DE1942700A1 - Electrophotographic plate - Google Patents

Description

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HASE XEROX LIHIXED ₁ London / England El ektr ο photographs one plate

The invention relates generally to electrophotography and refers in particular to a binder board, which can be used in electrophotography.

It is known that images are certain on the surface photoconductive insulation materials on electrostatic Paths can be formed and developed. The basic electrophotographic process is described in the ÜS patent pen 2 297 691. This method consists in charging a photoconductive insulation layer uniformly, whereupon the layer of the action of a Lioht-und-Sohatten-Bild is abandoned. This image discharges the charge the locations of the layer that have been irradiated by the light

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are. The electro-rotational latent formed on the surface Image emerges from the coniiguration of the Lioht-und-SehattQn-Bilde8. Optional A latent electrostatic image can be created on the plate by charging the plate in an image configuration will. The image is produced by applying a fine-grained Developer material made visible on the image provided with the image, wherein the Bntwioklermaterial consists of a colorant, which is referred to as an ioner, and a toner carrier, the powdery © Bntwloklermaterial is normally Sound sucked in those parts of the Sohioht that have retained a charge. On these catfish a powder * image formed that corresponds to the latent electrostatic η image. If the underlay film is relatively cheap, it is If you calibrate around paper, for example, then the powder image can be used directly be fixed to the plate, for example duroh Sohmelzen under the action of heat or duroh anI whether effect using a solvent. Optionally, the powder image can be transferred and applied to a sheet of the receiving material, for example a sheet of paper. the bow fi \ be xed. The general method outlined above is the subject of U.S. Patents 2,357,809; 2,891,011 and 3 079 342. - ^ ΐ

k You must have a photoconductive insulation layer in order to be effective dasu be able to have an electrostatic charge in the dark hold au, the charge when irradiated with Lioht must be discharged to a conductive substrate, bass different Photoconductive insulating materials can be used to make electrophotographic plates is known. Suitable photoconductive insulation materials, such as anthracene, sulfur, selenium or mixtures thereof, are described in ÜS Patent ahrift 2 297 691. These materials are generally Ib Blaubereloh or close to the UV-Berθioha sensitive, all with the exception of selenium

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the disadvantage beaifczon, daeo bio only loioht light-sensitive Bind Aiid serve reason, selenium is most common in electrical. photographic plates used. Glao-like in selenium adheres however, the kachteil on, in addition to a spectral viewing ability somewhat compared to the UV, blue and green areas of the spectrum is limited, and also the production of panels from vitreous selenium requires expensive and complicated methods such as vacuum evaporation. Besides that So layers made of vitreous selenium are only metastable insofar as they are easily converted into non-brewable crystalline forms Crystallize temperatures which are only slightly above the temperatures as they are electrophotographisohen in the Ubliohen Copy machines prevail, require personnel Solenplatten the use of a separate conductive substrate ohioht, preferably with an additional barrier layer that is applied to the substrate prior to application of the selenium photoconductor is applied. From these economic and technical considerations, many attempts have been made to use photoconductive insulating materials other than selenium for use in electrophotographic plates to develop.

It has been proposed to use various two-component materials in photoconductive insulation layers, which are described in electrophotographic plates are used. These consist of a photoconductive insulation material in the form of individual particles that are in an insulating Binders are distributed. Put the particles off a photoconductive material made of inorganic crystalline compounds which contain hotallions, then toeaumen such a photographing velocity and spectral response as it is for a Use in photographic plates are necessary. However, even if these plates are sensitive to a dye

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"Bind your sensitivities much lower than the jones of halls. These panels are generally Not considered reusable since it is necessary to have such high percentages of photoconductive pigment to achieve of sufficient sensitivity that it is difficult to achieve smooth surfaces which Ensure efficient toner transfer and end to end Suitable for cleaning before re-use. Another disadvantage of using disks of the Type based on an inorganic pigment binder, occurs is that these plates are only charged negatively and not by means of a positive corona discharge can. This property makes these panels unsuitable for large-scale use because of negative corona discharge much more ozone than a positive corona discharge generated, a negative corona discharge is also generally more difficult to control.

Zs has also been found to be organic photoconductive Dyes and a variety of polycyclic compounds along with suitable resinous materials for manufacture of photoconductive insulating soles, which are in binder-syp-plates are suitable can be used. However, these plates generally lack the sensitivity which fttr a use in usual electrophotography Koplervorriohtungen is necessary. In addition, these plates have no abrasion resistance and stability their use, especially at elevated temperatures.

