DE1472962A1 - Image generation method - Google Patents

Description

The invention relates to document-based integration of electrostatic images.

As is well known, one is made with aqueous ink or Tuaohe Image sensitive to treatment with water if no special precautions are taken. The creation of a "document-free" image with such inks is a problem, This is especially true when it comes to the detection of false solutions and the achievement of good ones Storage responsibility * for important documents requires attention.

909819/0920

BATH ORIGINAL

Bie lintwickl-di ^ electrostatic latent image with the help of a liquid. or ink is known, for example, from US Pat. No. 2,551,582. Ss there means that an electrostatic latent image can be developed with an electrostatically attractable finely divided liquid such as an ink mist. In the British patent 902,928 a method for .Ji ¹ UIS sigkeitsentwicklun ^ · electrostatic charge images is described which 3ioh an electrically insulating liquid serves, in ^which: an aqueous hase is eaiul ated ^;! in the liquid; ^ mentteilchen suspended Pi are thereby deposited on the principle of electrophoresis to the charged surface portions, i'iach de: n in de'r-be # - ⁱ * - 'cal PatentscLrift methods described 610,060 to 2% ■ AMSfÄ & J-b ^{keitswntwicklun!} .._, · electrostatic Laüunjybilder we-i an electiti ^ static later.tea picture developed with a fluid, the interfacial tension of which surpasses before a solid carrying an electro-static charge ^ at :: rial3 is influenced by the size and depth of the electrostatic field on the surface so that it is wetted selectively or differently according to the electrostatic charge pattern.

Further, a method in the "Belgian Patent 625,335 I3T described by de ^r n an electrostatic Ladun _o -3bild in or ax on a surface of a material of a photoleitfahi _t jeri Sohichi is formed inde ^ a of this material during or after the tiildgemäßen exposure juer is driven through an electrical field.

BATH ORIGINAL

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At the same time, this surface is not differentiated Way brought a liquid, whose surface tension ge ^ -en über the surface due to the presence and strength of the electrostatic Charges is influenced in such a way that the liquid the Surface selectively or according to the electrostatic charge pattern differentiated wetted.

For the development of an electrostatic charge image, Belgian patent specification 610 ObO describes color reactions between a compound in the developing liquid and a compound in the material to be developed, and it is noted that the generation of a visible image is achieved by the conversion of one or more compounds in the surface The material to be developed with one or more in a liquid phase has the advantage of firmly anchoring the generated image in the surface of the material and therefore g ^ geia. to make mechanical abrasion resistant. These color reactions can be activated or accelerated by heat and light, like. by incorporating catalysts into the material that carries the electrostatic charge image and / or into the development fluid.

It is an aim of the invention to »make visible, document-proof copies Using an aqueous ink on e lektrophot ο jraphi sham recording material su that can remove zinc ions.

909819/0920 _BAD ORIGINAL

In particular, it is an object of the invention to provide compositions for the fluid development to create the β loh for the document - ' true development of electrostatic charge images in an alkoxide-containing recording element.

Furthermore, it is an aim of the invention to provide several possibilities on-the-fly from an electrostatic image, as it is located on a photoconductive surface with photoconductive zinc oxide, document-proof, so create wish- and erasable images.

Sas goal of creating a document-proof image or a According to one embodiment of the invention, recording is thereby achieved achieved that on a Aufzeiohnungselement, preferably a electrophotographic element containing photoconductive zinc oxide, an aqueous composition (solution or dispersion) which, in addition to hexacyanoferrate (III) ions, contains an aromatic or heterocyclic primary or secondary amine, which optionally possesses an ohromophoric group, according to the image or the uncovering.

Under the influence of that supplied by the recording element Zinc ions, the amino compounds are quickly oxidized to dyes by the hexaoyanoferrate (III) ions and these dyes are feat adsorbed on the formed zinc heracyanoferraten.

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The aim is further achieved according to a second embodiment of the invention, that on a recording element, preferably an electrophotographic element, which contains hotconductive zinc oxide and which can provide zinc ions, (a) an aqueous composition (solution or dispersion), the hexaoxide canoferrate (III ) ions and (b) a cationic dye and / or a reducing agent is applied sequentially according to the image or the recording.

