DE2015848A1 - Method for loading an insulation layer - Google Patents

Description

Pateatanwälie
Dipl.ing.F-Weickniann · ■ _. _fjnGke

Munich

Soh / Gl,, - /. Ζ.3Φ6 (XD / 2356)

Xerox Corporation, Hochester, Yle \ r. York 14603, V. ^ tvA

Method of loading an insulation layer

The present invention relates to a method of loading an insulation layer, and relates in particular to a Method for loading an insulation layer that is necessary for! Implementation a hectography image generation method is used

The hectographic imaging method is, for example in British Patent 1,150,381. at performing this process is an imaging layer, which lies between two foils, in an imagewise configuration by an electromagnetic 'radiation and a

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electric field broken. The electric field can on different ways, for example in such a way that the imaging layer, which between the two foils is placed between a pair of electrodes, whereupon a voltage is applied between the electrodes will. An electric field can also be applied in such a way that an electrically insulating material is used in at least one of these films and a static charge is generated in the insulation layer. the Static charge can for example by friction, corona discharge or by carrying out the electrically insulating Layer between a pair of electrically conductive rollers, which are under voltage, created v / earth. In this way' the static charge is caused by an element that carries an electrical charge, as well as by an electrically insulating one Layer, the element carrying the charge in electrical Connection is brought to the electrically insulating layer is generated.

The hectographis imaging process sees the use of a hectography Sano.wich that of an electric light-sensitive material, which is located between a pair of sheets. In this imaging system is an image forming layer by coating in a conventional manner a layer of a photosensitive image forming material on a substrate. According to one embodiment, the image-forming layer consists of a light-sensitive one Material, for example made of a metal-free phthalocyanine, in a weakly cohesive binder is distributed. This coated substrate is called a donor. The other slide is usually called the "pick-up" ■ An electric field is created across this hectography sandwich created, in the usual way when this

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Sandwich, irradiated with a light-and-shadow image, that corresponds to the image to be reproduced. When separating the donor substrate or the donor sheet from the receiving sheet breaks the image-generating layer along'der the light-and-shadow pattern with which the image-generating Layer has been irradiated, defined lines. A part * of the picture layer is transferred to one of the foils, while the rest remains on the other slide so that one positive image, which is a duplicate of the original, is created on one slide, while negative scrolls the other Foil is created. Hectographic images with the greatest possible resolution are generated when relatively high electric fields are used. For example, it becomes a common one If a pair of electrodes is used, each on one side of the hectography sandwich, then voltages from 2000 - 20,000 volts applied. In the case of "hectographic image generation processes, when carrying out the electric field by a static charge "on one or both foils, between which the electrically light-sensitive Material is sandwiched, is provided, images are obtained with a lower degree of resolution.

There is therefore a need for a new method by which which has a static charge on one or both foils of the Hectography sandwich is applied, with the through ' However, this method also maintains an electric field that is sufficient to produce images with a to generate higher resolution than was previously possible.

The aim of the invention is therefore to create a loading method by means of which the disadvantages described above. to be overcome. Through the invention. Is a compared to the "

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Prior Art Much Improved Hectographic Imaging Process made available.

According to the invention, a charge-carrying element in brought electrical connection with an electrically insulating layer, whereby an electrical charge from the charge-carrying layer Element is transferred to the insulation layer. The once loaded insulation layer is then applied again, brought into the position in which there is an electrical connection with an element carrying a charge, whereupon a new loading takes place. The insulation layer can then be charged a third time or several times Element are supplied until electrical saturation is reached.

As mentioned above, in the case of the invention Hectographic imaging method achieves images with an improved resolution. According to the invention, either one film or the other film or both films of the hectography sandwich are electrically charged. That Sandwich of the donor sheet, the imaging layer and the receiving film can be drawn through two or more times between two elements carrying a charge. Further the sandwich can be pulled through a series of two or more charge-bearing elements, these elements are connected to a source of a voltage difference. Thereby a charge is placed on both surfaces of the hectography sandwich upset. Either the receiving foil or the donor foil or both foils can be used after the method according to the invention prior to bringing them together Formation of the hectography sandwich to be loaded. In the usual way, the sandwich is then lit with a light and

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201S8A8

'Shade pattern irradiated that is to be reproduced Picture corresponds.

.The charge-carrying element that is used to carry out the inventive Process used can be any conductive surface which is in electrical communication with an insulation layer is brought. These load-bearing ones Elements can, for example, be a corona discharge device as described in U.S. Patents 2,588,699, 2,777,957, and 2,885,556. senior Wires can also be used. Likewise, one can fall back on friction devices like them for example, in U.S. Patent 2,297,691 will.

Albeit other suitable devices as charge-carrying elements for carrying out the method according to the invention can be used, a conductive roller or roller jjaar (see U.S. Pat 2 980 834) and corona charge devices preferred. .....

Are used to carry out the method according to the invention Electrodes used, they can be made of any suitable conductive material. Typical conductive electrode materials are for example aluminum. Brass, stainless steel, copper, nickel, zinc, or mixtures thereof. Aluminum is preferred because it is readily available and is also a good leader.

The layer to be loaded according to the invention can consist of any suitable insulation material 'exist »Typical insulation materials are, for example, polyethylene, polyethylene

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terephthalate, cellulose acetate, paper, coated with plastic Paper, "for example, coated with polyethylene Paper, or mixtures thereof. Mylar, a polyester produced by the condensation reaction between ethylene glycol and Terephthalic acid and is manufactured by E.I. DuPont de Nemours & Company, Inc., is preferred because of its physical strength as well as its good insulation properties.

As mentioned above, either the donor sheet or the receiver sheet or both sheets can be used in the implementation of the inventive method as an insulating layer, the is to be charged according to the invention, use.

