US3755310A - Substituted bis(p-dialkylaminophenyl)methane photoconductors - Google Patents

Abstract

Novel organic photoconductors for electrophotographic elements as described. These novel photoconductors are bis-(pdialkylaminophenyl)methanes having a third substituent comprising an unsaturated alkyl group having two or four carbon atoms wherein an omega -carbon atom of the third substituent is fully substituted by aryl group(s), heterocyclic group(s) or combinations thereof.

Description

i1 flirted States Patent 1 r 3,755,310 Rossi 1 Aug. 28, 1973 1 1 SUBSTITUTED B1S(IP-DHALKYLAMHNOPHENYL)METHANE [5 6] References Cited PHOTQCONDUCTORS UNITED STATES PATENTS [75] Inventor: Louis J. Rossi, Rochester, N.Y. 3,140,948 7/1964 Stewart 96/48 3,627,525 12/1971 Looker e! a]. 96/15 [73] Asslgnee: Emma company 3,677,752 7/1972 Looker et a1. 96/1.5

Rochester, N.Y. Fl M M 1971 OTHER PUBLICATIONS 1e 8y Tadros et a1., .1. Chem. Soc. 1961, pp. 2687 to 2689. [21] Appl. No.: 143,605 Fus'on et al., J. Org. Chem., Vol. 27, pp. 1221-1223 Related US. Application Data 1962)- [62] Division of Ser. No. 862,923, Oct. 1, 1969, Pat. No.

3,647,431. Primary Examiner-John D. Randolph [52] US. Cl 2641/2403, 96/15, 96/16, [57] ABSTRACT 96/1 252/501 260/240 260/288 Novel organic photoconductors for electrophoto- 260/293'73 260/29375 260/293'79 graphic elements as described. These novel photocon- 260/306' 260/307 260,310 ductors are 'bis-(p-dialkylaminophenyl)methanes hav- 260/315, 260/326.15, 260/326.8, 260/329 ing a third substituent comprising an unsaturated alkyl 2605305 260/465 260/470 group having two or four carbon atoms wherein an 260/471 R, 260/516, 260/518 R, 260/558 A, w-carbon atom of the third substituent is fully substi- 260/558 260,558 260/570 D tuted by aryl group(s), heterocyclic group(s) or combi- [51] Int. Cl C09b 23/14 nations thereof [58] Field of Search 260/240.9, 570 D,

260/465 E, 470, 471 R, 518 R 5 Claims, No Drawings SUBSTITUTED 858G -DIALKYLAMINOPHENYL)METHANE PHOTOCONDUCTORS This is a division of US. Patent application, Ser. No. 862,923, Substituted Bis(P- Dialkylaminophenyl)Methane Photoconductors, filed October 1, 1969, now US. Patent 3,647,43l granted Mar. 7, 1972.

This invention relates to electrophotography, and is particular to photoconductive compositions and elements.

The process of xerography, as disclosed by Carlson in US. Pat. No, 2,297,691, employs an electrophotographic element comprising a support material bearing a coating of a normally insulating material whose electrical resistance varies with the amount of incident electromagnetic radiation it receives during an imagewise exposure. The element, commonly termed a photoconductive element, is first given a uniform surface charge, generally in the dark after a suitable period of dark adaptation. It is then exposed to a pattern of acvtinic radiation which has the effect of differentially reducing the potential of this surface charge in accordance with the relative energy contained in various parts of the radiation pattern. The differential surface charge or electrostatic latent image remaining on the electrophotographic element is then made visible by contacting the surface with a suitable electroscopic marking material. Such marking material or toner whether contained in an insulating liquid or on a dry carrier, can be deposited on the exposed surface in accordance with either the charge pattern or discharge pattern as desired. Deposited marking material can then be either permanently fixed to the surface of the sensitive element by known means such as heat, pressure, solvent vapor, or the like, or transferred to a second element to which it can similarly be fixed. Likewise, the electrostatic latent image can be transferred to a second element and devloped there.

Various photoconductive insulating materials have been employed in the manufacture of electrophotographic elements. For example, vapors of selenium and vapors of selenium alloys deposited on a suitable support and particles of photoconductive zinc oxide held in resinous, film-forming binder have found wide application in the present-day document copying applications.

Since the introduction of electrophotography, a great many organic compounds have also been screened for their photoconductive properties. As a result, a very large number of organic compounds have been known to possess some degree of photoconductivity. Many organic compounds have revealed a useful level of photoconduction and have been incorporated into photoconductive compositions.