The object is further achieved by a third embodiment of the invention daduroh achieved that aan on a recording element, preferably an electrophotographic lead containing zinc oxide and zinc ions, (a) an aqueous composition (solution or dispersion) containing hexaoyanoferrate (II) ions and (b) a cationic dye such as a triaryl methane dye Image or the recording one after the other.

The reducing agent composed according to the second embodiment can be applied with the cationic dye is preferred an aromatic or heterooyolic amine or a salt of that.

According to a variant of the second embodiment, a reducing agent can be used already to the hexacyanoferrate (ill) ions contained

BATH ORIGINAL

ι * ι e- \ J \ j -6-

can be added. It can be, for example, an oxidizable Aroraatic hydroxy compound of the hydroquinone type and / or a leuco compound act as they are in the under the same date filed patent application (Sohlüssel "Elektro-Kataleuko") is.

Ea has been observed that in an aqueous solution, the auier Hexaoyanoferrate (Hl) or hexacyanoferrate (II) ions are cationic Contains dye, flocculation is likely to occur on the formation of an insoluble reaction product between the dye cations and the hexacyanoferrate (III) or hexaoyanoferrate (II) ions is based. Therefore, a developing fluid that contains the compounds mentioned because of their short shelf life for a reproducible and document-proof "Tieder ^ abe sohlecht suitable.

The document-proof and water-resistant connection of the dye with the recording element containing zinc oxide is based on the Pickling effect of the zinc hexacyanoferrate formed in situ. During the Development of the electrostatic charge images on a material containing or supplying zinc ions becomes this material imagewise stained and colored on the stained surface parts. The pickling is particularly strong when neutral or weakly acidic aqueous developing solutions which contain ^ aliujahexacyanoferrat (ll).

BATH ORIGINAL

In order to bring the above-mentioned amines into solution in the aqueous, hexaoyanoferrate (III) -ions-containing developing liquid, because of their low water solubility in the form of their Dissolved salts · Preferably the solution will be almost acidic held because in the absence of zinc ions a low pH value the Prevents oxidation of the amines.

Strong acids such as sulfuric acid and hydrochloric acid are preferably used for acidification.

As amines for the application Zwooke of the invention can be primary and secondary AJiine are used in which the Aaino group is part of a conjugate system.

Particularly good results are achieved with compounds that contain a aromatic ring system which is substituted by at least one aluminum group, which is further characterized in that at least one position ortho to the amino group is unsubstituted and that in the other positions the aromatic system can be substituted by one or more 3ubstituenten in such a way that the Sum of the tfi values of the further substituents, preferably over -0.66 and equals or does not exceed plus 0.874.

(·· cr'-tferto for Aniline ", HR Jaff <5, Che.Rer. ^ (I955) 3. 222, Table 7 and 3. 225).

909819/0920

For primary amines, the examples are given that one of the correspond to the following formulas!

<κ \ s— _m "", ^ Vm "

A is an imlogene atom such as chlorine or bromine, a lower alkyl such as Methyl, an aoetylamino group or an aoetyl group, B a hydroxyl group or a primary amino group.

It should be noted that the other aibatituents of the aro * matieohen system also parts of a condensed aromatic, may be oyoloaliphatic or heteroylic rings. '

The following list of the aromatic primary amines that are preferably used provides more detailed information

2-kethyl-4-diethyla'i.inoaniline

ρ-diethy1aminoani1ine

p-dimethylaminoaniline

2.4 tons of 6-triaminochromatic benzene oil

2,4-IH.oethylaniline

3,4-Diaiainophenol

2.4 dialainophenol

p-phenetidine

Yeratrolamine

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2.5 - aiae thoxy ani 3, in

aniline

«Fr-naphthylanine

Benzi din

4 »4 '-diaainodiphenylamine and

"R-Aiaino-ß -naphthol"

Heterocyclic primary amines, which are suitable for the production of document-proof Ink copies are suitable for example 5-amino-benzothiazole, 6-a-ninobenzthiazole and 2-aminobenzothiazole.

Ala secondary amines are e.g. ... ionomethylaniline and diphenylaniline called. Compared to the non-tinted amines, the colored ones have Amines have the advantage that a greater selection of lighter colors can be used stands.