The charge-carrying element is expediently standing under a voltage of 15,000 - 20,000 volts, although higher voltages can also be maintained. The on the voltage transmitted to the electrically insulating layer is between about 5,000 and about 15,000 volts, 'is at Too low a voltage is applied across the imaging layer in the hectographic imaging process, then does not break the imaging layer in an imagewise configuration. For example, a Mylar cream film 0.075 mm (3 nils) thick and an Iylar donor sheet 0.050 mm (2 mils) thick is used, voltages of up to 20,000 volts can be transferred to the insulation layers. The preferred field strengths however, across the hectography sandwich is between 2,000 volts per 0.025 mm (1 mil) to about 4,000 volts per 0.025 mm (1 mil).

The method for performing the hectographic image generation process according to the invention imaging layer used

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may contain any suitable electrically photosensitive material. Such an electrically photosensitive material may be coated on an electrically insulating sheet to form a donor sheet which is used for performing the hectographic imaging process. On the other hand, in the embodiment of the hectograph imaging method in which the electric field is applied to the recording sheet by means of a static charge, the electrically photosensitive material may be coated on a conductive surface. Typical organic electrically photosensitive materials are quinacridones such as 2,9-Diraethylchinacridon, 4,11-dimethylquinacridone, 2, TO-dichloro-6,1 ^ -dihydrochinacridon, 2,9-dimethoxy-5- dihydroquinacridone 6,1, 2,4,9, Ii-tetrachloroquinacridone , solid solutions of ohinacridones and other compounds which are described in US Pat. No. 3,160,510, carboxamides, such as, for example, H-2 "-pyridyl-8,13-dioxodinaphtho- (2,1-2 ¹ , -3 ¹ ) -furan-6-carboxamid, 11-2 »- (1", 3 ", 5" -triazyl-8,13-dioxodinaphtho- (2,1-2 *, 3) -furan-6-carboxamid _f an thra- * (2,1) -naphtho- (2,3-d) -furane-9,14-dione-7, - (2'-methoxymethylphenyl) -carboxamide, carboxanilides, for example 8,13-Dioxodinaphtho- (2,1-2, 3 ') -furan-ö-carbox-m-chloroanilide, 8,13-dioxodinaphtho- (2,1-2 *, 3') -furan-6- carbox-p-cyanoanilide, triazines, such as 2,4-diaminotriazine, 2,4-di- (1'-anthraquinonylamino-ö-Ci "-pyrenyl) -triazine, 2,4-di- (1 ^l -anthraquinonylanino) -6- (1 "-naphthyl) -triazine, 2,4-di- (1'-naphthylamino) -6- (1'-perylenyl) -triazine, 2,4,6-tri- (1 ·, ^ 1 ", 1 '·' -PyrenylJ-triazine, benzopyrrocolins such as 2,3-phthaloyl-7,8-benzopyrrocoline, 1-cyano-2,3-phthaloyl-7,8-benzopyrrocoline, i-oyano-2,3 -phthaloyl-5- ^ nitro-7,8-bencopyrrocoline, 1-cyano-2,3-phthaloyl ^ -5-acetamido-7> 8-benzopyrrocoline, anti-rachinones, v / ie, for example

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1,5-bis- (ß-phenyläthy lamino) -anthraquinone, 1,5-bis- (3'-methoxypropylalnino) -anΐhraquinone, 1,5-bis- (benzylamino) -anthraquinone, 1,5-bis- (Phenylbutylamino) -anthraquinone, 1,2,5,6-di- (c, c'-Mphenyl) -triazole-anthraquinone: n, 4- (2'-hydroxyphenylmethoxyamino) -anthraquinone, azo compounds such as 2,4,6 -tris- (N-ethyl-N-hydroxyethyl-p-aminophenylazo) -phloroglucin, 1,3,5,7-tetrahydroxy-2,4,6,8-tetra- (N-me thy1-1 \ Γ- hydroxyethyl-p-aminophenylazo) naphthalene, 1,3,5-trihydroxy-2,4,6-tri- (3'-nitro-N-methyl-1-N-hydroxymethyl-4'-aminophenylazo) benzene, 3 -Hethyl-1-phenyl-4- (3'-pyrenylazo) -2-pyrazolin-5-one, 1- (3'-pyrenylazo) -2-hydroxy-3-naphthanilide, 1- (3 ^! - pyreneylazo ) -2-naplithol, 1 - (3'-pyrenylazo) -2-hydroxypyrene, 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'-nitrophenylazo) -2-hydroxy-3'-nitro-3-naphthanilide, salts and Parblacke of compounds derived from 9-phenylxanthene , such as the phosphotungstic acid color of 3, 6-bis- (ethylamino) -9, 2'-carboxyphenylxanthenonium chloride, the barium salt of 3-2'-toluidinamino-6-2 "-methyl-4" -sulfophenylamino-9-2 ¹ '' -carboxyphenylxanthene, the phosphomolybdic acid parblack of 3,6-bis- (ethylamino) -2,7-dimethyl-9-2 ^l -carbethoxyphenylxanthene chloride, dioxazines, for example 2,9-dibenzoyl-6, 13-dichlorotriphenodioxazine, 2,9-macetyl-6,13-dichlorotriphenodioxazine, 3, IO-dibenzoylainino-2, 9-diisopropoxy-6,13-dichlorotriphenodioxazine, 2,9-difuroyl-6, ^ - dichlorotriphenodioxfarazine, parblacks from plasmids, v / ie for example the lead colored lake of 2,7-dinitro-4,5-dibromofluorescein, the lead colored lake of 2,4,5> 7-tetrabromofluorescein, the aluminum colored lake of 2,4,5,7-tetrabromo-10,11,12 , 13-tetrachlorofluorescein, bisazo compounds such as, for example, 21, IT ^f -di [1- (1 '-Haphthylazo) -2-hydroxy-8-naphthyl] -adipdianine, 11,11' -di-1- (1 '-ITaphthylazo ) -2-hydroxy-8-naphthylsuccindianide, bis-4, 4'- (2 "-hydroxy-

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• 8 ¹ IN, N '-diterephthalamid-1 -naphthylazo) -bipheny1, 3,3' -Me thqxy-4,4 '-diphenylbis- (1 "-azo-2" -hydroxy-3 "-naphthanilide, pyrenes, such as "for example 1, 3, 6,8-tetracyanopyrene, 1,3-dicyano-6,8-dibromopyrene, 1, 3, 6,8-tetraaminopyrene, 1-gyano-6-nitropyrene, phthalocyanines, such as metal-free phthalocyanine in the ß-Eorm, copper phthalocyanine, tetrachlorophthalocyanine, metal-free phthalocyanine in the "xn-Porm (compare, the ÜS patent 3 357 989), metal salts and. Earblacks of azo dyes, such as the Galcium color lake of 6-3rom-1 (1'- sulfo-2-naphthylazo) -2-naphthol, the barium salt of 6-cyano-1 (1'-sulfo-2-naphthylazo) -2-naphthol., the calcium lake of 1- (2'-azo-naphthalene-1'-sulfonic acid ) -2-naphthol, the color lake of 1- (4'-ethyl-5'-chlorazobenzene-2'-sulfonic acid) -2-hydroxy-3-naphthoic acid, and mixtures thereof.