Typical of these organic photoconductors are the triphenylamines and the triarylmethane leuco bases. Optically clear photoconductor-containing elements having desirable electrophotographic properties can be especially useful in electrophotography. Such electrophotographic elements can be exposed through a transparent base if desired, thereby providing unusual flexibility in equipment design. Such compositions, when coated as a film or layer on a suitable support, also yield an element which is reusable; that is, it can be used to form subsequent images after residual toner from prior images has been removed by transfer and/or cleaning. Thus far, the selection of various compounds for incorporation into photoconductive compositions to form electrophotographic layers has proceeded on a compound-by-compound basis. Nothing as yet has been discovered from the large number of different photoconductive substances tested which permits effective prediction, and therefore selection of the particular compounds exhibiting the desired electrophotographic properites. 7

It is, therefore, an object of this invention to provide a novel class of photoconductors having high photosensitivity when electrically charged.

It is another object to provide novel photoconductorcontaining compositions which exhibit high electrical speeds.

It is a further object of the invention to provide an improved process utilizing the novel photoconductors described herein.

Still another object of this invention is to provide electrophotographic elements containing the novel photoconductors described herein.

These and other objects of the invention are accomplished by employing certain substituted bis(p dialkylaminophenyl)methanes as photoconductors. These materials are characterized by having a third substituent attached to the methane carbon atom, this substituent generally being an unsaturated alkyl group having two or four carbon atoms and having its 0) (terminal) carbon atom fully substituted by aryl heterocyclic groups or combinations thereof. Typical third substituents include an m,m-diaralkenyl group, an m-aralkynyl group, an w,%-diaralkadienyl group, etc. The unsaturated alkyl group can have additional substituents on positions other than the m-carbon atom, and the aryl groups and heterocyclic groups attached to the m-carbon atom can be substituted or unsubstitutd.

A large number of substituted diarylmethanes and triarylmethanes have exhibited photoconductive prop erties when used as photoconductors in electrophotographic elements. Typical of these are the leuco base of malachite green, bis(4- dimethylaminophenyhmethane, bis(4- dimethylaminophenyl)-p-dimethylaminostyrylmethane and bis(4-dimethylaminophenyl)phenylmethane as described in British Patents 984,965 and 980,879. Also, diarylmethane compounds have been usedas activators for zinc oxide photoconductors. Such uses are described in British Patent 1,141,666. According to this invention, it has been found that the photoconductors described herein have enhanced speed and/or stability over those photoconductors described in the prior art.

The preferred substituted bis(p-dialkylaminophenyl) methanes useful as photoconductors in this invention are characterized by the following formula:

2. an alkyl group having one to six carbon atoms e.g.,

methyl, ethyl, propyl, butyl, isobutyl, including a substituted alkyl group having one to six carbon atoms such as a. alkoxyalkyl e.g., ethoxypropyl, methoxybutyl,

propoxymethyl, etc.,

b. hydroxyalkyl having two to six carbon atoms e.g., 3-hydroxypropyl, Z-hydroxyethyl, etc.,

c. cyanoalkyl, e.g., 3-cyanopropyl, Z-cyanoethyl,

cyanomethyl, etc.,

d. haloalkyl having two to six carbon atoms e.g., 2-

chloroethyl, 3-bromopropyl, etc.,

e. aralkyl e.g., benzyl, phencthy], etc., X represents any of the following groups:

1. alkoxy having one to four carbon atoms, e.g., me-

thoxy, ethoxy, propoxy, butoxy, etc.,

2. halogen such as chlorine or fluorine,

3. hydroxy, I

4. an alkyl group having one to four carbon atoms e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, including a substituted alkyl group having one to four carbon atoms such as a. alkoxyalkyl e.g., ethoxypropyl, methoxybutyl,

propoxymethyl, etc., b. hydroxyalkyl, e.g., hydroxypropyl, hydroxyethyl,

hydroxymethyl, etc., and

5. alkylthio e.g., methylthio, ethylthio, etc.;

Y represents any of the following groups:

1. alkoxy having one to four carbon atoms e.g., me-

thoxy, ethoxy, propoxy, butoxy, etc.,

2. halogen such as chlorine, or fluorine,

3. hydroxy,

4. hydrogen,

5. an alkyl group having one to four carbon atoms e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc. including a substituted alkyl group having one to four carbon atoms such as a. alkoxyalkyl e.g., ethoxypropyl, methoxybutyl,

propoxymethyl, etc. and b. hydroxyalkyl, e.g., hydroxypropyl, hydroxyethyl,

hydroxymethyl, etc.;

