939-02-25 1942-04-28 Radio Inventions Inc Electrolytic recording paper
US3490941A (en) * 1966-03-29 1970-01-20 Philips Corp Impregnated paper for reproduction processes
FR2034352A1 (en) * 1969-03-20 1970-12-11 Muirhead Ltd Electrolytic recording process
JPS5133742B2 (de) * 1972-03-24 1976-09-21

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916510B1 (de) * 1970-12-14 1974-04-23

Also Published As

Publication number Publication date
DE3163695D1 (en) 1984-07-05
WO1981002139A1 (fr) 1981-08-06
FR2474739A1 (fr) 1981-07-31
JPS57500234A (de) 1982-02-12
EP0044844A1 (de) 1982-02-03

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