DE1797342A1 - Multilayer board - Google Patents

Description

Patent attorneys Dipl. - Ing. R ¥ eickmann, Dr. Ing.A.Weickmann

Dipl.-Ing. H. "Weickmann, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. R A.Weickmann, Dipl.-Ghem. B. Huber

8 MUNICH 27, DEN

MÖHLSTRASSE 22, CALL NUMBER 48 3921/22

f / 661

Dr.Sch./St

RANK XEHOX LIMIOJSD,
London UOW. l / England

Multilayer board

Addendum to patent ....... (patent application P 15 97 877.5

R 46892IXa / 57e)}

The invention relates generally to photoconductive materials lind refers Aich particular elektrographiseh © plates that are used in electrophotography "The invention provides a further development of the Patentsohrii't ■ ■■ .... ...- · (P 15 97 877.5 (R46 892 IXa / 57e)) as well as the process described in Belgian patent specification 703 605 »

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BATH ORIGINAL

There are methods for producing iron frames known, for example, the photographer! © which OffsetäruolrverXaiirenf oils xerography or the like "Bsi xerography, wi it © in OCE

ι - ■

Ü.So patent specification 2 297 691 is described, a Base plate made of a material with a relatively low electrical resistance, for example © in metal »a paper or the like, which has a photoconductive insulation coating has »electrostatically charged in the dark. Dsr loaded Uberaug is then exposed to a photograph "The La" · fertilize will quickly increase proportionally to the © round plate the intensity of the light at the exposed areas ο The charge becomes essentially in the unexposed areas keep *. After such an exposure, the coating is contacted with electroscopic marking parts in the dark * These particles adhere to the places where the electrostatic charge remains "and form a powder image" which corresponds to the electrostatic image ". This method is used in the U.S. Patents 2,659,670, 2,753,308 and 2,788,288 described «The powder image can be applied to a polie made of a transfer material transferred v / ground, whereby a positive or negative print can be obtained. Is the baseplate relative cheap, then it can be useful to apply the powder image directly fix the plate itself. A detailed description of the xerography process can be found in a book by Dessauer and Clark with the title "Xerography and Related Processes" (Focal Press Limited, 1965).

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As in the aforementioned 1T "S" patent 2,297,691 Running can be suitable inorganic and organic Materials for making the photoconductive insulating layer on which the electrostatic latent image is created will be used * If many photoconductors are also used or have been tried, I still have selenium as daa technically most useful material for use in electrical: phot © graphic plates highlighted.

Although selenium Ms is the most appropriate photoconductor for use in the SLektrophotographie today "so stick this element still several drawbacks to · For example, there is a downside to using τοη selenium is _f that it is not completely panchromatic _t but only responds to wavelengths are shorter than approximately 5800 A. Furthermore, electrophotographic plates made of selenium are expensive. A third problem with the use of selenium is the difficulty then faced in how to apply this material to a substrate to form an electrophotographic plate. Furthermore occur at elektrographisQhen plates containing selenium photoconductive layers, often problems due to the poor HaftvereiJgens between the photoconductive layer and the substrate to "differences in Wärmeauedehnung awiaohea the substrate and Her photoconductive Sohioht can a ReiBsn Waue peeling ά · τ photoconductive layer.

ORIGINAL

cause of the substrate. A xerographic © plate is made In a normal machine, a considerable two-way operation di £ f © ~ between the cold periods when the plate is not in use and the unavoidable heating due to the height exposed to the heat sink during the copy cycle., The adhesion problems are even greater when the photoconductive layer is applied to a flexible tape substrate that is placed around belt pulleys »a continuous one Bending the photoconductive layer often leads to cracks, and a separation from the substrate. Is a barrier layer provided, then further © problems arise «because this Zid.aehan« The layer must adhere well to the substrate and to the selenium-containing surface under the influence of a bending stress. The selection of an interlayer material that has good adhesion is limited by the requirement; that the intermediate layer must be sufficiently insulating in the dark and not in the areas struck by the light may have an overly isolating effect.