R and R each can be the same or different substituents each representing any of the following:

an aryl group, e.g., phenyl or naphthyl, including a substituted aryl group such as a. alkoxyaryl, e.g., ethoxyphenyl, methoxyphenyl,

propoxynaphthyl, etc.,

b. aminoaryl, e.g., aminophenyl or aminonaphthyl,

c. hydroxyaryl, e.g., hydroxyphenyl, hydroxynaphthyl,

d. alkylaminoaryl, e.g., methylaminophenyl, me-

thylaminonaphthyl, etc. and also including dialkylaminoaryl, e.g., diethylarninophenyl, dipropylaminophenyl, 4-diethylamino-2-tolyl, etc.,

e. arylaminoaryl, e.g., phenylaminophenyl, diphenyl-aminophenyl, N-phenyl-N- ethylaminopbenyl, etc.,

f. cyanoaryl, e.g., cyanophenyl, cyanonaphthyl,

etc.,

g. haloaryl, e.g., chlorophenyl, bromophenyl,

chloronaphthyl, etc.,

h. aryl substituted with an acyl group having the formula wherein R is hydroxy, hydrogen, aryl, e.g., phenyl, naphthyl, etc., amino including substituted amino, e.g., diloweralkylamino, lower alkoxy having one to four carbon atoms, e.g., butoxy, methoxy, etc., aryloxy, e.g., phenoxy, naphthoxy, etc., lower alkyl having one to four carbon atoms, e.g., methyl, ethyl, propyl, butyl, etc.,

i. alkaryl, e.g., tolyl, ethylphenyl, propylnaphthyl, 2. a heterocyclic group including a substituted heterocyclic group containing 5 to 6 members in the hetero-nucleus and including at least one sulfur, selenium, oxygen or nitrogen atom such as a thienyl group e.g., a benzothienyl group, a pyrrolyl group, e.g., a nitropyrrolyl group, a pyrrolidinyl group, e.g., a pyrrolyl group, a pyrrolinyl group, a benzopyrrolyl group, e.g., an indolyl group, a carbazolyl group, a furyl group, e.g., a furfuryl group,

a benzofuryl group, etc., a pyridyl group, an alkylpyridyl group, etc., a piperidyl group, a quinolyl group, a pyranyl group, 'a benzopyranyl group, a

pyrazolyl group, an oxazolyl group, a thiazolyl group, etc.;

R represents any of the following groups:

1. hydrogen 2. an aryl group, e.g., phenyl including a substituted aryl groups such as a. alkoxyaryl e.g., methoxyphenyl, etc.,

b. aminoaryl e.g., aminophenyl, aminonaphthyl,

etc.,

c. hydroxyaryl, e.g., hydroxyphenyl, hydroxynaphthyl, etc.,

d. alkylaminoaryl e.g., methylaminophenyl, me-

thylaminonaphthyl, etc., and also including dialkylaminoaryl, e.g., p-diethylaminophenyl, dipropylaminophenyl, etc.,

e. arylaminoaryl, e.g., phenylaminophenyl, diphenylaminophenyl, N-phenyl-N- ethylaminophenyl, etc.,

f. nitroaryl, e.g., nitrophenyl, nitronaphthyl, etc.,

g. cyanoaryl, e.g., cyanophenyl, cyanonaphthyl,

etc.,

h. haloaryl, e.g., chlorophenyl, bromophenyl, chloronaphthyl, etc.,

i. aryl'substituted with an acyl group having the formula wherein R is hydroxy, hydrogen, aryl, e.g., phenyl, naphthyl, etc. amino including substituted amino e.g., diloweralkylarnino, lower alkoxy having one to four carbon atoms, e.g., butoxy, methoxy, aryloxy, e.g., phenoxy, naphthoxy, etc., lower alkyl having I to 8 carbon atoms e.g., methyl, ethyl, propyl, butyl, etc.,

j. alkaryl e.g., tolyl, ethylphenyl, propylnaphthyl,

etc., 3. an aliphatic alkyl group having one to four carbon atoms e.g., methyl, ethyl, propyl, butyl, isobutyl, R; and R when taken together with the carbon atom to which they are attached, represent a heterocyclic group including a substituted heterocyclic group containing 5 to 6 members in the hetero nucleus and including at least one sulfur, selenium, oxygen or nitrogen atoms such as an indolinylidene group, a 3-alkyl-2-benzothiazolinylidene group, a 3-a1kyl-2-benzoxazolinylidene group, a 3-alkyl-2- benzoselenazolinylidene group, a 3-alkyl-2- benzimidazolinylidene group, etc.; it is zero or one with the provision that n is zero when R,,and R are taken together to represent a covalent bond. Typical compounds which belong to the herein described general class of photoconductive materials include the following listed in Table I below.

