DE2100184A1 - Imaging process - Google Patents

Description

Patent attorneys Dipl.-Ing. E Weickmann,

Dipl.-Ing. H. Weickmann, Dipl.-Phys. Dr. K. Fincke XMY Dipl.-Ing. F. A. "Weickmann, Dipl.-Chem. B. Huber

8 MUNICH 27, DEN

Case XD / 1921 möhlstrasse 22, phone number 483921/22

XEEOX CORPORAiDION, Xerox Square, Rochester, N.Y. 14603 / USA

Imaging process

The invention relates to an imaging method based on the contact-reflex principle with a multilayer recording medium, the imaging layer of which is between a donor sheet and a receiving sheet is arranged and has an electrically photosensitive material that when exposed to an electrical Field and electromagnetic radiation is breakable.

Reproduction systems employing a photosensitive recording medium generally require expensive and extensive ones Exposure devices with optical elements, which create a light pattern on the photosensitive recording medium focus. No optics are required when producing a reproduction of a see-through image on a scale of 1: 1, because the transparent image is brought into direct contact with the recording medium and is transilluminated. This kind of However, reproduction is not possible if an opaque original image is used.

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Up to now it was "not possible to use the so-called multilayer process according to the contact-reflex principle. This multilayer process is known, for example, from British patent specification 1,150,381. It was previously of the opinion that the image-forming layers used in the multilayer process were not transferred from a donor sheet to a sheet If a sufficiently intense radiation were used that would penetrate the image-forming layer independently of radiation reflected from an image surface, a reflection method has many advantages over other reproduction methods. First and foremost, it is inexpensive and requires little space perform. find a contact reflex ^V requires no optics. optics good quality are expensive. Therefore, in an imaging process without optics significant cost savings. Further, by the arrangement of an original to be copied on the recording medium instead of at a point determined by the focal length of an optical system, it is possible to reduce the space requirement and thus to increase the versatility of a reproduction device.

The object of the invention is therefore the image generation using the multi-layer process to make it suitable for the reflex principle. In particular, the generation should be laterally correct Images on opaque documents may be possible.

A method of the type mentioned at the outset is designed according to the invention to achieve this object in such a way that on one side of the recording medium an original to be copied is applied and an electromagnetic one through the recording medium Radiation is exposed that an electric field is generated at the imaging layer and that when it is present electrical field a separation of the donor sheet from the receiver sheet is carried out.

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In the method according to the invention, a multilayer recording medium is used which consists of an electrically photosensitive Imaging layer is formed between a transparent donor sheet and a transparent receiver sheet is. This multilayer arrangement is brought into contact with an image to be copied, the image-forming layer becomes a exposed to an electric field and the image to be copied is illuminated through the multilayer arrangement. That Light reflected on the image in the surface parts not belonging to the image exposes the image-forming layer on the the side facing away from the light source. Surprisingly, light is transmitted through the imaging layer, though the donor sheet is mostly tinted throughout. This is an exposure of the image to be copied and a reflection on this image are possible. As will be explained, the Image-generating layer exposed from both sides in the areas not belonging to the image, while such ropes of the image-forming layer, which lie on the surface parts of the image to be copied belonging to the image, only from one side to be exposed. If the multilayer arrangement is separated in an electric field, the imaging layer breaks and it breaks the result is an image-wise distributed pattern on the donor sheet and on the receiving sheet, one of which is a negative image, the other a positive image of the original image

It can be a reversed positive image of a positive original image getting produced. For example, a transparent donor sheet or receiver sheet can be used that is made opaque in a manner to be described.

Another possibility for generating a correct-sided positive image on an opaque base according to the invention The process consists of using a transparent original on the receiving sheet To illuminate donor sheet and receiving sheet and then that

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change electric field before the multi-layer arrangement after the process described in British Patent 1,216,741 is separated. A positive, reversed image results on the donor sheet when the multilayer arrangement is separated. An opaque support preferably wetted with an activating agent for the imaging layer is used in place of the receiver sheet and the multilayer assembly is restored. Then it becomes an electric Field applied again to the multilayer arrangement, the polarity being set to match that during imagewise exposure. In this electric Field, the multilayer arrangement is then separated again, and it results on the opaque base a positive and laterally correct picture. In some cases, the above process can also be performed if the Original image is on the donor sheet. A positive, right-sided image is then obtained on the transparent donor sheet, if the electric field is not reversed after the irradiation but before the separation of the multilayer arrangement. In order to obtain a correct and opaque image, the field is after the exposure, but before the separation of the Multi-layer arrangement reversed. After separation, an opaque pad, preferably with an activating liquid is wetted, used instead of the dispenser sheet, and the multilayer arrangement is restored Then a new electric field is generated on the multilayer arrangement, which has the same polarity as during exposure When this arrangement is separated, there is a peeltives and right-sided image on the opaque surface.

The method according to the invention is particularly suitable for producing transparent images. Such pictures are usually used in projectors.

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The invention is described in the following with the aid of exemplary embodiments shown in the figures. Show Ss

1 shows the section of a recording medium suitable for the method according to the invention,

Fig. 2 the exposure of the Aufaeichnungsträgers beie method according to the invention,

3 shows the separation of the multilayer recording medium and FIG

4 shows a preferred embodiment for irradiating the copying images with the action of an electric field on the image-generating layer.

In Fig. 1, an image forming layer 2 is shown, dit electrically photosensitive material 3 dispersed in a binder 4 contains. This layer is removable on the surface of a donor sheet · 5 · Am receiving sheet is in contact with the imaging layer 2 and thus completes the multilayer recording medium.

