EP0044844B1 - Paper for electro-sensitive recording - Google Patents

Paper for electro-sensitive recording Download PDF

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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
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EP
European Patent Office
Prior art keywords
layer
paper according
electrosensitive
paper
bismuth
Prior art date
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EP81900302A
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German (de)
French (fr)
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EP0044844A1 (en
Inventor
Claude Raymond Riou
Christian Henri Gabriel Nodin
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Aussedat Rey SA
KDP Keller Dorian Papiers SA
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Aussedat Rey SA
KDP Keller Dorian Papiers SA
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Priority to AT81900302T priority Critical patent/ATE7584T1/en
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    • 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.

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

Abstract

New electro-sensitive compositions which can be used for a recording paper. The composition according to the invention contains in particular a Bi or Sb halide and a divalent metal halide chelating the first halide. The recording system can operate on about 10V with a very short pulse.

Description

La présente invention concerne un système chimique capable de changer de coloration d'une manière irréversible lorsqu'il est soumis au passage d'un signal électrique.The present invention relates to a chemical system capable of irreversibly changing color when subjected to the passage of an electrical signal.

L'invention concerne également le papier d'enregistrement électrosensible correspondant à ce système chimique.The invention also relates to the electro-sensitive recording paper corresponding to this chemical system.

Il existe plusieurs types connus de systèmes d'enregistrement électrographique. On entend par « enregistrement électrographique » un enregistrement électrique par voie directe au moyen d'une électrode en forme de stylet.There are several known types of electrographic recording systems. The term “electrographic recording” means an electrical recording by the direct route by means of an electrode in the form of a stylus.

On connaît, par exemple, les papiers à étincelage qui comprennent une base noire masquée par une couche de pigments blancs. Ces pigments sont carbonisés ou volatilisés sous l'action d'une étincelle électrique et un signal électrique peut ainsi être transformé en une trace noire sur le papier. De tels papiers nécessitent le choix d'une tension élevée et dégagent des odeurs gênantes durant l'enregistrement.We know, for example, sparkling papers which include a black base masked by a layer of white pigments. These pigments are charred or volatilized under the action of an electric spark and an electrical signal can thus be transformed into a black trace on the paper. Such papers require the choice of a high tension and give off annoying odors during recording.

On connaît également des papiers électrolytiques au sein desquels se produit une réaction chimique chromogène lors du passage du courant correspondant au signal électrique. De tels papiers électrolytiques peuvent fonctionner sous une tension relativement faible, mais l'intensité du courant doit être importante et le degré d'humidité doit rester élevé, ce qui conduit à des contraintes de stockage. De plus, les deux types précités de papiers ont une vitesse d'enregistrement limitée.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.

On connaît encore les papiers diélectriques dans lesquels se déroule un processus électrostatique. La mise en oeuvre de ces papiers est compliquée et la tension doit être élevée. Les machines qui les utlisent sont de plus encombrantes et coûteuses.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.

On connaît aussi un papier pouvant être qualifié de thermographique, en ce sens qu'une trace colorée résulte de l'application d'une chaleur due au passage d'un courant électrique à des chlorures métalliques inclus à une couche électro-sensible.Also known is a paper that can be qualified as 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.

Il s'agit, notamment, du brevet français 72-47 058 (2177 280) qui décrit un papier électroenregistreur composé d'un substrat (papier), d'une couche bonne conductrice de l'électricité et d'une couche électro- sensible.These include, in particular, French patent 72-47 058 (2177 280) which describes an electro-recording paper composed of a substrate (paper), a layer which is good conductor of electricity and an electro-sensitive layer. .

Ce brevet français décrit l'emploi dans ladite couche électrosensible de l'un ou de l'autre des halogénures capable de provoquer la formation d'une trace par réaction électrochimique ou énergie calorifique correspondant au passage d'un courant à travers les couches du papier d'enregistrement.This French patent describes the use in said electro-sensitive layer of one or the other of the halides capable of causing the formation of a trace by electrochemical reaction or heat energy corresponding to the passage of a current through the layers of the paper. registration.

Ce papier ne peut être considéré comme ayant des propriétés particulièrement remarquables, étant donné que les exemples fournis font appel à l'application d'une tension de 70 volts, c'est-à-dire devant être considérée comme relativement et en tout nettement supérieure à la tension maximale basse que l'on cherche à obtenir.This paper cannot be considered to have particularly remarkable properties, given that the examples provided call for the application of a voltage of 70 volts, that is to say to be considered as relatively and in all clearly greater at the low maximum voltage that one seeks to obtain.