Another type of plate is often self-photoconductive Polymers In combination with sensitizing dyes or Lewis acids to form photoconductive insulating layers used. However, these polymeric organic photoconductor plates have a disadvantage that they are expensive to manufacture

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let »whereby they are also brittle and poorly attached to the carrier substrate cling. The number of these photoconductive insulation resistors is also deformed duroh heat, whereby they are for use in automatically operating electrophotographic soles Devices are unsuitable, because in these devices often strong lamps and thermal melting devices, which heat the electrophotographic plate are installed.

There is therefore a need for improved photoconductive insulation materials that are stable, sensitive and reusable electrophotographic plates were made can be.

The aim of the invention is to provide an electrophotographic image Plate which does not have the above-described Baohteile owned. Throughout the invention are electrophotographic Plates provided the sensitivities which extend over considerable parts of the visible spectrum. These plates can be reused and have a high overall sensitivity as well as a high Thermal stability compared to the previously available ones reusable panels «Within the scope of the invention Furthermore, the acquisition of a photoconductive iBolatlonamaterlals falls, that is suitable for use in electrophotographisohen Disks are suitable both in systems that are used only once and in systems that are reused are usable. The photoconductive insulation layer according to the invention for an electrophotographic plate is very resistant to abrasion and has a relatively high resistance to heat deformation. Overall, the duroh owns the present invention for Disposed electrophotographic plate exhibits a wide range of valuable physical properties.

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The invention provides an electrophotographic plate created which has a new photoconductive layer. This layer consists of a quinaoridone pigment In a resin binder, the glnacridone pigment being the The following general formula corresponds to t

OH ^

for ^Q ^ ⁰ ^^ * OCH ₅ , ⁰ ^ 2 ^ 3 ^or H 'a® aromatic _e aliayklioohe or aliphatic

Group represents. Tuck special class of Ohinacridon-pigmen-fess and procedures mi her Herstellting be closer to the d @ r deutsohon patent. ..., .. (patent application corresponding to US application Serial Ho. 854 634 of August 22, 5968, which was filed on the same day as the present application at the German Patent Office under the processing core Z 260 (ΧΓ / 23Ο1)).

The quinaoridon / Hars photoconductor described above can be applied to any suitable carrier subotrate or cast as a self-supporting film. The plate can optionally be made with any suitable materials be overslept. Pie chinaoridon / resin photoconductor layer can be used for the production of many Sandwich configurations adjoining a dleelectronsohe Layer can be used. Ser-like configurations will be by Golovln et al in "A Hew Electrophotographic Prccess, Bffooted by Keane of Combined Electric Layers ", Doäclady. Akad.Hauk SSSR Volume 129 * Mr. 5, pages 1008-1011, November /

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Described December 1959. It was found that the pro » percentage of the respectively used »described above Quinacridones, but to achieve sufficient sensitivity required in a plate is very low 1st. Because of this Tatoaohe the mechanical properties of the photoconductive layers essentially determined by the properties of the binder. According to the invention can use a variety of bonding agents, these bonding agents from soft thermoplastics to hard networked laocon vary. In this way the physical Properties of the finished photoconductive layer by selecting the appropriate resins according to the specific ones Requirements can be varied globally. Xn this These photoconductive layers are related to many previously known binder / suspension of inorganic pigments Superior as these known suspensions require a relatively high percentage of inorganic pigaent so that in this case the inorganic pigment essentially has the physical properties of the finished photoconductive Layer determined. Ba is the percentage of quinaoridone pigment required If is relatively low, the photoconductive plate can have a very hard and very smooth surface. on in this way many of the residual parts adhering to the previously known pigment / binder plates are eliminated. These Haohteile were due to the large amounts of pigment very rough and abrasion-prone surface for Uokzuf watches.

Even if each of the quinacridones falling under the formula given above can be used to produce the photoconductive layer according to the invention, it is nevertheless preferable to use those quinacridones in which R is GH, C ₂ H, or mixtures thereof, and in which H ¹ M- / o) means that these materials are highly light-

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eapfindlioh are and deliver the best pictures *

Some of the new quinacridones described above can be used alone or in combination with other compounds in any suitable mixture can be used, with the addition of the silver, zirconia, oligomies, polymers, copolymers or Questions about it

The new inventive quinacridones are manufactured naoh a process which consists in a compound of the general forasl ^x

H °

where B stands for OH ", OX, OGH ₅ , 0O ₂ He or halogen stent, bit SOOl ₂ in BieethyliorMUEid and then with 2E" HHg, where R * stands for an aromatic, alinjicliaohee or aliphatic amine "su vernisohen.