The image generation layer 2 serves as a light-sensitive element and as a coloring agent for the image to be generated. Toggle "particular coloring agents such as dyes and pigment materials can be provided in the Bilderzeugungssohicht to the color of the · image produced to intensify or modify preference · -. 'As the image forming layer is selected so that it has a high sensitivity and at the same time has an intense color, so that high-contrast images are generated. The image-generating layer can have a homogeneous structure and consist, for example, of a solid solution of two or more pigment substances. It can also have a heterogeneous structure and, for example, contain pigment particles dispersed in a binder, such as it is shown in Fig. 1. The thickness of the imaging layer is for the homogeneous or the heterogeneous structure

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ORIGINAL INSPECTED

between about 0.2 / U and about 10 / U, generally about 0.5 up to approx. 5 / U and preferably at approx. 2 / U, the weight ratio from light-sensitive pigment to binder can vary between approx. 10: 1 and approx. 1:10 in the case of the heterogeneous structure In general, it has been found that ratios in the range from about 1: 4 to 2: 1 show the best results, which is why this range is preferably used.

The binder used in the heterogeneous imaging layer or the material used in connection with the photosensitive material of the homogeneous layer may be any of them suitable cohesive-white insulating material or from such a material Material exist that is converted into the cohesive-white state “Typical such substances are microcrystalline waxes such as: Sunoco 1290, Sunoco 5825, Sunoco 985, all available from Sun Oil Co .; Paraflint Rö, available from the Moore and Munger Company; Paraffin waxes such as: Sunoco 5512, Sunoco 3425 available from Sun Oil Co .; Sohio Parowax, available from the Standard Oil of Ohio; Hydrogenated oil waxes such as Capitol City 1380 available from Capitol City Products Co., Columbus, Ohio; Caster Wax L-2790 from Baker Caster Oil Co .; Vitikoto L-304 from Duro Commodities; Polyethylene like: Eastman Epolene N-11, Eastman Epolene C-12 available from Eastman Chemical Products Co .; Polyethylene DYJT, Polyethylene DYLT, Polyethylene DYDT, all available from Union Garbidt Corp .; Marlex TB 822, Marlox 1478, available from Phillips Petroleum Co .; Epolene 0-13, Epolene C-10, available from Eastman Chemical Products, Co .; Polyethylene AC8, Polyethylene · AC612, Polyethylene 1.0324 available from Allied Chemicals; modified Styrenes such as: Piccotex 75, Piocotex 100, Piocotex 120, available from Pennsylvania Industrial Chemical; Vinyl acetate-ethylene copolymer such as: Elvax Resin 210, filvax Resin 310, Elvax Resin 420, available from E.I. duPont de Nemours & Co., Inc .; Vistanex L-80 available from Enjay Chemical Co .;

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Vinyl chloride-vinyl acetate copolymers such as: Vinylite VYIiP, available from Uncion Carbide Corp .; Styrene-vinyl toluene copolymers; Polypropylenes and mixtures of these substances · Preferably an insulating binder is used because it allows a greater electric field strength to be used »

Usually d; -? suitable for the process according to the invention Imaging layer applied to a substrate referred to above as the donor sheet. The combination the imaging layer and the donor sheet is referred to as a donor. Become self-supporting imaging views used, a backing is used if the layer is structurally breakable in the ^> State is shifted. The combination of a structurally weak imaging layer and a supporting base is also referred to as a donor. If a binder is used, so can the electrically photosensitive material is mixed with the binder in the usual way, for example by ball milling be. After the proportions of the image-forming layer have been mixed, it is applied to a support in the desired amount.

The imaging layer can be in any desired color, either their natural color or that of the binder or an additional color or pigment exploited who may or may not be photosensitive · Different combinations of these photosensitive and not light-sensitive coloring agents can produce the desired coloring in the image layer.

The donor sheet 5 and the receiving sheet 6 can be of any suitable type electrically insulating or electrically conductive material exist. Electrical insulating materials are preferred applied because they use polymeric materials with high strength allow. Furthermore, the donor sheet and the receiving sheet are at least partially permeable to the electromag-

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magnetic radiation to which the imaging layer is sensitive reacts, since in the method according to the invention the electromagnetic radiation through the multilayer arrangement towards the copying image occurs and is reflected on this through the donor sheet or through the receiver sheet and onto the Imaging layer acts. Typical insulating materials are polyethylene, polypropylene, polyethylene terephthalate, cellulose acetate, Polyester, paper, plastic, for example polyethylene, coated paper, vinyl chloride-vinylidene chloride copolymers and mixtures of these substances. Mylar (a polyester formed by the condensation reaction between ethylene glycol and terephthalic acid available from E.I. duPont de Nemours & Co., Inc.) is preferably used because of its durability and excellent insulation properties. This kind of polymeric materials of high strength not only enable the Formation of a solid base for the positive image or negative image generated on the donor sheet and the receiver sheet, but in addition they form an electrical barrier between the electrodes and the imaging layer, thereby creating electrical flashovers can be avoided when the image-forming layer is brought into the electric field. on this provides a useful multi-layer arrangement when an insulating donor sheet and a conductive receiver sheet are used.

The donor sheet and the receiving sheet can also contain substances that are transparent, but after imaging can be treated to change their appearance For example, transparent sheets can be coated with a mixture of silver benate, benzic acid and protocatechic acid as described, for example, in U.S. Patent 2,910,377. A reaction occurs when the coated sheet is heated in the layer that results in a visible change in leaf color.

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Another way to change the appearance of the transparent donor sheet or receipt sheet "consists of at least one surface with a penetrating liquid to coat which, when heated, creates a microscopic pattern of different cohesion on the surface of the sheet generated. When heated, the surface is fish with a microscope Covers irregularity formed by hemispherical bumps or protrusions that scatters light. Different Substances and processes for this are described in US Pat. No. 3,111,584.