La présente invention vise à remédier aux inconvénients de la technique antérieure en proposant un nouveau papier d'enregistrement faisant intervenir la complexation d'un halogénure de bismuth ou d'antimoine par un halogénure de métal divalent afin de former une espèce stable plus réactive.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.

Cette caractéristique permet d'atteindre des résultats surprenants quant aux seuils du courant électrique utilisé pour générer la trace, de tels seuils étant notablement inférieurs à ceux atteints par les techniques actuellement connues.This characteristic makes it possible to achieve surprising results with regard to the thresholds of the electric current used to generate the trace, such thresholds being notably lower than those reached by currently known techniques.

Selon l'invention, on forme une trace permanente dans un papier d'enregistrement électrographique grâce à l'injection locale d'électrons à l'aide d'au moins une électrode de marquage portée à un potentiel négatif, dans une couche électrosensible.According to the invention, 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.

Le papier d'enregistrement électrographique selon l'invention se compose des couches suivantes, dans cet ordre :

  • 1. une couche de substrat qui peut être, notamment, une couche de papier (épaisseur préférée : 50µ),
  • 2. une couche bonne conductrice de l'électricité, capable de fournir des ions positifs pour compenser un défaut en charges positives dans la couche électrosensible supérieure : on utilisera, notamment, une couche d'aluminium contrecollé, ou le couple aluminium-carbone, en poudre, dans un liant convenable,
  • 3. une couche supérieure électrosensible contenant :
    • - un halogénure de bismuth ou d'antimoine, de manière tout à fait préférée BiCI3 ou SbCl3, en fonction du degré de pureté du sel de bismuth, ces composés pourront, éventuellement, être accompagnés d'une petite quantité d'acide chlorhydrique afin, de manière connue de l'homme de l'art, d'éviter la présence d'oxychlorure susceptible d'inhiber la réaction chromogène,
    • - un halogénure de métal divalent susceptible de complexer l'halogénure de bismuth ou d'antimoine pour donner une espèce stable plus réactive se dissociant lors du passage du courant et effectuant une réaction d'oxydo-réduction avec l'aluminium ; on citera notamment les halogénures de Mg, Ca, Ba, Sr, Mn, Fe, Co, ou Ni, etc..., de plus, la présence d'eau de cristallisation permet de conserver une conductivité ionique constante,
    • - un oxyde semi-conducteur sous forme pigmentaire qui, en plus de son rôle opacifiant, intervient dans les réactions d'oxydo-réduction provoquées par le passage du courant ; on citera notamment les oxydes suivants : Ti02, Sn02, ZnO, AI203, kaolin ; pour améliorer le résultat obtenu, on pourra éventuellement, effectuer un traitement de surface de cet oxyde, d'une manière connue de l'homme de l'art ; on peut utiliser un mélange de plusieurs oxydes de ce type, notamment TiO2/kaolin,
    • - un liant polymérique qui assure la cohésion de la dispersion et, en outre, en fonction de son acidité, modifie le caractère acidobasique du milieu et donc la qualité des inscriptions obtenues ; comme liants préférés, on citera les liants polyvinyliques, polyacryliques et les polymères halogénés,
    • - un plastifiant destiné à assurer la conservation des propriétés mécaniques de la couche ; des plastifiants convenables sont les phtalates, les adipates, etc...
The electrographic recording paper according to the invention consists of the following layers, in this order:
  • 1. a layer of substrate which can be, in particular, a layer of paper (preferred thickness: 50 μ),
  • 2. a layer which is good conductor of electricity, capable of supplying positive ions to compensate for a defect in positive charges in the upper electro-sensitive layer: in particular, a layer of laminated aluminum, or the aluminum-carbon couple, will be used. powder, in a suitable binder,
  • 3. an electro-sensitive upper layer containing:
    • - a bismuth or antimony halide, very preferably BiCI 3 or SbCl 3 , depending on the degree of purity of the bismuth salt, these compounds may possibly be accompanied by a small amount of hydrochloric acid in order, in a manner known to those skilled in the art, to avoid the presence of oxychloride capable of inhibiting the chromogenic reaction,
    • - A divalent metal halide capable of complexing the bismuth or antimony halide to give a more reactive stable species dissociating during the passage of the current and carrying out an oxidation-reduction reaction with aluminum; mention may be made in particular of the halides of Mg, Ca, Ba, Sr, Mn, Fe, Co, or Ni, etc., moreover, the presence of water of crystallization makes it possible to maintain a constant ionic conductivity,
    • - a semiconductor oxide in pigment form which, in addition to its opacifying role, is involved in the redox reactions caused by the flow of current; we will notably mention the following oxides: Ti0 2 , Sn0 2 , ZnO, AI 2 0 3 , kaolin; to improve the result obtained, it may be possible to carry out a surface treatment of this oxide, in a manner known to those skilled in the art; it is possible to use a mixture of several oxides of this type, in particular TiO 2 / kaolin,
    • - A polymeric binder which ensures the cohesion of the dispersion and, moreover, according to its acidity, modifies the acid-base character of the medium and therefore the quality of the inscriptions obtained; as preferred binders, mention will be made of polyvinyl, polyacrylic binders and halogenated polymers,
    • - a plasticizer intended to ensure the conservation of the mechanical properties of the layer; suitable plasticizers are phthalates, adipates, etc.