Bit the novel ohinaoridonen according to the invention, any suitable organic binding system can be used for the production of the photoconductive solution according to the invention, he hares suitable for the purposes according to the invention should have a lower electrical resistance than about 10 ° and preferably a resistance of more than 10 ¹² Ohe / oa under the conditions for electrophotographic use. From typieohen harps are following erwtthntt fnexBOplastea "such as OlefinpoXraere _t as SB polyethylene or polypropylene, Polyaere that abetaaeen of bees, such as polybutyldiene,

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Polyisobutylene and polychloroprene, vinyl and vinylidene polymers, such as polystyrene, styrene / aoryl nitrile copolymers, Aoryl nitrile / butadiene / styrene terpolyaere, polyethylmetheorylate, Polyacrylates, polyacrylate bonds, polyacrylonitrile, Polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride. Polyvinyl carbazole, polyvinyl ether and polyvinyl ketones, fluorocarbon polymers such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastics with hetero chains, such as polyamides, polyesters, polyurothanes, Polypeptides, Casein, Polyglycols, PolysulXide and Polycarbonates, eovio sellulose-containing polymers, vie for example regenerated cellulose, cellulose acetate or cellulose! Harse that can be hardened can also be used in for example phenolhoria, aminoharia, such as beiepielaweiee Urea / ioraaldehyde resins and molamine / ioriaaldehyde resins, non-saturated polyester resins, epoxy resins, silicone polymers, Alkydhmrao and Puranhair. Different Oopolyaeren and Mieohungen from the haraen mentioned above can also apply Elageeetst · Zuoätilioh besides the above listed Hareen koaeoen also all other suitable materials in question.

He inventively wet Ohlnaoridone can la daa dissolved or absorbed connective hair using well-known methods, for example by vigorous listening Shear action, with Toriugaweloe a tereahlen on the same side takes place · Typical methods consist in iron weddings in a lugelaUhle or in a Waliennühle, in a sand mill, 1 »an ultra-low noise, in a high-speed noise as well as in every combination of these Methods. One can: any suitable · ratio of pigment adhere to bars. Concerned on the weight of the quinacridones as well as dry Haraes, the appropriate range varies from about lsi Ms about 1a40. The best. Results

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been within a preferred range of approximately 134 to about 1:10. Let optimal results can be achieved by keeping a ratio of about 1: 4, “Even if the greatest sensitivity to light is Figment / Hara ratio of 1: 1 to 14 is achieved, ■ o rises then ooh with higher hagment consentratioiisn the Ink conductivity on. Because «optimal Qlolohgevioht svlsohen the high sensitivity and the dark conductivity at a ratio of about 1 * 4. It should be pointed out » that the amount «of the In the preferred area »Ingöfleteten photoconductor merklioh below the crowd liogt, dl · previously used star production of panels were wet from an inorganic photoleltond Binders exist. These known plates have a satisfactory electrophotographic sensitivity only achieved »if the Plgment / Bars ratio at least 2t1 is.

The possibility that "invention agem & se lower pigment / Hars ratios ± ÖB9 can be adhered to, creates one clear part of the gate compared to the state of Steohnlk, there a smaller amount of the relatively expensive pigment component is necessary, and in this way the production of very smooth lifting material is achieved as a result of the high Binding agent content possible. The small amount of the set Material has only a minor effect on the physical «Without bigenso-like characteristics of bindoharees. So can a bars be selected because "the usual expansion, the desired smooth · »hardness, viscosity» solution medium ~ persistence, solvency or the like possessed, whereby for it Oerthr is given »that the pigment does not have these properties influenced to a significant extent

Should the Ohinaoridon / Harsj-? Ila up on a substrate?

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become dead, various materials can be used as the substrate. Materials suitable for this purpose are, for example, aluminum, steel, moaning, glan coated with metals or tin oxide, semiconducting plastics and Hanse, paper and other common materials with a conductivity at the point of use of> 10 ΟΐΏ-om or with a surface conductivity of> 10 ⁸ ohn square. A suspension of pigment, resin and solvent (or the pigment / resin coating) can be applied to the conductive substrates using known painting or treatment methods Electrically coating, coating using a Mayer rod, coating by dipping, coating using a Omkehrwalsen insole, or the like. Spraying in an electric field is only necessary to achieve the smoothest surface, while coating by dipping is preferred in the laboratory for two-dimensional reasons Production of films from the respective binders. For example, Chinaoridon / Spoaqr plates can be hardened in such a way that a crosslinking agent is sugeset, which is followed by baking in an oven. The baking is carried out in the same manner as in the burn-in of other Laoken _e for the urine using the same and similar pigments Anstricheweoke be used. A very favorable feature of the quinacridones according to the invention is that they are resistant to chemical decomposition at the temperatures which are normally maintained when stoving a large number of lacquers. Therefore, these quinacridones can have very hard and shiny photoconductive coatings with surfaces similar to those of automotive

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or kitchen equipment XGoken, be constricted.