Normally opaque or translucent fabrics can also be used in the method of the invention when they are at the time of application of the image layer can be made transparent. In some cases, the actuating agent used in the imaging may be also make the donor sheet and / or the receiving sheet transparent. For example, a mineral oil can be used to to put a paper donor sheet and receiver sheet in the transparent state. After imaging the oil is removed and the paper in its initial state set back. Various other substances that can be used as activating agents can also be paper make temporarily transparent and therefore be used in the method according to the invention.

Other heat sensitive materials can be used with the donor sheet and the receiver sheet and used to change the Serve light transmission. One such substance is a liquid crystal which is reversible when the temperature changes Changes from the opaque to the translucent state.

Many other substances with variable light transmission can also be used in the method according to the invention, for example diazo films, which have opaque colors

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Form treatment with ammonia. Am such procedure is as a Kalvar method that works with diazonium compounds, known. In this process, a very thin layer of approx. 0.013 mm is applied to a film made of polyester, for example. When a sheet of this material is irradiated with ultraviolet light in the range of about 3500 to about 4150 X units, the diazonium compound decomposes and releases nitrogen in the form of tiny bubbles. These glass bubbles can then expand by heating the leaf, which causes tiny bubbles to appear in the plastic coating, which act as light-scattering Elements work and change the light permeability of the sheet.

Further processes and substances for changing the light transmission of donor and receipt sheets are known to the skilled person

For the donor sheet and the receiver sheet, preferably those substances are used that have a transparent one on one side and have conductive coating. Fabrics such as conductive cellophane and aluminum-coated plastic pads such as aluminized mylar are preferably used, as they make a transparent electrode superfluous. Furthermore, conductively coated, transparent fabrics are preferred used because the electric field at the multiplex arrangement can be generated without arranging the image to be copied in the electric field, which would be the case if separate Electrodes would be used.

As can be seen from Fig. 1, the layer 2 contains an electrically photosensitive material 3. Typical organic suitable substances are quinacridones such as 2,9-dimethylohinacridone, 4,11-dimethylquinacridone, 2,10-dichloro-6,13-dihydroquinaoridone, 2, 9-dimethoxy-6,13-dihydroohinacridone, 2,4 »9,11-tetraohlorohinaoridone, and solid solutions of quinacridones and other compounds described in US Pat. No. 3,160,510; Garbozamides such as N-2 ^w -pyridyl-8,13-dioxodinaphtho- (2,1-2, 3 ') - furan-6-carbox-

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amide, N-2 ⁿ - (1 ^w , 3 ", 5 ⁿ -Dioxodinaphtho- (2,1-2, 3 ') -Euran-6-earboxwnid, Anthra- (2,1) -naphthol (2, 3-d) -furan-9,14-dione-7- (2'-methylphenyl) -carboxamide; carboxanilides such as: 8,13-dioxodinaphtho- (2,1-2.3 ') -furan-6-carbox -p-methoxyanilide, 8,13-dioxodinaphtho- (2,1-2 ¹ , 3 'J-furan-o-carbox-p-methylanilide, 8,13-dioxodinaphtho- (2.1-2% 3M-furan 6-carbox-m-chloroanilide, 8,13-dioxodinaphto- (2,1-2 », 3 ') -furan-6-earbox-p-cyananilide j Triazines such as: 2,4-diaminotriazine, 2,4-di - (1 · -anthraquinonylamino) -6- (1 ^w -pyreiyrl) -triazine, 2,4-di- (1'-anthraquinonylamino) -6- (1 ^w -naphthyl) -triazine, 2,4-di- ( 1'-naphthylamine) -6- (1'-p / erylenyl) -triazine, 2,4,6-iri-d ', 1 ^w , 1 ^nl -pyrenyl) -triar, in; benepyrrocoline like 2,3-phthaloyl -7i8-tenzpy ^T · acolin, 1-Oyan-2,3-phthaloyl-7,8-lienzpyrrocolin, 1-cyano-2,3-phthaloj -S-acetamido-V ^ -laenBpyrrocolin; anthraquinones such as:. 1.5 -Bis- (ß-phenylethylamino) -anthraquinone, 1,5-bis- (3'-methoxypropylamino) -anthraquinone, 1,5-bis- (tienzylamino) -anthraquinone, 1,5-bis- (phenylami no) -anthraquinone, 1,2,5,6-di- (c, c'-diphenyl) -thiazolanthraquinone, 4- (2'-hydroxyphenylmethoxyamino) -anthraquinone; Azo compounds such as: 2,4,6-! Dris- (N-ethyl-N-hydroxyethyl-p-aminophenylazo) -phloroglucinol, 1 »3» 5,7-tetrahydroxy-2,4,6,8-tetra- (N -methyl-N-hydroxyethyl-p-aminophenylazo) -naphthalene, 1,3,5-trihydroxy-2,4,6-tri- (3'-nitro-N-methyl-N-hydroxymethyl-4 '- «Binephenylaeo) -benzene , 3'-methyl-1-phenyl-4- (3'-pyrenylazo) -2-pyrazolin-5-one, 1- (3'-pyrenylazo) -2-hydroxy-3-naphthanilide, 1- (3'- Pyrenylazo) -2-naphthol _T 1- (3'-pyrenylazo) -2-hydroxy-3-methylxanthene, 2,4,6-tris- (3'-pyrenylazo) -phloroglucinol, 2,4,6-tris- ( 1'-phenanthrenylazo) -phloroglucinol, 1- (2'-methoxy-5'-nitro-phenylazo) -2-hydroxy-3'-nitro-3-naphthanilide; Balzlöeungen salts and compounds which are abeleitet of 9-phenylxanthen, such as phosphorus-tungsten-molybdenum dye Ton3,6-bis (ethylamino) -9,2'-carboxyphenylxanthenoniumchlorid, barium salt of 3-2 ^l -Toluidinamino-6.2 ^H -methyl-4 ^lf -sulfophenylamino-9-2 ¹¹ '-carboxyphenylxanthene j Phoephor-molybdenum dye of 3,6-bis- (ethylamino) -2,7-dimethyl-9,2 · -cari thoxyphenyl-xanthenoniumchlorid} Dioxazine wit: 2,9-dibenzoyl-6,13-dichlorotriphenodioxazine, 2,9-diaoetyl-6,13-dichlorotriphenodioxazine, 3,1O-dibenzopylamino-2,9-diisopyropoxy-6,13-