TABLE I 3,3Diphenylallylidene-4,4'-bis(N,N-diethyl-mtoluidine.) ll

3-Phenyl-2-propynylidem-4,4'-bis(N,N-diethyl-mtoluidine) III 3-Phenyl-3-(2-thienyl)allylidene-4,4'-bis(N,-N- diethyl-m-toluidine) IV 5 ,5 -Diphenyl-2,4-pentadienylidene-4,4'-bis(N,N- diethyl-m-toluidine) V 2-[ 2 ,2-bis( p-diethylamino-o-tolyl )ethylidene ]-3- ethylbenzothiazoline VI 3-(4-Diethylamino-Z-phenylallylidene- 3-( 4-Diethylamino-2-methylphenyl )-3- phenylallylidene- 4,4'-bis(N,N-diethyl-m-toluidine) XII 3 ,3 -Bis( 4-diethylaminophenyl)allylidene-4,4- bis(N ,N-dimethyl-m-toluidine) VIII 3 ,3 -Diphenylallylidene-4,4 -bis( N,N-diethyl-manisidine) IX 3 ,3 -Diphenylallylidene-4,4 -bis( N,N-diethyl-2,5 xylidine) X 3 ,3 -Diphenylallylidene-4,4 '-bis( N,N-diethyl-2- chloroaniline) XI 3 ,3-Bis( 4-methoxyphenyl)allylidene-4,4 '-bis( N,N- diethyl-m-toluidine) XII 3 ,3-Diphenylallylidene-4 ,4 '-bis( N-ethyl-mtoluidine) XIII 3 ,3 -Diphenylallylidene-4,4 '-bis( N,N-dibenzyl-mtoluidine) XIV 3 -p-N,N-diethylaminophenyl-2-propynylidene-4,4 bis (N ,N-ethyl-N -2-hydroxyethyl-m-toluidine) 3-Phenyl-2-propynylidene-4,4'-bis(N-2-cyanoethyl- N-ethyl-m-toluidine N-ethyl-m-toluidine) Electrophotographic elements of the invention can be prepared with the photoconducting compounds of the invention in the usual manner, i.e., by blending a photoconductor-containing material. Mixtures of the photo-conductors described herein can be employed Likewise, other photoconductors known in the art such as those described in Light, Belgian Patent 705,117, dated Apr. 16, 1968, can be combined with the present photoconductors. In addition, supplemental materials useful for changing the spectral sensitivity or electrophotosensitivity of the element can be added to the composition of the element when it is desirable to produce the characteristic effect of such materials.

The photoconductive layers of the invention can also be sensitized by the addition of effective amounts of sensitizing compounds to exhibit improved electrophotosensitivity. Sensitizing compounds useful with the photoconductive compounds of the present invention can be selected from a wide variety of materials, including such materials as pyrylium dye salts including thiapyrylium dye salts and selenapyrylium dye salts disclosed in VanAllan et al., U.S. Pat. No. 3,250,615; fluorenes, such as 7,12-dioxo-13-dibenzo(a,h)fluorene, 5,- l0-dioxo-4a,l l-di-azabenzo(b)fluorene, 3,1 3dioxo-7- oxadibenzo(b,g)fluorene, and the like; aggregate-type sensitizers of the type described in Light, Belgian Patent 705,117, dated April I6, 1968; aromatic nitro compounds of the kinds described in U.S. Pat. No. 2,610,120; anthrones like those disclosed in U.S. Pat. No. 2,670,284; quinones, U.S. Pat. No. 2,670,286; benzophenones U.S. Pat. No. 2,670,287; thiazoles, U.S. Pat. No. 2,732,301; mineral acids; carboxylic acids, such as maleic acid, dichloroacetic acid, and salicyclic acid; sulfonic and phosphoric acids; and various dyes, such as cyanine (including carbocyanine), merocyanine, diarylmethane, thiazine, azine, oxazine, xanthene, phthalein, acridine, azo, anthraquinone dyes and the like and mixtures thereof. The sensitizers preferred for use with the compounds of this invention are selected from pyrylium salts including selenapyrylium salts and thiapyrylium salts, and cyanine dyes including carbocyanine dyes.