Da3 was preferably used as an oxidizing agent for the A.uin Hexaoyanoferrate (III) is aluminum hexaoyanoferrate (III).

During the oxidation of the said amino can either directly Dyes can be formed or there are colored overlay components, which: ait an azo compound such as 2-A..iinoaz ο benzene azine form dyes.

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I t

The aqueous devolatilization fluids used according to the invention as a liquid component preferably contain only water, but they can also be ashed with other liquids or contain diluents for adjusting the viscosity. The aqueous pickling liquids preferably contain 0.5 to 27% potassium ferricyanide (III) or potassium hexacyanoferrate (III). The aqueous Entwicklungszusaramensetzungeh preferably contain ο to ο o5 to 2 y "of the above amines in addition, from 5 to 2 / t> potassium hexacyanoferrate (III). The aqueous solutions of the cationic dyes to the duroh Kaliumheiacyanoferrat (II) and / or Kaliumhexacyano- ^l '* - ~ f errat (Hl) stained Fläohenteile be applied, the different types may contain cationic dyes, but triphenylmethane, oxazine and thiazine dyes are particularly suitable. The developing liquids on the Gruhdlaje kätionisoher dyes contain from 3 to 20 70 of the katlonisohen dye.

In addition, all erfindungsgeaaß applied Bntwioklungsflüssigkeiten 0.5 may contain a surfactant to 20 'frs. In this way, the surface tension can be reduced, for which the addition of water-soluble organic substances such as methanol, ethanol, acetone, methyl ethyl ketone, acetic acid, hydroquinone, lauryl sulfonates, dodeoyl sulfonates, saponins and polycyclic derivatives is suitable.

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Further useful surface-active substances are available from K .. Lindner in "Textile auxiliaries and Wasohrohstoffe", Wissensohaftliohe Verlagsgeselleohaft m.b.H., 1934 »Stuttgart described.

In addition, up to eu 10> Substances are used that reduce the drying speed of the ink, such as glycerin, Glycol and sorbitol, as well as binders that are soluble in water or dispersible with water such as gum arabic, carboxymethyl cellulose, casein, Polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyacrylate, polystyrene, waxes, silicates and colloidal silica.

The oxidation of the above-mentioned amines can be cationic Colorings still contain zinc oxide on the surface Aufzeiohnungseleiaentea are adsorbed where potassium hexaoyanoferrate (lll) reacted with an aain so that a color image obtained by an oxidized amine can be given a different color. The method according to the invention for generating document-proof Ink copies and ink images can be used in various recording and developing techniques in which Recording elements that supply zinc ions use nerie-, but that The method is suitable in its various ways especially for use with d * jr fluid development, which for Development of electrostatic charge images on layers that serve Zinc oxide and especially in an insulating bin

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Yard tea contain photoconductive zinc oxide. In this case it delivers The photoconductive zinc oxide is used for the acidic and color-forming Implementation of necessary zinc ions.

According to a first preferred embodiment, a liquid A, which consists of an aqueous solution of potassium hexaoyanoferrate (ll) exists, according to an electrostatic charge pattern and according to one of the development methods described in Belgian patents 610 060 and 625 335 on a photoconductive Zinc oxide-containing material with a hydrophobic character is deposited. This creates the charged surface parts of this material pickled, while the uncharged parts remain hydrophobic «. This selective hydrophobic / hydrophilic differentiation is used to to wet the image-stained area parts by means of an aqueous liquid B which contains a cationic dye. On the The cationic dye is adsorbed on the stained surface areas and forms a document-proof color image.

Kaoh a «wide preferred embodiment, which is used for all known methods of liquid development for electrostatic Charge images can be used »becomes a Sntwioklumgsflüeaigkeit 0, the xalium hexaoyanoferrate (III) and one of the primary ones just listed or contains secondary amines, corresponding to an electrostatic Deposit charge image onto a photoconductive material containing photoconductive zinc oxide. Doroh the in situ formed

909819/0920 bad original

Zinionen will be the. Oxidation reaction of the amine with the Xaliumhexacyanoferrat (III) in the way beaoh accelerated that immediately firmly adsorbed color image is generated.

fntwioklungafluasigke.it C can also be used in one electronic recording asysteni be used as it is in the U.S. Patent 2,577,894. Here will worked with a modulated flow of air or gas loaded with the ink particles.