Typical inorganic electrically photosensitive materials are, for example, gadmium sulfide, cadmium sulfoselenide, zinc oxide, zinc sulfide, sulfur, selenium, mercury sulfide, lead oxide, lead sulfide, cadmium selenide, titanium dioxide, indium trioxide "or similar. . ' :

In addition to the organic materials mentioned above, other organic materials can also be used in the image-forming layer, for example polyvinyl carbazole, 2,4-t) is- (4,4'-diethylaminophenyl) -1, 3,4-oxadiazole, IT-isopropylcarbazole , Polyvinylanthracene, triphenylpyrrole, 4,5-diphenylimidazolidinone ,, 4, S-diphenylimidazolidinethione, 4,5-t> is- (4 ^l -aminophenyl) -imidazoidinone, 1,2,5, ö-Ieträazacyclooctatetraen- (2,4, 6,8), 3,4-di- (4'-methoxyphenyl) -7,8-diphenyl-1,2,5,6-tetraazacyclooctatetraene (2,4,6,8), 3,4'-di (4) -phenoxyphenyl) -7,8-dipheny1-1,2,5,6-tetraazacyclooctatetraen- (2,4,6,8),

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314,7,8-tetramethoxy-1,2,5,6-tetraazaoyclooc tatetraen- (2,4,6,8), 2-mercaptobenzothiazole, 2-phenyl-4-a-naphthylidenoxazolone, 2-phenyl-4-diphenylidenoxazolone , -2-phenyl-4-p-raethoxyb enzy1idenoxaz olone, 6-hydroxy-2-phenyl- (p-dimethylaminophenyl) -benzofuran, 6-hydroxy-2,3-di- (pmethoxyphenyl) -benzofuran, 2,3,5, 6-tetra- (p-methoxyphenyl) -furo- (3,2f) -benzofuran, 4-dimethylaminobenzylidenebenzhydrazide, 4-dimethylaminobenzylideneisonicotinic acid hydrazide, furfurylidene- (2) -4'-dimethylaminobenzhydrazide, 5-benzylideneaminoacazenaphthene (4-benzylideneaminoacenaphthene-3, IT, N-dimethylaminobenzylidene) -p-lI, N-dimethylaminoaniline, (2-nitrobenzylidene) -p-bromaniline, Ν, Ν-dimethyl-N ¹ (2-nitro-4-cyanobenzylidene) -p-phenylenediamine, 2,4 -Diphenylquinazoline, 2- (4'-aminophenyl) -4-phenylquinazoline, 2-phenyl-4- (4'-dimethylaminophenyl) -7-methoxyquinazoline, 1,3-diphenyltetrahydroimidazole, 1,3-di- (4'-chlorophenyl ) -tetrahydroimidazole, 1,3-diphenyl-2-4'-dimethylaminophenyl) -tetrahydroimidazole, 1,3-di- (p-tolyl) -2- [quinolyl- (2 '-)] - tetrahydroimidazole, 3- (4'-dimethylaminophenyl-5- (4 "-methoxyphenyl) -6-phenyl-1,2,4-triazine, 3-pyridyl- (4 ') - 5- (4'-dimethylaminophenyl) -6 -phonyl-1,2,4-triazine, 3- (4'-aminophenyl) -5,6-diphenyl-1,2,4-triazine, 2,5-bis- [4'-aminophenyl- (1 ') ] -1,3,3-triazole, 2,5-bis- [4 '- (N-ethyl-IT-acetylamino) -phenyl- (i')] -1, 3,4-triazole, 1,5- Diphenyl-3-methylpyrazoline, 1,3,4,5-tetraphenylpyrazoline, 1-pheny1-3- (p-methoxystyryl) -5- (p-methoxyphenyl) -pyrazoline, 1-methyl-2- (3 ', 4' -dihydroxymethylene-phenyl) -benzimidazole, 2, (4'-dimethylaminophenyl) -benzoxazole ,. 2- (4'-methoxyphenylbenzothiazole, 2,5-bis- [p-aminophenyl- (1)] -1,3,4-oxadiazole, 4,5-diphenylimidazolone, 3-aminocarbazole and copolymers and mixtures of these compounds.

Other materials are organic donor-acceptor (Lewis-_ acid-Lewis base) charge transfer complexes consisting of aromatic donor resins, such as phenol / alde-

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hyd resins, phenoxides, EpoxiverMndungeii., polycarbonates, - urethanes ,,. Styrene or the like, v / elqhe are complexly linked to electron acceptors, for example 2,4,7- trinitro-Srflupr.enone, 2,4,5,7- tetranitro-9-fluorenone,: picric acid, 1,3 ^, 5 -Trinitrobenzene, chloranil ,, 2 _; , ^^ Di.chlorbenzoi-. chinone. Anthraquinone-2-carbpxylic acid, 4-nitrophenol, maleic anhydride, metal halides of metals and metalloids of. Groups IB and II - VIJI. des, periodic. Systems, for example aluminum chloride, 23inc chloride _r iron (.III) chloride,

~ Magnesium chloride, calcium iodide ,. Strontium bromide, chromium bromide ,. Arsenic triiodide, magnesium bromide., Tin (IIJ-ehlox-id or the like, boron halides, such as, for example, boron trifluoride, Ketones, such as, for example, beneophenone and, anisil ,,. Mineral acids, v / ie, for example sulfuric acid,, organic, carboxylic acids, like for example. Acetic acid and maleic acid, succinic acid, citraconic acid, sulonic acid, such as for example 4-thuoisulfonic acid, or. Mixtures thereof. It is note that many of the materials identified above, in addition to the charge transfer complexes

/ can be sensitized by means of a charge transfer / complexing method. Many of these materials .Can by means of a dye sensitized in the manner earth v / that their _spectral-: response curves narrows ^ verbreitei-t or. increase. ,. .