In the French additional patent 91 579 the use of phthalocyanine in a Hars or in an amorphous inorganic Binder described as a xerographic plate » ! Show off the many advantages of using phthalocyanine In conjunction with a resin or with an amorphous inorganic binder, there are also some There are disadvantages. A downside to using

109819/1587

ORIGINAL

Phthalocyanine in a blend agentphofcoreceiver is' that toner carefully designed for use in the present available electrostatic machines, in which selenium is used as a photoreceiver, can be produced with the Phthalocyanine surface react. There is a second disadvantage in that phthalocyanine coatings are practically incompatible with the usual Brush materials such as rayon and rabbit fur, cleaned. Furthermore, phthalocyanine in a binder photoreceptor has a disadvantage that 3S owing to an uncontrolled increase in sensitivity over the course of the year Operation leading to overexposure of the photoreceiver leads, is decomposed. In addition, increasingly less dense images are obtained during operation.

The object of the present invention is to provide an electrographic Plate which does not have the disadvantages described above. The present invention provides a Electrographic plate created which has a sensitivity possesses, which is essentially visible to the whole Spectrum appeals. Furthermore, the invention has a size alektrographlsche plate an improved adhesion between flor photoconductive Sohioht and the substrate. This plate leaves siah repeatedly in xerography as well as in other electrostatic Use picture viewing systems. The inventive electrographic plate has a high thermal stability, so that the temperature can be used

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.. BAD ORIGINAL

that occur when operating an electrostatic machine. The inventive electrographic plate also has valuable physical properties. It is even suitable for effective transmission and can be relieved of a new one Use clean in a simple and thorough manner. During operation, it suffers significantly less degradation. In addition, there is no increase in sensitivity. Another gate part of the electrographic according to the invention Plate consists in "that it can be manufactured in a simple and inexpensive manner". It also falls within the scope of the invention an improved electrographic imaging process.

According to the present invention, there is provided an electrographic plate made, which consists of a conductive substrate, over which an intermediate layer let applied, which consists of approximately 10 - 50 u of phthalocyanine in an insulating resin binder, this layer being covered with a layer which consists of about 0.5-5 μ selenium. This plate k is essentially opposite the entire visible spectrum sensitive because the selenium-containing layer is primarily sensitive to light in the blue, green and UV range while the phthalocyanine-containing intermediate layer mainly focuses on the red and near infrared regions The spectrum. As a binder resin for the phthalocyanine containing In any event, a hara can be selected that is a optimal adhesion between the selenium containing

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Sohisht töid dom Subs feral; ensures Starch coating of the Phtlialocyanr.a imd binder containing. Layer IaI ⁴ : the layer containing the relatively thin selenium creates a clektrographische plate with a very high sensitivity and with panöhroaatisehen properties which nevertheless eortisi; is a v / irksase toner transfer medium and can be cleaned in a simple manner before being used again. Through the creation of a plate, as described above, can be essentially all the advantages of PthaloeyaMn / binding Mittal plate achieve and at the same carrier using ₃ Toner and cleaning agents, the "have been already optimized in a careful way for use with selenium. DarUfcerhinaua nutasfc the above-described plates are very little affected _{and essentially do not suffer from 2 setsmig s} and sswfer even after thawing cycles denser images during operation.

The conductive substrate disposed beneath the phthalocyanine-containing intermediate layer can be made of any suitable material that has the ability to serve as a support for the electrographic plate. iypioche conductive materials include metals such as zE ₀ aluminum, brass, stainless steel, copper, nickel or zinc,

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BATH ORIGINAL

Conductive coated glass, for example with zinc oxide, indium oxide or aluminum coated glass, similar coatings Plastic substrates or paper made by adding suitable Chemicals or by conditioning in a humid atmosphere to such a degree that a sufficient Water content is present to make the material, conductive, conductive has been made »

The selenium-containing layer can consist of selenium or a suitable selenium alloy or a mixture of other materials with selenium. Typical selenium alloys or selenium-containing mixtures are, in the case of Spielswelso, cadmium selenia _f cadmium sulfoselenide, mixtures of sulfur and selenium * such as those in the US patent 2 297 691 are described, mixtures of arsenic and selenium, as described, for example, in the Xi, So Patent 2,822,300, mixtures of selenium and tellurium, as described for example in US Pat. No. 2,803,541, arsenic selenide, tellurium selenide and mixtures of these selenides. A mixture of arsenic and selenium is preferably used because such a mixture can be heated without it crystallizing. The sol-containing layer can contain various sensitizing additives, for example the halogen dopants which are the subject of French Patent 1,505,803 .

