DE1772775B2 - Electrophotographic recording material - Google Patents

Description

light predicts whether an organic compound will be used in the manufacture of electrophotographic recording materials is usable.

The object of the invention is to provide an electro-photographic recording material which can be produced in an advantageous manner with continuous photoconductive ones leading to an advantageous image resolution Specify layer that is characterized by high photosensitivity and both positive and negative Can be charged, and also suitable for both reflex and bireflex processes is.

The invention is based on the knowledge that the specified object is particularly advantageous Way can be solved in that organometallic compounds of a precisely defined structure as photoconductors be used.

The invention relates to an electrophotographic recording material made from optionally a support and a photoconductive layer with an organometallic photoconductor and optionally a sensitizing dye that thereby is characterized in that it is an organometallic compound with a metal atom of the photoconductor Group IVa or Va of the Periodic Table of the Elements to which at least one aminoaryl radical is bound is, contains.

The group name corresponds to the periodic system of the elements, as it is, for example in the "Handbook of Chemistry and Physics", 38th edition, pp. 394 and 395, is given.

Metals of groups IVa and Va of the Periodic Table of the Elements are thus silicon, germanium, Tin and lead from group IVa and phosphorus, arsenic, antimony and bismuth from group Va.

The invention achieves the electrophotographic Recording materials are available that are versatile due to their versatility, high photoconductivity and easy producibility and high image resolution lead, since their photoconductive layers are very uniform and not corpuscular due to the fact that they can be produced from photoconductor solutions.

The organometallic compounds which can be used according to the invention Photoconductors can be substituted on the metal atom by a wide variety of substituents, however at least one of the substituents should be an aminoaryl radical.

The amino radical can be in any position of the aromatic ring or nucleus. Particularly Good results are obtained if the aryl radical is a phenyl radical and if the amino radical is also located is in the 4 or para position.

The metal atom of the organometallic photoconductors which can be used according to the invention can, for example be substituted by the following substituents:

a) a hydrogen, sulfur or oxygen atom,

b) an alkyl radical,

c) an optionally substituted aryl radical, e.g. B. an aminoaryl, alkylaryl or haloaryl radical,

d) an oxygen-containing residue, ζ. B. an alkoxy or aryloxy radical,

e) an optionally substituted amino radical, e.g. B. a mono- or diarylamine radical or one Mono- or dialkylamine residue,

f) a heterocyclic ReGt and

g) an organometallic radical with a metal atom from group IVa or Va of the periodic System of elements.

Advantageous photoconductors for producing the photoconductive Recording materials according to the invention can be represented by the following structural formulas :

T-Ar-M ₀ , D
G

T-Ar

"J

T - Ar - Mb.

i ^Q

E E

T - Ar - M ₀₁ M », Ar - T

G G

(D

(2)

(3)

(4)

T-Ar-]

T - Ar- 1

M ₀₂

Herein mean:

E, G, L and Q a) each one hydrogen atom,

b) in each case an optionally substituted aryl radical, e.g. B. each one Phenyl radical, a naphthyl radical, a dialkylaminophenyl radical or a dialkylaminonaphthyl radical, each having preferably 1 to 8 carbon atoms in the alkyl groups,

c) in each case an alkyl radical with 1 to 8 carbon atoms,

d) each an alkoxy radical with 1 to 8 carbon atoms,

e) each an aryloxy radical, e.g. B. a phenoxy radical,

f) in each case one aminoresl of the formula

R ₂

wherein R ₁ and R _{2 are} hydrogen atoms

are or alkyl radicals with 1 to 8 carbon atoms; n or
g) in each case a heterocyclic radical having 5 to 6 ring atoms, at least one of which is a nitrogen atom, ie, for example a triazolyl or a pyridyl radical;
T is an amino radical, 7. B. an alkylamino radical having 1 to 8 carbon atoms or an arylamino radical, e.g. B. a phenylamino radical;
Ar is an aromatic radical, e.g. B. a

Phenyl or naphthyl radical;

Ma ₁ and M _{02 are} identical or different metals from group IVa of the Periodic Table of the Elements;

Mb a metal from Group Va of the Periodic Table of the Elements;
D a radical of the meaning given for E, G, L and Q as well as an organometallic radical with a metal atom from group IVa of the Periodic Table of the Elements or together with E an oxygen or sulfur atom and J a radical for E, G, L and Q given meaning and additionally together with E an oxygen or sulfur atom.