A titre indicatif, la dimension des grains des oxydes précités pourra être choisie entre 0,1 et 5 µ, et de préférence autour de 0,3 µ.As an indication, the grain size of the abovementioned oxides may be chosen between 0.1 and 5 μ, and preferably around 0.3 μ.

La couche électrosensible décrite ci-dessus doit naturellement présenter une conductivité électrique suffisante pour permettre le passage d'un courant électrique entre l'électrode de marquage et la couche bonne conductrice de l'électricité. Une conductivité électrique satisfaisante pourra être choisie entre 1 000 et 10 000 ohms/cm2.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 .

Lorsque la couche bonne conductrice de l'électricité est constituée de poudre d'aluminium et de poudre de carbone, la dimension des grains peut y être choisie entre 0,1 et 3 µ, et de préférence autour de 0,3 µ.When the layer which is a good conductor of electricity is made up of aluminum powder and carbon powder, the grain size can be chosen there between 0.1 and 3 μm, and preferably around 0.3 μm.

Dans la couche électrosensible, on a découvert qu'il était nécessaire d'établir un rapport, en poids à sec, de 0,5 à 3/1 environ, de préférence d'environ 1/1, en ce qui concerne le rapport de l'oxyde (ou des oxydes lorsqu'on les utilise en mélange) au liant de la couche.In 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.

Pour préparer la couche électrosensible selon l'invention, on fait passer les différents constituants dans un broyeur à billes, le mélange de l'halogénure de bismuth (ou d'antimoine) et d'un halogénure de métal divalent étant cependant dissous au préalable dans de l'éthanol ; le mélange sortant du broyeur à billes est couché sur la couche bonne conductrice de l'électricité, qui peut consister, comme indiqué plus haut, en un support d'aluminium, à raison de 7 à 25 g/m2 environ. On effectue ensuite un séchage.To prepare the electro-sensitive layer according to the invention, 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.

La mise en oeuvre du papier selon l'invention consiste à appliquer à l'électrode-stylet un certain courant dont la tension et l'intensité correspondent au signal à reproduire. L'extrémité de l'électrode est mise sensiblement en contact avec la face supérieure de la couche électrosensible selon l'invention, laquelle est couchée sur la couche bonne conductrice de l'électricité, laquelle est elle-même déposée sur un substrat (papier). Lorsque le signal électrique est envoyé à l'électrode, il se produit un phénomène d'échange ionique entre la couche bonne conductrice de l'électricité et la couche électrosensible, une trace apparaissant dans cette dernière en raison du déplacement de l'équilibre redox existant.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). . When the electrical signal is sent to the electrode, an ion exchange phenomenon occurs between the layer which is a good conductor of electricity and the electrosensitive layer, a trace appearing in the latter due to the displacement of the existing redox equilibrium. .

Il est naturellement essentiel, pour qu'un tel procédé soit intéressant, que le seuil de réponse à une impulsion électrique soit aussi faible que possible, et que le système fonctionne pour des tensions appliquées également aussi faibles que possible, comme le comprendra aisément l'homme de métier. Cependant, les systèmes connus actuellement ont un seuil d'impulsion de l'ordre de 1 ms et fonctionnent sous des tensions qui sont au minimum de 50 V et souvent supérieures.It is naturally essential, for such a method to be interesting, that 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. However, 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.

Au contraire, selon l'invention, on abaisse le seuil d'impulsion à 100 µs au moins, et on travaille sous une tension qui peut être de l'ordre de 10 V et une intensité comprise entre 75 et 200 µA.On the contrary, according to the invention, the pulse threshold is lowered to at least 100 μs, and one works under a voltage which can be of the order of 10 V and an intensity between 75 and 200 μA.