The intermediate layer can consist of any suitable phthalocyanine,

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"^ ⁵ OfHGlNAL

which is distributed in an insulating binder »consist, lypishe phthalocyanines are aluminum phthalocyanine, aluminum polychlorophthalocyanine, Antiraon phthaloeyanine, barium phthalocyanine, Beryllium thalo cyanine, CadmiTimhexadecachlorphthalocyanine, Cadisiiimphthalooyanin, Calciumthaloeyanin, Cerphthalocyanin » Chromophthalocyanine, oobalt phthalooyanine, cobalt chlorophthalocyanine, Copper-4-aminophthalocyanine, copper bromochlorophthalocyanine, Copper-4-ohlorphthalooyanin, copper-4-nitro- * phthalocyanine, copper phthalooyanine, copper phthalocyanineilphonate, Copper polychlorophthalocyanine, deuterium phthalocyanine, Dysprosine phthalocyanine, erbium phthalocyanine, europio phthalocyanine, Gadolinium phthalocyanine, gallium phthalocyanine, germanium phthalocyanine, Hafnium thalooyanine, halogen-substituted Phthalocyanine, holmium thalooyanine, indium thalooyanine, iron phthalocyanine, Egg polyhalophthalocyanine, lanthanum phthalocyanine, Lead phthalocyanine, lead polyol phthalocyanine, cobalt hexaphenyl phthalocyanine, Copper pentaphenylphthalooyanine, iithine phthalocyanine, Lutetium thalooyanine, magneaium thalooyanine, Manganese phthalooyanin, mercury phthalocyanine, holybdenophthalooyanin, Kaphthaiοcyanin, Neodymphthalooyanin, Hickelphthalooyaiiin, Nickelpolyhalogenph thai ο cyanin, Oemlumphthalooyanin, Palladlumphthalocyanin, Palladium chlorophthalooyanin, alkoiphthalooyanin, Alkylaminophthaiοcyanin, alkylmeroaptophthalooyanin, Aralkylamlnophthalooyanin, Aryloxyphthalooyanln, Arylmercaptophthalocyanin, Copper phthalooyanine piperidine, cyoloalkylaminophthalocyanine, Dl alkyl aminophthal ο oyanine, diaralkylairiinophthalo-

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JBÄOÖRIQINAL.

- oyanin, Dicyolοalkylaminophthaiοoyanin, Hexadeoahydrophthalooyanin, Imidomethylphthalooyanin, 1,2-Iaphthalooyanin, 2,3 * Raphtnalocyanin, Octaaxaphthalocyanin, sulfur phthalocyanine, Se traasaphthalo phthalocyanine, tetra-aoetylaalnophthalocyanln 4, tetra-aminobenzoylphthalooyanin 4, tetra-aaijaophthalocyanin 4-! Tetrachloromethylphthalocyanin, Tetradiaaophthalocyanine, Tetra-414 ~ dimethyloctaazaphthalooyanin, Ietra-4,5-Diphejiylenedioxydphthalocyanine, Tetra-4,5-Diphenylootaaaaplithalocyanin, Tetra- (o-methylamlophthalocyanine, tetra-methylamlophine, tetra-methyl-tenzothiazoyl-phthalocyanine, tetra-methyl-tenzothiazoyl-phthalocyanine, tetra-methyl-tenzothiazoyl-tarethyl-tenzothiazoyl-phthalocyanine, tetra-methyl-amethyl-tenzothiazoyl-phthalocyanine, tetra-methyl-tenzothiazoyl-thaloethyl-tenzothiazoyl-phthalocyanine, tetra-o-methyl-tenzothiazoyl-phthaloethyl Tetra-naphthotriazolylphthalocyanin, tetra-4-naphthylphthalocyanin, Setra nitrophthalooyanin 4, Ietra-peri-naphthylene-4,5-octa-aBaphthalocyanln, tetra-2,3 ~ _f Phenylenoxydphthalocyanlxi tetra-4tHienyloctaaBaphthalooyanin, Tetraphenylphthalocyanin, 5etraphenylphthaiοoyanin, Setracarbonsäure, Tetraphenylphthalooyanlntetrabariumoarboxylat, Tetraphenylphthalocyanine, tetraphenylphthalooyanine tetrac aloitunoarboxylate, tetrapyridyl phthalocyanine, tetra-4-trifluoromethylmeroaptophthalooyanine, tetra-4-trifluoromethylphthalooyanine, 4,5-thionaphthenootaamaphthalocyanine, flatlnph-thalooyanln, kalluiaphthalooyanln ₍ Samarium phthalooyanin, silver phthalooyanin, Sillsü-UÄphthalocyanin, sodium phthalooyanin, eulfonlertee Fhtimlooyanin, thorium thalooyanin, Ihxiliuiuiaphthalooyanin, p Tin phthalooyanin, titanium phthalooyanln, oranphthalooyanln, Vanadium phthalooyanin, Ttt * rblu «phthalooy« nln, Zlnkohlorphthalooyanin, Zinkphthalooyanin «owl» Hlaohnneen, d * rr «t« going

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named compounds, diners, trimers, oligomers, polymers, Copolymers or mixtures thereof.

