DE2340014A1 - FILM FOR ELECTRIC COLOR RECORDING - Google Patents

Description

DR. BERG DIl ¹ L.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS

8 MUNICH 86, POST BOX 86 0245

Dr. Berg Dipl.-Ing. Stapf, 8 Munich 86, PO Box 86 02 45

Your reference Our reference 8 MUNICH 80

Your ref. Our ref. 24 249 MauerkircherstraBe 45 7/8/1973

Attorney file 24 249

Kabushiki Kaisha Ricoh, Tokyo / Japan

Foil for electrical color recording

The invention relates to a sheet for electrical color recording, with which an image or a copy of an original can be recorded electrically.

When recording an image or a copy of an original, for example by means of a facsimile receiver

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(0811) 98 82 72 Telegrams: BERGSTAPFPATENT Munich Banks: Bayerische Vereinsbank Munich 453100

98 70 43 TELEX: 05 24 560 BERGd Hypo-Bank Munich 389 2623

⁹⁸ 33 ¹ ° Postscheck Munich 653 43 -808

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or an output device of a computer, must be on Electricity-sensitive foils are used, which are not difficult to handle, a high Have a degree of accuracy and whose operating costs are low, but with which a recording of an image of a document can be performed at high speed.

Heretofore it has been common practice for example in a facsimile system to apply for recording an electrolytic process, electric Entladuagsverfahren or an electrostatic method, säic a facsimile Ar _"t, iJLng before;! A template of electrical signals to produce None satisfies this Verfahran. however, the aforementioned requirements.

In the case of the electrolytic. Recording method becomes a Recording film made by impregnating paper or other similar material made with polyhydric phenol, and an anode made of iron is used. A voltage is impressed on the recording film, the foil must be moist to produce a brown image of iron dye by electrolysis. This method however, it has several disadvantages. Since the film should be damp or wet when recording,

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difficulties arise in handling the film. Also, the use of wetter or wetter results Foils often cause corrosion of parts of the facility. In addition, those applied to foils of this type can be used Images in tint, contrast, resolving power as well as in their lifespan to be desired.

In the recording process that works with flashover or discharge, a white-colored layer, which by applying a titanium oxide mixed with a resin binder on a carrier carbon layer a recording film is formed, exposed to a high voltage discharge to parts of the white-colored Destroy layer and expose the underlying carbon layer, so that on the recording sheet an image of the template can be produced. However, this method also has various disadvantages at. Due to the use of a high voltage discharge, special precautions must be taken during operation to be hit. If the white colored layer is destroyed, the resin binder will be burned, which creates (unpleasant) smells. Parts of the white-colored layer are destroyed and affected in turn, the facility is disadvantageous. The recording sheet itself is fragile and difficult

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because it consists of many layers. Those applied to the recording films of this type Images are inherently not harmonious and balanced.

In the electrostatic recording method, a voltage is applied by means of an abutment Electrode on a recording sheet with a dielectric Layer embossed, which is applied to a carrier material, the paper or another may be similar material which is treated so that it is electrically conductive, so as to the Recording sheet to form an electrostatic latent image which develops into a visible image will. However, the development of the latent image into a visible image requires a developing device thereby complicating the step-by-step process and taking a long time passes before the visible image is established. In addition, those produced by this process can be used Pictures in the goodness leave much to be desired.

It has also been proposed to use color developing films for recording, from

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which, for example, is described in Japanese Patent Publication 22,341,63; their handling depends on the effect of an electrical current flowing through it. This type of recording sheet generally has a coloring layer 3 (hereinafter referred to as color layer spoken), which is applied to a conductive layer, which in turn is on a insulating support 1 is provided, as shown in FIG. To record information on this type of film is an electrode 5 connected to a terminal of a power source 4 in Full contact with the conductive layer is kept while one is connected to the other connection of the energy source 4 connected recording electrode 5 is used to scan the color layer 3 to so impress a voltage on the paint layer 3, while the passage of a current by means of a fixed graphical representation or a graphical material obtained signals is controlled.

As can be seen from Figure 1, the voltage applied to the paint layer 3 is perpendicular to the longitudinal extending surface of the color layer 3 aligned.

