DE1955000A1 - Electrophotographic plate - Google Patents

Description

C ^ I.fr ;. Γ. "*:" - "T-PJi ₁

S ₁ H- ¹ OiCIi =. ,, .V '\ nr.!'. Rincka
Dipl. L4 FAI V.! -, ^ ... um

t CJr.cL · .; 27, i <iii, iLlr. 22

Sch / Gl ■ g / 769 3 / 23S5

RAIK XEIlOX LIMIDEED, LOlBQiT / EIiCILAIlO

Slektrophotog-raphlsclie plate

The ±; rfindung "relates generally to the field d ^c ir lilektropliotographie oesielit and in particular to sine binder plate which is suitable for use in the BlaJctrophotographie ■.

It is known that images can be formed and developed on the surface of certain photoconductive insulating materials in an electrostatic manner. The .Grundxerographieverfaiirc-n is the subject of US Pat. No. 2 297 c. This process consists in uniformly loading a photoconductive insulating layer, whereupon this layer is irradiated with a sight-and-eye image. Through this

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Irradiation will discharge the charge at the points on the layer that are hit by the power. The electrostatic latent image formed on the layer corresponds to the configuration of the light-and-shadow image. Optionally, an electrostatic latent image can be formed on the plate such that the plate is loaded in an image configuration. This image is made visible in a way that a finely divided SNT] Wicklermaterial is deposited on the layer provided with the 3ild consisting of a colorant, v / ith which referred to as toner, and a Tonerträgsr exists. The powdery developer material is normally attracted to those parts of the layer which have a charge

have retained. In this way a powder image is formed, corresponding to the electrostatic latent image. If the document sheet is relatively cheap, i.e. is it ' 'For example around paper, then the powder image can be applied directly the plate are fixed, for example by melting under the action of heat or by a solvent treatment. Optionally, the powder image can be transferred to a sheet of absorbent material such as paper and grounded on this arch. The above described, This general method is the subject of U.S. Patents 2,357,809, 2,891,011 and 3,079,342.

■ So that the photoconductive insulation layer in v / irksaraer7V / eise ■ j can work, it must be able to operate an electrical

keep static charge in the dark and the charge in one! Irradiation with light to discharge a conductive substrate au; - j That various photoconductive insulation materials "" ziöy * Manufacture of electrophotographic plates are used 1

can, i3t known. Suitable photoleitonde Isolationsriiaf & ^ i "fialien, such as anthracene, sulfur, selenium or ^ '' mixtures of these materials," are described in ^US-Patent:; \ . 2 297 691. These materials have im

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generally in the blue or in the near UV range a sensitivity, however, all materials with the exception of selenium can only be used in a limited way in that they are only slightly sensitive to light. For this reason, selenium is the most common material used in electrophotographic Plates is used. Vitreous selenium that is most commonly used for a variety of reasons, but is afflicted with the laughing stock that its spectral? Responsiveness somewhat limited to the UV, blue and green regions of the spectrum, with the addition of the production of vitreous selenium plates requires expensive and complicated methods such as evaporation ic · vacuum. Perner, vitreous selenium layers are only metastable insofar as they are only slightly above the temperatures Temperature, as in usual electrophographic photographic Copy machines easily turn out to be unusable recrystallize crystalline forms. Furthermore, selenium plates require the use of a separate conductive substrate layer, A further barrier layer is preferably applied to this before the application of the uelen photoconductor. the end Λ / economic considerations have therefore already made many attempts undertook to see photoconductive insulating materials other than selenium for use in electrophotography Develop plates.