Even if the intermediate layer can consist of any suitable phthalocyanine, it is preferable to use a metal-free phthalocyanine which has a relatively high photoerapindilicity. Of the various polymorphic porms of metal-free phthalocyanines, the α «and" X "forraen are to be preferred, since these are known to have a very high photosensitivity. Optimal results are obtained with the polymorphic crystalline "X ⁿ form of a metal-free phthalocyanine (cf. British patent specification 1 116 553), since this form gives the highest photosensitivity together with the lowest dark discharge. The various forms of metal-free phthalocyanine can be found in distinguish simple catfish by comparing their X-ray diffraction patterns and / or their infrared spectra (cf. French patent 1 508 173) «

The phthalocyanine can be in finely powdered form in the binding material be in any suitable photoconductor to binder ratio. Based on a weight base of phthalocyanine components / dry Binder extends the appropriate range from about 2: 1 to about It15. Optimal results are obtained when ratios from about 1) 4 to about 1:10 must be adhered to, so this area is the most

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BATH ORlQINAL.

au prefer. The phthalocyanine pigments can be dissolved in the or melted binders by any suitable method are concentrated, for example by stirring with strong shear effects, preferably grinding on the same side Such methods sedai a grinding in a ball mill, a grinding in a craft, a sand grinding, a stirring by means of ultrasound, a Hoohgeechwindlgkeltssampling and any suitable combination of these methods is mentioned. In addition to adding the phthalocyanide particles to the dissolved or melted binder material, these can It also affects the trooked powdered binding material or a slurry of the binding material prior to heating the same or its dissolution are added ο

The selenium-containing layer as well as the phthalocyanine and binder-containing layer can be of any suitable thickness. A plate is preferably produced which has a selenium-containing layer with a thickness of approximately 0.5 to approximately 5 μm and covers a layer containing phthalocyanine / binder, the thickness of which is approximately 10 to approximately 50 μm Sensitivity to the entire visible spectrum as well as a noticeably reduced sensitivity to fatigue and shows a considerably reduced degradation during operation, an effective toner transfer as well as a very high thermal stability and a very high abrasion resistance. Optimal results are being made using

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obtained from plates that contain a selenium-containing schioht about 1 - 3µ thick, which is a phthalocyanine / binder containing plate with a thickness of about 10 to about 15 u coversυ

The binder material for the phthalocyanine pigment in the intermediate layer can consist of any suitable, substantially insulating, film-forming organic resin. The binder preferably has good adhesion to selenium and mixtures which contain selenium, as well as to the selected conductive substrate material * As mentioned above, the resin can be selected primarily with regard to its adhesion to the respective selenium-containing layer and to the respective substrate material , irrespective of the insulating properties} which it possesses when exposed to light »Typical insulating film-forming binders are urea and melamine-aldehyde resins, polyimide resins, polycarbonate resins, silicone resins, epoxy and epoxy / phenol resins, polyvinyl carbazole and polyester . When using polycarbonate resins, optimum adhesion is achieved both to the substrates and to the layer containing selenium on top, and excellent photosensitivity is also observed * Therefore, polycarbonates are preferred as binders for the phthalocyanine in the intermediate layer.

Γ: *. © Slurry of pigment, binder and

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.., BADORfGINAt

(or the pigment / binder base melt) can be applied to the substrate can be applied by any of the customary painting or airing methods, for example by spraying, floating, squeegeeing, electrostatic coating, dipping, applying by means of an orphan or the like. Haohdem the pigment / binders! ttel-Zwi s ohenschloht has been formed, the selenium-containing composition can be applied by any suitable method. Coating by vacuum vapor deposition is preferred, since a smooth and uniform layer in an amorphous state is achieved on this catfish.