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It is believed that the operation of the paint layer 3 is caused by a variety of effects including oxidation and reduction caused by the movement of electrons and ions upon application of the voltage, the heat effect of a current or Joule's heat, and the impingement of Electrons due to thermal electron emission on the color developing layer. Here, the resistance created by the layer 3 must be reduced in order to obtain a high quality image. The high resistance of the color layer 3 during the passage of a current would disturb the mobility of the ions xv :, d electrons as well as the Err: \ acfunc, ^ n -Joule * scher ΐί'ό · Γ.ν. ~, Whereby in turn the density of the developed color would be diminished. When a needle-shaped electrode is used as the recording electrode, a formed image may be divided into several parts, and continuity may be lacking due to the high resistance.

The need to increase the resistance of the paint layer reduce, were previously by the as coloring or coloring agent and binders, there are limits to the materials used. This has to be increased costs and a narrow color range from which one could choose.

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The invention is intended to eliminate the aforementioned disadvantages of the conventional recording films, their mode of operation or their usability depends on the effect of a current flowing through them. Accordingly, the = invention is a film for electrical Color recording or a color recording film with an electrically conductive layer of low thickness create which on a coloring or coloring layer is applied, which is discolored or which is colored when a voltage is applied.

In the color electric recording sheet according to the invention, the applied voltage is not perpendicular aligned to the longitudinal surface of the clear film, as has previously been the case with a similar type of conventional recording sheet, but rather it is aligned along the plane of the longitudinal surface as the color layer of the recording film is coated with a conductive layer of thin thickness. The operation of the color recording layer according to the invention depends mainly on the thermal effect caused by the resistance the conductive layer on the abutting recording electrode and the impact of electrons due to thermal emission from the recording electrode on the paint layer. One

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The phenomenon of degradation occurring in the color developing layer takes place by the thermal electrons breaking through the conductive layer and onto the Coloring or coloring material can also hit be a promotional factor. It is also interesting that the electrical paint layer is covered by a relatively low voltage applied to it is heated almost to its melting point. Parts of the conductive layer are removed by melting or evaporation and lead to a kind of catalytic Effect in dyeing or decolorizing the paint layer.

The most important feature of the invention is that regardless of the resistance value, a color or Coloring material can be used so that a composition for forming the color layer of a an almost infinite range of compositions can be selected. This way either can Material which stains very well can be selected and used, and any color can be selected that is to be developed. In addition, the use of the electrical color sheet according to the invention brings benefits the additional advantage that the electrode can be easily handled during operation.

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The invention thus creates a thin electrically conductive layer on an electrical paint layer of the Foil is provided. When the thin conductive layer is scanned with a recording electrode, an image the original can be recorded on the slide by information signals when the color image of the electrical Coloring or coloring material is controlled by these signals.

The invention will be described below on the basis of a preferred embodiment with reference to the accompanying drawings explained in detail. Show it:

FIG. 1 schematically shows a conventional recording sheet, the mode of operation of which depends on the effect of a current, and one used to record information on the film Facility; and

FIG. 2 schematically an electrical color recording film according to the invention and one used for recording information on the film Furnishings.

The composition of the materials used to make an electrical colored sheet according to the invention

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and their manufacturing method are described below.

As shown in Figure 2, an electrical ink drawing sheet has a carrier 11, one applied thereon Color layer 13 and a thin conductive layer 13 applied to the color layer.

Any material selected from the group including synthetic resin in Foil form, glass in foil form, fabric, paper, synthetic and transparent paper.

The coloring material for the layer 12 can a mixture of a coloring material or materials selected from the materials of group (I) are, and be a binder or binders selected from the materials of group (II); one such mixture preferably comprises a coloring material or materials and a binder or binding agent in the range of a weight ratio of 2O: 1 to 1: 2. The mixture is for example by means of a ball mill and kneaded by means of a Rod applied to the surface of the carrier 11, un a layer with a thickness of 1 to 100 u to manufacture.

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Of course, the color layer 12 can be vapor deposited a material or materials from group (I) can be applied to the carrier 11 alone.