It should also be noted that the electrically photosensitive. Particles themselves may consist of any suitable one of the aforementioned electrically photosensitive materials or of more than one such material, whether organic or inorganic. These particles can be dispersed in solid solution in any suitable insulating resin _; or be copolymerized with * this independently of. indeed-

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matter whether the resin itself is photosensitive or not. This particular type of particle may be particularly desirable when the dispersion of the particles is to be facilitated intended to avoid undesirable reactions between the binder and the photosensitive material or between the photosensitive Material and the activator to prevent. In addition, similar purposes can be fulfilled. Typical resins of this type are polyethylene, polypropylene, polyamides, polymethacrylates, Polyacrylates, polyvinyl chlorides, polyvinyl acetates, polystyrene, polysiloxanes, chlorinated rubbers, Polyacrylonitrile, epoxy compounds, phenolic compounds, hydrocarbons resins as well as other natural resins such as resin derivatives, as well as mixtures and copolymers of these substances.

The "x" form phthalocyanine is preferred because of its excellent photosensitivity. However, any other suitable phthalocyanine can also be used for the preparation of the image-forming layer according to the invention. The phthalocyanine used can be in any suitable crystal form. It can be substituted in the king part as well as in the straight chain part. A more detailed description of the phthalocyanines and their syntheses can be found in the book "Phthalocyanine Compounds" by FH Moser and AL Thomas, ₍ published by Reinhold Publishing Company, 1963. According to the invention, any suitable phthalocyanine can be used. can be described as compounds which have 4 isoindole groups linked via 4 nitrogen atoms in such a way that they form a conjugated chain These compounds correspond to the general formula (G ₈ H ^ i ₂ ) JJ, where

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R for hydrogen, deuterium, lithium, sodium, potassium, silver, ¹ copper, beryllium, magnesium, calcium, zinc, cadmium, barium, mercury, aluminum, gallium, indium, lanthanum, neodymium, samarium, europium, gadolinium, dysprosium, holmium , Erbium, thulium, ytterbium, lutecium, titanium, tin, hafnium, lead, silicon, germanium, thorium, vanadium, antimony, chromium, molybdenum, uranium, manganese, iron, cobalt, nickel, rhodium, palladium, osmium and platinum, and η is a number greater than 0 and equal to 2 or less than 2. If appropriate, any other suitable phthalocyanines can also be used, for example ring-substituted or aliphatically substituted metallic and / or non-metallic phthalocyanines. As mentioned above, any suitable phthalocyanine can be used to prepare the photoconductive layer according to the invention. Typical phthalocyanines are the following: aluminum phthalocyanine, aluminum polychlorophthalocyanine, antimony phthalocyanine, bearium phthalocyanine, beryllium phthalocyanine, cadmium hexadecachlorophthalocyanine, cadmium phthalocyanine, calcium phthalocyanine, cerophthalocyanine, chromophthalocyanine, chromophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-phthalocyanine-phthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-phthalocyanine-phthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, copper-chlorophthalocyanine, cobalt-chlorophthalocyanine, beryllium phthalocyanine, bearium phthalocyanine, beryllium -4-nitrophthalocyanin, Kupferphthaiοcyanin, Kupferphthaiocyaninsuifonat, Kupferpolychlorphthalocyanin, Deuteriophthalocyanin, Dysprosiumphthalocyanin, Erbiumphthalocyanin, Europiumphthalocyanin, Gadoliniumphthalocyanin, gallium, Ge rmaniumph thai ο phthalocyanine, Hafniumphthalo.cyanin, halogensubstuierte phthalocyanines, Holmiumphthalocyanin, indium, iron phthalocyanine, Eisenpolyhalogenphthalocyanin, Lanthanphthalocyanin, lead phthalocyanine, Bleipolychlorphthalocyanin, Cobalt hexaphenyl phthalocyanine, copper pentaphenyl phthalocyanine, lithium phthalocyanine nin, lutecium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine,

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Quecksilberphthalocyanin, Molybdänphthalocyanin, lleodymphthalocyanin, IIickelphthalocyanin, Nickelpolyhalogenphthalocyanin, Osmiumphthalocyanin, palladium phthalocyanine, Palladiumchlorphthalocyanin, alkoxyphthalocyanines, Alkylmerkaptophthaiοcyanine, Aralkylaminophthalocyanine, Aryloxyphthalocyanine, Arylmerkaptophthalocyanine, Kupferphthalocyaninpiperidin, Cycloalkylaminophthalocyanine, Dialkylaminophthalocyanine, Diaralkylaminophthalocyanine, Dicycloalkylaminophthalocyanine, Hexadecahydrophthalocyanin, imidomethyl phthalocyanine, 1, 2-naphthalocyanine, 2,3 - ITaph thai ο cyan in, llaphthalocyanin, Octaazaphthalocyaninschwefelphthalocyanin, tetra-4-acetylaminophthalocyanin Tetraazaphthalocyanin, tetra-4-aminobenzoylphthalocyanin, tetra-aminophthalocyanin-4, 4-dimethylo Tetrachlorraethylphtlialocyanin, Tetradiazophthalocyanin, tetra-4, otaazapb.thalocyanin, tetra-4 ₉ 5-diphenylenedioxydphthalocyanine, Tetra-4, i-diphenyloctaazapVithalocyaniri, Tetra- (6-methylbenzothiazoyl) -phthalocyanine, Tet ra-p-metuylphenylaminophthalocyanine, tetrainethylphthalocyanine, tetranaphthotriazolylphthalocyanine, tetra-4-naphthylphthiialocyanine, tetra-4-nitrophthalocyanine, tetraperinaphthylene-4, 5-octaazaphthalocyanine, tetraazaphthalocyanine , Tetrapheny! phthalocyanintetracarbonsäure, Tetraphenylphthalocyanintetrabariuracarboxylat, Tetraphenylphthalooyanintetracalicumcarboxylat, Tetrapyridy! phthalocyanine, tetra-trifluormethylmerkaptophthaiocyanin 4, tetra-4-1Äcifluorraethyiphthalocyanin, 4,5-Thionaphthenoctaazaphthalocyanin, Platinphthalocyanin, Kaliuraphthalocyanin, Rhodiuraphthalocyanin, Samariumphthalocyanin, Silberphthalocyanin, silicon phthalocyanine llatriumphthalocyanin, sulfonated phthalocyanine, Thoriumphthaiοcyanin, Thulium phthalocyanine, tin chlorophthalocyanine, tin phthalocyanine, titanium phthalocyanine, uranium phthalocyanine, vanadium phthalocyanine, ytterbium phthalocyanine, zinc