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diehlortriphenodioxazine, 2,9-difuroyl-6,13-diehlortriphenodioxazine; Colors of fluorescein dyes such as: lead dye of 2,7-dinitro-4,5-dibromofluorescein, lead dye of 2,4,5,7-tetrabromofluorescein, aluminum dye of 2,4,5,7-tetrabromo-10,11,12, ^ -tetrachlorofluorescein; Bisazo compounds such as: N, N '-Di- / "1 - (' -naphthylazo) -2-hydroxy-8-naphthyl_7-adipdiamide, H, JP-Di-I- (I'-naphthylazo) -2-hydroxy-8 -naphthylsuccinidamide, bis-4,4 ^l - (2 ^M -hydroxy-8 ^tt -N, N ^l -diterephthalamid-1-naphthylazo) -biphenyl, 3,3'-methoxy-4,4'-diphenyl-bis- ( 1 ^w azo-2 ^w -hydroxy-3 "-naphthanilide); Pyrenes such as 1,3,6,8-tetraaminopyrene, 1-cyano-6-nitropyrene; Phthalocyanines such as: metal-free β-phthalocyanine, copper phthalocyanine, tetrahalophthalocyanine, the x-type metal-free phthalocyanines, known from US Pat. No. 3,357,989; Metal salts and salt solutions of azo colors such as: calcium lactate of 6-bromo-1- (i'-sulfo-2-naphthylazo) -2-naphthol, barium salt of 6-cyano- (1- (1'-sulfo-2-naphthylazo) - 2-naphthol, calcium liquor of 1- (2'-azonaphthalene-1'-sulfonic acid) -2-naphthol, calcium liquor of 1- (4'-ethyl-5'-chlorazobenzene-2'-sulfonic acid) -2-hydroxy-3 -naphthoic acid and mixtures of these substances.

Typical inorganic compounds are cadmium sulfide, cadmium sulfoselenide, Zinc oxide, zinc sulfide, sulfur selenium, mercury sulfide, lead oxide, lead sulfide, cadmium selenide, titanium dioxide, indium trioxide and similar.

Other organic substances including organic donor-acceptor (Lewis acid-Lewis base) complexes with charge-transferring properties can be found in the British patent 1 150 381.

In addition to the charge-transferring complex substances, many of the other substances mentioned above can also be further sensitized. using the charge transfer complex method. Many of these substances can be color sensitized, to broaden or increase their sensitivity spectrum,

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21O018 A

Bs should also be noted that the electrically photosensitive Substances themselves consist of one or more suitable electrically photosensitive substances mentioned above which can be organic or inorganic and dispersed with any suitable insulating resin, in solid solution or copolymerized, the resin itself may or may not be photosensitive. This particular one Particle type is favorable to facilitate the dispersion of the particles, undesirable reactions between the binder and the photosensitive material or between the photosensitive Material and the activating agent to avoid and to serve similar purposes. Typical resins of this type are polyethylene, polypropylene, polyamides, polymethacrylates, polyacrylates, polyvinyl chlorides, polyvinyl acetates, polystyrene, Polysiloxanes, chlorinated rubber cards, polyacrylonitrile, epoxy resins, Phenolic resins, hydrocarbon resins and other natural resins such as rosin derivatives as well as mixtures and copolymers of these substances.

Preferably the x-form of phthalocyanine is used because it has excellent photosensitivity. However, any other suitable phthalocyanine can also be used to realize the image-forming layer suitable for the process according to the invention. The phthalocyanine used can be in be in any suitable crystal form. It can be substituted or unsubstituted in the ring parts and in the straight chains be. In this context, reference is made to a book by 7.H. Moser and A, L. Thomas with the title "Phthalocyanine Compounds, "Reinhold Publishing Company, 1963, which is a detailed description of the phthalocyanines and their synthesis contains.

FIG. 2 shows the process step of irradiating the image to be reproduced with electromagnetic radiation. The multiplex arrangement 1 includes a dispensing sheet 5 _f, an image forming sheet 2 and a receiving sheet

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6, which rests on an image 7 to be reproduced. This image contains printed areas 8 and non-printed areas 9, In the illustrated package, the donor sheet 5 and the receiving sheet 6 are electrically conductive with a thin, transparent coating Material provided so that they perform a double puncture in the method according to the invention · Except for their function As a donor or receiving sheet, they also serve as electrodes, . to the one voltage of the voltage source 10 via a resistor 11 can be switched on. The electric PeId can can be produced in a wide variety of ways. In general, the multilayer arrangement between electrodes becomes different brought electrical potential. In the case of an electrically insulating donor and receiving sheet, an electrical Charge is applied to one or both of the sheets before or after the multilayer assembly is formed by any of the known methods will. Static charges can be generated by touching the sheet or pad with an electrically charged electrode be transmitted. Either or both sheets can also be charged by using corona discharge devices of the in U.S. Patents 2,588,699, 2,777,957 and 2,885,556 Kind be used. Furthermore, conductive rollers according to US Pat. No. 2,980,834 or a friction device can be used US Pat. No. 2,297,691 or other suitable devices can be employed.