It has been proposed to use various Zv / egg component materials in photoconductive insulation layers that are used in electrcphotographie Had to be entered to use. These Materials consist of a photoconductive insulation material in 3iii23lteilchenfora, which is in an insulating Binder is dispersed. The particles consist of one photoconductive material made of inorganic :: crystalline yerbiii-

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manure, containing a metallic ion, intestinal v / ground a satisfactory photographic speed and f is a good spectral Ansprechveriiiogen '' · * ² - * sine use in xerographic plates ersielt. However, even when sensitized with a dye, these plates are generally much less sensitive than selenium. These plates are generally considered unusable because it is necessary to use such a high percentage of photoconductive pigment in order to achieve sufficient sensitivity that it is difficult to obtain smooth surfaces which are effective for effective i 'Onerransferimj and a subsequent cleaning before re-use are suitable. A further disadvantage that occurs when using plates consisting of an inorganic pigment and a binding agent is that these plates can only cover negatively and not through a positive corona discharge. This property is unsuitable for practice at this point, since a negative corona discharge generates much more ozone than a positive corona discharge and is generally more difficult to control.

It was also found that o :: gar-i: iche photolei.tendo Dyes and a variety of poivcycli ^ cher compounds together with suitable resin materials to form photoconductive ones Insulation layers suitable for use in binder-like panels can be used. However, these disks generally do not have the degree of sensitivity which for a use in usual electrophotographic copier- ^ ei:: iotv · jr.dig are. In addition, the plates lack abrasion resistance

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and operational stability. especially at elevated temperatures.

In another type of plate, self-photoconductive polymers are used often in combination with sensitizing dyes or Lewis acids with the formation of photoconductive insulation layers used. These polymeric organic photoconductor plates generally have the disadvantage that they are expensive to manufacture, plus they are are brittle and have poor adhesion to the carrier substrates own. A variety of these photoconductive iso ~ iatioiisschichten is formed in the warmth, so that such Layers for use in automatic electrophotographic apparatus are unsuitable. Powerful lamps and heat melters are often used in such devices used. These heat sources heat the electrophotographic plate.

There is therefore a continuing need for improved photoconductive insulation materials, from which stable, sensitive and reusable electrophotographic Plates can be made.

The aim of the Srfindimg is the creation of an electrophotographic Plate, which no longer has the disadvantages described above, by the invention electrophotographic plates provided, their Sensitivities spread over considerable parts of the "visible Span the spectrum. The plates according to the invention are Can also be reused, regardless of their overall sensitivity as well as their thermal stability compared to those previously available reusable plates are significantly improved. The panels can be used both in systems and in decien

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only ■ one-time use is intended, as well as in systems, aimed at repeated use. The plates according to the invention are ir .; essential abricbos-constantly and have a relatively high perforation temperature.

The present invention makes an electropho tograr! '. It ehe Plate made available containing a new photoieitcnde '· Has layer. This layer consists of one. Ohinaeridone pigment in an Ilarc binder, the ohinacridone being the The formula given below corresponds to:

O - ^E \ x ^>^> ^ / ^IT - \ ^ \ _ CH ~! IHC - (Q Λ

"'OK

ClTHGH ₂ -.

where R is CH ₇ , 'C-IL, OCH. ,, CC ₀ H ₁ - or a halogen and R' is COOH, COOGa / 2, SO ₃ Ii or SQ, Ca / 2; This class of chiriacridone pigments as well as the methods of their production are described in the German patent specification. ... ..- ^! ■ (Patent application, which was the same as the varlieger.de application under the processing drawing Gase 2 · .2ί) ϋ (Zlj / ^f 2334) 'submitted vmrde).

The above-described photoleitc-r.de Ohinacridöii / iläf-s-- '' layer can be wc-ried on any suitable support or as a self-supporting pin. Dia had '.' lcanii if necessary with suitable Ilateriali ^ ii ü ": 3r3chlc: itet. J) Ie pliotolöitende Ghinacridoii / llarz-ociiichi: Icänii sur