Typical advantageous organometallic photoconductors used in the manufacture of an electrophotographic Suitable recording material according to the invention are, for example:

Triphenyl-p-diethylaminophenylsilane,

Methyl-diphenyl-p-diethylaminophenylsilane,

Triphenyl-p-diethylaminophenylgerman,

Triphenyl-p-dimethylaminophenylstannane,

Triphenyl-p-diethylaminophenylstannane,

Diphenyl-di- (p-diethylaminophenyl) -stannane,

Triphenyl-p-diethylaminophenylplumban,

Tetra-p-diethylaminophenylplumban,

Phenyi-di- (p-diethylaminophenyl) -phosphine,

Bis (p-diethylaminophenyl) phosphine oxide,

Tri-p-dimethylaminophenylarsine,

Tri-p-diethylaminophenylarsine,

2-methyl-4-dimethylaminophenylarsine oxide,

Tri-p-diethylaminophenylbismuthine,

Methyl-di- (p-diethylaminophenyl) arsine,

Methyl-di- (p-diethylaminophenyl) -phosphine,

Diphenyl-p-diethylaminophenylsilane,

p-diethylaminophenylarsine,

Tetrakis- [diphenyl- (p-diethylaminophenyl) -

plumbyl] methane,
Tetrakis- [diphenyl- (p-diethylaminophenyl) -

stannyl] -stannane,

Bis- [phenyl- (p-diethylaminophenyl)] -dibismuthin tri- (p-diethylaminophenyl) -phosphine sulfide and
Di- (p-diethylaminophenyl) thioxotine.

Those required for the production of an electrophotographic recording material according to the invention Organometallic photoconductors can be produced by known processes. For example, the Aminoaryl lead compounds and the aminoaryl tin compounds according to the method described in J.A.C.S. 54, 3726-9 (1932), or according to the method described in J. Org. Chem. 15, p. 994 (1950) will. The aminoaryigermanium compounds can be prepared according to the method described in CA. 60, p. 395d Process to be synthesized. The production of Aminoarylbismuthinen is for example in J.A.C.S. 63, pp. 207 to 211 (1941). Aminoaryl derivatives of arsenic can also be described in J. Indian Chemical Soc. 16, pp. 515-518 (1939) Process to be synthesized. Compounds containing phosphorus and antimony with aminoaryl radicals

ίο can in turn, for example, after the in CA. 28, pp. 3392 ³ , and CA. 40, p. 4689 ⁶ , described processes can be prepared.

The electrophotographic recording materials according to the invention can be used in a more conventional manner Way to be produced, d. i.e., by mixing a dispersion or solution of a photoconductor, for example with a binder, if this is necessary or desirable, and applying the obtained Dispersion or the coating composition on a layer support or, if appropriate, deformation of the Coating compound to form a self-supporting carrier. Mixtures can also be used to produce the photoconductive recording material according to the invention the photoconductor can be used. Furthermore, the photoconductors used according to the invention can optionally be mixed with other known photoconductors.

The electrophotographic recording material according to the invention may further optionally be conventional Additives contain, in particular, compounds that reduce the spectral sensitivity of the material change, especially sensitizers or sensitizers for the photoconductors.

A wide variety of known ones are suitable for sensitizing the photoconductors used according to the invention Sensitizers. Sensitizers that have been found to be particularly advantageous are those made from pyrylium, Thiapyrylium- or selenapyrylium salts exist, as for example in the USA. Patent 3 250 615.