According to a third preferred embodiment, the elements of Contains both of the preceding forms, a fluid image is created with Help the development fluid 0 naoh one of the in the btlgisohen Patent specifications 610 060 and UZ 625 335 liquid development methods described and then this liquid image with an aqueous solution containing a cationic dye deoed. This allows the color image formed by oxidation to appear be covered in a document-free manner with a cationic dye, so that color images of the most varied of color gradations and high color strengths are generated,

The potential oxidation of the induction medium in the development liquid is excluded by first applying the solution as shown in the image the Heiaoyanoferrat (III) ions applied to the recording material and then optionally the solution of a reducing agent, such as one of the amines listed above together with a

9 0 9 819/0920 bad original

Ί H / ά 3 O ά -H-

cationic dye and then the hexacyanof errat (unions containing solution are applied.

It can of course be carried out on a single recording material successive development with solutions of different amines and, if necessary, subsequent application of aqueous, cationic ones. Compositions containing dyes receive multicolored images! * » when the cationic dyes are a different color than the have dyes formed by oxidation of the amines.

The following examples illustrate the invention. example 1

225 g of photoconductive zinc oxide are added to 500 ml of a 4? KLgen methanolic solution of Flexbond D I3 (trademark for a misoh polymer of 85 parts of vinyl acetate and 15 parts of vinyl stearate from Colton Chemical Company, Cleveland, Ohio, USA). The mixture is ground in a ball mill for 48 hours, whereupon the following composition was added with thorough scrutiny it will

Solution of Flexbond D 13 (tfaren-

symbol) in ethanol 500 ml

Solution of monobutyl phosphate in ethanol 10 .al

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Solution of succinic acid in dimethylformamide 10 ml

Ι7 ΐ5β solution of fluorescein (C.I 45 350) in ethanol 10 ml

The photoconductive dispersion is applied to a paper backing that is covered with an aluminum foil is laminated in a ratio of 10 ^ m applied per liter with the help of a ^ "alzan application stone and dried.

The photoconductive layer is after drying by means of corona discharge to -300 volts / om duroh a voltage of -7000 volts on the Corona wires charged and then 0.7 seconds ia with a 75 watt lamp at a distance of 10 seconds through a slide exposed. "Then the latent image is shown with the schematic shown in FIG Development apparatus developed

The sohematisoh shown in Fig. 1 includes the communication apparatus an ink roller 10 and a guide roller 11. The ink roller 10 is moistened with ink from bath 12. A doctor blade 13 regulates the supplied · amount of ink. The ferry roller 11, which is in contact with the Support 15 is standing, presses the recording material I4 with its photoconductive substrate 16 against the ink orphan 10, which wets with ink is. In the embodiment of the present invention, the ink roller 10 is provided with a helical corrugation. The grooves

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have a depth of ο.2 mm and a vertex angle tone 60 · Sas Recording material H becomes between the guide whale «x 11 and the tin tonwalze 10 carried out at a speed of ron 2 "/ min.

Developing fluid brought up in this way becomes duroh mixture of the following solutions A and B be reitet ι

Solution Ai p-Äthojqranilin-Hydroohlorid 1 g Yasser iOf al Solution Bt Xalium hexaoyanoferrate (III) 1 g

Yasser 100 ml

The 'finte settles on the uncharged surface parts and forms After drying, a positive purple-blue image that cannot be washed off with water.

A more intensely colored positive image is obtained by using it a developing ink containing the one described above in which however replaces the solution B with the following composition is

ialiumhexaoyanof errat (ill) 2 « Picric acid 2 « Yasser 100 al

909819/0920

** & ORIGINAL,

If the p-jttfeoiyaailinhydroohlorid of solution A through one of the

Replaced the following amine hydrochlorides, the following are obtained in each case iarbs toffbildert

2,5-Dimetlioxyenilin-Hydroohlorid t reddish brown

Veratrolamine hydrochloride t gray

5,4-diaminophenol hydrochloride t brown

p-Dimethylaminoaniline hydrochloride »orange

p-diethylaainoaniline-hydroohlordid ι purple blue

Example 2

A photoconductive material as described in Example 1 is placed on a paper carrier with a specific resistance of 10 ohm.om. applied. After charging the schioht as in Example 1 a non-transparent original is episkopisoh projected onto the photoconductive layer for 30 seconds.