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Manufacture of multi-layer SanCvich configurations adjacent to an electrical layer 'can be used. These Üandwich-IIoiifi-urationen resemble the configurations, as described by Golovin et al in "A l'.e \ i Electrophotographic PiOcess, Effected by Means of Combined Electric.-layers", Doklady.Akaä.ITaufc SSSR Volume 129, Hr. 5, pages 1003-1011, Kovember-Deseniber 1959. 3s it was found that the percentage of the quinacridones described above, which is necessary to achieve a sufficient level of discovery in a plate, is very low. Hence the mechanical properties of the photoconductive layer? ¹ , iu essentially according to the properties of the 3inder.iiL.telc ·. A variety of cross-linked binders can be used in accordance with the invention, these binders varying from different thematic resins to hard crosslinked synthetic resins. In another way, the physical properties of the finished photoconductive layer can be varied within wide limits, namely by selecting the appropriate tt'arse. In this respect these conductive layers are vis- ible. The previously known binder suspensions of inorganic pigments, which require a relatively high concentration of inorganic pigments, are unsuccessful, since in the known layers the inorganic pigment used in v / it determines the synthetic properties of the ferticon photoconductive layer. Dr. If the percentage of quinacridone pigment is relatively low, the photoconductive plate can have a very flat and very smooth surface. In this way, many disadvantages of the previously known Pi ^ er-t / aiiide ^ i ^ tsl ^ latter were verrsi'e'ö.en .. As a result of the large figures they contain, these plates have a very rough and aoric-prone surface.

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Even if each of the quinacridones falling under the general 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 2 is CH ₃ , C 1 H ₅ or mixtures thereof, and 'R ¹ S0..Ca / 2 means that these materials are highly sensitive to light and provide the most satisfactory images.

Some of the quinacridones described above can be used alone or in combination with other compounds, in any suitable mixture, including üinore, Trimers, oligomers, polymers, copolyners, or mixtures thereof come into imprint. '

Any suitable organic binder resin can be used in combination with the new quinacridones to produce the photoconductive layer according to the invention. The Harr used according to the invention should have a greater resistance s, ls approximately 10 and preferably a greater 7 / ider stand than 10 Chm pj? O cm under the conditions of electrophotographic use. 7or. Typical resins are the following: Thermoplastics, such as olefin polymers, see 3. Polyethylene and polypropylene, polymers derived from dienes, v / ie example. ^r eis3 polybutadiene, polyisobutylene and polychloroprene, vinyl and vir.iidenpolynere, v / ie for example polystyrene, styrene / acrylonitrile copolymers, acrylonitrile / 3utadiene / 3tyrene corpolynere, polyethyl methacrylate, polyacrylates, polyacrylic compounds, polyacrylonitrile, polyvinyl chloride Polyvinyl carbazole, polyvinyl ethers and polyvinyl ketones, ZLucrkohlenstoff-Polymers, such as polytetrafluoroethylene and polyvinylidene fluoride, ThemoT; laste nit hetero chains, v; ie e.g. polyamides, polyesters,

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Polyurethanes, polypeptides, casein, polyglycols, polysulfides and polycarbonates, as well as cellulosic polymers such as regenerated cellulose, cellulose acetate and cellulose nitrate, IPerner come thermosetting resins in JJ-rage, such as phenolic resins, amino resins, e.g. urea / formaldehyde resins and melamine / formaldehyde resins, unsaturated Polyester resins, epoxy resins, silicone polymers, alkyd resins and uranium resins. Different copolymers as well as mixtures of the resins given above may optionally be used. In addition to those given above Resins can also be any other suitable material may be used.

The quinacridones according to the invention can be dissolved in the ' or melted binder resin can be mixed in by known methods, for example by vigorous stirring with one another Sh-effect, preferably at the same time a grinding he follows. Typical methods include the following: Sin Vemalilen in the ball mill, a grinding in a grinding roller, a sand grinding, an ultrasonic stirring, a high-speed mixing or any combination of these! methods. Any suitable pigment: resin ratio can be maintained. The appropriate range of the ratio of ChinacridorTto dry resin on a weight basis - 'extends from about 1: 1 to about 1:40. For best results, the ratio is about 1: 4 to about 1:10 is. Optimal results are obtained when the ratio is around 1: 4, even the largest Photosensitivity is achieved with pigment: resin ratios of 1: 1 to 1: 4, but it nevertheless increases with the higher pigment concentrations the dark conductivity on.