Other suitable sensitizers are, for example, fluorenes, e.g. 7,12-dioxo-13-dibenzo (a, h) fluorene; 5,10-dioxo-4a, ll-diazabenzo (b) fluorene; 3,13-dioxo-7-oxadibenzo (b, g) fluorene; Trinitrofluorenone, tetranitrofluorenone and the like. Furthermore, suitable sensitizers are, for example, aromatic nitro compounds, such as those used, for. See U.S. Patent 2,610,120 are described, anthrones, e.g. B. the anthrones, quinones, known from US Pat. No. 2,670,285, as known, for example, from US Pat. No. 2,670,286, benzophenones, e.g. B. from the U.S. Patent 2,670,287 known compounds, thiazoles, e.g. B. that from the U.S. Patent No. 2,732,301, mineral acids, carboxylic acids, e.g. B. maleic acid, dichloroacetic acid and Salicylic acid, sulfonic acids and phosphoric acids and finally a wide variety of dyes, such as. B. Triphenylmethane, diarylmethane thiazine, azine, oxazine, xanthene, phthalein, acridine, azo, anthraquinone dyes and the like

In addition to pyrylium, thiapyrylium and selenapyrylium salts, fluorenes and Carboxylic acids and triphenylmethane dyes have proven to be particularly advantageous sensitizers.

If a sensitizer is used to produce the electrophotographic recording material, so this can in the usual way in the coating compound or for the production of a self-supporting

Element used mass are incorporated. photoconductive layer about 1 to about 99 parts by weight Production of an electrophotographic on percent. The proportion is preferably Drawing material according to the invention, however, is the photoconductor on the coating compound or on the Use of a sensitizer does not necessarily require photoconductive layer 10 to about 60 weight. However, there are already small amounts of 5 percent.

The photoconductive layers can be the usual ones increase in electrophotographic sensitivity strength. Usually the photoconductors have If layers on supports are preferably sensitizers, they have a thickness of about det. The optimal amount of a sensitizer in each individual case. 0.00254 to about 0.0254 cm, measured in front of the dryer can be very different. It depends on the ion. The layer thicknesses are preferably around individually used sensitizer as well as from 0.005 to about 0.015 cm, measured before drying, the photoconductor to be sensitized. In general, although of course also photoconductive pickups It has been found to be useful to use the sensitizing drawing materials with photoconductive layers Sators in concentrations from about 0.0001 to about other starches can be beneficial. 30 percent by weight based on the weight of the film support of the electrophotographic imaging member Coating compound to be used. Prior drawing material of the invention can be in any extract the sensitizers in concentration are one of the usual ones for the production of photoconductive substances Nen of about 0.005 to about 5 percent by weight, related to recording materials, be added to known support on the total weight of the coating composition, d. H. from any of the familiar usual used. 20 electrically conductive carrier, for example made of paper

For the production of electrophotographic up at a relative humidity above 20 _^0/0, from drawing materials of the invention are the conventional aluminum-paper laminates, metallic foils, z. B. aluminum known film-forming, polymeric binders ge minium and zinc foils, metal plates, for example, which have a suitable dielectric strength be aluminum, copper, zinc, brass and galvanized seats and the good electrically insulating, film-forming 25 th plates or made up of layers that are supported by low supports or binders. Suitable binders are generated by metal vapors, for example, consisting of a styrene-butadiene mixture - for example, silver and aluminum vapors, polymers, silicone resins, styrene-alkyd resins, SiIi-Con-alkyd resins, soy-alkyd resins, polyvinyl chloride, those that have been shown to consist of a carrier such as polyvinylidene chloride, copolymers of vinyl acetate and a polyethylene terephthalate film, with a darden chloride and acrylonitrile, polyvinyl acetate, mixed on layered layer with a semiconductor, dispersed polymers of vinyl acetate and vinyl chloride, poly-gated in one Binders. Such conductive vinyl acetals, e.g. B. polyvinyl butyrals, polyacrylic acid capable layers with and without insulating separating and methacrylic acid esters, z. B. polymethyl methacrylic layers are described, for example, in the USA patent, poly-n-butyl methacrylates, poly (isobutyl methacrylates) 3,245,833.

aicylates) and the like, polystyrenes, nitrated polystyrenes, other particularly advantageous conductive layers Polymethylstyrenes, isobutylene polymers, polyesters, can be made from the sodium salts of carboxy ester ore. B. Polyäthylenalkaryloxyalkyleneterephthalaten, Phe- lactonen of polymers from maleic anhydride and Molformaldehyde resins, ketone resins, polyamides, vinyl acetate are produced. Procedure for Her-Pol carbonates, polythiocarbonates, poly- (ethylene- 40 position of such conductive layers are with glycol-bishydroxyäthoxyphenylpropanterephthalaten). for example in US Patents 3,007,901 and copolymers of vinyl haloarylates and vinyl 3,267,807.

