Electrophotographic copying process
United States Patent 1 Bartlett et a1.  
 1 1 ELECTROPHOTOGRAPHIC COPYING PROCESS [75] lnventors: Richard F. Bartlett, Burlington;  
 Laura K. Case, Winchester. both of Mass.  
 [73] Assignee: ltek Corporation, Lexington. Mass.  
 [22] Filed: Sept. 3, 1969 [21] Appl. No.: 855,026  
 [52] US. Cl. 96/l.4; 96/1 R; 96/1 E; 96/1.5; 96/1.6 [51] Int. Cl G03g 13/22 [58] Field of Search 96/1, 1.5. 1.6, l E, 1.4; 252/501; 117/175 [56] References Cited UNITED STATES PATENTS 3.037.861 6/1962 Hoegl ct a1. 96/1 3.042.517 7/1962 Wainer 96/48 3.042.519 7/1962 Wainer 96/48 3.081.165 3/1963 Ebert 96/1 3.232.755 2/1966 Hoegl ct a1... 96/1 3.287.122 11/1966 Hocgl 96/l.5 3.429.701 2/1969 Kochlcr 96/1 3,451.81 1 6/1969 Brynko 96/1 3.600.169 8/1971 Lawton 96/l.5 3.620.748 11/1971 Fichtcr 96/48 Primary E.\&#39;aminer-Roland E. Martin. Jr. Attorney. Agent, or FirmHomer 0. Blair; Robert L. Nathans; W. Gary Goodson [4 1 Apr. 22, 1975 [57] ABSTRACT This disclosure relates to an electrophotographic copying process suitable for use in a multiple copying system. The process is characterized by use of an electrophotographic medium comprising photosensitive organic compounds which are either (1) insulating prior to irradiation and substantially permanently conductive subsequent to irradiation or (2) conductive prior to irradiation and substantially permanently insulating subsequent to irradiation. The proccess comprises the steps of exposing the electrophotographic medium to a pattern of activating radiation to produce a latent image with a conductivity pattern that is irreversible and permanently altered and externally applying an electrical charge at any suitable time thereby forming an electrostatic pattern which can be developed by any of the known electrophotographic developing techniques. By consecutively repeating the steps of charging and developing, an indefinite number of prints can be made which are comparable in image quality and density to the original with a single step of exposure to the pattern of activating radiation. Consequently, a multiple copy system results which is substantially faster than conventional electrophotographic systems due to elimination of a requirement for repeated exposure of the electrophotographic medium to a source of activating radiation for each copy.  
 7 Claims, No Drawings ELECTROPHOTOGRAPHIC COPYING PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to improvements in electro- 5 photography and more particularly, to an electrophotographic multiple copying system and to an electrophotographic medium useful therefor.  
 coating is then exposed to a light image. The charge leaks off rapidly to the base plate in proportion to the intensity of light to which any given area is exposed. After such exposure, the coating is contacted with electrostatic marking particles in the dark. These particles adhere to the areas where the electrostatic charges remain forming a powder image corresponding to the electrostatic image. The powder image can then be transferred to a sheet of transfer material resulting in a positive or negative print, as the case may be, having excellent detail and quality. Alternatively, where the base plate is relatively inexpensive, as of paper, it may be desirable to fix the powder image directly to the plate itself.  
 coating materials are subject to dark decay i.e., the 4 conductivity pattern in the light exposed areas decreases rapidly with passage of time and the latent electrostatic image fades until it is ultimately lost. Consequently, for a multiple copying system where an excess of about three copies is desired, it is necessary to reexpose the electrophotographic medium to light in an image pattern prior to each development operation. This involves a decreased speed in the copying process and complex copying equipment.  
 SUMMARY OF THE INVENTION This invention is predicated upon the discovery that certain organic photosensitive compounds can be exposed to a pattern of activating radiation to produce a latent image therein whose conductivity pattern is irreversible and will not dark decay. Based upon this irreversible conductivity pattern, an electrophotographic medium may be formulated that may be exposed to a 6 source of activating radiation in an image pattern and thereafter may be used for making one or a multiplicity of copies using known development procedures without the requirement for re-exposure after development of each copy.  