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The optimal balance between sensitivity and Dark fading is at a ratio of approximately 1: 4. It should be noted that the range of the photoconductor used in your preferred area is significantly below of the photoconductor lines, which are in the previously known inorganic photoconductive binder plates vei7v: ondet will. Only then will a satisfactory one be found in these well-known plates achieved electrophotographic sensitivity, when the pigment: resin ratio is at least 2: 1.

Invention geniy.sse compliance with lower pigment: resin ratios represents a clear advantage over the state of the art, since the relative value is smaller expensive pigment is required. Forner makes this possible the production of very smooth coatings due to the high binder content. The small I-length of the added I-Iate- ■ rials have only a slight influence on the physical Properties of the binder resin. In this way one can use resins with the desired softening range, nit the desired smoothness, hardness, toughness, solvent resistance or solubility-or, select the like, it is ensured that the pigment does not affect these properties to any noticeable extent.

Should the quinacridone / Hars pilm be piled on a substrate v / ground so one can look at different producer materials serve. Are materials suitable for this purpose Aluminum, steel, brass, metallized or with sense oxide coated glass, semiconducting plastics and resins, Paper and other common materials with a conductive

8-1 speed at the time of the use of ~ y> 10 Ohiri-cn or a surface conductivity of "Ü> 10 rrJio / square inch. The

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Pigment / resin / solvent slurry (or the pigrient / Resin melt) can na.ch known conductive substrates Application or coating methods applied v / earth, the following of such methods being mentioned: A Spraying, floating, squeegeeing, ultrasonic coating, a. stripping with an I-tayer rod, an immersion coating, a coating with üin]: honor coating rollers or similar. A spray in an electric Field may be preferred for the smoothest surface, while dip coating in the laboratory for convenience is preferred. The setting, drying and / or hardening of these panels e ?? in the '»' ice as they are to the frenzy of]? the end . the respective binders is suggested. For example Ghinacridone / Dpoxy-Ilatten can be hardened in the V / eise ' that a crosslinking agent is added, before treatment in an oven is carried out in the same way, how to use them for the production of iUinbrenniacken of the same resins and similar pigments is adhered to. A valuable advantage of the quinacridones according to the invention is that they are resistant to chemical decomposition at the temperatures that are normally used adhered to in the production of many Liin'oreriulacken. will·. Therefore they can be in "be * har-je and complementary £" .ioto-conducting coatings are constricted, with "this Cbornuce Have surfaces similar to those vcr. Automobile break-ins: - lacquers or kitchen lacquers are similar.

The thickness of the quinacridone / Bindenit-cei-Pilms 100 may μ schwan.ron from about 1 to about, and z _"t; ar depending on the required properties of self-supporting films künr.e :: example not in thicknesses of less than approximately 10x. u are made. Derarti ^ s Pilrr.c lasser, located at the ei :: fr.o: .-

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Handle most of them while maintaining a thickness range of 15 - 75 U. On the other hand -worden coatings preferably having a thickness between 5 "'iu: d prepared μ 30 Using bestirnter compounds and certain objectives ec is zwecknäscig to apply a protective coating, this coating should normally not exceed the thickness of a photoconductive coating and preferably no more.. than 1/4 the thickness of the coating Any suitable coating may be used, for example an ITitrocelulose lacquer coating.

The following examples illustrate various preferred embodiments of the present invention. ^{Unless otherwise stated, the 1} I ¹ OiI and frozen data relate to weight.

example 1

An electrophotographic plate is made in the manner that initially about 6 parts of Pliolite S53, a styrene / butadione copolymer resin, that from the Goodyear Tire and Rubber Company is marketed, about 43 parts of xylene and about I part of a ghinacridone pint of the formula;

be annihilated. This mixture is poured into a glass vessel, the steel ball ^ : Λτ has a diameter: .er; se: ·: before; 3,?. no. (1/3 inoli)