Ceci représente des avantages essentiels de l'invention.This represents essential advantages of the invention.

Les exemples suivants illustrent l'invention sans toutefois en limiter la portée. Dans ces exemples, on a utilisé comme substrat une feuille de papier (50 µ) et comme couche bonne conductrice de l'électricité une couche d'aluminium (9 µ) contrecollée sur le papier. Comme il a été dit plus haut, ceci n'est cependant pas limitatif.The following examples illustrate the invention without, however, limiting its scope. In these examples, a sheet of paper (50 μ) was used as substrate and as a good electrically conductive layer an aluminum layer (9 μ) laminated to the paper. As said above, this is not, however, limiting.

Exemple 1 (Composition électrosensible selon l'invention)Example 1 (Electrosensitive composition according to the invention)

  • - Ti02 (AT1 de THANN & MULHOUSE) 40 g- Ti0 2 (AT1 from THANN & MULHOUSE) 40 g
  • - Vilit MC 34 (maléochlorure de vinyle-Hüls) 40 g- Vilit MC 34 (vinyl maleochloride-Hüls) 40 g
  • - Méthyléthylcétone (MEC) 128 g- Methyl ethyl ketone (MEC) 128 g
  • - Acétate d'éthyle (AE) 128 g- Ethyl acetate (AE) 128 g
  • - DOP (dioctylphtalate RHONE-POULENC) 9,6 g- DOP (RHONE-POULENC dioctylphthalate) 9.6 g
  • - BiCI3 3 g- BiCI 3 3 g
  • - MgCl3, 6H20 2,73 g- MgCl 3 , 6H 2 0 2.73 g
  • - Alcool éthylique 3,8 g- Ethyl alcohol 3.8 g
Exemple 2Example 2

On prépare la même composition que dans l'exemple 1, en utilisant cependant du chlorure de nickel au lieu du chlorure de magnésium et une quantité différente d'alcool éthylique. Ces deux modifications sont les suivantes :

  • - NiCl2, 6H20 3,18 g
  • - Alcool éthylique 12 g
The same composition is prepared as in Example 1, however using nickel chloride instead of magnesium chloride and a different amount of ethyl alcohol. These two changes are:
  • - NiCl 2 , 6H 2 0 3.18 g
  • - Ethyl alcohol 12 g

Exemple 3Example 3

On prépare une composition selon l'invention comme selon l'exemple 1, en utilisant toutefois du chlorure de manganèse au lieu du chlorure de magnésium, et une quantité différente d'alcool éthylique ; ces deux modifications sont les suivantes :

  • ― MnCl2, 4 H2O 2,65 g
  • - Alcool éthylique 15 g
A composition according to the invention is prepared as in Example 1, however using manganese chloride instead of magnesium chloride, and a different amount of ethyl alcohol; these two modifications are as follows:
  • - MnCl 2 , 4 H 2 O 2.65 g
  • - Ethyl alcohol 15 g

Exemple 4Example 4

On prépare la composition électrosensible selon l'invention suivante :

  • - Ti02 (AT1) 40 g
  • - Vilit MC 34 40 g
  • - MEC 80 g
  • - AE 80 g
  • - DOP 16,8 g
  • - BiC13 3 g ―CaCl2 4,5 g
  • - HCI 0,288 g
  • - Alcool éthylique 6 g
The electrosensitive composition according to the following invention is prepared:
  • - Ti0 2 (AT1) 40 g
  • - Vilit MC 34 40 g
  • - MEC 80 g
  • - AE 80 g
  • - DOP 16.8 g
  • - BiC1 3 3 g ―CaCl 2 4.5 g
  • - HCI 0.288 g
  • - Ethyl alcohol 6 g

Exemple 5Example 5

On prépare une composition comme selon l'exemple 4, en utilisant cependant une quantité différente d'oxyde de titane, du kaolin, une quantité différente de DOP et en supprimant l'acide chlorhydrique. Ces modifications sont les suivantes :

  • - Ti02 (AT1) 10 g
  • - Kaolin (Dinkie A de ENGLISH CHINA CLAYS) 30 g
  • - DOP 9,6 g
  • - HCI 0 g
A composition is prepared as in Example 4, however using a different amount of titanium oxide, kaolin, a different amount of DOP and removing hydrochloric acid. These changes are as follows:
  • - Ti0 2 (AT1) 10 g
  • - Kaolin (Dinkie A from ENGLISH CHINA CLAYS) 30 g
  • - DOP 9.6 g
  • - HCI 0 g

Les résultats obtenus pour les compositions correspondant aux exemples ci-dessus sont rassemblés dans le tableau ci-après. La densité de trace a été mesurée à l'aide d'un densitomètre à réflexion du type MACBETH RD 100.The results obtained for the compositions corresponding to the examples above are collated in the table below. The trace density was measured using a reflection densitometer of the MACBETH RD 100 type.