Where a sensitizing compound is employed with the binder and organic photoconductor to form a sensitized electrophotographic element, it is the normal practice to mix a suitable amount of the sensitizing compound with the coating composition so that, after thorough mixing, the sensitizing coumpound is unifonnly distributed in the coated element. Other methods of incorporating the sensitizer or the effect of the sensitizer may, however, be employed consistent with the practice of this invention. In preparing the photoconductive layers, no sensitizing compound is required to give photoconductivity in the layers which contain the photoconducting substances, therefore, no sensitizer is required in a particular photoconductive layer. However, since relatively minor amounts of sensitizing compound give substantial improvement in speed in such layers, the sensitizer is preferred. The amount of sensitizer that can be added to a photoconductorincorporating layer to give effective increases in speed can vary widely. The optimum concentration in any given case will vary with the specific photoconductor and sensitizing compound used. In general, substantial speedgains can be obtained where an appropriate sensitizer is added in a concentration range from about 0.000] to about 30 percent by weight based on the weight of the film-forming coating composition. Normally, a sensitizer is added to the coating composition in an amount by weight from about 0.005 to about 5.0 percent by weight of the total coating composition.

Preferred binders for use in preparing the present photoconductive layers are film-forming, hydrophobic polymeric binders having fairly high dielectric strength which are good electrically insulating film-forming vehicles. Materials of this type comprise styrenebutadiene copolymers; silicone resins; styrene-alkyd resins; silicone-alkyd resins; soyaalkyl resins; poly(vinyl chloride); poly(vinylidene chloride); vinylidene chloride-acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate-vinyl chloride copolymers; poly (vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(methyl methacrylate,)po ly(n-butyl methacrylate), poly(isobutyl methacrylate), etc; polystyrene; nitrated polystyrene; polymethylstyrene; isobutylene polymers; polyesters; such as poly[ethylene-co-alkylenebis(alkyleneoxyaryl) phenylenedicarboxylate] phenolformaldehyde resins; keton resins; polyamides; polycarbonates; polythiocarbonates; poly[ethylene-co-isopropylidene-2,2-bis(ethyleneoxyphenyl) terephthalate]; copolymers of vinyl haloarylates and vinyl acetate such as poly(vinyl m-bromobenzoate-co-vinyl acetate); etc. Methods of making resins of this type have been described in the prior art, for example, styrene-alkyd resins can be prepared according to the method described in U.S. Pat. Nos. 2,361,019 and 2,258,423. Suitable resins of the type contemplated for use in the photoconductive layers of the invention are sold under such tradenames as Vitel PEll, Cymac, Piccopale 100, Saran 1 -220, Lexan 105 and Lexan 145. Other types of binders which can be used in the photoconductive layers of the invention include such materials as parafiin, mineral waxes, etc.

Solvents useful for preparing coating compositions with the photoconductors of the present invention can include a wide variety of organic solvents for the components of the coating. For example, benzene; toulene; acetone; 2-butanone; chlorinated hydrocarbons such as methylene chloride; ethylene chloride; and the like; ethers, such as tetrahydrofuran and the like, or mixtures of such solvents can advantageously be employed in the practice of this invention.

in preparing the coating compositions utilizing the photoconducting compounds disclosed herein, useful results are obtained where the photoconductive substance is present in an amount equal to at least about 1 weight percent of the coating composition. The upper limit in the amount of photoconductive material present can be widely varied in accordance with usual practice. It is normally required that the photoconductive material be present in an amount ranging from about 1 weight percent of the coating composition to about 99 weight percent of the coating composition. A preferred weight range for the photoconductive material in the coating composition is from about weight percent to about 60 weight percent.

Coating thicknesses of the photoconductive compo sition on a support can vary widely. Normally, a wet coating thickness in the range of about 0.001 inch to about 0.01 inch is useful in the practice of the invention. A preferred range of coating thickness is from about 0.002 inch to about 0.006 inch before drying, al though such thicknesses can vary widely depending on the particular application desired for the electrophotographic element.

Suitable supporting materials for the photoconductive layers of the present invention can include any of the electrically conducting supports, for example, conducting papers; aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, zinc, brass, and galvanized plates; vapor deposited metal layer such as silver, nickel or aluminum on conventional film supports such as cellulose acetate, poly(ethylene terephthalate), polystyrene and the like conducting supports.