  The electrophotographic copying process according to the invention comprises exposing to a pattern of activating radiation an electrophotographic medium comprising either (I) an insulating photosensitive organic 10 Compound which after irradiation becomes permanently conductive or (2) a conducting organic compound which after irradiation becomes permanetly insulating, thereby producing a latent image whose conductivity pattern is irreversible and permanently altered, and developing the latent image using standard developing procedures. For example, the electrophotographic medium may be developed by charging the exposed media whereby the charge leaks off to the base plate in the exposed areas in proportion to the intensity 0 of the activating radiation, contacting the charged plate sheet of transfer material resulting in a positive or negative print, as the case may be, having excellent detail and quality, and finally, fixing the powder image to the transfer material by application, for example, of heat.  
 The organic photosensitive compounds contemplated by the subject invention include the reaction products of spiropyran with organic halogen derivatives capable of forming hydrohalide acids upon illumination with light, various triarylmethanedyes, aryl substituted pyrylium-3-oxides, aryl substituted indenone oxides, systems comprising cyanine dye bases and organic halogen derivatives capable of formation of hydrohalide acids upon illumination with light, systems comprising diphenylethylenes in combinations with organic halogen compounds capable of formation of hy- 0 drohalide acids upon illumination with light, systems comprising N-vinyl carbazole in combination with organic halogen compounds capable of formation of hydrohalide acids upon illumination with light, and systems comprising leuco xanthene dyes in combination 5 with organic halogen compounds capable of formation of hydrohalide acids upon illumination with light. These organic photosensitive compounds will be described in greater detail below.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic media of the invention typically comprises a base material coated with an organic photosensitive compound selected from one of the following groups:  
  I. Systems comprising cyanine dye bases and organic halogen derivatives capable of formation of a hydrohalide acids upon illumination with light. Cyanine dye bases for photographic use are known and described in US. Pat. No. 3,102,8l0incorporated herein by reference. They are conventionally used as super sensitizers in silver halide photography. Cyanine bases useful for the subject invention are characterized by the fol- 5 lowing general formula:  
 wherein d and e each represents a positive integer&#39;of from 1 to 2; n represents a positive integer of from 1 to 4; R represents an organic radical selected from the group consisting of alkyl, aralkyl and aryl groups; R represents hydrogen or a cyano group; and Q and Z each represents the nonmetallic atoms necessary to complete a heterocyclic organic nucleus containing from 5 to 6 atoms in the ring.  
 Cyanine dye bases characterized by the above genl 10 4-[ l-ethyl-2-( lH)-quinolylidene)methyl]quinoline I CH-CH=CH-C//=C\ N 1 l C a 2 #5 N eral formula may be symmetrical or unsymmetrical, of 2-[ 1-cyano-5-( l-ethyl-2( 1H )-quinolylidene)-l,3- varying chain lengths; and they may have substituents pentadienyl1quinoline 5 \x l c CH CH: CH- H =CH-cHr H-c l N/ d l C H5 on the rings or on the chain. Examples of several types are depicted below:  
 I. SYMMETRICAL COMPOUNDS I C2 H 2-[ 3-( l-ethyl-2( ll-l)-quinolylidene)propenyl1quinoline 2-[ 2-methyl-3-( 3-ethyl-2( 3H )-benzothiazolylidene propenyl]benzothiazole 2-[ 7-( 3-ethyl-2( 3H )-benzothiazolylidone l ,3,5- 35 heptatrienyl]benzothiazole 2. UNSYMMETRICAL BASES 0 I HCH=c/-/--\ 2-[ 3-( 3-ethy]-2( 3H )-benzoxazolylidene )propenyl]- 5O quinoline 4-[2-methyl-3-(l-ethyl-2(1H)- quinolylidene)propemyl1quinoline 5 c=cH-c/;- cH- i C N C H;  
 4-[ l-cyano-5-( 3-methyl-2( 3H)-benzothiazolylidene H C CH 1 ,3pentadienyl1quinoline 3 l CH3 m; c CH N 3 &#34;&#34;3 N I l C H 3 4-[(3-ethyl-2( 3H )-benzothiazolylidene )methyl]quino- N 2 line H Additional examples of cyanine dye bases as well as 3 C methods for the preparation of these materials and starting materials useful therefor can be found in the above noted US. Patent as well as in l-lamer, The Cya- C nine Dyes and Related Compounds, Interscience Pub- No lishers, 1964, Chapter 11. N ,2  
  2. Systems comprising the spiropyrans and organic halogen derivatives capable of formation of a hydroha- 3 O lide acid upon illumination with light. The spiropyrans 3 are disclosed in US. Pat. No. 3,100,778, incorporated 0 H C CH herein by reference, and may be represented by the fol- 3 lowing structural formula: N 0  
  C I8 6 N n I R R 3 och c .3 Details for formation of these compounds as well as N 0 other representative samples may be found in the l H above noted US. Pat. No. 3,100,778. 6 3 3. Systems comprising N-vinyl carbazoles in combination with organic halogen derivatives capable of formation of hydro-halide acids upon illumination with light. The N-vinyl carbazoles are disclosed in US. Pat.  