The following examples illustrate the invention without representing it restrict. All prices and percentages relate to calibration, provided niolit stated differently, based on weight

example 1

3 electrographic hats are made in the following catfish!

a) A 125 u (5 mils) dloke aluminum foil is covered with a 15-u-Sohioht from an amorphous selenium by vacuum evaporation naoh in the U.S. Patent No. 2,970,906 beaohiohtet.

b) a solution is prepared by approx

109819/1587 ORIGINAL BATHROOM

Dissolve 2 ropes of a poly carbonate resin (Lexan Grade 145) commercially available clay from the General Electric Company in about 10 ropes of dioxane and about 10 parts of dichloromethane. This solution is about 0.3 Leile metallfreiea phthalocyanine in the "X ^fl - orm added. This solution is then applied to an aluminum substrate to a dry thickness τοη approximately 15 p. slurried. The layer of pigment and binder is dried for a period of about 5 hours at a temperature of about 10O ⁰ C.

c) The procedure described under (b) is repeated » After the pigment and binder layer has dried a 2-micron layer of amorphous selenium is applied over the phthalocyanine interface applied by vacuum evaporation.

Each of the 3 plates is then electrostatically charged to a positive voltage by passing a corona discharge unit, maintained at about 6000 YoIt, across the plates about three times, as described in US Pat. No. 2,588,699. Each plate is then (/ CL-2OO SPyp 2? 42) irradiated with white Moht using a General Electric tungsten quartz iodine lamp having a Parbtemperatur of about 280O ⁰ K. The loan-induced discharge properties of each plate are continuously reduced

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BAD ORiGlNAl

Using a vibrating Monore tongue electrometer for transparent samples (Monore transparent probe vibrating reed electrometer) measured. Each plate is then recharged to a positive voltage, and wherein daa filter is placed between the light source and the plate by means of a CS2-63-Piltera, which is brought from the Corning glass company in the trade _$ irradiated. The filter transmits about 87 $> of the visible iloth with wavelengths greater than 630 mu, but less than 1 % below 580 mu. The sensitivity of each of the 5 plates to the red light is measured.

The results show that the selenium plate that opposes light is sensitive in the blue, green and UV region of the spectrum, to which the red region responds only to a very low degree. In contrast, the phthalocyanine plate is in the red and infrared range more sensitive than in the UV range. The plate covered with selenium has a sensitivity that is similar to that of the responds essentially to the entire visible spectrum.

The phthalooyanine plate (not overlaid) and the selenium layer Phthalocyanine plates are then each electrostatically using a corona discharge device, the operates at a positive voltage of approximately 6000 volts, charged. The plates are then used for a period of time of 1 second using a black and white slide

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ORIGINAL

positive in a Simmons-omega-D-3-enlarger is provided, which with a f / 4.5 ~ MnSe and a Wolframlichtajielle which operates at 2950 ⁰ K, "irradiated. The amount of light incident on the plates is approximately 4 pus candles. The electrostatic images obtained are then developed by cascading electroscopic marking particles over their surfaces according to the method described in US Pat. No. 2,618,551. The powder images obtained are then electrostatically transferred to paper receiving sheets by the method described in US Pat. No. 2,576,047. This process is repeated until each plate has produced 1000 copies of the profitable image. The results show that the non-coated plate produces copies that slowly lose density. The results are visible to the eye after producing approximately the 5 "copy. After making about 100 copies using the non-coated plate, the image on the sheet is extremely light and pale. When using the phthalooyanine plate provided with a selenium coating, on the other hand, the 1000 × image produced has the same quality as the first image, the image corresponding to the projected image. The disk sensitivity under operating conditions is therefore affected by the coating. While the uncoated plate decreases in sensitivity to an increased degree after a few charge / dissolution cycles, the plate coated with selenium shows only a slight increase in sensitivity during operation

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BATH ORIGINAL

■ - 18 -

This is an advantage for outsiders as well Plate compared to a coated plate appears to be, this is nevertheless not the case, since there is an uncontrolled increase in sensitivity with each cycle arrives, whereby the niehtttbereogene plate to a degree is irradiated, which exceeds the HaS required for the plate. This overexposure, in turn, has the generation less dense images result. When using the plate coated with selenium, the sensitivity increases slowly so that the plate does not become exposed and consequently no change in the quality of the generated image is to be determined "

After a few cycles of charge, irradiation, and transfer using the 2 above-mentioned plates (non-coated Phthalocyanine plate and with selenium ffbersofclitete Phthalooyaninplatte) an attempt will be made to remove each of the Plates using a rabbit fur coat as well as one Cleaning rayon brush. Babel will step in the removal of Xoner or the like. Significant from the non-soled plate Difficulties arise while the coated plate is instantly visible can be cleaned thoroughly.