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contains. Grinding takes place on a Red Devil Quickie Hill (Gardner-Laboratorics) for a period of about 1/2 hour to produce a homogeneous dispersion. After grinding, the dispersion is applied to 0.125 rom (5 mils) aluminum foil using a pull-off stick (ITr. '36) "". · When the sug-having a thickness of about 20 u "has, is at about 10O ⁰ C for a period" of dried for about 2 hours in air. The plate: is ^"v by means of a corona discharge to a positive voltage of Chliessend" un- "ans ferry brought 650 volts, and according to a method as described in the US Patent 2 will be described 777,957, for example, the loaded disk.. is finally presented for 15 seconds in Zontakt with a Pilmpositiv means of a ¥ olframlampe irradiated with a I'arbtemperatur of 34CC ⁰ TI. the light amount of the irradiation plane approximately 57 i \ ioskerzen. the electrostatic latent image formed on the plate is then in the ' ., 'iron - developed that pigmented electroscopic marking particles are cascaded across the plate according to the process as described, for example, in US Pat. No. 2,613,551. The powder image developed on the plate is electrostatically applied to a . Transfer the recording sheet and. Melt it onto this sheet by w'ärrae. The image on the recording sheet is of very good quality and corresponds t the original.

Example 2 · '·. - ... ..:, - ■ - ■; "

An electrophotographic plate is made by first making about 2 parts of Silicone SPu-82, a methylphenyl silicone resin marketed by the G-eneral Electric Company, about 4-0 parts of xylene μηά about 1 Rope of a ghinacridon Γlam of the Fornel:

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O ₂ H ₅

be mixed. This plate is brought to a positive AirCangsspannung ungeführ of 290 volts, "irradiated and err,... ^R -v iekelt 3ild The obtained" has a satisfactory atoll quality. ... ". -". "-..-

Examples ρ - 4 '-,

Two v electrophotographic plates / ground in the V; else mfd assumes that about 1 part Vinylite VjTITS, a Copolyneres of vinyl chloride und'Vinylacetat which -is brought from the Union Gt ^ Mdc Corporation in the trade, ungefUhr 10-I ¹ DIIS , Diet hy-lketone. And about 1 rope of one
the För-rael; * - '"■ · ^;

Br

Il

CITHCK

. COOH -

are mixed ". The plate is coated, cured, charged, irradiated and developed according to the method described in Example "4 ^ O 7'it -j.

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is, while according to Example 2, the plate is negatively charged to YoIt. The image obtained has a good quality.

Examples 5-6

Two electrophotoeraphic plates are placed in place made that initially about 1 part Vinylite ΥΪΙΤ3, about 10! 'rush lOiäthy! ketone and about 1 part "of one Forriel quinacridone pignorits:

d OOOOa / 2

COOOa / 2 ^υ

mixed v / earth. The plate is coated, cured, loaded, irradiated and developed according to the method described in Example 1. However, until the implementation of Example 5, the plate is set to a positive voltage - o: 530 volts brought, while the mat is negatively charged to 630 YoIt in implementing the HLeI-.spiels sixth Besides, good BilCer be obtained.

Examples? - S.

3 an electric watch hat is produced in the 'li'eiEe, ilars first about 1 part Vinylite 711: 3, about IC Peile- dietkylketc :: and about 1 part ei ::. es Quinacridone ri- ~ nientE of Jörne !:

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S0 ₇ Ca / 2

be mixed. The plate is made according to that described in Example 1 V / eise. coated, hardened, loaded and developed. However, in performing Example 7, the plate is brought to a positive voltage of 410 volts while according to example 8 the plate is charged negatively to 605 volts. Doing so will take good pictures using this Plates scored.

Examples - 10

Two elektrophotographxsche wex'den plates prepared in such a way that initially about 100 parts of a 10 follow solution of polyvinyl carbazole in !, benzo about 5 parts of cyclohexanone, and about 1 part of the quinacridone according to Example Pigraents are mixed. 1 These plates are coated, cured, loaded, irradiated and developed in the manner described in Example 1. However, at. When performing Example 9, the plate was brought to a positive voltage of approximately 130 volts; and when performing the example, it was brought to a negative voltage of approximately 215 volts. Images of good quality are thereby obtained.