(I) Electric coloring material

(a) Examples of metal sulfides: ZnS, Sb ₃ S ₃ , ^In 2 ^S 3 ^u «ä ·

(b) Examples of metal oxides:

Rb-O ₄ , Cs ₂ O ₃ , ZnO, Cd ₂ O-, HgO, GaO, Ga ₃ O ₃ , InO, TiO ₂ , SnO ₂ , Pb ₂ O ₃ , V ₂ O ₅ , Nb ₂ O ₅ , Ta ₃ O ₅ , SbO ₂ , Sb ₂ O ₃ , Cr ₃ O ₃ , CrO ₃ , MoO ₃ , W ₃ O ₃ , TeO ₂ , TeO ₃ , MnO ₂ , Re ₃ O ₇ , RuO ₄ , OsO ₄ , Co ₂ O ₃ , Co ₃ O _4, among others

(c) Examples of metallic acids:

HSbO ₃ , HVO ₃ , HBiO ₃ , H ₂ SeO ₃ , H ₃ TiO ₃ ,

H ₃ SnO ₃ , H ₃ SeO ₄ , H ₃ MoO ₄ , H ₃ WO ₄ , H ₃ UO ₄ ,

H ₃ SbO ₃ , H ₃ SbO ₄ , H ₄ TiO ₄ , H ₄ MoO ₃ , H ₄ Sb ₃ O ₇ ,

H ₅ TaO ₅ , H ₅ SbO ₅ , HgTeOg, H ₁₀ SnO ₁₅ , HgPbOg,

₁₂ O _40- / * 30 H ₂ O,

O ₁₂ O ₄₀ , / * 30 H ₂ O,

₁₂ O ₄₀ _ / * 30 H ₂ O et al

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(d) Examples of salts of metallic acids:

The salts of the metallic acids described under (c) are for example:

K ₂ MoO ₄ , Na ₂ MOO ₄ , CaMoO ₄ , PbMoO ₄ , Na ₀ Mo ₀ O _nc '17 H ₀ O,
Na ₄ / MOg0 ₂₆ _ / * 12 H ₂ O,
(NH ₄ ) ₆ ^ M0 ₇ 0 ₂₄ _ / * 4 H ₂ O,
(NH ₄ ) ₆ Z.Cr ₂ Mo ₁₂ 0 ₄₂ _ / * 2 H ₂ O et al

(e) Other metal compounds:
CuSCN, PbSCN and others

(f) Thermochemical coloring or coloring material:

Zinc stearate + diphenylcarbazole, iron stearate + 1-formy1-4-phenylsenicarbazide

etc., form materials of this coloring subgroup for example chelate compounds due to the thermal effect of a current.

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(II) binder or binding agent:

(a) Examples of oil-soluble resins:

Pliolite S - 5B styrene-butadiene copolymer

sat _f manufactured by Goddyear Tire and Rubber Co.

Pliolite S - 7 same as nylon resins above

Styrene methyl methacrylic acid ester butyl acrylate Acrylic resin

Polyvinyl pyrrolidone polyvinyl acetate et al.

(b) Examples of water soluble resins:

Polyvinyl alcohol (P.V.A.) manufactured by

Dow Chemical Co.

conductive or conductive

Polymer 261 manufactured by

Calgon Co.

i.a.

(c) Other binders or binders: gelatine, starch paste, etc.

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The thin conductive layer 13 on the paint layer 12 can either by evaporation in a vacuum or by a spraying or atomization process on the layer 12 of one of the aforementioned materials or on the surface of a mixture of one of the materials mentioned above and one above in the group (II) listed binders or binders are applied. The surface resistance of the color layer 13 is then less than 10 (- ^ 2.) Or is preferably in the range from 10 ³ to 10 (U-).

(III) Thin materials forming the conductive layer:

(a) Metals:

Fe, Co, Ni, Al, Cu, Au, Ag, Zn, Ti, In, etc.

(b) Metal compounds:

*** CuBr, **

, SnO ₂ , CuI, *** CuBr ₂ , ** CuBr,

FeS ₂ et al

For recording an image of an original by means of information signals on one of the various The electric color recording sheet made of the materials listed above is one having

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one terminal of a power source 14 connected electrode in abutment at a corner of the thin conductive Layer 13 brought, and a connected to the other terminal of the power source 14 recording electrode 16 used to scan the thin conductive layer 13 by controlling the passage of a Current in the film to produce an image from the information on the film by means of the information signals.