Example 2
2 electrographic plates are made as follows!

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(a) Bine -20-u-Sehieliv made of amorphous selenium is applied in a vacuum a brass foil with a thickness of 50 u (2 mils) vapor-deposited «

(b) Mae BesciiicfetungslSsting is prepared by about 4 ropes of a Polycarbönatharaeß (Merloh is H-90 ₉ gebraoht the tone of Moliay Chemical Company in the trade) are gelöat loluol in about 20 parts', 2u about 10 Steep of this solution is about 1 part of the α »form of aetaULfreiea Hithalocyanin is given * Bixie brass foil with iaer Bioke of 50u (2 mils) by dipping slit of this mixture up to a Srookendioke of about 17% . öesehichtet "The resin is then dried by heating at about XOO ⁰ C for a period of about 1 hour. A layer of amorphous selenium is then vapor-deposited onto the resin surface in a vacuum to a thickness of approximately 5 microns.

Each foil is then bent over a radius of 50 ram (2 inches). FoUe ₉ on which the selenium layer sits directly on the measuring surface _s suffers cracks in the selenium _s. With considerable flaking. The polie, which has the shiialocyanine / binder resin intermediate layer, shows no tucks in the selenium layer, and its coating adheres firmly to the base.

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^: " ^Sf -iAÖ ORIGINAL

A coating solution is prepared by dissolving about 1 rope of a silicone resin (SR-82, available from the General Electric Company) in about 3 parts xylene. About 0.3 ropes of metal-free phthalocyanine are added to this solution ^H X ⁿ -l? Ona added. This solution is sprayed onto an aluminum substrate to a dry film thickness of about 50 yds. The plate is then heated to about 100 * 0 during a time period of about 1 hour * A O _s 5 ~ p-Sohicht of amorphous selenium is deposited ansohlie ~ ßend on the resin surface ", the plate is electrostatically charged by a corona Entladungsvorriohtung that at a positive voltage of about 6000 YoIt works * charged. The plate is then approximately 1 second duroh Aufprojizieren a Schwärs white diapositive in a Sisamons-omega-DJ-enhancer exposed The Vergröße "rer is provided with a f / 4» 5- * lens and a tungsten light source ₉ at a Parbtemperatur of 2950 ⁰ K works, provided. The incident on the plate on Liohtmenge is approximately 4 footcandles <> The electrostatic latent image obtained is sohen Harkierungsteilohen About developed by cascading electroscope! Its surface after the US Patent 2,618, 551 beschriebe- NEN method. The powder image obtained is electrostatically transferred to a paper receiving sheet by the method described _{in TJ.S 0 patent specification 2,576,047.} That

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Image on the sheet "has a good quality and corresponds the tried-on picture. The plate is then again used in the process described above as long as until 500 copies have been made. The picture on the 500 * sheet has the same quality as the image produced on the first sheet and corresponds to the one projected on it Image"

Example A.

A coating solution is prepared by about 5 parts of an aromatic 3? _S olylmidharzes which has been prepared by reacting pyromellitic with a diamine and from EI is ont de Sfemoura & Company commercialized 3? (Pyre ~ Wed.-ILK 692, 12 fatty substance content), is dissolved in about β ropes of dimethylformamide ^. X "form. This mixture is then coated onto an aluminum layer with a sock thickness of approximately 10 yds. The resin is then cured for a period of approximately 1 hour at approximately 200 ° C amorphous selenium is then formed on the Hara surface by vacuum evaporation * The plate is then charged, irradiated and developed according to the method © described in Example 3. This achieves a good image that matches the original

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* 22 -

, Picture corresponds. The plate can be in a simple manner by means of to clean a rabbit fur »! subject of spontaneous generation of 600. Copies are still copies of the same quality how she owns the image generated first "

Example 5

A coating solution is prepared by dissolving about 1 x part of a melamine / formaldehyde resin, Üformite MM-47, which is marketed by Rohm & Haas Company, in about 10 parts of butanol. About 0.4 part of the oc form of metal-free phthalocyanine is added to this solution. The mixture is then applied to an aluminum substrate to a dry film thickness of approximately 30 microns. The resin is cured by heating the plate to about 150 ° C for a period of 2 hours. An approximately 4µ thick layer of amorphous selenium is then placed on top of the hardened. Resin surface evaporated in a vacuum. The plate is then loaded, irradiated and developed according to the method described in Example 3 “A picture of good quality is obtained” which corresponds to the original picture. The plate can be cleaned in a simple manner using a Heyon brush. After 450 copies have been produced, the image produced is still of the same good quality as was found in the image produced first.