An especially useful conducting support can be prepared by coating a transparent film support material such as poly(ethylene terephthalate) with a layer containing a semi-conductor dispersed in a resin. A sutiable conducting coating can be dispersed in a resin. A suitable conducting coating can be prepared from the sodium salt of a carboxyester lactone of a maleic anhydride-vinyl acetate copolymer, cuprous iodide and the like. Such conducting layers and methods for their optimum preparation and use are disclosed in US. Pat. Nos. 3,007,901, 3,245,833 and 3,267,807.

The compositions of the present invention can be employed in photoconductive elements useful in any of the well known electrophotographic processes which require photoconductive layers. One such process is the xerographic process. In a process of this type, an electrophotographic element held in the dark, is given a blanket electrostatic charge by placing it under a corona discharge to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial dark insulating property of the layer, i.e., the low conductivity of the layer in the dark. The electrostatic charge formed on the surface of the photoconductive layer is then selectively dissipated from the surface of the layer by imagewise exposure to light by means of a conventional exposure operation such as for example, by a contactprinting technique, or by lens projection of an image, or reflex. or bireflex techniques and the like, to thereby form a latent electrostatic image in the photoconductive layer. Exposing the surface in this manner forms a pattern of electrostatic charge by virtue of the fact that light energy striking the photoconductor causes the electrostatic charge in the light struck areas to be conducted away from the surface in proportion to the intensity of the illumination in a particular area.

The charge pattern produced by exposure is then developed or transferred to another surface and developed there, i.e., eitherthe charge or uncharged areas rendered visible, by treatment with a medium comprising electrostah'eally responsive particles having optical density. The developing electrostatically responsive particles can be in the form of a dust, or powder and generally comprise a pigment in a resinous carrier called a toner. A preferred method of applying such a toner to a latent electrostatic image for solid area development is by the use of a magnetic brush. Methods of forming and using a magnetic brush tone applicator are described in the following US. Pat. Nos: 2,786,439; 2,786,440, 2,786,441; 2,811,465; 2,874,063;

- 2,984,163; 3,040,704; 3,117,884 and reissue Re been described in the patent literature, for exmmple, U.S. Pat. No.

2,297,691 and in Australian Patent 212,315. In dry developing processes the most widely used method of obtaining a permanent record is achieved by selecting a developing particle which has as one of its components a low-melting resin. Heating the powder image then causes the resin to melt or fuse into or on the element. The powder is, therefore, caused to adhere permanently to the surface of the photoconductive layer. in other cases, a transfer of the charge image or powder image formed on the photoconductive layer can be made to a second support such as paper which would then become the final print after developing and fusing or fusing respectively. Techniques of the type indicated are well known in the art and have been described in a number of U.S. and foreign patents, such as U.S. Pat. Nos. 2,297,691 and 2,551,582, and in RCA Review, vol. (1954) pages 469-484.

The compositions of the present invention can be used in electrophotographic elements having many structural variations. For example, the photoconductive composition can be coated in the form of single layers or multiple layers on a suitable opaque or transparent conducting support. Likewise, the layers can be contiguous or spaced having layers of insulating material or other photoconductive material between layers or overcoated or interposed between the photoconductive layer or sensitizing layer and the conducting layer. It is also possible to adjust the position of the support and the conducting layer by palcing a photoconductor layer over a support and coating the exposed face of the support or the exposed or overcoated face of the photoconductor with a conducting layer. Configurations differing from those contained in the examples can be useful or even preferred for the same or different application for the electro-photographic element.

The following examples are included for a further understanding of this invention.

EXAMPLE 1 A composition in the form of a dope consisting of the following materials is coated at a wet thickness of 0.004 inch on a poly(ethylene terephthalate) film support containing a conducting layer of the sodium salt of a carboxyester resin lactone:

Photoconductor 0.25 g.

Polymeric binder [Vitel 101, 1.00 g.

a polyester resin sold by Goodyear Tire and Rubber Co.

comprising poly (4,4|'-isopropylidenebisphenoxyethyl-co-ethylene terephthalate)] Sensitizer-Rhodamine B 0.01 g.

Dichloromethane 9.60 g.

In a darkened room, the surface of the photoconductive layer so prepared is charged to potential of about +600 volts under a corona charger. The layer is then covered with a transparent sheet bearing a pattern of opaque and light-transmitting areas and exposed to the radiation for an incandescent lamp with an illumination intensity of about 75 meter-candles for 12 seconds. The resulting electrostatic latent image is developed by cascading over the surface of the layer negatively charged black thermoplastic toner particles on glass bead carriers. The quality of the image reproduced using the various photoconductors described herein are set forth in the following table.