The strength of the electrical generated on the multilayer Peldes depends on the structure of the recording medium and the substances used. For example, they are highly insulating If substances are used for the receiving sheet and the donor sheet, a much stronger peId can be generated than with relatively conductive material. However, the required field strength can easily be determined. Becomes an au high potential applied, an electrical flashover occurs in the multilayer arrangement on, creating an arc between the electrodes. If the potential is too low, so the image material layer is not distributed in an image-wise manner

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transfer. If, for example, a Mylar receiving sheet 0.08 mm thick and a Mylar donor sheet 0.05 mm thick are used, potentials in the order of magnitude of 20,000 V can be connected to the electrodes. A field strength on the multilayer arrangement in the range from approx. 790 V / 0.01 mm to approx. 2750 V / 0.01 mm is preferably generated on the electrically insulating material. Since relatively high potentials are used, it is beneficial to include a resistor in the circuit to limit the flow of current. Resistances on the order of about ₀ 1 to about 20,000 megohms are usually sufficient.

As can be seen from Fig. -2, the electromagnetic radiation 12 passes through the donor sheet 5 and hits the imaging layer 2. Some of the radiation passes through the imaging layer and the receiving sheet 6 and hits the image 7 to be reproduced Surface parts 9 belonging to the image, a large proportion of the electromagnetic radiation is reflected through the receiving sheet 6 onto the image-forming layer 2, so that these parts of the image-forming layer facing away from the light source are irradiated. In the surface parts 3 belonging to the image, the electromagnetic radiation is absorbed and a very small or no portion is reflected onto the image-forming layer 2, so that the relevant parts of the image-forming layer 2 are only irradiated from the side facing the radiation source. Surprisingly, only a small proportion of the radiation from the opposite direction is required in order to generate a radiation difference and thus an image-wise distributed breaking of the image-generating layer. The amount of light transmitted through most of the imaging layers is as above. 10 # of the amount that activates the layer during normal exposure. Only about 60 to 75 # This transmitted clear need of the reflected image to be reproduced on ü η non-printed parts to cause an image-wise distributed fracturing the Bildstoffichicht. The actual required

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The amount of light changes depending on the sensitivity of the electrically photosensitive material in the image layer and of course the opacity of the binder, the donor sheet, the receiver sheet and the optional existing electrodes.

A source of visible light, ultraviolet light, or other suitable electromagnetic radiation can be used to irradiate the image layer. The electrically photosensitive material is selected so that it is sensitive to the wavelength of the electromagnetic radiation used. It should be noted that different electrically photosensitive substances have different sensitivity spectra and that the sensitivity spectrum of many electrically photosensitive substances through Color sensitization can be narrowed or broadened, so that it has, for example, more panchromatic properties receives. Furthermore, the electromagnetic radiation is selected so that it is applied to the unprinted or white Surfaces of the image to be reproduced is reflected. The amount of radiation is usually of sensitivity of the electrically photosensitive material present in the image-forming layer. Sufficient for most fabrics an exposure on the order of 100 to a few 10,000 luxsec. Usually 215 to 540 Luxsec satisfactory results can be obtained for some imaging layers which are colored black, for example applied up to approx. 27,000 Luxsec.

In Fig. 3, the step is to separate the multilayer assembly shown schematically after exposure to electromagnetic radiation. The donor sheet 5 is replaced by the recipient sheet 6 separated, which lies on the image 7 to be reproduced. During the separation, the electric field is removed from the voltage source 10 also maintained via resistor 11. The direct over the image area parts of the image 7 lying parts of the

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21OO18A

The image-forming layer 2 now adhere to the receiving sheet, while those overlying the surface parts that do not belong to the image Parts of the image material layer 2, which from both sides of the were exposed to electromagnetic radiation, are present on the donor sheet 5. When separating donor sheet and Receiving sheet thus results in a positive image of the original 7 on the receiving sheet 6, and a negative image of the original 7 the donor sheet 5.

The image generation layer 2 is thus transferred to the receiving sheet 5 in those areas which correspond to the image areas of the μ image 7. This is because the imaging layer 2 is disposed on the donor sheet 5 so as to be releasable. In order to facilitate handling and storage of the donor sheets, a non-breakable imaging layer 2 is generally used on a donor sheet 5 which, when the imaging process is carried out, is rendered structurally breakable so that it can be broken by an electric field and exposure to electromagnetic radiation. The method for achieving such a state of the image-forming layer is also referred to as activation. The activation step can be carried out in various ways, for example, layer by heating the image forming layer or \ applying a substance to the surface of the imaging ™ or entrapping a substance into the _imaging; layer, so that it makes the imaging film peelable when properly treated. The substance used in this way is called an activating agent. It should preferably have a high specific resistance in order to avoid an electrical flashover in the multilayer arrangement. In general, it is desirable to improve commercial Akti-tives by removing ron impurities that could cause a higher conductivity. This is done by passing the liquids through a clay filter column or by using another suitable purification process. Generally speaking, the activating agent must be made of a suitable material

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exist which has the aforementioned properties. In the present description, an activating agent is intended Not only those substances are understood that are normally referred to as solutions, but also those Substances, some of which are solvents, swelling agents or softening agents for the imaging layer. The activating agent can be introduced at any point in the process prior to the separation of the multilayer arrangement.