In particular, when a voltage is applied to the thin conductive layer across the recording electrode 16 by means of a Information signal is impressed, a current flows in the thin conductive layer 13 from a contact point between the recording electrode 16 and the Layer 13 to the electrode 15. The resistance at the Contact point on layer 13 is what is referred to as contact resistance and is very high, so that the generated at the contact point Heat is relatively high so. that the corresponding part of the color layer 13 is colored. Simultaneously thermal electrons are generated by the recording electrode 16 and the thin conductive one Layer 13 supplied in the parts where they break through the layer 13 and penetrate into the layer 12, whereby degradation takes place at layer 12. As a result, the parts of the conductive layer 13 to which the voltage is impressed by abutting the recording electrode 16, either by melting

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or evaporation removed as a result of the heat generated here, and a kind of catalytic effect is formed in the thermal discoloration reaction. That way then will an image of the template is created on the slide and recorded by removing the surface of the thin conductive Layer 13 is scanned during the passage of the current from the first mentioned to the last mentioned Layer, i.e. from the conductive layer into the color layer, is controlled by information signals. The recorded The image is very clear, clearly delineated and has a high density.

example 1

A mixture of 10 parts of H ₂ MoO ₄ . 2 H ₃ O, 2 parts of Pliolite S-7 (trademark) and 30 parts of toluene (each in parts by weight) were placed in a ball mill and kneaded for 15 minutes. Then, the mixture was applied to the surface of a sheet of readily available tracing paper by means of a stick to form a layer about 5µ thick thereon, and was thereafter dried for half an hour with the layer of 100 ° dry air C is exposed.

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An electrically conductive layer was applied to the electrical paint layer prepared in the above-described manner by evaporating aluminum in vacuo under a pressure of 10 mm Hg. The applied conductive layer had a surface resistance of 10 SL . The electric color developing recording sheet thus prepared was tested by scanning its surface with Toshafax manufactured by Tokyo Aircraft Meters Company and passing an alternating current of about 100 V through the conductive layer. This created a clear, sharp, black positive image or a copy of the original.

Example 2

A mixture of 10 parts of ZnO, 2 parts of PVA and 30 parts of methanol (each in parts by weight) was placed in a ball mill and kneaded for 4 hours. The mixture was then applied to the surface of a sheet of high quality commercially available paper by means of a stick to form a layer about 10µ thick and was then ^{dried at 100 °} C. for half an hour.

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An electroconductive layer was formed on the electrical paint layer prepared as described above applied by evaporation of aluminum in vacuo at a pressure of 10 mm Hg. The senior The layer had a surface resistance of 10 The electrical color recording layer thus prepared was tested in that its surface with the Toshafax specified in Example 1 was sampled and a direct current at about +75 V was passed through. In this way a dark or black-brown positive image or copy of the original produced.

Example 3

A mixture of 10 parts of V ₃ O ₅ , 3 parts of RP 505 (manufactured by Monsanto Company) , 5 parts of water and 25 parts of CH ₃ OH (each in parts by weight) was placed in a ball mill and kneaded for 8 hours. The mixture was then applied to the surface of a sheet of high quality commercially available paper by means of a stick to form a layer about 5µ thick thereon

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form, and then 1/2 hour was dried by the dry air layer was exposed to 100 ⁰ C.

An electrically conductive layer was formed in the above-described electrical paint layer by evaporating aluminum in a vacuum under a pressure of 10 mm Hg applied. The applied conductive layer had a surface resistance of 10 -TL. . The on electric color recording sheet produced in this manner was tested in that its surface was scanned with the prescribed Toshafax and a direct current at + 10OO V was passed through the photoconductive layer. It became a clear, sharp, flawless, black positive image or copy of the original created.

Example 4

A mixture (1) of one part zinc stearate, 5 parts P.V.A. and 20 parts of methanol (each parts by weight) and a mixture (2) of one part of diphenylcarbazone, 1O share P.V.A. and 20 parts of methanol (also in parts by weight), were introduced into separate ball mills and each kneaded for 4 hours. The mixes

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(1) and (2) were then mixed together and applied to the surface of an im Commercially available polyester film is applied to form a layer thereon about 10µ thick, and was then dried at 80 ° C. for 1/2 hour.