TABLE II Photoconductor Image Quality none none reproduced I good w good VI good VII good VIII good EXAMPLE 2 Example I is repeated except the sensitizer employed is 2,4,7-trinitro-9-fluorenone. The photoconductors used and the quality of the image obtained are set forth in Table III.

TABLE IV. Photoconductor Image Quality VI good X good XII good XIV good XV good EXAMPLE 3 Example 1 is repeated using 2,6-bis(4-ethylphenyl)- 4-(4-n-amyloxyphenyl)thiapyrylium perchlorate as the sensitizer. The photoconductors used and image quality obtained are set forth in the following Table IV.

TABLE IV Photoconductor Image Quality lII good VII good The following composition is sheared in a Waring Blender The following composition is sheared in a Waring Blendor for thirty minutes at room temperature.

Binder-Lexan 145 [tradename of General Electric Company for a poly(4,4'-isopropyl-idenediphenylcarbonate)]. [.0 g. Sensitizer-l2,6diphenyl-4-(4-dimethylaminq phenyl)]thiapyrylium perchlorate 0.025 g. Dichloromethane 9.6 g.

Photoconductor I (0.025 g.) is then dissolved in the resultant mixture which is then coated at 0.04 inch wet thickness on a poly(ethylcne terephthalate)support which has been precoated with an evaporated nickel conducting layer. The element is then dried at F.

The element is charged, exposed and developed in the manner described in Example 1. A good reproduction is obtained.

The photoconducting compounds of this invention can generally be prepared by synthesis familiar to those skilled in the art. Typical preparations are set forth in the following Examples.

EXAMPLE 5 Anal. Calcd. for C H N (516.8): C, 86.0; 11, 8.60; thienyl, nitropyrrolyl, pyrrolidinyl, pyrrolyl, pyrrolinyl,

N, 5.40. benzopyrrolyl, indolyl, carbazolyl, fury], furfuryl, ben- Found: C, 86.3; H, 8.3; N, 5.6. zofuryl, pyridyl, alkylpyridyl, piperidyl, quinolyl, pyra- EXAMPLE 6 benzopyranyl, pyrazolyl, oxazolyl and thiazolyl; Preparation of 3-Phenyl-2-propynylidene-4,4- R and R when taken together with the carbon atom bis(N,N- diethyl-m-toluidine) to which they are attached can also represent a hety the Procedure of Example 5, gof p y erocyclic group including a substituted heterocypropargyl al ehy gof y toluclic group selected from the group consisting of an idine, 11.4 g. of urea and 15.8 ml. of concentrated hyi d li lid group, a 3 1k l 2 drochloric acid in 200 ml. of methanol are reacted to hi li lid group, a 3 1k 1 2 form 26.0 g. of the subject compound as a tan crystalbenzoxazinylidene group and a 3 2 line Solid, P- moo-122C benzoselenazolinylidene group;

Analcalcd- C31H38N2(438'7): C, H; R is selected from the group consisting of 1) hydrogen; 2) phenyl; 3) naphthyl; and 4) substituted Foundi 35.4; phenyl and naphthyl wherein the substituent is se- The invention has been described in detail with parlected from the group consisting of alkoxy amino ticular reference to preferred embodiments thereof, hydroxy, alkylaminm dialkylamino, awhmino, but it will be understood that variations and modifica nogen, cyano halogen, alkyl and acyl having the tions thereof, be effected within the spirit and. scope of formula the invention. WM, Am" V, O a

1 claim: 3 l. A compound having the formula: R

wherein R is hydroxy, hydrogen, phenyl, naphthyl, amino, dialkyl-amino, alkoxy, aryloxy and lower alkyl; R and R when taken together can also represent a i X R covalent bond; and

n is zero or one with the provision that n is zero when \R R and R,, are taken together to represent a covay r- Y lent bond.

g 2. 3,3-Diphenylallylidene-4,4'-bis(N,N-diethyl-m l h toluidine).

L 3. 3-Phenyl-2-pr0pynylidene-4,4'-bis(N,N-diethylg m-tolurdine).

4. 2-[2,2-bis( p-diethylamine-otolyl) ethylidene]-3- ethylbenzothiazoline.