This projection is done using a camera that is connected to a Sehneider Xreuznaoh Xenar 4.4 lens (focal length 21 cm, aperture 5.6) was equipped.

The light source consisted of two Sylvania Green Hvfatt lamps. the Length of the light source from the light source to an original 84 cm.

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The development took place as in Example 1, but with a development

wioklungsflü3sijkeit that was received by Veriüiaohun ^ 'one aqueous solution of 2,4-biaminophenol hydrochloride and a aqueous Kaliumheiaoyanoferrat (III) solution.

An erasable positive brown image was obtained.

Immediately after the application of this developing liquid the phütoleitfi'hije layer between a second a Talzenpear iiindurohleitung. The second pair of rollers is also arranged in such a way that as shown in Fig. 1 and described in Example 1. The ink roller, however, is now made with an aqueous solution of a cationic dye such as methylene blue, thionvin violet (0,1.52000) or Brilliant Cresylblue (CI. 5I0I0) wetted. Through this the brown dye picture is overdecorated so that blue ones are erasable Images are obtained.

Example 3

The following were used to prepare a photoconductive dispersion Products mixed in a ball mill »

P / 25 (. Tare name for a
Solution of a polyacrylate resin in acetone,

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from Böhm & Haas G.m.b.H., Darmstadt

the market brewed) 50 ml

4-paste solution from Vinnapaa B 5OO / 4O VX (Trademark for a polyvinyl acetate of Waoker-Chemie-G.m.b.H., Munich,)

in methylene chloride 25 ml

Acetone 25 al

Zinc oxide as in Example 1 22.5

10% solution of mono- and di-isopropyl-

orthophoaphat (1 * 1) in ethanol 1.5 g

The dispersion obtained was applied to an aluminum sheet by dewing in such a way that the amount of zinc oxide was 15 g / μm.

A latent electrostatic image was created on the photoconductive So not produced in the run-of-the-mill as in Example 1. The development took place in an apparatus as shown in Fig. 1 bowed iat. However, in this case, she was one of the 11th Guilds Aluminum cylinder with a Durohmesser tone 15 om and a length Ton 25 oa · You ink orphan 10 was made of stainless steel 18/8 and had a diameter of 60 m and a length of 25 om. The surface of the ink orphan was corrugated in such a way that the Billen touched each other. The groove was V-shaped with a depth and width of 0.5 mm. The ink roller 10 rotated freely in the ink container 12 so that the filler was filled with ink. The ink was

909819/0920 BAD OWQlNAt

duroli capillary forces recorded in the groove.

The photoconductive material 14 is between the ink roller 10 and the Guide roller 11 at a speed of 3 m / min hinduohgeleitrfc, the latent image facing the corrugated ink roller 10. The developing liquid from Example 1 is used.

About the contrast between the exposed and the not exposed To increase areas, a voltage of -10 volts will iwisohen the Guide roller 11 and the ink roller 10 applied

Example 4

To 500 ml of a Qjtdgaa. 150 g of photoconductive zinc oxide are added to an alcoholic solution from Flexbond £ 15 (trade mark). 10 ml of an 10% aqueous solution of monobutyl phosphate are added with vigorous drilling.

This mixture is ground in a ball mill for 24 hours and then diluted to a dispersion with 500 ml of a 4Mg alcoholic solution of the copolymers Flexbond J) 1J (farenzeiohm). a

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lOjbige Bernsteins'.lure solution of dimethylformamide in 10 ml 0.1> solution of Hhodamin B (CI45 ¹ 7O) in ethanol 10 ml

thus obtained photoconductive composition is duoh dipping applied to a conductive paper carrier.

Photoconductive Sohioht gets old with the help of a corona device with a voltage of -βοοο volts on the corona wires to -400 Volts / om charged. Subsequently, the charged photoconductive Shift 0.4 seconds with a 75 »Tatt lamp at a distance from 10 om duroh a Ma beliohtet.