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Bin coating solution is prepared by dissolving about 1 rope of urea / formaldehyde harses (Uformit® F-240 ₈ available from Rohm & Haas Company) in a mixture of about 5 ropes of xylene and about 5 ropes of butanol. This solution becomes about 0.15 part of the α form of. metal-free phthalocyanine added. An aluminum substrate is coated with the mixture to a dry film thickness of about 15 microns. The plate is then ^{heated to about 150 0} O for a period of about 1 hour to cure the resin. Then a layer about 2 microns thick is applied layered from selenium "The plate is then loaded, irradiated and developed according to the method described in Example 3." A picture corresponding to the original picture is obtained with good quality. After 900 copies have been produced, the picture produced is the same Quality like that first repro-. ' ■

duced picture.

example "J

A coating solution is prepared by approximately 70 parts of an epoxy resin (Epon 1007, which is available from Shell Chemical Gompany) in about 80 parts of ethyl cellosolve, an ethyl glycol monoethyl

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-.24-

ether marketed by Union Carbide Corporation. To this solution are added about 40 pounds of phenolic resin (Methylon 75201, available from General Electric Company) and about 9 pounds of urea / formaldehyde resin (Uformite P-240, available from Rohm & Haas Company). The mixture is stirred to ensure complete dissolution. About 20 parts of the "X" form of metal-free phthalocyanine are added to this solution. An aluminum substrate is coated with this mixture to a dry film thickness of about 40 microns. The plate is then erhitztο to 180 ⁰ C during a side breakdown of .ungefähr 2 hours to cure the resins Sine 6-a-layer of amorphous selenium is then vacuum evaporated on the resin surface · The plate is then charged, exposed and after in Example 3 described method developed. Thereby, an image corresponding to the original image is obtained with a good quality on V of the plate. After making 200 copies, the resulting image will be of the same quality as the first reproduced image *

Example 8

Its coating solution is prepared by approx Approximately 2 parts of a tinylcarbazole polymer (Xuvlcan H-170, available from the Badische Anilin- und Soda-Fabrik)

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10 ropes of toluene are dissolved. About 0.2 ropes of the "X" form of metal-free phthalocyanine is added to this solution. An aluminum substrate is mixed with this solution to a dry film thickness of approximately 11 γ. coated. ^{The plate is then heated to approximately 30 °} C. for a period of 1 hour in order to ensure that the solvent is removed. A 1.5 micron thick layer of amorphous selenium is then applied over the resin surface by vacuum vapor deposition. The plate is then charged »irradiated and developed according to the method described in Example 3. A good picture is obtained that corresponds to the original picture on the plate. After 950 copies have been made, the resulting image will be of the same quality as the first reproduced image.

Example 9

A coating solution is made by approximately 2 ropes of a glycerine triestore of 50 # hydrogenated wood resin (Staybellt Ester 10, available from Hercules Powder Company) in about 10 ropes of toluene. This Solution will be about 0.25 ropes of a finely divided chlorinated Copper phthalocyanine (Cyan Green 15-3100 available from the American Cyanamide) added. An aluminum substrate becomes by floating with this mixture to a dry dioke coated by about 45u * Then a 5u thick is made

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BATH ORIGINAL

Layer of about 90 pounds of selenium and 10 pounds of tellurium formed on the resin surface. The disk is then loaded, irradiated and developed according to the method described in Example 3. A picture with a good quality that corresponds to the original picture is obtained thereby · tray of the When producing 250 copies, the resulting image will be of the same quality as the first reproduced image.