The activating agent should preferably have a relatively low boiling point so that the image produced can be fixed can be done by evaporation of the activating agent. If desired, the fixation can be done by at most low levels Warming can be accelerated. It should be noted, however, that the invention is based on the use of relatively evaporable Activating agent is not limited. Activating agents with a very high boiling point have also been used successfully, which cannot evaporate. These include, for example, silicone oils such as Dimethy! Polysiloxane and long-chain, aliphatic Very high boiling point hydrocarbon oils commonly known as transformer oils. One such Oil is Wemoo-C transformer oil, available from the Westinghouse Electric Co. Although these are less digestible Do not dry active detergent through evaporation, the image fixation can be achieved by touching the final image with an absorbent sheet such as a sheet of paper, take place, which soaks up the activation liquid. Any suitable evaporative or non-evaporable activating agent so can be used. Typical activating agents are Sohio Odorless Solvent 3440, an aliphatic one (Kerosene) hydrocarbon content, available from the standard Oil Co. of Ohio, carbon tetrachloride, petroleum ether, Freon 214 (tetrafluorotetrachloropropane), other halogenated hydrocarbons such as Ohlorform, Methylenohlorid, Triohloräthylen, Perchlorethylene, chlorobenzene, trichloromonofluoromethane, trichloro

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trifluoroethane, ethers such as diethyl ether, diisopropyl ether, dioxane, Tetrahydrofuran, ethylene glycol monoethyl ether, aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, hexane, gyelohexane, gasoline, mineral acids and white mineral oil, vegetable oils such as coconut oil, babussu oil, decane, dodeean and blends these substances. Sohio Odorless Solvent 3440 is preferably used, as it is completely non-toxic and non-toxic has a relatively high point of inflammation.

In a preferred embodiment of the invention Method is a rolling movement in ^; relocatable optical system used, which has the double function of the action of an electric field on the recording medium and the generation the electromagnetic radiation for the image to be reproduced. This optical system either becomes stationary arranged while the recording medium is moved past tangentially in contact therewith, or it is over the Rolled stationary recording medium »The optical system is preferably rotatably mounted in a fixed position, so that the multilayer recording medium can be passed under it in contact. In Fig. 4 is one such rotatable optical system shown. It contains a cylinder 17 with a transparent base 201, located in the cylinder a tubular source of electromagnetic radiation, e.g. an incandescent lamp or a fluorescent lamp 203 « A reflective shield 205 surrounds the radiation source 203 so that its radiation is directed onto a segment of the cylinder 201 is thrown. The transparent cylinder 201 can be made of any suitable material suitable for the electromagnetic Radiation is permeable. The cylinder consists in the most general case of glass, the electromagnetic radiation lies in the visible part of the spectrum. Other transparent material can also be used if there is transparent to electromagnetic radiation used is. Plastic material such as polymethyl methacrylate, which is used under the Name Plexiglas from Höhm & Haas and under the name

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Lucite from B.I. duPont de Nemours & Co., Inc. is available, can be used. On the circumference of the transparent cylinder 201 is a layer of electrically conductive material 207 arranged. It can consist of any electrically conductive material that is suitable for electromagnetic radiation is permeable. Suitable substances are, for example, aluminum, gold, silver, copper, magnesium and other metals. they form thin layers on the cylinder so that they are transparent to the electromagnetic radiation used. Preferably a glass cylinder coated with tin oxide is used.

The conductive coating 207 on the cylinder can either be obtained by applying a thin conductive film directly to the cylinder Outside of the cylinder can be formed, or there will be a conductive coating on a transparent film backing on the Cylinder pulled up, whereby the conductive layer is pressed against the outer surface of the cylinder. A conductive coating such as aluminum on a transparent and flexible polyethylene terephthalate film can be firmly attached to a transparent Cylinder are drawn up, whereby an outwardly insulated and electrically conductive coating is formed on the cylinder will.

The thickness of the conductive coating 207 can be varied within wide limits. Usually it is about 0.001 to about 0.1 / U. However, other values can also be used.

The conductive coating 207 is provided with an insulating film 209 which forms an electrical barrier between the conductive Cover and the materials that come into contact with the cylinder forms. Such insulating films are preferably made of polymeric materials with high dielectric strength. Typical such substances are polyethylene, polypropylene, polyester, polyethylene terephthalate ι polystyrene and cellulose acetate. Further electrical insulating materials with the required permeability for electromagnetic radiation are known to those skilled in the art

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Mylar is preferred because of its durability and excellent insulation properties. Mylar with a transparent and conductive vapor-deposited metal coating on the one hand is very suitable, as there is one conductive and one insulating after pulling it onto the cylinder Layer "forms.

According to a preferred embodiment of the invention, there is an electrical voltage source in the transparent cylinder 201 arranged, which supplies a high DC voltage to the conductive layer. This voltage source can by usual concentric Bearings at one end of the cylinder must be grounded and connected to a second electrode so that a electric field can be generated, which is adapted to the imaging process to be carried out. It can also a voltage source arranged outside the cylinder is provided be, wherein an electrical connection between the conductive layer and the voltage source via a sliding or Rolling contact of the concentric bearing of the cylinder is made.

Also in Fig. 4- is a multilayer record carrier 11 showing a receiver sheet 215, an imaging layer 217 and a donor sheet 219 contains. The donor sheet 219 is provided with an electrically conductive base 220. This can consist of a transparent cover, e.g. made of cellophane or a vacuum vapor deposited metal having a thickness which is at least 80% Guaranteed permeability for electromagnetic radiation. Under the multilayer recording medium 11 is an original document 221 is arranged in optical reflex contact with the recording medium 11. Document 221 can also be arranged on a base 223, which is grounded together with the voltage source 211, so that an electrical field is generated on the recording medium 11. By connecting the conductive surface 220 to earth and thus to the

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Voltage source 211 creates an electric field on the recording medium that does not affect the original document. This arrangement is preferably implemented because the Original document does not represent a variable influencing the image generation process.