L'homme de l'art pourra apporter des modifications aux exemples non limitatifs qui viennent d'être décrits, et ce sans sortir du cadre de l'invention.

Figure imgb0001
Those skilled in the art can make modifications to the nonlimiting examples which have just been described, without departing from the scope of the invention.
Figure imgb0001

Claims (14)

1. Electrographic recording paper consisting of lower substrate on which a good electricity conducting layer is deposited, the latter being coated with an electrosensitive upper layer, the electricity conducting layer being capable of providing positive ions to offset a defect of positive charges appearing in said electrosensitive layer, and the conductivity of said electrosensitive layer being sufficient to allow the passage of the current between a pencil-electrode substantially applied on its upper face and said electricity-conducting layer, characterized in that said upper electrosensitive layer contains a bismuth or antimony halide or a divalent metal halide capable of chelating the bismuth or antimony halide.
2. Paper according to claim 1, characterized in that the bismuth or antimony halide consists of BiC13 or SbCl3, and in that a small quantity of hydrochloride acid is possibly added to offset the defect of purity of the bismuth salt.
3. Paper according to claim 1 or 2, characterized in that the divalent metal halide is chosen from magnesium, calcium, barium, strontium, manganese, iron, cobalt or nickel halide, namely chlorides.
4. Paper according to any one of claims 1 to 3, characterized in that said electrosensitive layer contains, in addition to said bismuth or antimony halide, and said divalent metal halide,
- one or several semi-conductors in pigmentary form,
- a polymeric binding agent,
- a laminating agent.
5. Paper according to claim 4, characterized in that said oxide is chosen from Ti02, Sn02, ZnO, AI203 and kaolin and mixtures thereof, and in that this oxide can be surface-treated.
6. Paper according to claim 4 or 5, characterized in that the binding agent is chosen from polyvinylic, polyacrylic binding agents, and the halogenous polymer.
7. Paper according to any one of claims 4 to 6, characterized in that the laminating agent is chosen from the phthalates and adipates.
8. Paper according to any one of claims 1 to 7, characterized in that the dry weight ratio of oxide to the binding agent, in the electrosensitive layer, varies between 0.5 and 3/1, and is preferably near 1/1.
9. Paper according to any one of claims 1 to 8, characterized in that the electricity-conducting layer consists in a laminated aluminium layer.
10. Paper according to any one of claims 1 to 8, characterized in that said electricity conducting layer consists in aluminium powder and in carbon powder in a binding agent.
11. Paper according to any one of claims 1 to 10, characterized in that said electrosensitive layer is applied on the electricity-conducting layer in the proportion of about 7 to 25 g/m2 before being dried.
12. Electrosensitive composition for electrographic recording paper such as defined in any one of claims 1 to 8.
13. Paper according to any one of claims 1 to 11, characterized in that said electrosensitive layer contains in particular:
― TiO2, BiCl3 and MgCl2, 6 H2O, or,
― TiO2, BiCl3 and NiCl2, 6 H2O, or,
― TiO2, BiCl3 and MnCl2, 4 H2O, or,
― TiO2, BiCl3 and CaCl2, or,
- TiO2/kaolin, BiCl3 and CaCl2.
14. Electrosensitive composition for electrographic recording paper such as defined in claim 13.
EP81900302A 1980-01-30 1981-01-30 Paper for electro-sensitive recording Expired EP0044844B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81900302T ATE7584T1 (en) 1980-01-30 1981-01-30 ELECTRICAL SENSITIVE RECORDING PAPER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8002315A FR2474739A1 (en) 1980-01-30 1980-01-30 ELECTROSENSITIVE RECORDING SYSTEM AND PAPER
FR8002315 1980-01-30

Publications (2)

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

Family

ID=9238149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81900302A Expired EP0044844B1 (en) 1980-01-30 1981-01-30 Paper for electro-sensitive recording

Country Status (5)

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

Citations (1)

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

Also Published As

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

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