Example 10

A coating solution is prepared by dissolving about 2 parts of a polycarbonate rarse (Lexan Grade 145, available from General Electric Company) in about 10 parts of dioxane and about 10 parts of dichloroethane. About 0.3 ropes of finely divided metal-free phthalocyanines in the α-form are added to this solution. Does aluminum substrate get old by floating this mixture on)? a xrock dioke of about 9 η coated. An approximately 20µ thick layer of approximately 90 # selenium and approximately 10 $ tellurium is then applied to the resin surface by the method described in US Pat. No. 2,745,327. This plate is then loaded, irradiated and developed according to the method described in Example 3. Thereby, an image of excellent quality which corresponds to the original image is obtained. After making 200 copies, the image formed is of the same quality as the image reproduced first.

109819/1587 ^y BATH ORIGINAL

- 27 - Example 11

An epoxy-phenol coating solution is prepared according to the procedure described in Example 7. 25 microns (25 mil) thick brass foil is mixed with this solution to a dry thickness of approximately 14 y. coated. The plate is then heated ^{to approximately 40 °} C. for a period of approximately 5 hours to partially cure the resin. An approximately 2 u thick layer of about 17 $> arsenic and about 83 # Selenium is then transferred to the resin surface after in IT. See Patent 2,822,300 method described. ^{The plate is then held at about 120 °} C. for a period of about 40 hours for the resin to cure completely. This plate is then loaded, irradiated and developed according to the method described in Example 3. A good quality image that corresponds to the original image is preserved. After creating 1000 copies, the image created will be of the same quality as the image reproduced first »

The materials and conditions given in the above examples are merely exemplary in nature. Various other materials, such as those noted above, as well as various other conditions can also be used or applied, whereby

109819/1587

BAP ORIGINAL

- 28 -

borrowed results can be achieved. The selenium-containing layer and / or the hot-dialocyanin / binary oil-resin layer can also be mixed with other materials in order to improve, sensitize or otherwise modify their properties or to give them a synergistic effect or spectral sensitizers are added. The multilayer plate according to the invention can also be used in other fields in which photoreceptors with a broad spectral sensitivity are required, for example in a Yidikon system.

109819/1587

BATHROOM 0RJ6INAL.

Claims (1)

Claims; 1.) multilayer board, in particular electrographic board, marked by (a) a conductive substrate, (b) an intermediate layer overlying this substrate, with a thickness of about 10 to. about 50 ju, said intermediate layer consisting of a finely divided phthalocyanine dispersed in an insulating resin binder, and (o) a layer that extends over this intermediate layer and has a thickness of about 0.5 to about 5 microns, this layer containing selenium. 2ο plate according to claim 1, characterized in that the Interlayer has a thickness of about 10 to about 15 U. 3. Plate according to claim 1 or 2, characterized in that the tlberzugssohioht has a Dloke of about 1 to about 3 μ . 4 plate according to one of the tests 1-3, daduroh marked 109819/1587 BATH ORIGINAL - 30 -dad dao phthalocyanine is a metal-free phthalocyanine 5. Plate according to claim 4 »characterized in that the metal-free phthalocyanine from the a-? orm, the "!" form or mixtures of these forms » 6. Plate according to claim 4, characterized in that the metal-free phthalocyanine is a phthalocyanine in the polymorphic crystalline ⁿ X ⁿ ~? Orm. 7. Plate according to any one of claims 1-6, characterized in that the upper layer consists of a mixture of Arsenic and selenium consists " 8 «plate according to claim 1-6, characterized in that the upper layer consists essentially entirely of selenium. 9. Plate according to one of claims 1-8, characterized in that the upper layer on the intermediate layer applied by vacuum evaporation. 10. Plate according to one of claims 1-9 »gekenneeichnet characterized in that the ratio of phthalocyanine au the Harnesses »wipe about 2: 1 to about 1 ι 15 wt. 56 fluctuates. 109819/1587 11. Plate according to claim 10, characterized in that the ratio τοη about 1 s 4 Me about 1:10 Weight # fluctuates 12. Plate according to claim 10 or 11, characterized in that that the resin binder is made of a polycarbonate resin 13. ElektrographiacheB image generation method, characterized in that (a) an electrostatic latent image is formed on a plate according to any one of Claims 1-12, and (b) the latent image with an electroscopic marking material to form a visible image is contacted according to the latent image. 14. The method according to claim 13, characterized in that the electrostatic image is generated by uniformly electrostatically applying the surface of the plate is charged and the plate is exposed to an image of activating electromagnetic radiation will. Method according to inepruoh 12, characterized in that since the visible image is transmitted on a recording sheet and steps (a) and (b) are repeated. 109819/1587 ORIGINAL Blank page