The following examples serve for further specific explanation the invention. They represent some preferred embodiments of the method according to the invention. Shares and Percentages relate to weight, unless otherwise stated.

example 1

A commercially available metal-free phthalocyanine is first purified by leaching in o-dichlorobenzene and the associated removal of organic impurities. Since this leaching results in the less sensitive crystalline β-form, the desired X-form is prepared according to Example 1 from US Pat. No. 3,357,989. The X-form of phthalocyanine is used for the production of an imaging layer in the following way: approx. 5 g of the X-form of phthalocyanine become approx. 5g Algol Yellow GC, 1,2,5,6-Di- (C, C- diphenyl) thiazole anthraehinone, CINr. 67300, available from General Dyestuffs, and about 2.8 g of purified Watehung Red B, 1- (4'-methyl-5'-chlorobenzene-2'-sulfonic acid) -2-hydroxy-3-naphthoic acid, CI No. 16865 available from EI duPont de Nemours ft Co. was added. The Watehung Red B is cleaned as follows: Approximately 240 g of Watehung Red B were slurried in about 2400 ml Sohio Odorlese Solvent 3440, a mixture of keroain components available from the Standard Oil Co. of Ohio. The slurry is then heated to a temperature of about 65 ° C. and held at that temperature for about 30 minutes. Then it is filtered with a sintered glass filter. The pests are then again with petroleum ether (90 to 120 ⁰ C), available from Matheson, Coleman and Bell (Matheson Company,

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■ "23 ■ ·

East Rutherford, Hew Jersey), slurried and with a sintered glass filter filtered. The solids are then dried in an oven at about 50 ° C.

Approx. 8 g of Sunoco Macrocrystalline Wax Grade 5825 with an ASTM-D-127 melting point of 66 ° C and about 2 g of Paraflint RG, a paraffin material with low molecular weight, available from from Moore & Munter Co., New York City, approx. 144 ml petroleum ether (90 to 120 ° C) and approx. 40 ml Sohio Odorless Solvent 3440 are put in a glass jar together with the pigments entered, which contains pebbles with a size of 13 mm. The mixture is then made by rotating the glass jar ground at approx. 70 rpm for approx. 16 hours. Then the Mixture heated for about 2 hours at about 45 ° 0 and cooled to room temperature. The mixture is then ready for coating a donor pad ready. In its paste-like state, it becomes 0.05 mm thick in subdued green light Mylar (a polyester formed by the condensation reaction between ethylene glycol and tetraphthalic acid, available from the B.I. duPont de Hemours & Go., Inc.) with a wire-wound Spreading stick Mr. 36 up to a layer thickness of approx. 7 »5 / u when dry. The shift and the mylar sheet are then dried in the dark and at a temperature of about 33 ° C for about 30 minutes. The shift will then activated by applying Sohio Odorless Solvent 3440 with a soft brush and a 0.05mm thick Mylar reception sheet placed on the activated imaging layer.

The multilayer assembly thus formed is then placed with the dispenser side down on the tin oxide surface of a NESA glass electrode. An image to be copied is placed on the receiving sheet, and an electrode made of black paper is placed on the picture, which is connected to the positive pole of a volumetric voltage source of 9000 T connected is. The negative pole of the voltage source is connected to the NESA coating via a 5500 megohm resistor. At

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The evenly distributed light becomes a white lightbulb up through the NESA glass and the dispenser sheet projected through it, with a total energy of approx. 22 600 Iiuxsec on the donor side of the imaging layer. After the irradiation, the black paper electrode removed from the donor along with the original image and the receiving sheet, and is on the receiving sheet a positive, laterally correct transparency image. A negative, reversed image is on the donor sheet.

Example 2

The procedure of Example 1 is repeated with the difference that before the original image is placed on the receiving sheet the imaging layer is exposed to an irradiation in the electrical peId of 9000 V, whereby a total energy of approx. 5400 Luxsec. During this irradiation, the NESA electrode with the positive pole is the paper electrode connected to the negative pole of the voltage source. The electric field is switched off while an original image is on the receiving sheet and the original image is on the paper electrode is launched. When the electric field is switched on again with the same polarity as in Example 1, this becomes Original image irradiated through the NESA electrode and the multilayer arrangement with a total of 15,800 Luxsec. at Separation of the multilayer arrangement in the electric field results a reversed negative image on the dispenser, a reversed positive image on the receiving sheet.

Example 3

First, an imaging layer with electrically photosensitive Substances dispersed in a binder. Oa. 100 parts Naphthol Red B, code 20-7575, available from the American Cyanamide Company, are reagent-ethylene diamine dissolved. The solution is immediately filtered with a coarse filter

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pier filtered, the filtrate is mixed with an equal volume of reagent isopropanol. The naphthol red B is excreted in the alcohol and removed with a centrifuge. After separating the ethylenediamine and the alcohol, the electrically photosensitive material is washed successively with isopropanol, a volume mixture in the ratio 2: 1 of isopsopanol and deionized water and with five washing processes with deionized water and filtered until the filtrate is neutral. The material is then washed successively with dimethylformamide and methanol until the filtrate is pale yellow in color. The naphthol red B is then ^{dried at 40 0} O in vacuo, Oa. 3 parts of the purified naphthol red B are mixed with approx. 60 parts of petroleum ether cleaned in a clay filter and ground for approx. 48 hours in a ball mill.

A binder is made by adding about 1.5 parts of Paraflint RG, a low molecular weight paraffin material available from Moore & Hunger Co., New York City, about 3 parts of Polyethylene DYLT, available from Union Carbide Corp., about 3 parts 0.5 part of a vinyl acetate-ethylene copolymer, available under the name Elvax 420 from JS. I. duPont de Nemours Inc., and about 2.5 parts of a modified polystyrene, available as Piccotex 100 from Pennsylvania Industrial Chemical Co., can be mixed with about 15 parts Sohio Odorless Solvent 3440. The mixture is heated until dissolved and then cooled. The mixtures of binder and pigment are then ground together in a ball mill for about 16 hours. After grinding, the mixture is kept at approx. 65 ^° C. for approx. 2 hours, after which approx. 45 parts of isopropyl alcohol are added. The mixture is then ball milled again for 20 minutes. The resulting imaging material is then applied to a 0.08 mm thick Mylar sheet with a spreader set for a spreading gap of 0.11 mm. The dispenser thus formed is dried at ei ner temperature of about 46 · C ^0.