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chlorphthalo.cyanine, zinc phthalocyanine, other phthalocyanines, which are described in the above-mentioned book, as well as mixtures, dimers, trimers, oligomers, polymers, copolymers or mixtures thereof. ·

The most important physical property which is to have the ^paintings-% generating layer is that the layer after its manufacture or after a suitable activation. is breakable. The layer must be structurally weak to such an extent that the application of an electric field together with the effect of electromagnetic radiation on the electrically light-sensitive materials breaks the image-forming layer. Furthermore, the layer must respond to the application of a field, the strength of which is below the field strength 11θ £ ξΐ, which causes electrical breakdown or arcing across the imaging layer. Another term for the expression * ^r weakly cohesive "is therefore" breakable by a field ".

The imaging layer serves as a light responsive Element of the system as well as a coloring agent for the finished one generated image. Preferably the imaging layer is Chosen in the way that they have a high responsiveness possesses, at the same time it is intensely colored, so that an image with high contrast due to the invention System can be formed. The imaging layer can be homogeneous. You can, for example, from a solid solution consist of two or more pigments, where one or more of the pigments are electrically sensitive to light. The imaging layer can also be heterogeneous, i. it can consist, for example, of pigment particles that are present in are dispersed in a binder.

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One method of achieving weak cohesion in the imaging layer is to use a relatively weak, low molecular weight material. For example, in a homogeneous one-component imaging layer, a monomeric compound or a low molecular weight polymer complexed with a Lewis acid to make the compound or polymer have a high photo-responsiveness can be used. If a homogeneous layer is used in which two or more components are contained in solid solution, then either one or both components of the solid solution can consist of a material with a low molecular weight Layer has the desired low level of cohesiveness. The same also applies to heterogeneous imaging layers. Even if the binding material in the heterogeneous system can itself be photoconductive, it is nevertheless not necessary that the material have this property. It is possible to select materials that only serve as binding materials, specifically only on the basis of their physical properties, without their sensitivity to light having to be taken into account. The same also applies to homogeneous two-component systems in which light-sensitive materials with the desired physical properties can be used. Another method of making the image forming layer poorly coherent can also be used. For example, suitable mixtures of incompatible materials, such as a mixture a.ur. a polysiloxane resin with a polyacrylic ester resin, used either as a tie layer in a heterogeneous system or in conjunction with a "homogeneous" system in which the photosensitive material either one of the incompatible components (which are complex with one another) Acid bound

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den are) or can consist of a separate and further component of the layer. The thickness of the imaging layer is preferably between about 0.2 and about 10 microns, generally between about 0.5 and about 5 microns. and preferably at about 1 u.

The ratio of photosensitive pigment to the binder, based on volume, is in the heterogeneous System about 10: 1 to about 1:10, however, ratios have been found to be between about 1: 4 to about 2: 1 will give the best results, so this range is a preferred range.

The binding material in the heterogeneous imaging layer or the material used in conjunction with the pigment materials Used in the homogeneous layer can be made of any suitable weakly cohesive insulating material or consist of materials that can be made weakly cohesive. Typical materials are, for example, the following: Microcrystalline waxes, such as Sunoco Ί290, Sunoco 5825 and Sunoco 985, each available from Sun Oil ' Co., Paraflint RG, available from Moore and Munger Co., paraffin waxes such as Sunoco 5512, Sunoco 3425, available from Sun Oil Co., Sohio Parowax, available from the Standard. Oil of Ohio, waxes made from hydrogenated oils such as Capitol City 1380 wax available from Capitol City Products, Co., Columbus, Ohio, Caster Wax 1-2790 available from Baker Caster Oil Co., Vitikote L-304 available from Duro Commodities, Polyäthylene, such as Eastman Epolene IT-11, Eastman Epolene C-12 available from Eastman Chemical Products Co., Polyethylene DYJT, Polyethylene DYIT, Polyethylene DYTSTP and Polyethylene DYDT, each available from Union Carbid Corp. receives-

009842/1665

borrowed, Marlex TR 822 and Marlex 1478, available from the Phillips Petroleum Co., Epolene 0-13, and Epolene 0-10, available from Eastman Chemical Products Co., Polyethylene A08, Polyethylene A0612 and Polyethylene AO '324 are available from Allied Chemicals, modified styrenes such as Piccotex 75, Piccotex 100 and Piccotoex 120 are available from Pennsylvania Industrial Chemical, vinyl acetate / ethylene copolymers, such as Elvax Resin 210, Elvax Resin 310, and Elvax Resin 420 available from E.I. DuPont de llemours & Co., Inc., Vistanex MH and Vistanex L-80, available from Enjay Chemical Co., vinyl chloride / vinyl acetate copolymers, for example Vinylite VYLI ?, available from Union Carbide Corporation, styrene / vinyltoluene copolymers, Polypropylenes and mixtures thereof. The use of an insulating binder is preferred because since they use a larger amount of electrically light-sensitive Pigments permitted.