The electrostatic latent image obtained is transferred to an apparatus as shown soheuiatically in FIG.

In this apparatus, the material to be developed is brought into contact with the pickling liquid described below at a speed of 2 m / min. The roller 10, which brings this pickling liquid to it, is helically grooved. 2 mm and an apex angle of ^ 0 ° "the Durchlaufgeschwindi £ -. ness of the photoconductive material 14 corresponds to the Üinfang3 _ö e3chwindigkeit the 'ialze 10, the zoom performs the Beizflüsaigkeit the uppermost part of the grooved TTalze 10 koiauien with the photoconductive layer in contact Me. Pickling liquid "is a 2% aqueous solution of KalumhexacyanoferratCll) ·

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Ί Η /

Immediately after this pickling fluid has been applied, the Photoconductive layer carried out between a second pair of folds, that as well as achematic. shown in Fig. 1, is arranged. the Application roller 10 and the guide roller 11 both have a smooth one Surface.

The Auftrajav / alze 10 brings the picture-etched material with a 1? * The aqueous solution of crystal violet in contact. This cationic paraffin becomes solid on the bildge.näß stained planar parts absorbed. An intensely colored positive image is obtained.

Example 5

A latent electrostatic image, as described in Example 1, is developed as in that example, with the difference however, since the development fluid is produced by Addition of 100 ml of a 2-fold aqueous solution of potassium hexaoyanoferrate (III) to 100 ml of an aqueous Löaunj containing 2 g of Veratrolaninhydroohlorid and 1 g of Direct Black (C.I. 30245), an aao dye with free amino groups. A gray image is obtained.

BATH ORIGINAL 909819/0920

Example 6

The following photoconductive composition was made on a 80 g heavy barite wallpaper applied

Photoconductive a zinc oxide 37.5 g Mixed polymer clay vinyl acetate and Yinyllaurai (85/15) ¹ O g

Xthanol 153 ml

After drying, the thickness of the photoconductive 3ohioht was 25 and the photoconductive layer 16 of the recording material 18, which is in contact with a negative original 19 is 1 minute exposed with a 75 watt lamp 20 at a distance of 10 cm, as shown in Fig. 2a, and then with a Scheiaatiseh developed the apparatus shown in Fig. Zb.

The guide wale 2I ₁ which touches the carrier 15 is connected to the positive pole and the smooth ink orphan 22 to the negative pole of a 100 volt DC power source 23. The smooth ink orphan is made of stainless steel 18/8 and has a diameter of 25 mm. The exposed photoconductive material is passed between the smooth ink whale 22 and the guide whale 21 at a speed of 1 a / min. The developing liquid is the same as in Example 1. A positive, true, purple-blue image 24 is obtained.

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ORIGINAL INSPECTED

Example 7

An electrostatic latent image is formed on a photoconductive selenium plate in a known manner. This latent electrostatic Image is made with a Ijelgen dispersion of p-phenitidine hydrochloride made visible in hexane. The electrophoretically developed image is pressed against a paper, the surface of which is zinc oxide and that beforehand with a 2% aqueous solution of Potassium hexacyanoferrate (III) has been treated with pH 2. A smudge-proof, purple transfer image is obtained on the paper.

Example θ

Its photoconductive composition, which was prepared as in Example 4, is applied to a support of 70 g glassine paper in a ratio of 12 square meters / liter. Exposure and development are as shown in FIG. The exposure takes place for 6 seconds through a slide with a 75 watt lamp at a distance of 10 cm. The ink roller 25 has a diameter of 59 mm, is corrugated in a helical manner and is made of stainless steel 18/8. The screw groove 26 has a depth of 0.2 mm and a bottom angle of 60 °.

909819/0920 originally inspected

The guide roller 27, which comes into contact with the carrier 15, has a diameter of 30 μm and consists of aluminum. The ink roller 25 has a speed of 100 Uradrehun ^ s per minute and forms a Fltissigkeitsmini3ku3 28 se ^ en, the 16th to be developed photoconductive 3chicht While ier Bntwicklunj is the Tintenr / Alze 25 nit the positivon pole and the guide roller 27, with dea jie _o ative pole of a 200 volt direct 3tro: ai £ uelle 29 connected.