  No. 3,037,861 as monomers for the formation of phowhere Y represents independently, substituent raditosensftlve polymers may be represented by the cals in at least two of the substituent positions, said subfollowmg general formula: stituent radicals being selected from the group consisting of NO OCl-l Cl, Br, I, and F, the substituents in said positions consisting of at least one but not more than two NO groups, and each-R is a a independently selected from the group of hydrogen and N lower alkyl. Representative examples of spiropyrans corresponding to the general formula are set forth below:  
  I CH C/&#34;l2 where a is a whole integer of from O to the number of replaceable hydrogen atoms on the aryl nucleus and each Y represents substituent radicals such as lower alkyl and lower alkoxy (i.e.,-up to 4 carbon atoms), amino nitro, halo, and the like. The preferred substituent is bromo. Representative compounds corresponding to the above general formula include:  
 3-bromo-9-vinylcarbazole 3,6-dibromo-9-vinylcarbazole 9-vinylcarbazole 3-chloro-6-bromo-9-vinylcarbazole 3-methyl-6-bromo-9-vinylcarbazole 3-methoxy-6-bromo-9-vinylcarbazole, and  
 3-nitro-6-bromo-9-vinylcarbazole 4. Systems containing phenyl substituted pyrylium-3- oxides. These compounds are disclosed in US. Pat. No. 3,141,770 incorporated herein by reference, as sensitizers for photoconductive layers. The aryl substituted pyrylium oxides correspond to the formula:  
 per-  
 py y  
 2,6-bis( 4-ethylphenyl)-4-( 4-methoxyphenyl) pyrylium perchlorate 2,6-bis(4-ethylphenyl)-4-(4-methoxyphenyl) pyrylium fluoborate 6-( 4-dimethylaminostyryl )-2,4-diphenylpyrylium perchlorate 2,6-bis( 4-dimethylaminostyryl)-4-phenylpyrylium perchlorate 6-( l,methyl-4-p-dimethylaminophenyl-l ,3-  
 butadienyl)-2,4-diphenylpyrylium fluoborate 4-(4-dimethylaminophenyl)-2,6-diphenyl pyrylium perchlorate 5. Triphenylmethane dyes corresponding to the formula:  
 where X is an anion, for example the anion of a weak acid such as hydrogen cyanide, hydrochloric acid, hydrobromic acid, hydriodic acid, hydrothiocyanide and the like, and a and Y are as defined above with Y preferably in the para position. Compounds of this nature are well known in the art and include dyes such as methyl violet, ethyl violet, crystal violet, malachite green, the wool violets, aniline blue, light green S8and many others. Representative examples of compounds corresponding to the above formula can be found in US. Pat. No. 3,275,442 incorporated herein by reference. 6. Systems comprising the diphenylethylenes in combination with organic halogen compounds capable of formation of hydrohalide acids upon illumination with light. The diphenylethylenes may be represented by the following formula:  
 where a and Y are as above defined with Y preferably in the para position.  