5.A compound selected from the group consisting of 3-Phenyl-3-( Z-thienyl)allylidene-4,4'-bis(N,N-diethyl-m-toluidine),

5 ,5 -Diphenyl-2,4-pentadienylidene-4,4 -bis( N ,N-

diethyl-m-toluidine),

3-(4-Diethylamino-2-methylphenyl)-3- phenylallylidene-4,4-bis(N,N-diethyl-mwherein R R R and R are each selected from the group consisting of hydrogen, alkyl having 1 to 6 car- 40 bon atoms and substituted alkyl wherein the substitutent is selected from the group consisting of allcoxy, hydroxy, cyano, halogen and phenyl;

X is selected from the group consisting of halogen,

hydroxy, lower alkoxy, lower alkyl and substituted mhfldmelv I lower alkyl wherein the substituent is selected from f R f y the group consisting of lower alkoxy, hydroxy, cy- 'N Y 'F l,

an), halogen, h and i 3,5-P1phenylallyhdene-4A-bis(N,N-d|ethyl-manis- Y is the same as X above with the added inclusion of 9),

h d 3,3-Qrphenylallyl1dene-4A'-bis(N,N-diethyl-2,5- R and R each can be the same or different substituy f ents selected from the group consisting of l) phep y y i .N- i hyl-2- ny]; 2) naphthyl; 3) substituted phenyl and naphchlomflnillfle),

thy] wherein the substituent is alkoxy, amino, hyyp y y s(N,

droxy', alkylamino, dialkylamino, arylamino, cydiethyl-m-toluidine),

aho, halogen, alkyl and acyl having the formula 3,3Diphenylallylidene-4,4-bis y A 0 3,3-Diphenylallylidene-4,4'-bis (N,N-dibenzyl-m- R toluidine),

3-p-N,N-diethylaminophenyl-Z-propynylidene-4,4'-

wherein R is hydroxy, hydrogen, phenyl, naphthyl, a- 50 bis (N-ethyLN-Z-hydroxyethyl-m-toluidine), and mino, dialkylamino, alkoxy, aryloxy and lower alkyl; 3-Phenyl-2-propynylidene-4,4'-bis (N-Z-cyanoethyland 4) a heterocyclic group including a substituted het- N-ethyl-m-toluidine). erocyclic group selected from the group consisting of 9 UNITED STATES PATENT OFFICE EERHFECATE Di toRRtowoN Patent 3,755,3 Dated August 28, 1973 Inventor(5) Louis J. ROSSi I It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 12, line 36, diethylamine should read -diethylamino--.

, Col. 12; line 56, "MA-bis" should read M-bis.

Signed and sealed this 25th day of December 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents

Claims (4)

1. 2. 3,3-Diphenylallylidene-4,4''-bis(N,N-diethyl-m-toluidine).
2. 3. 3-Phenyl-2-propynylidene-4,4''-bis(N,N-diethyl-m-toluidine).
3. 4. 2-(2,2-bis(p-diethylamine-o-tolyl) ethylidene)-3-ethylbenzothiazoline.
4. 5. A compound selected from the group consisting of 3-Phenyl-3-(2-thienyl)allylidene-4,4''-bis(N,N-diethyl-m-toluidine), 5,5-Diphenyl-2,4-pentadienylidene-4,4''-bis(N,N-diethyl-m-toluidine), 3-(4-Diethylamino-2-methylphenyl)-3-phenylallylidene-4,4''-bis(N, N-diethyl-m-toluidine), 3,3-Bis(4-diethylaminophenyl)allylidene-4,4''-bis (N,N-dimethyl-m-toluidine), 3,3-Diphenylallylidene-4,4''-bis(N,N-diethyl-m- anisidine), 3,3-Diphenylallylidene-4,4''-bis(N,N-diethyl-2,5-xylidine), 3,3-Diphenylallylidene-4,4''-bis(N,N-diethyl-2-chloroaniline), 3,3-Bis(4-methoxyphenyl)allylidene-4,4''-bis(N,N- diethyl-m-toluidine), 3,3Diphenylallylidene-4,4-bis (N-ethyl-m-toluidine), 3,3-Diphenylallylidene-4,4''-bis (N,N-dibenzyl-m-toluidine), 3-p-N,N-diethylaminophenyl-2-propynylidene-4,4''-bis (N-ethyl-N-2-hydroxyethyl-m-toluidine), and 3-Phenyl-2-propynylidene-4,4''-bis (N-2-cyanoethyl- N-ethyl-m-toluidine).