Examples 11-12

Electrophotographic plates are produced in the 'v / eise, that initially about 100 parts of a 10% polyvinyl carbazole solution in benzene, about 5 parts "cyclohexanone and

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-.17 -

about 1 rope of the ohinacridone pignient according to example 2 be mixed. These plates are made according to the 'in Example 1 described way coated, hardened, loaded, irradiated and developed. However, in performing Example 11, the plate is set to a positive voltage of approximately ISO volts and during the implementation of example 12. · on one brought negative voltage of about 180 volts. In doing so, images of good quality are obtained,

2Ieon the materials described in the previous examples other materials can also be used, as described above were enumerated, "can be used, whereby other proportions can also be observed. In addition," other materials the ghinacridone pigment or the pigment / resin masses can be added to improve or modify their properties. The inventive pigments and / or pigment / resin masses can also by means of a Sensitization of paraffins, if necessary should. You can also use other photoconductors, namely both organic and inorganic, can be combined.

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Claims (16)

1P _ Claims Cu electrophotographic plate, characterized in that it represents; α it has a photoconductive layer which contains a quinacridone pigment and a binding material, the quinacridone-r Pigment of the formula: ■ ' vrorin R for GH ,, G ₀ H ₁ -, OGIL., OG ₀ Hr-. a halogen or a twisted pair thereof and P1 ¹ COOH, GOOC
Mixtures thereof means corresponds. statements thereof and Pl ¹ GOOH, G00Ca / 2, SO ₇ II, 30 ~ Ca- / 2.'ocLfc 2. Plate according to claim 1, characterized in that dö-ss
Bindenateria.1 consists of an organic Ilara. , 3. plate na.ch claim 1 or 2, characterized in that: onnzeichV-; that R stands for GH-, öpHr- or mixtures thereof. 4. Plate according to claims 1, 2 or 3, thereby geJj ^ nnsetichneiD:} · -. that R 'stands for SO _r Ga / 2. -: --.--; 5. Plate according to one of claims 1-4, characterized in that the photoconductive layer consists of a serbstr-i ·,. ·: Supporting layer. . . '". ■ -:. ^: 0098 19 / TA89 ^ßAD 6. Plate according to one of claims 1-4, characterized in that that the photoconductive layer is on a support substrate is located. 7. Plate according to one of claims 1 - 6, characterized in that that the ratio of the quinacridone pigment to the binder material is between about 1: 1 and about 1:40 fluctuates. . 8. Plate according to one of claims 1 - 6, characterized in that that the ratio of quinacridone pigment to binder material varied from about 1: 4 to about 1:10. 9. Plate according to any one of claims 1-6, characterized in that the "ratio of quinacridone pigment to Binding material is approximately 1: 4. 10. Plate according to one of claims 1 - 9 _t, characterized in that the pliotoconductive layer has a thickness of approximately 1 Ms approximately 100 γι * 11. Plate according to one of claims 1-9, characterized in that the photoconductive layer has a thickness of about 3 to about 30 microns. 1.2. Plate according to one of claims 1-11, characterized in that that the photoconductive layer has a coating layer on it. 13. Plate according to one of claims 1 - 12, characterized in that that the thickness of the photoconductive layer is greater than about 10 ji. 009819 / U89 ORIGINAL 14. Plate .nach one of claims 1 to 12, characterized in that the thickness of the photoconductive layer is approximately 15 to approximately 75 y. amounts to. 15. Processor, with the formation of a latent electrostatic charge, characterized in that electros l; ati .-; ch the photoleiuor.de layer cine :: · electrophotographic plate according to one of claims 1 - 14 "is loaded, v. ^r 03: the layer is not irradiated with a gate of alitivic electromagnetic radiation. 16. The method according to claim 15, characterized in that £ ε.εε the plaques using electrically attractable marking particles developed v / ird. .17. Method according to Ansi ^ ruch 15, characterized in that: the plate is zv: eii.: al a cycle with crr: o:; en, which aua 3α-load, i3os "jrahlori in 3iidkonfi3uration und 3ntv / ickeln bssto :. '. Ü09819 / U89- BATH ORIGINAL