  7. Phenyl substitued indenone oxides corresponding to the structural formula:  
 where a and Y are as above defined and Y is preferably in the para position.  
  8. Systems comprising leuco xanthenes in combination with organic halogen compounds capable of formation of hydrohalide acids upon illumination with light, said leuco xanthenes corresponding to the formula:  
 where a and Y are as above defined.  
  The organic halogen compound which decomposes to a hydrohalide acid in the presence of light suitable for the present invention preferably is a highly halogenated aliphatic or aromatic hydrocarbon, most preferably one having bromine substitution. Preferred materials of this nature include carbon tetrabromide bromoform, brominated alkyls such as pentaand hexabromoethane, a,a,a-tribromoacetophenone, and halogenated sulfoxides and sulfones selected from the group:  
 where R R and R are hydrogen, chloro-, or bromo-, and X is hydrogen, chloro-, or bromo, provided that at least one X is chloro-, or brom0-, and preferably, each X is chloroor bromo-. Representative examples of the above formulae include:  
 0 I! 5-CC/ n 0 O n 5-637 o 0 so u C237 O 3 N 0 C/ CH;  
 and  
  Each of the above compounds yields a halogen free radical when the bond joining a halogen atom to a polyhalogenated carbon atom is ruptured upon exposure to light. The presently preferred compounds for the invention are carbon tetrabromide and tribromoacetophenone which are readily available commercially in the requisite purity. In the manufacture of the electrophotographic medium according to the present invention, a photoconductive layer containing at least one of the photosensitive organic compounds selected from one of the groups described above is applied to a suitable support. The photoconductive layer can contain besides one or more of the organic photosensitive compounds, other compounds which confer the properties desired to the photoconductive layer and/or to the composition from which the layer is formed. Thus, in themanufacture of the photoconductive layer according to the present invention, one or more polymers can be added as binding agents to the composition in the formation of the photoconductive layer; preferably, a polymer with high specific resistivity (i.e., with a specific resistivity higher than ohmcm). Polymers particularly suitable as binding agent for the photoconductive layers are natural resins, such as dammar resin, gum arabic and manilla gum; microcrystalline waxes; modified natural substances such as cel lulose diacetate and cellulose triacetate, cellulose acetobutyrate, ethyl cellulose, ethyl cellulose stearate or other cellulose derivatives; polyesters or other modified colophonium resins and esters gums; polymerisates such as polyethylene, polystyrene and copolymers of styrene, polyvinyl acetate and copolymers of vinyl acetate, polyvinylacetals of formaldehyde, acetaldehyde, butyraldehyde, polyacrylic acid esters and polymethacrylic acid esters and coumarine-indene resins; and polycondensates such as glycerol-phthalate resins or other glyceryl polyesters, alkyd resins, polyethylene glycol esters, diethylene glycol polyesters, formaldehyde resins and silicon resins.  
  In the choice of a suitable binding material, there is no restriction to polymers. Low molecular weight compounds can be used or mixtures of low and high molecular weight compounds or semipolymerized materials which are polymerized or condensed in situ or undergo cross-linking according to methods known in the polymer arts.  
  If desired, suitable plasticizers such as dibutyl phthalate, dimethylphthalate, dimethylglycolphthalate, tricresylphosphate, triphenylphosphate, monocresyldiphenylphosphate, etc. in quantities amounting to 10 to 30 percent by weight of the binding agent can be added to the compositions in the formation of the photoconductive layers.  
  The thickness of the layer is not critical, but is determined by the requirements for each individual formulation. Good results are obtained with electrophotographic layers which vary in thickness between 1 and 20 microns and preferably between 3 and 10 microns. Layers which are too thin possess an insufficient insulating power whereas layers which are too thick require long exposure times.  
  Other materials may be added to the photoconductive layer as is known in the art. For example, pigments, compounds which influence the gloss and/or the resistivity, compounds which prevent ageing or oxidation or which influence thermostability of the layers may be added. In addition, compounds which cause a change in the spectral selectivity of the photosensitive compound may be included so as to provide for activation of the layer from activating radiation within a predetermined portion of the spectrum.  