The developing liquid was produced by means of 7 _; ai ^ chen an aqueous solution of 2-methyl-7-a2iino'benzthiazole hydrochloride with an aqueous potassium hexaoyanoferrate (III) solution.

A positive, erasable purple-blue image 30 is obtained.

Example 9

200 jbI of a 10 / ds ** solution of ron 31! AYS ^- SLITE SSTEa 10 (a glycerin-Beter of hydrogenated rosin marketed by The Hercules Powder Company Ino #, Wilmington, Del., USA) in ethylene chloride are 2 al to a 105 * dgen solution of monobutyl phosphate in ethanol and 30 g of conductive cintoxy powder added. The laughter is ground in a gel mill for 4 levels. Kit of this photoconductive dispersion is coated on a paper support, the surface of which is covered by kaolin, namely by dew application in one

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BATH ORIGINAL

Men ^ e of 20 g per> jra. The photoconductive dis ^ eraionachioht vjird dried at 40 ° 0.

The dry photoconductive layer obtained is charged by a corona discharge to -300 V / om and then exposed through a slide for 6 seconds using a 75 watt lamp at a distance of 10 approx. The electrostatic latent image is developed with a developing machine such as is authentically in Pig. 1 wad is described in Example 3.

The photoconductive layer bearing the latent image becomes one For ζ liquid from a 25% aqueous solution of potassium hexacyanoferrate (lll) in this developing machine ait a speed of 2 m / min, brought into contact.

Immediately after the application of this liquid, the photoconductive Material is passed between a second pair of T-rollers that is also arranged as shown in Fig. 1. The applicator roller applies the image-wise pickled photoconductive layer with a 1? fig aqueous solution of methylene blue in contact. The cationic dye is firmly adsorbed on the stained surface parts and becomes an intense one positive blue image is obtained.

BATH

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Example 10

For 100 ml of a 10-day solution of AEOOLOR 5460 (a Monsanto Chemicals Ltd., London, marketed chlorinated polyphenyl resin 2 ml of a 10 / oijen solution of Monobutyl phosphate in ethanol and 50 g photoconductive zinc oxide powder added. This mixture is ground in a ball mill for 4 hours and then dipped onto a barite in an amount of 20 g / m² Paper carrier applied. The photoconductive layer obtained after drying is charged, imagewise exposed and developed, as described in Example 9, in a developing liquid containing 2 g of 2,4-diaminophenol and 1 g of potassium hexaoyanoferrate (III) to 100 ml of water contains · Finally, this · material undergoes a post-treatment with a 2> strength aqueous Faoein solution, which is applied with the ink roller of the second roller pair

Example 11

2 ml of a 10bigen solution of monobutyl phosphate in ethanol and 50 g of a photoconductive zinc oxide powder was added to 100 ml of a 1Obigen Solution of OUMAB HBSIN F 25 (trademark for a coumarone-indole resin from Barrett Chemicals, New York, USA) in methylene chloride. The whole was milled in a ball mill for 4 hours. üirz before the application, 4 «lL of a sweet solution of amber

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^:: BAD ORIGINAL

Acid in ethanol was added to the photoconductive dispersion. then the dispersion was in a ratio of 20 g per <im on one Glassine paper of 60 g per square meter is applied.

After drying, the photoconductive zinc oxide was charged, imagewise exposed and developed as described in Example 1 is, but with a developing substance, the 2 g of 3i4-diraethoxyaniline and 1 g Laliumhexacyanoferrat (III) per 100 ml of water contains.

Example 12

To a solution of 30 g of Plexigum P 25 in 300 ml of Soluol, 90 ″ g of photoconductive zinc oxide and 6 ml of a 10% solution of monobutyl phosphate in ethanol were added. This mixture was ground thoroughly in a ball mill and then mixed with 200 ml of toluene and 12 ml of a 5 / & solution of succinic acid in ethanol added, the ^{photoconductivity:;.} .hije g dispersion was in a ratio of 20 per CJM on a per ^ aininpapier and dried at 40 ° C.