A mixture of · microcrystalline wax and polyethylene is preferred because such a mixture is weakly cohesive and acts as an isolator.

If the image-forming layer is not sufficiently weakly cohesive to enable image-wise breaking, then it is expedient to include an activation step when carrying out the method according to the invention. The activation stage can in many shaper: done, for example, by heating the image forming layer so that this layer is softened, or by dropping _j bring a substance on the surface of the image forming layer or by Mix in a substance in the image forming layer, wherein such a substance the Zusammenhaitevermögen the layer decreases or a decrease

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BATH ORIGINAL

of cohesion favors. The substance used in this way is called an "activator". The activator should preferably have a high specific resistance so that electrical breakdown through the graphic system is avoided. It is also generally advisable to clean activators with technical degrees of purity in order to remove impurities which can contribute to increasing the conductivity. This can be accomplished by letting the fluids run through a clay column, and any other cleaning method can also be used. In - '/' general, the activator can be of any suitable material having the above mentioned properties exist. The term “activator” should be understood not only to mean materials which are commonly referred to as solvents, but also materials which are partial solvents, swelling agents or softening agents for the image-forming layer.

It. it is generally preferable to use an activator, which has a relatively high boiling point, so that a Fixing the image obtained after evaporation of the Activator can be done. If necessary, the image can be fixed more quickly by heating it slightly be effected. It should be noted, however, that the invention does not rely on the use of these relatively volatile Activators is limited. Rather, you can carry out of the image suction process also very successfully high-boiling non-volatile activators are used, for example silicone oils such as Dimethy! polysiloxane ', as well as very high boiling long chain aliphatic hydrocarbons oils that - "commonly used as. transformer oils be-, for example '.'enco-G transformer oil, the

009842/1665

marketed by Westinghcus Electric Co. Although these less volatile activators cannot be removed by evaporation, image fixing can be accomplished by contacting the finished image with an absorbent sheet, such as paper, which sheet absorbs the activator liquid. Therefore any volatile or non-volatile activator can be used. Typical activators include Sohio Odorless Solvent 3440, an aliphatic hydrocarbon fraction (kerosene) available from Standard Oil Co., Ohio, carbon tetrachloride, petroleum ether, Freon 214 (tetrafluorotetrachloropropane), other halogenated hydrocarbons such as chloroform, methylene chloride , Trichlorethylene, perchlorethylene, chlorobenzene, irichlormonofluoromethan, tetrachlorodifluoroethane, trichlorotrifluoroethane, amines, such as pormamide, dimethylformamide, ethers, such as diethyl ether, diisopropyl ether, dioxane, benzene, alcohol, alcohol, alcohol, such as, for example, benzoethylene, methyl alcohol, methyl alcohol, methyl alcohol, methyl alcohol, methyl alcohol, methyl alcohol, methyl alcohol, tetrahydrofluoroethane, tetrachlorodifluoroethane, aromatic methyl alcohol, Hexane, cyclohexane, gasoline, mineral fuels and v / ice mineral oil, with vegetable oils such as coconut oil, babussu oil, palm oil, olive oil, castor oil, peanut oil, nipple oil, decane, dodecane or mixtures thereof also being embossed preferred because it is an excellent insulator and evaporates easily. ₍

While the imaging layers can be made as self-supporting " pilms, these layers are typically coated onto a sheet called a donor sheet or substrate. For the sake of simplicity, the combination of imaging and donor film is referred to as a donor. The electric

0098A2 / 1665 _BAD original

pigment sensitive to violet and the insensitivity to electri- The pigments are usually borne directly in the homogeneous system mixed. If a binder is used, the pigments 25.B. are mixed separately into the binding material, using the usual methods of mixing pesticides, for example by grinding in a ball mill. Perner Both pigments can be added directly to a binding material and be dispersed in this, for example by grinding in a ball mill or by heating the binder to a Temperature above its melting point, whereupon the pigments are dispersed in the fluid binding material by simple mixing will. After mixing the components of the imaging layer will apply the desired amount to a substrate. piled up. According to a particularly preferred embodiment of the invention, an image generation layer consists of the electrically photosensitive pigment and. the electrically insensitive to light Pigment, the pigments being dispersed in a binder and the dispersion on a transparent one and electrically insulating donor sheet has been coated.

A source of visible light, a source of UV light or any other source of suitable electromagnetic Radiation can be used to irradiate the imaging layer in performing the hectographic imaging process be used. The electrically photosensitive material is selected in such a way that it responds to the wavelength the electromagnetic radiation used. It it should be noted that various electrically light-sensitive Materials have different spectral responses, with the spectral response being many electrically photosensitive materials through a dye, awareness can be modified, either

0098 427 1 685 ₀

to increase or narrow the spectral response of the material to a certain value or to broaden the response to a panchromatic response to achieve.

When performing the plectographic imaging process it is possible to use the loading process according to the invention either to apply before or after irradiating the image-forming layer with electromagnetic radiation. For example Either the donor film or the receiving film or both films can be electrically operated by the process according to the invention loaded v / ground. If at least one of the foils is at least partially transparent to the electromagnetic radiation, then the hectography sandwich can be made, followed by the imaging or exposure stage of the imaging process can be carried out. Y / ally can load the donor foil according to the method according to the invention and then irradiated with a pattern of electromagnetic radiation prior to making the hectography sandwich will. Furthermore, in cases where the electrically photosensitive materials are used, light fatigue may occur show that the imaging layer is irradiated with a pattern of electromagnetic radiation, opposite v / elcher it is sensitive before the inventive loading. The sequence of the stages of the process according to the invention including the activation step carried out, if necessary, can also be varied according to requirements without leaving the faucets of the invention.