acetate, e.g. B. Copolymers of vinyl-m-bromo-The electrophotographic recording material benzoate and vinyl acetate and the like. Processes for the manufacture of materials according to the invention can be used within the scope of Such binders are disclosed in numerous 45 commonly known electrophotographic process patents described. So is the production of ren, to carry out photoconductive layers Styrene-alkyd resins from the USA, for example, are required. Such a patent specification 2,361,019 and 2,258,423 known. driving is the well-known xerographic process. Other types of suitable binders, which can be used for As already explained, in such a forex Preparation of Photoconductive Recording Material- Graphic Processes Using Electrophotography rialien can be used according to the invention, are initially electrostatically charged with material, inderr for example paraffin and mineral waxes. pass it under a corona discharge

For the production of the electrophotographic recording. The charge is sliding on the photoconductive

Drawing materials according to the invention can due to the insulating properties of the layer

also the most varied of customary known solutions, i.e. the low conductivity of the layer in the dark

Medium used, such as benzene, retained. The electrostatic charge on de

Toluene, acetone, 2-butanone, chlorinated hydrocarbons- surface of the photoconductive layer is dam

substances, e.g. B. methylene chloride and ethylene chloride, selectively derived by eil the surface

further ether, z. B. tetrahydrofuran, as well as mixtures is exposed slide, for example after the be

this solvent. 60 knew contact copying processes or through lenses

When making the electrophotographic projection, creating on the photoconductive layer

Recording materials should contain the proportion of photo- a latent image is generated. By exposure

Conductor at least about 1 percent by weight, based on the surface of the photoconductive record:

the coating compound or the layer. The materials in this way becomes the charge of the photc

upper concentration limit of the photoconductor can be very 65 conductive layer in relation to the intensity d (

to be different. Is derived for the production of the photoconductive radiated light. That on d <

capable material of the invention a binder, photoconductive layer, remaining charge pattern <

then the proportion of the photoconductor in the or latent image can then be developed, i.e. h., visible

ίο

Made by electrostatically applying to the layer it became absorbable in a cold ammonium chloride solution Particles of optical density applied stirs. The dark red ethereal layer obtained will. The electro- used for development was dried over anhydrous sodium sulfate, Static attractable particles can be in the form of a blue residue, which after removal of the Dust, e.g. B. a powder, pigment in a resinous 5 solvent was obtained in 20 ml shaped binder, d. H. a toner, or dissolved in a chloroform, whereupon 400 ml of the solution becomes liquid Developer can be applied to which absolute alcohol has been added. In one with the developer particles being in a liquid, rotating vacuum reactor, the entire volume was electrically insulating binders are located. Develop- ment reduced to about 300 ml, whereupon the solid settlement process of this type are known and are filtered off, washed and in the air at room for example in U.S. Patent 2,297,691 and temperature dried. There were 18.4 g of one in Australian Patent 212,315. solid white mass obtained. The reaction product

In the case of electrophotographic reproduction processes, 450 ml of ligroin and then

ren, e.g. B. xerographic processes in which to recrystallize again from 425 ml of ligroin. It was

Development particles are used, of which 15 represent the 10.8 g reaction product in the form of a solid

a component of a low-melting white mass with a melting point of 132 to

If it is made of resin or plastic, it is possible to obtain the ent- 134.5 "C.

wrapped photoconductive material from the action of "" _. , ·,, To expose to heat and thereby ^{fix the developer powder B} > Production of triphenyl-p-diethylammophenyl permanently on the surface of the photoconductive layer. In other cases, a transfer of the developed image from the photoconductive mixture of 1.44 g (0.06 mol) of magnesium shavings, capable layer onto a second receiving layer of 30 ml of distilled tetrahydrofuran and 4 , 6 g (0.02 mol) follow, the distilled p-bromo-N, N-diethylaniline used in the transfer being the final copy for 15 minutes. 25 lug heated to reflux temperature. The volume of such processes are known and are used in the reaction mixture was then reduced to about half by means of a water feature in the USA. Mixture at reflux temperature for 1 hour, vol. 15 (1954), pp. 469-484. was heated. The temperature was then reduced to below