An electrically conductive layer was formed on the electric paint layer applied in the above-described manner applied by evaporation of indium in vacuo at a pressure of 10 mm Hg. The on this A thin conductive layer applied in this manner had a surface resistance of 5 χ 1O - »i ·. She was through Scanning the surface with the aforementioned Toshafax was tested and a direct current at + 500 V was passed therethrough; this resulted in an excellent, positive image or copy.

Example 5

A mixture of 5 parts of ZnO, 5 parts of In ₃ O ₃ , 2 parts of PVA and 30 parts of CH ₃ OH (parts by weight each) was placed in a ball mill and kneaded for 8 hours. The mixture was then applied to the surface of a sheet of commercially available tracing paper using a stick to form a layer

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of 5µ thick and was then dried ^{by dry air at 100 ° C for 50 minutes.}

A transparent CuI film of several - » L · was applied to the surface of the electric paint layer applied in this way by evaporating copper in a vacuum under a pressure of 10 mm Hg; the applied layer was then exposed to iodine in vapor form. The thin conductive layer or the CuI film applied in this way had a surface resistance of 10 −jL · . Experiments and investigations which were carried out by scanning the surface of the electrical color recording film with the aforementioned Toshafax and by applying a DC voltage at +300 V have shown that by means of the film a dark or black-brown clear, sharp positive image, or a corresponding figure were produced.

Example 6

A mixture of 10 parts of (NH ₄ ) ^ O ₇ O ₃₄ .4H ₂ O, 2 parts of a copolymer of crotonic acid and acrylic acid ester and 30 parts of methanol was placed in a ball mill and kneaded for 10 hours. The mixture

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was then applied to the surface of a sheet of commercially available tracing paper by means of a stick to form a layer thereon about 5µ thick, and was dried in ^{100 ° C dry air for 30 minutes.}

An electrically conductive layer was formed on the surface of the electrical paint layer thus applied by evaporation of indima in a vacuum under a pressure of 10 mm Hg is applied so that the applied conductive layer has a surface resistance of about 1000 would have. Try that by scanning the surface of the electrical. Γcolor recording sheet by recording Information passed showed that a clear, black positive image was created.

Example 7

An electrically conductive layer was formed on the surface of the electric paint layer applied in the same manner as in Example 6 by spraying SnO ₂ under a pressure of 10 mmHg in a gas mixture of 95% argon and 5% oxygen

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upset. The electrically conductive layer had a surface resistance of about 10 k «A_.

When the same tests described in FIG. 6 were carried out, a clear, sharp, black, positive image was obtained created.

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Claims (11)

2340QU P a te η ta η s ρ rü che M. Foil for electrical color recording, marked by an electrical paint layer (12) and a thin, electrically conductive layer applied to it Layer (13) which is scanned with a recording electrode (16) in order to form the electrical color layer (12) to color and to create an image of a template by means of electrical signals. 2. Film according to claim 1, characterized in that the electrical color layer (12) consists of at least one Metal sulfide, a metal oxide, a metallic acid, a salt of metallic acids, other metal compounds and thermal dyes. 3. Foil according to claim 1, characterized in that the electrical color layer (12) consists of an electrical Color material or materials and a binder or binders is composed. - 25 - 409809/0905 4. Foil according to claim 1, characterized in that the electrical coloring or coloring material or materials at least one metal sulfide, a metal oxide, a metallic acid, a salt of metallic acids,
comprises another metal compound and a thermal paint material. 5. Film according to claim 3, characterized in that the binder or binders are at least one oil-soluble Resin, a water-soluble resin and other binders. 6. Film according to claim 1, characterized in that the thin electrically conductive layer (13) at least comprises a metal and a metal compound. 7. Foil according to claim 1, characterized in that the thin electrically conductive layer (13) consists of one the thin electrically conductive layer-forming material and at least one binder is composed. - 26 - A0 9 809/0905 8. Film according to claim 7, characterized in that the thin electrically conductive layer (13) forming Material has at least one metal and one metal compound. 9. A film according to claim 7 _f, characterized in that at least one binder has at least one oil-soluble resin, a water-soluble hair and other binders. 10. roll according to claim 1, - characterized in that the electrical color layer {12) by evaporation or Application is made in a vacuum. 11. Foil according to claim 1, characterized in that the thin electrically conductive layer (13) by evaporation, Sputtering or vacuum application is formed.