When carrying out the loading process according to the invention an element carrying a charge is brought into electrical connection with an electrically insulating layer. the a charge-bearing surface of the element becomes the electrical one

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BATH ORIGINAL

insulating layer approximated to the minimum distance, which is the transfer of an electrical charge from the charge-bearing element to the electrically insulating layer enables. V / ird is the distance between the charge-bearing Element and the electrically insulating layer reduced to a certain value between 12 mm and 0.25 mm (1/2 to 0.010 inches), charging occurs in the space between the two elements, being a Part of the charge on the charge-carrying element on the insulation layer is transmitted. If the distance is completely reduced, then there is a free direct excitation of the charge until the voltages both on the surface of the insulation layer as well as on the surface of the ßine charge-carrying element have adjusted to each other or a maximum ratio have reached, whereupon the charge transfer finally stops. In practice, however, there is such a perfect contact in which the distance is completely reduced to zero becomes difficult to realize. Therefore, the charge transfer takes place under conditions in which the one charge The load-bearing element and the insulation layer abut one another, with locations at which the two meet Elements at a maximum distance of a few thousandths and are located. There are also places where a minimal Distance is present, in which case the elements are slightly pressed against each other and in actual fact contact are located. Another charge transfer niche sinus is contained in the field emission. Reaches the electric field in the free space about 10 volts / cm, then a field emission occurs of electrons, whereby the charge transfer to the insulation layer is also achieved.

The advantages which are achieved by the loading process according to the invention can also be found in the attached ei " ¹

009842/1665

-2A-

Drawing closer.

Figure 1 is a side sectional view of a hectography sandwich, that to carry out the process according to the invention is used.

Figure 2 is a side sectional view which is shown in schematic form Way the process stages of the loading process according to the invention as well as the process steps of the hectographic imaging process shows.

In the figure 1 an image generation layer 2 is shown, which consists of an electrically photosensitive material 4 ″ because it is dispersed in a binder 3. This dispersion .is on the surface of the donor sheet 5. A recording sheet 6 rests on the image generation ^ chic ht 2 and completes the hectography sandwich.

First, a commercially available metal-free phthalocyanine is purified by o-dichlorobenzene extraction to remove organic impurities. Since this extraction stage provides the less sensitive β-crystal form, the desired "x ^{! L} -form is produced in the manner that about 100 g of the B-form are dissolved in about 6CO ecm sulfuric acid, which is followed by precipitation The solution is poured into about 3000 ccn ice washer. The precipitate is then washed with water to achieve neutrality. The a-phthalocyanine purified in this way is then ground for a period of 6 days with salt and slurried in Desalt the distilled water, followed by washing on a vacuum filter and then washing with methanol until the initial filtrate is clear

BATH ORIGINAL 009842/1665

2G15848

After vacuum drying to remove residual methanol, the phth, alocyanin- ^II x "-PorrQ produced in this way is used to make the imaging layer g of Algol Yellow GG (1,2,4,6-Ui- (GYC ¹ -diphenyl) -thiazolanthraehinone, CI No. 67300, available from General Dyestuffs) and approximately 2.8 g of a purified Watchung Red B (1- ( 4'-Methy1-5'-chlorazobenzene-2'-sulfonic acid) -2-hydroxy-3-naphthoic acid, GI No. 15865, available from EI DuPont de Nemours & Go., (Which compound is purified in the following manner: approximately 240 g of Watchung Red B in about 2400 ml Sohio Solvent 3440, a mixture of kerosene fractions, available from the standard Oil Company of Ohio, slurried. the slurry is then heated to a temperature of about 65 ⁰ O and on this Temperature for a period of about 1/2 hour de held. The slurry is then filtered through a sintered glass filter. The solids are again with petroleum ether (90 - 120 ⁰ G), that of Matheson ,. Coleman and Bell Division of the Matheson Company, East Rutherford, New Jersey, slurried and filtered through a sintered glass filter. The solids are then dried in an oven at approximately 50 ° G.).

About 8 g Sunoco Microcrystalline Wax Grade 5825 with an ASTM 127-melting point of 66 ⁰ C (151 ⁰ E) and approximately 2g Paraflint® RG, a paraffin material of low molecular weight, available from Morre & Munger Company, New York City, as well as about 320 ml petroleum ether (90-120 ^p C) and about 40 ml Sohio Odorless Solvent 3440 are placed together with the pigments in a glass vessel containing 12 mm flint pebbles. The mixture is then in the

Preferably ground, that the Gla sgefäss is rotated at about 70 UPRA Einei during ¹ period of about 16 hours. The mixture is then heated for about 2 hours to about 45 G ⁰ and allowed to cool to room temperature. The mixture is then ready to be coated onto the donor substrate. The paste-like mixture is then placed under a darkened green light on a Mylar sheet with a thickness of 0.050 mm (2 mils) (a polyester made by the condensation reaction between ethylene glycol and terephthalic acid and manufactured by EI DuPont de liemours & Co., Inc . is placed on the market) by means of a peel rod wrapped with a wire (Hr-. 36). A coating with a thickness of approximately 7 1/2 u is obtained after drying. The coating as well as the thick Mylar film 0.050 min 2 hours are then in the dark at a temperature of about 33 ^o ö for a period of i / dried.

FIG. 2 shows the optical activation stage during implementation of the hectographic imaging method using a donor sheet having a coated imaging sheet, the coating being described in dex above Wise carried out. The activator can be applied by any suitable method, for example by brushing, by applying to the surface using a smooth or rough roller, by pouring on, by steam condensation or similar. Figure -2 shows an embodiment before, according to which the Aktivatorfruid 201 to the Imaging layer 203 is sprayed from the container 205. Subsequent to the application of the activator fluid, the Imaging layer placed between donor sheet 207 and receiving sheet 209. This sandwich will be consecutive sent through rollers 211 and 213. In certain cases

009842/1865 bad original

the activator stage of the hectography process can be omitted will. For example, a hectography sandwich can be used in which the imaging layer 2G3 first has been produced and which has a low hold-together so that the activation can be omitted. In In this case, the recording sheet 209 can be applied to the surface of the Imaging layer 203 can be applied directly. However, it is generally preferred to include an activation step in carrying out the process.