The electrophotographic recording material reduced 3 ° half reflux temperature, whereupon the

the invention can be used in the context of reproduction mix quickly with a solution of 7.7 g (0.02 mol)

processes are used in which the various triphenyltin chloride in 50 ml of distilled tetrahydro-

most types of radiation are used, d. i.e., furan was added. The obtained mixture became

electromagnetic radiation as well as nuclear radiation then heated to reflux temperature for 1 hour

lungs. This means that the photoconductive layer is left to stand over and over. Thereupon

Drawing material of the invention, for example, was not in 1 liter of a stirred mixture of ice and

only in the context of xerographic processes, but ammonium chloride filtered. The failed low

also in the context of xeroradiographic methods, the propulsion was dissolved in 320 ml of absolute alcohol,

can be turned. whereupon the solution cooled to room temperature and

In the following, the production of some, 40 was first filtered. The filtrate was in a refrigerator

for the production of an electrophotographic cooling, whereupon it is filtered and the precipitated low-

Drawing material according to the invention suitable blow was dried in air at room temperature.

Photoconductor are described. 4.4 g of white crystals were obtained. The crystals

,,,,, were recrystallized from 125 ml of absolute alcohol.

A) Preparation of p-dimethylaminophenyl-Tnphenyl ^ _{In this wdse were 2J g reac} ti _on sprodukt with

stann at _a melting point of 100.5 to 102 ^r C.

To a "" .. _, ._

Mixture of 1.96 g (0.28 gram atoms) lithium- C) Preparation of tetra-p-diethylammoplumban

wire and 400 ml of dry diethyl ether after a mixture of 6.5 g (0.27 mol) of magnesium,

Mallinckrodt was within 10 minutes 50 20.5 g (0.09 mol) of distilled p-bromo-N, N-diethyl

a solution of 26 g (0.13 moles) of p-bromo-N, N-di-aniline and 90 ml of distilled tetrahydrofuran became

methylaniline was added in 1000 ml of dry ether. while stirring vigorously for 45 minutes

The resulting mixture was then heated to flow temperature for 15 minutes and then with a mixer

heated on a steam bath. Thereupon approximately 11.1 g (0.04 mol) of lead dichloride and 60 ml were distilled

Fähr 1 g of a lithium dispersion is added, whereupon 55 tem tetrahydrofuran is added. The received dark

the mixture was heated to reflux temperature. brown reaction mixture was then lanj for 8 hours

The mixture was then heated to reflux on a steam bath. The reaction measures

narrowed to ¹ U of its original volume. To was left to stand overnight and then filtered

At this point in time the reaction started and the reac- From the filtrate separated after about 15 to 20 ml

The mixture turned out to be white crystals for about 30 minutes without standing for 60 minutes. The crystal

drove external heat to reflux. These were filtered off, whereupon the filtrate was poured into a mixture

The brown mixture obtained was then added to about 3 liters of an ice-ammonium chloride solution

IV heated and stirred at reflux temperature for _{2 hours.} At room temperature, the mixture was

then extracted through glass wool into a vigorously stirred then with 300 ml of chloroform. The chlorine Mixture of 44.6 g (0.116 mol) of triphenyltin chloride 65 form extract was over anhydrous sodium sulfί

and filtered 200 ml of ether. The reaction mixture dried, whereupon the solvent in vacuo

was stirred at room temperature for 3 hours. The oil obtained was in 25 n

and then left to stand overnight. Then stirred in absolute alcohol, whereupon filtered, m

11 12

Acetone washed and recrystallized from 45 ml of acetone G) Production of bis (p-diethylaminophenyl) -

was sated. There were obtained 0.35 g of white crystals having a melting point phosphine oxide 220.5 to 221.5 ⁰ C.