The beading of the films to the Ohinaoridon and binder Icann between about 1 and about 100 microns each according to the desired properties. Let self-supporting films For example, it cannot be produced in a suitable manner in a diagram of less than about 10%. The suitable block these films in terms of handling is between 15 and 75 microns. On the other hand, coatings are preferably in one Dioken range of 5-3Ou established. Ee is cheap, one Apply protective coating. The thickness of this coating should usually not be the thickness of a photoconductive coating exceed and preferably not by much than 1/4 of the thickness of the coating. Any suitable coating can be applied, for example a nitrocellulose coating -laok.

The following examples illustrate the invention without it to restrict. The rope and percentages relate to unless otherwise stated »on the weight.

example 1

An electrophotographic plate is made in such a way that first about 6 ropes of Pliolite 85B, a styrene / Sutadiene copolymer resin available from Goodyear Sire and Rubber Company, about 43 ropes of lylol and about 1 rope of an Ohinaoridon-Hgmente formula

GE ₃

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be mixed «The Misohung is poured into a glass bottle containing a certain amount of steel balls (3.2 na). Milling is then carried out using a Red Devil Quiokie Hill (Gardner Laboratories) for a period of approximately 1/2 hour. In this way a homogeneous dispersion is obtained "LAOH the grinding, the dispersion is brought to a Alumlniuafolie with a Dloke of O ₁ 125 (5 mils) by using an Br. 36 ~ Drahtab8iehstabes (Ho, 36 wire draw-down rod) on The oversug is left to dry in the air at approximately 100 ° 0 for a period of approximately 2 hours. The plate is then charged with a positive voltage of approximately 650 volts by means of a corona discharge, the method described in US Pat. The loaded plate is irradiated for 15 seconds in contact with a film-positive by means of a tungsten lamp. The color temperature of the lamp is 34OO ° K. The amount of solder at the irradiation plane is approximately 57 Yusskersen. The electrostatic latent image that has formed on the plate is developed by cascading pigmented slectroscope marking parts dissolve this through heat. The image on the recording sheet is of good quality and corresponds to the original. *

Example 2

An electrophotographic plate is manufactured in such a way that that suerst about 2 ropes of Silicone SR-82, one Methylphosphorus silicone knuckle that is commercially brewed by the General Sleotrlo Company, about 40 fil xylene

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and about t Heil a China Worldon-Plgments of the Pormel

H 0 O ₀

r \ "

be mixed. The one made from this mixture Plate will age positively with an initial voltage of approximately 290 volts charged · The image obtained has a satisfactory one Quality.

Examples 3-4

Two electrophotographic plates are made by mixing about 1 rope of Vinylite VTHS, a copolymer of Vinyl chloride and vinyl acetate sold by Union Carbide Corporation, about 10 ropes Diethyl ketone and about 1 rope of an Ohinaorldon

Pigment »of the formula

^{Ä PH} OH ₂ HHO - / θ),

H Ö

H'

Layer the solution on a plate and harden it. The plate is loaded, exposed and developed in the manner described in Example 1, but according to Example 3 the plate is charged positively to a voltage of 480 volts and according to Example 4 to a negative voltage of 835 volts . The image quality obtained is excellent in each case.

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Belflplele 5-6

Two electrophotographic plates are made in the manner that aunäohst about 1 rope Tinylite TXHS, about 10 parts of diethyl ketone and about 1 part of an OhInaoridon pigment the formula

veraiooht, whereupon the Hieonung is drawn onto a plate and hardened. The plate is then loaded, exposed and developed in the manner described in Example 1. The plate according to Example 5 is charged with a positive voltage of 530 tonnes and the plate according to Example 6 is charged with a negative voltage of 630 volts. Good pictures are obtained.

Examples 7-8

Sine electrophotographieobe plate is made in such a way that eunaohst about 1 rope Tinylite TXHS, about 10 ropes of ethyl ketone and about 1 rope of an ohinaoridon pigment the formula

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miss oh t «earth, whereupon the mixture is piled on a plate and is hardened. The plate is then loaded and developed according to the manner described in Example 1. However, the plate according to Example 7 is positive Voltage of 410 volts and the plate according to Example 8 charged a negative voltage of $ 60 volts. It will obtained excellent images using the plates.