According to a preferred embodiment, after application of the receiving sheet 209 on the image absorbing layer an electric field across the hectographic sandwicli conductive rollers 211 and 211a and conductive rollers 213 and 213a applied. These rollers are connected to the voltage source 215 and the resistor 217 connected. The Dortator film and the Recording film 207 and 209 are preferably used in the same way, that they are over the ends of the Walser) 211 and 213 by about 12 mm protrude so that arcing across the nip hinwec is avoided. Generally, a voltage of about 15,000 volts is applied between rollers 211 and 211a and applied between rollers 213 and 215a. It has found that if a poly ethylene tere, phthala t-foil 0.050 or 0.075 ram (2 or 3 mils) thick as Donor sheet 207 and receiver sheet 209 at one speed At approximately 50 mm (2 inches) per second, the first pair of rollers is applied approximately 67QO volts to the Foils and the second orphan couple about 10,500 volts to the Dispenses foils. A third "orphan couple" can also be used. Under the conditions described above, thereby a static load in the foils of about 12,000 Volt achieved. This value lies in the range of the saturation value - tes for a polyethylene terephthalate sol. If necessary, can

00984 * / 1S <no '** ^left! _BATH ORIGINAL

the conductive rollers are placed under spring pressure so that they exert a slight pressure on the hectography sandwich exerting a more effective contact between the rollers and the hectography sandwich. Besides that a leadership effect is achieved in this way.

Optionally, the charge-carrying elements in Figure 2, namely the rollers 211, 211a and 213 as well as 21Ja through a Corona discharge device, conductive rod, or wire.

The direction of charge indicated on the rollers in FIG. 2 can also be reversed, ie the rollers 211 and 213 can be made negative and the rollers 211a and 213a can be made positive. The charge-carrying hectography sandwich then moves towards a transparent plate 219, on which it is irradiated with a light image 221. The light image 221 can be a light that is projected through a slide. It can also be any light information projected from an opaque object. In the case of a continuous procedure, the light image is preferably projected through a slit in such a way that there is no or only a relatively small movement between the projected light image and the hectography sandv / I. The hectography sandwich then passes roller 223, which serves as a guide for this sandwich and acts as a support point for pulling the sandwich. Optionally, the malt 223 can be replaced by a sharp edge, rod, or wire. When the hectographic sand is split up, the image-forming layer 205 breaks up along the edges of the irradiated areas and leaves the surface of the donor film 207, which was irradiated with the light 221. after the -

009842/1666 _BAD original

When separation is complete, one finds the irradiated parts of the .Image generation layer 203 on one of the foils 20? and 209, v / while the non-irradiated parts on the other slide be held back. The parts therefore represent a positive image on one. Polie and an ITegative on the other slide, Compared to the images, the images have an improved resolution which is achieved by the hectographic image generation method have been produced, in the implementation of which the sandwich is loaded only once.

Other of the above can also be used to carry out the invention materials given can be used with similar results. In addition, other materials can be used can be added to improve the properties of the imaging layer otherwise change or improve. For example, various dyes, photosensitizers or electrical sensitizers such as Lewis acids can be added to the various layers.

09842 / 166S

Claims (17)

- 30 claims Loading method, characterized in that a) brought an electrically insulating layer into electrical connection with an element carrying a charge wherein an electric charge is transferred from the charge bearing member to the insulating layer will, and b) step a) is repeated at least once. 2. The method according to claim 1, characterized in that step a) is repeated twice. 3. The method according to claim 1, characterized in that step a) is repeated as often as is necessary to bring the electrically insulating layer to its saturation point to charge. 4. The method according to any one of claims 1 - 3, characterized in, that stage a) is carried out and repeated in such a way that the insulation layer moves backwards being in electrical communication with this layer at least two charge-bearing elements in succession be moved. 5. The method according to any one of claims 1-4, characterized in that that the element used, carrying a charge, or at least one of the elements carrying a charge a conductive roller. 6. The method according to any one of claims 1-4, characterized in that the used, there is a load-bearing member \ or at least one of a charge-bearing Elenente from a Koronaeiitladungseinrichtung. 009842/1665 BATH ORIGINAL. 7. The method according to any one of claims 1 - 4 ,, characterized in that the used, a charge-carrying element or at least one of the load-bearing elements consists of a senior staff. . ' 8. The method according to any one of claims 1-7, characterized- * draws that the used electrically insulating layer on one side with an electrically photosensitive mate-. rial is coated «- 9. The method according to claim. 8, characterized in that the electrically photosensitive material used is an organic one is electrically photosensitive material. 10. The method according to claim 9, characterized in that the organic electrically photosensitive material used is eiji phthalocyanine. "11 *. Image-forming process, characterized in that a weakly cohesive electrically photosensitive image-forming layer between a donor sheet and a receiving sheet is brought, wherein at least one of the foils has an electrically insulating layer, an electric field is applied across the imaging sheet, the imaging sheet with a pattern of electromagnetic radiation to which the image diffraction layer is sensitive is, is irradiated and the imaging layer is broken in an imagewise configuration in such a way that the Sandwich is separated, with the Bildzexi-ungsschicht the Exposure to an electric field "., Which after the method according to claim 1 is made available, 12. The method according to claim 11, characterized in that An activator is sent to the Bilderzeugmigs before the separation 009842/1665 BATH ORIGINAL of the sandwich is applied. 13. The method according to claim 11 or 12, characterized marked- ■■■; net that the electric field is made available in such a way that the sandwich is carried out between two oppositely charged electrodes, with at least
one of the electrodes consists of a conductive roller. 14. The method according to claim 11 or 12, characterized in ■ net that the electric field is made available in such a way that the sandwich is made by the ionization point
at least one corona discharge device is performed. 15. The method according to any one of claims 11-14, characterized in that ' that the image-forming layer used comprises an organic, electrically photosensitive material, which is dispersed in a binder. 16 ·. Process according to Claim 15, characterized in that the organic, electrically photosensitive material used consists of a detail-free phthalocyanine. 17. The method according to any one of claims 11-16, Ge characterized '■ indicates that at least the donor used
; or the recording film used is at least partially transparent to the electromagnetic radiation used, and the image-generating layer is irradiated through the transparent film. Q098A2 / 1665 BATH ORIGINAL