A homogeneous mixture of 37.5 g (0.276 moles)

D) Preparation of tri-p-dimethylammophenylarsine 5 phosphorus trichloride and 33.1 g (0.222 mol) Ν, Ν-di-

ethylaniline was for 2.5 hours on a steam

A mixture of 26.8 g (0.222 mol) Ν, Ν-dibade was heated, whereupon the reaction mixture was cooled to space methylaniline and 50 g (0.276 mol) arsenic trichloride and slowly stirred in was heated on the steam bath for 2 hours and 1 Liter of water was poured. The resulting solution then poured into 800 ml of water while stirring. io was then was then filtered by addition of 300 ml of 10 ° / ₀ sodium The resulting mixture was made alkaline followed by sodium hydroxide solution and the filtrate by the addition of about 350 ml of a two 100-ml portions of methylene chloride. Made the 10 ° / ₀ sodium hydroxide solution alkaline combined extracts was dried over anhydrous. The gummy precipitate, which dried from sodium sulfate, whereupon the solvent separated, was washed with ligroin and then stripped off on a steam bath. The back-200 ml of methylene chloride dissolved. The solution was remaining oil was dried in 200 ml of boiling ligroin over anhydrous sodium sulfate, whereupon the mixture was stirred, whereupon it was filtered while hot and the filtrate was removed from the solvent in vacuo. The room temperature was cooled. In this way, residue was recrystallized from a mixture of 50 ml of abso- 0.34 g of white crystals with a melt alcohol and 20 ml of chloroform. 20 point 126.5 to 128 ⁰ C received. The recrystallized reaction product was then The following examples are intended to further describe the invention in air at room temperature. To illustrate this. Way were 0.94 g of white crystals with a
Melting point of 237 to 24O ⁰ C obtained. example 1

_ _x , _T. , _. ,. . ,. There were coating compositions of the following

E) Manufacture of Tn-p-diethylaminophenylarsine components made:

While stirring, a mixture consisting of. .

8.64 g (0.36 mol) magnesium, 27.6 g (0.12 mol) distil photoconductor u, i3 g

lated p-bromo-N, N-diethylaniline and 120 ml of distilled binder 0.50 g

Lated tetrahydrofuran, put on reflux sensitizer 0 002 2 for 1 hour temperature heated. The brown mixture obtained

was then added dropwise with methylene chloride 5 ml over 10 minutes

a solution of 7.3 g (0.04 mol) of arsenic trichloride in

70 ml of distilled tetrahydrofuran were added so that the mixture was then further refluxed. On by hand on a conductive layer of the sodium, heating was continued for 2 hours, whereupon the salt of a carboxy ester lactone is prepared, as described in the mixture in a stirred mixture of ice and US Pat. No. 3,120,028, which is filtered through an ammonium chloride solution became. The yellow precipitate again deposited on a conventional cellulose acetate film support was located in air at 4 °, applied in such a way that layers of room temperature were dried and then obtained from a thickness, measured wet, of 0.010 cm. Mixture of 500 ml of absolute alcohol and 300 ml. The elements obtained were then recrystallized from a Tem-chloroform. There were 11.1 g obtain a temperature kept of 32.2 ⁰ C, yellow solid precipitate. The finished elements were then carried out with a positive recrystallization from a mixture of 600 ml of 45 tive or a negative corona discharge alcohol and 300 ml of chloroform, 7.6 g of one were carried out until the surface potentials, like white crystalline reaction product with one obtained by measurement with an electrometer, about melting point of 211.5 to 214 ° C. 600 V reached.

The photoconductive recording

F) Production of 2-methyl-4-dimethylaminophenyl 5 <> materials were then by means of a 3000 ⁰ K-

arsine oxide tungsten light source through a gray scale level

tray exposed. The exposure caused a «

A mixture consisting of 20.3 g (0.15 mol) reduction in the surface potential of the record

Ν, Ν-dimethyl-m-toluidine and 27.0 g (0.15 mol) of arsenic depletion material under each level of the gray scale of

The trichloride was reduced to its original potential V ₀ for 20 minutes on the steam bath

heated, whereupon the reaction mixture with stirring potential F, the exact value of which depends on the irradiated

was poured into 1 liter of water. The solution obtained depends on the amount of light in lux.