  In the manufacture of the electrophotographic media of the present invention, it is desirable that the photosensitive material or photoconductive layer be coated onto a base or support layer. This base or support layer should be an electrically conductive material or an insulating material provided with an electrically conductive layer. By the term electrically conductive,&#34; it is meant that the base layer have a specific resistivity which is less than that of the photoconductive layer, i.e., in general, less than 10 ohm centimeters and preferably less than 10 ohms centimeters. The backing layer may be of any suitable material such as wood or rag content paper, pulp paper, plastics such as, for example, polyethylene terephthalate (Mylar) and cellulose acetate; cloth, metallic foil and glass provided that the backing layer is of sufficient strength, conductivity and durability to satisfactorily serve as a reproduction carrier. The preferred form of the backing layer is a thin sheet which is flexible and durable.  
  The electrophotographic medium of the invention is preferably prepared by dissolving the organic photosensitive compound and other applicable materials such as the binder in a suitable organic solvent such as benzene, acetone, glycol-monomethylether and the like, dependent upon the solubility characteristics of the components. The solution or dispersion thus obtained is uniformly spread over the surface of a suitable support, for example, by centrifuging, spraying, brushing or whirl coating and the layer is permitted to dry.  
  An electrophotographic medium in accordance with this invention is used for single or multiple copying in a manner analogous to a conventional xerographic processes with modification being in the processing sequence. The electrophotographic medium is imagewise exposed to a pattern of activating radiation whereby the exposed portions of the layer are made permanently conductive with unexposed portions remaining permanently insulating or the exposed portions are made permanently insulating while the unexposed portions remain conductive, dependent upon the particular organic photosensitive material used. The electrophotographic medium is then charged positively or negatively, by means of, for example, a corona discharge with a charging apparatus maintained at about 6,000 to 7,000 volts. The charge immediately leaks from the conductive portions of the electrophotographic medium and is retained on the non-conductive portions, thereby forming a latent electrostatic image conductive, but becomes insulating upon exposure, a  
 negative latent image will form upon charging due to leakage in the exposed portions. If the medium is ini.  
 tially insulating, the sequence can be modified to some extent by charging before exposure. In this manner, upon exposure, the charge leaks off in the exposed portions. The latent electrostatic image is then developed using procedures known in the art such as by dusting with a developer consisting of a mixture of a carrier and a toner. The carrier used may be, for example, tiny glass balls, iron powder or other inorganic substances or organic substances. The toner may consist of a resin carbon black mixture or a pigmented resin of a grain size of about 1 to 100 microns, preferably 5 to 30 microns.  
  The finely distributed toner particles adhere to the parts of the electrophotographic medium in the nonconductive areas, but not to the portions of the electrophotographic medium in the conductive areas. In this way, a visible image is formed. With the same toner, but with change in the polarity of the corona discharge, there can also be obtained reversal images of the mats ter. The visible image can be easily wiped off. It therefore has to be fixed ifa single copy only is to be formed. Fixing can be accomplished, for example, by briefly heating using an infrared radiator. The temperature required is less if the heat treatment is carried out in the presence of vapors of solvents such as chloroethylene, carbon tetrachloride or ethyl alcohol. The fixing of the powder image can also be accomplished by steam treatment. Images characterized by good contrast are produced.  
  Where multiple copies are required, it is necessary to transfer the visible toner image to a copying medium using procedures known in the art. For multiple copying, the step of exposure in the above described process can be eliminated and the cycle for producing copies would involve charging the electrophotographic medium, cascading toner particles over the charged medium, transfering the toner image to a transfer sheet and fixing the image on the transfer sheet. This process can be repeated almost indefinitely until the electrophotographic medium physically deteriorates.  
  The invention will be more fully illustrated by the following examples.  