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The dispenser is then placed on the tin oxide surface of a NESA glass plate with the imaging layer applied to the tin oxide. The imaging layer is applied by applying of Sohio Odorless Solvent 3440 activated with a brush and a multilayer arrangement is formed by adding a transparent PiIm made of polypropylene is placed on the activated dispenser as a receiving sheet. An original picture is placed on the receiving sheet and a black paper electrode is placed on it, which is connected to the positive Pole of a DC voltage source of 8500 V is connected. The NESA electrode is connected to the negative pole of the voltage source connected, and during the action of the electric field on the record carrier, the original image is with a white incandescent lamp through the NESA electrode and the multilayer arrangement illuminated through it. The total energy impinging on the donor side of the imaging layer is 452 Luxsee. When separating the multilayer arrangement in the electrical Field results in a positive, right-sided image on the receiving sheet, on the donor sheet a negative, reversed image.

Example 4

The procedure from Example 3 is repeated with the difference that the original image to be reproduced is on the tin oxide surface placed on the NESA glass plate and the multilayer arrangement is placed with the donor side down on the original image. The imaging layer is through Applying Sohio Odorless Solvent 3440 Activated, followed by a sheet of polypropylene on the activated imaging layer is launched. A sheet of electrically conductive and transparent cellophane is applied to the polypropylene film as second electrode is applied, and when the electric field is switched on, the multilayer recording medium is transmitted through irradiated through the transparent cellophane electrode, whereby the total incident energy of the white incandescent

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lamp on the receiver sheet side of the imaging layer 290 Luxsec is. When separating the multilayer arrangement in electric field results in a negative, reversed image on the polypropylene receiving sheet, a positive mirror image on the donor sheet.

Example 5

The procedure from Example 1 is repeated with the difference that before the separation of the multilayer arrangement, the polarity of the electric field is reversed. When the multilayer arrangement is separated, there is a positive, however Reversed image on the donor sheet. The receiver sheet is then removed and it becomes a sheet made of polyethylene coated paper moistened with Sohio Odorless Solvent 5440 and placed on the image on the dispenser sheet, which is located on the NESA electrode. The black one The paper electrode is placed on the polyethylene coated paper, and the electric field is generated with the same voltage.

Voltage and polarity switched on again as in the case of the irradiation in Example 1. When the electric field is switched on, separated the polyethylene coated paper from the dispenser sheet. The result is a positive and laterally correct picture on the paper, this picture was previously on the donor sheet.

Example 6

The procedure of Example 2 is repeated with the difference that a clear, transparent and smooth film is one Copolymers of styrene and acrylonitrile ("Polyflex 200"), the soluble in acetone, partially soluble in toluene and insoluble in heptane, coated with a penetrant and treated according to Example 3 of US Pat. No. 3,111,584. Diet. Film is used as the receiving sheet. He's going to that Image absorbent layer applied, with its coated side

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facing away from the layer. After the separation, the coated The surface of the receiving sheet facing away from the image evenly exposed to short but intense radiation, as used in the thermographic copying process described in U.S. Patent 2,891,165. As a result of this radiation, the receiving sheet is light-scattering over its entire surface, so that a black positive Copy of the original image on a white background results.

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Claims (14)

Claims Imaging process based on the contact-reflex principle with a multilayer recording medium, the image-forming layer of which is arranged between a donor sheet and a receiver sheet, and an electrically photosensitive material has, which is breakable under the action of an electric field and electromagnetic radiation, thereby characterized in that a template (221) to be copied is placed on one side of the recording medium (11) and is passed through the The recording medium (11) is exposed to electromagnetic radiation through that at the image-forming layer (217) an electric field is generated and that a separation of the donor sheet (219) from the existing electric field Receiving sheet (215) is carried out. A method according to claim 1, characterized in that the imaging layer (217) is activated by the action of an activating agent is made structurally breakable, 3. The method according to claim 1 or 2, characterized in that the original to be copied (221) to the receiving sheet (215) is applied. 4. The method according to claim 1 or 2, characterized in that the original to be copied (221) to the donor sheet (219) is created. 5. The method according to any one of claims 1 to 4, characterized in that that an imaging layer (2) is used, which contains an electrically photosensitive image forming material (3) dispersed in a binder (4). 6. The method according to claim 5, characterized in that the electrically light-sensitive material (3) «in organic Material is used. 10 9828/1754 7. The method according to claim 6, characterized in that a metal-free phthalocyanine is used as the organic material (3). 8. The method according to any one of claims 1 to 7 »characterized in that the light permeability of the donor sheet (219) and / or the receiving sheet (215) can be changed. 9 * Method according to claim 8, characterized} that the light transmission is carried out after the donor sheet (219) has been separated from the receiver sheet (215). 10. The method according to any one of claims 1 to 9 »thereby characterized in that electromagnetic radiation in the visible Area of the spectrum is used. 11. The method according to any one of claims 1 to 10, characterized in that an electric field with a field strength from 790 V / 0.01 mm up to 2750 V / 0.01 mm is generated. 12. The method according to any one of claims 1 to 11, characterized in that the electric field on the image-forming layer (217) changed after the irradiation of the original to be copied (221) and the separation in this changed PeId is carried out. 13. The method according to claim 12, characterized in that also at least one of those on the donor sheet and the receiver sheet generated images with a substrate wetted with an activating agent for the image generation layer in Is brought into contact that an electric field on the imaging layer with the same polarity as before change of the electric field is generated and that the substrate is separated from the sheet carrying the image in this electric field with the image being transferred to the substrate. 109828/1754 14. The method according to any one of claims 1 to 11, characterized in that an electrical PeId on the image-forming layer (217) generated and this an evenly distributed electromagnetic radiation to which they are sensitive is suspended before the original to be copied is placed on one side of the recording medium (11). 10Ü823 / T75A eers iie