Examples 9-10

Two electrophotographic plates are made in such a way that first about 100 cords of a 10% solution of polyvinylcarbazole in beneol, about 5 ropes of cyclohexanone and about 1 rope of the Ohinaoridon-Plgments according to Example 1 are mixed. Hit help of this mix will be Plates coated and cured, whereupon they loaded, exposed and developed naoh the procedure described in Example 1 will. The plate according to Example 9 is applied to a positive voltage of approximately 180 volts and the plate from Example 10 to a negative voltage of approximately 215 volts charged. Good quality images are obtained.

Examples 11-12

Electrophotographic plates are produced in such a way that that initially about 100 ropes of a 10 $ polyvinyloarbazole solution in benzene, about 5 ropes of cyclohexanone and about 1 rope of the ohinaoridone pigment according to β Example 2 are mixed. The mixture is coated onto plates and hardened, whereupon the plates are described in Example 1 To be loaded, attached and developed in a manner, · The plate according to Example 11 is set to a positive voltage of about 150 volts and the plate of Example 12 on one negative voltage of about 180 volts “Se be charged

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Good quality images received.

For the production of the plates according to the invention can also in addition to the materials mentioned in the examples, materials listed above may be used. The same result β β is obtained, additional results can be achieved by others Materials the Ohlnaoridon pigments or the pigment / Urine masses are added in order to improve the properties au or otherwise modify it. The invention Pigments and / or pigment / Hars-Kassen can optionally The colors are separated. You can also be with others Photoconductors, both organic and inorganic, mixed or otherwise combined.

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Claims (1)

10 /; 7 0 0 Claim *! Cl. Slektrophotographlsohe plate »marked by a photoconductive Sohioht, which an Ohlnaeridon-Plgment and a Contains binder material, the chloridone pigment being used the formula where R stands for OH ^, C ₂ Hc, OCH ₃₁ OC ₂ Hr, a halogen or mixtures thereof and R ^{1 means} an aromatic group, a hetero group, an allcyclic group "an aliphatic group or a mixture thereof" corresponds. 2. plate naoh claim 1, characterized in that the Binding material consists of an organic resin. 3. plate naoh claim 1 or 2, characterized in that R stands for OH ₇ , CUHe or Hisohungen thereof. 4. plate naoh claim. 1 or 2, indicated by the fact that R »stands for HH _- VTA. 5 » Plate naoh one of the preceding claims, characterized in that the photoconductive layer is a self-supporting Sohioht lsi ;. 6. Plate according to one of claims 1-4 »geken & r» characterized in that the photoconductive layer is located on a TrS.- gersubstrat. 009809/1260 BATH ORIGINAL 7 * Plate according to one of the preceding claims, as it is indicated that the ratio of Acridon-Pigmont ssvL binding material varies between approximately 1: 1 and approximately 1:40. 8. Plate naoh one of the preceding claims, daduroh gokeniiceiolinet, daos dao ratio doa Ohlnaoridon-Pigments to your binding material from about 1: 4 to about 1:10 sways, 9 «Plate according to one of the preceding claims, daduroh gekemuseiohnet, because the ratio of Chinaoridon pigment au Binding material is approximately 1: 4, 1Oo plate according to one of the preceding claims, daduroh characterized in that the photoconductive material has a thickness of from about 1 to about 100 µm. 11. Plate naoh. one of the claims 1-4, characterized thereby, that the thickness of the photoconductive layer is about 5 to about 30 µm. 12. Plate according to one of claims 1-4, daduroh marked that the photoconductive layer carries a coating. 13th plate after. Claim 5, characterized in that the Dioke of the photoconductive layer is more than about 10u. 14o plate according to claim 5 , because it is known that the thickness of the photoconductive material varies between approximately 15 and approximately 15 η. 15 Process βατ Formation of a latent electrostatic charge 009809/1260 duagsmnsters on a photoconductive soleplate ₉ in that the photoconductive layer of an electrophotographic material is electrostatically charged according to one of the claims 1-4 and the layer of the action has to "apply" a pattern of activating, electromagnetic radiation 16. The method according to claim 15, characterized in that the electrostatic latent image formed is developed using an electrically conductive method. 17 · The method according to claim 15 »characterized in that the plate is guided at least once through a cycle ₉ which consists of a loading, a catfish irradiation and a development. 0 0 9 8 0 9/1260 ^BAD