 EXAMPLE 1 A baryta coated paper is coated with the following:  
 N-vinylcarbazole 0.1 grams carbon tetrahromide 0.5 grams National Starch Resyn 0.125 grams No. 284300 tctrahydrofuran IO ml The coated paper is air dried and exposed to an image pattern of activating radiation using a low pressure Mercury Hanovis lamp held about 8 inches from the surface of the coated paper for a period of about l0 minutes. The paper is then charged using a corona charger applying about 7,000 volts negative charge to the surface of the coated paper. The paper is then developed by cascading a resin-carbon black toner mixture over the coated paper in known manner. The carbon adheres to the exposed areas and may be fixed by application of heat to give a permanent image.  
 EXAMPLE 2 The procedure of Example 1 may be repeated except that the electrostatic charge applied to the exposed copy medium is reversed and the power image is transferred to a copy medium and fixed thereon. This process can be repeated for as many as 500 cycles yielding 500 copies, the entire process involving only a single exposure to the source of activating radiation.  
 EXAMPLE 3 A baryta coated paper is coated with a composition having the following components:  
 N-vinylcarbazolc Hcxabromoethanc National Starch Resyn No. 28-! 300 Tetrahydrofuran EXAMPLE 4 The procedure of Example 1 is repeated substituting 2,4,6-triphenylpyrylium-3-oxide for the N- vinylcarbazole and eliminating the carbon tetrabromide.  
 EXAMPLE 5 The procedure of Example 1 is repeated substituting a 2-[3-( l-ethyl-2( lH)-quinolylidene)propenyl] quinoline for the N-vinylcarbazole, all other steps remaining the same.  
 EXAMPLE 6 The procedure of Example 2 is repeated with the additional steps of storing the exposed copy medium in a darkened chamber for a period of 4 weeks. Thereafter, the copy medium is recharged and copies are prepared by forming and transferring a powder image to a receiving sheet. This process is characterized by the absence of a second exposure step.  
 EXAMPLE 7 The procedure of Example 1 is repeated substituting tribromoacetophenone for carbon tetrabromide.  
  We claim: 1. A process for forming one or more copies of an original comprising the steps of:  
 a. forming a copy medium by coating a support with an organic photosensitive material which undergoes a substantially irreversible chemical change upon being struck with actinic radiation to substantially permanently alter its conductivity, said photosensitive material comprising an N-vinyl carbazole and an organic halogen derivative capable of forming a hydrohalide acid upon being struck with actinic radiation;  
 b. exposing said copy medium to an image pattern of actinic radiation representative of said original whereby said irreversible chemical change occurs;  
 c. applying an electrical field across said exposed copy medium thereby providing an electrostatic image pattern; and,  
 d. developing said electrostatic image pattern with image-forming materials to form a visible image of said original.  
  2. A process of claim 1 wherein the electrostatic image pattern is developed by contacting the copy medium with a finely divided particulate toner material and the toner is fixed to said electrophotographic medium.  
  3. A process of claim 2 where the toner is fixed by heat.  
  4. A process of claim 1 wherein the electrostatic image pattern is developed by contacting the copy medium with a finely divided particulate toner material to provide a visible toner image, transferring the toner image to an image-receiving sheet, and fixing the toner image pattern on the receiving sheet.  
  5. A process for producing multiple copies of an original comprising:  
 a. forming a copy medium by coating a support with an organic photosensitive material which undergoes a substantially irreversible chemical change upon being struck with actinic radiation to substantially permanently alter its conductivity, said photosensitive material comprising an N-vinyl carbazole and an organic halogen derivative capable of forming a hydrohalide acid upon being struck with actinic radiation;  
 b. exposing said copy medium to an image pattern of actinic radiation representative of said original whereby said irreversible change occurs;  
 c. applying an electric field across said exposed copy medium thereby providing an electrostatic image pattern;  
 d. developing said electrostatic image pattern with image-forming materials to form a visible image of said original; and,  
 e. repeating steps c. and d.  
  6. A process of claim 5 wherein step c. is accomplished by charging one surface of the copy medium by corona discharge.  
  7. A process of claim 6 wherein step d. is accomplished by contacting the copy medium with a finely divided particulate toner material to provide a visible toner image, transferring the visible toner image to a copy receiving sheet, and fixing the toner image on the copy receiving sheet.