After drying, the photoconductive layer was synchronized with it a negative original 19 a minute with a 75 T7att lamp at a distance of 10 Ons and then in an apparatus as shown in Fig. 4. The applicator roller

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BATH ORIGINAL

25 is a cylinder made of stainless steel with a 18/8 Durchaeuser 25 aiu .and a Ln ₁ ^ e of 25 cm. The surface of the jalze is provided with a ucliraubon-shaped sifflun ^. The grooves 26 have a depth of 0.5 m and a vertex angle of 0.5.

The ends of this applicator roll are filled with a pickling liquid as described in Example 4. This liquid is held in the grooves by xapillary lifts, the guide roller 27 is an aluminum cylinder with a _; a diameter of 15 µm and a length of 25 square meters.

The exposed photoconductive material Ίθ, desdeii ^ hotoconductive 3ohicht 16 with the grooved roller 25 moistened by heating fluid 3 ^ is in contact, is between these \ 7alters and the J? uhrung3walze passed through at a speed of 5 m per minute.

During the passage of the photoconductive material 18, which the latent Image is deceptive, between the rollers a 400 volt DC voltage is applied between the two Y-folds by placing the guide roller 27 with the positive one Pole and the applicator roller 25 alt deg negative pole of an equal Power source 52 connects.

After application of the Beisflüasigkeit 5I, the material becomes between a pair of smooth tails, but between them no voltage is applied and its feed roller with a point

909819/0920 bad original

wässri has been wetted _o en solution of cresyl Blue (CI 5 "Ό1θ). A positive abrasion resistant blue image is obtained.

The optical sensitization of the photoconductive layer is successful performed iait 1 ml of a 1 fig solution of fluorescein sodium salt (CI. 45350) in methylglycol, with 4 al of an o, 1; »igen solution of Chrome Azurol S (C.I. 43825) in methylene glycol or with 1 ml of a o, i7 «lgen solution of iioue bengal (CI. 45440) in methylglycol.

-Patentana claims-

909819/0920 ^BAD

Claims (1)

Dr. Expl. Claims .1.) Process for the spontaneous generation of erasable images duroh image or Application of clay liquid on a recording element containing zinc oxide according to the record, thereby characterized in that an aqueous composition is used, in addition to Heiaoyanoferrat (III) ions contains aromatic or heterooyolic primary or secondary amine 2 · Process for creating erasable images by image or application of liquid to a recordable zinc oxide containing recording element, thereby Marked that one after the other a) an aqueous composition containing Eexaoyanoferrat (III) ions and b) an aqueous one containing a cationic dye Solution are applied. 909819/0 920 3. The method according to A. 1, characterized in that that, one after the other a) an aqueous composition, the hexacyanoferrate (III) ions contains, and b) an aqueous solution, the ala reducing agent an aromatic or heterocyclic alaine containing, can be applied. 4. The method according to A. 2 and 3 marked as “characterized”, that a) an aqueous composition containing hexacyanoferrate (III) ions, and b) an aqueous, a cationic dye and as a reducing agent containing an aromatic or heterogeneous amine Solution can be applied one after the other. 5. The method according to A. 1, characterized in that that as an aaiino connection connection a connection with a ' aromatic system is used which is substituted by at least one primary amino group and in which at least a ortho position, based on this aaino group, is unsubstituted is relaxed, while in other positions the aromatic system BATH ORIGINAL 909819/0920 duroh one or more substituents is substituted in such a way that the currents of the 6th -> 7th of the other substituents - exceeds 0.66 and is not greater than plus 0.874. 6. The method according to A. 1, characterized in that that a primary A; ain der or is used, where A is chlorine, bromine, lower alkyl, Aeetylaaino or acetyl and B is hydroxyl or A'iiino. 7. The method according to A. 1, characterized in that that the aqueous composition is acidic, 8. Process for the generation of non-erasable images by means of image or recording media Application of liquid to a recording element containing zinc oxide, characterized in that that one after the other ) an aqueous, hexacyanoferrate (II) ion containing setzun ^, and b) an aqueous one containing a cationic dye 3eiziut3 applied 9Ö9819 / 0920 _BA D ORIGINAL 9. The method according to Α · 5 »characterized in that that al3 katicniocher .ye a Triar.yliethan-i'arbatoff uses will· 909819/0920