was then by adding 180 ml of a 10 ° / ₀ igen The results of the measurements carried out wui

Sodium hydroxide solution made alkaline. The out- plotted in a diagram in which di

Any precipitate was then measured with ligroin. 60 Surface potentials V for each exposure level

wash and then applied in a boiling mixture against the logarithm of the exposure

dissolved by 50 ml of ligroin and 17 ml of chloroform, wor- was.

on the total volume by concentrating to 45 ml The so-called shoulder sensitivity is de

was decreased. Overnight, a yellow numeric expression separated by 10 ⁴ multiplied by dei

solid precipitation, which in air at room temperature 65 inverse value of the exposure in meter-candle-secui

door was dried. In this way, 0.47 g was obtained which is required to reach the surface potential

To reduce reaction products with a melting point of 214 from 600 V by 100 V,

up to 217 ° C. The sensitivity in the sag area ά

13th

The density curve is the numerical expression of A 10 ⁴ multiplied by the inverse of the exposure B, in meter-candle-seconds, required to reduce the V high surface potential to 100 volts. 5 C

The sensitivities of the various photoconductive recording materials made from the following table I. In the table, the letters A, B and C mean the following:

no sensitizer was used; 2,6-bis- (4-ethylphenyl) -4- (4-amylo.xyphenyl) -thiapyrylium perchlorate was used as a sensitizer used;

2,4-bis- (4-ethylpheny!) - 6- (4-styrylsytryI) -pyrylium perchlorate was used as a sensitizer used.

The binder consisted of [4,4'-isopropylidenebis (phenyloxyethyl) -co-ethylene terephthalate].

Table I. example

Photoconductor

Sensitizer Positive
sensitivity
on the shoulder A.
B.
C. 160
200
400 A.
B.
C. 10
500
320 A.
B.
C. 5
630
250 A.
B.
C. 400
120
400 A.
B. 12th
100 B.
C. 40
50 A.
B.
C. 32
160
250 A.
B.
C. 23
250
230 B. 120 B.
C. 50
200

a)

b)

d)

e)
f)
G)

H)

Methyl-diphenyl-p-diethylaminophenylsilane. Triphenyl-p-dimethylamiiiophenylstannane .. Triphenyl-p-diethylamino-phenylstannaii .... Diphenyl-di- (p-diethylaminophenyl) -stannane

Triphenyl- (p-diethylaminopheny]) plumbane.

Tetra-p-diethylaminophenylplumban

Tri-p-dimethylaminophenylarsine

Tri-p-diethylaminophenylarsine

2-methyl-4-dimethylaminophenylarsine oxide. Tri-p-diethylaminophenyl bismuthine

Example 2

The procedure described in Example 1 was repeated with the exception, however, that the coating compositions were composed as follows:

Photoconductor: 0.97 ■ 10- ³ MoI per g of solids in the coating mixture, sensitizer: 2%, based on the weight of the coating composition and binder: 6.0 g.

The sensitizer used consisted of 4- (4-bis- [2 - chloroethyl] - aminophenyl) - 2,6 - diphenylthiapyrylium perchlorate.

The binder consisted of a polycarbonate

resin made by reacting phosgene with a dihydroxydiarylalkane or made by Ester exchange between diphenyl carbonate and 2,2-bis-4-hydroxyphenylpropane.

The sensitivities obtained are shown in Table IT below.

Table II example

Photoconductor 100 volts, sensitivity im

Slack area of the blackening curve

Positive I negative

a)
b)
c)
d)
e)

Methyldiphenyl-p-diethylaminophenylsilane .. Triphenyl-p-dimethylaminophenylstannane ..

Triphenyl-p-diethyl-aminophenylstannane

Diphenyldi- (p-diethyl-aminophenyl) -stannane Triphenyl-p-diethylaminophenylplumbane ... Tri-p-diethylaminophenylarsine

120 950 150 1100 250 3400 1400 2000 380 630 230

Example 3

With the coating compounds described in Examples 1 and 2, further layer substrates, as described in Example 1, coated. In a darkened room, the surfaces were the photoconductive layer charged to a potential of about +600 V under a corona discharge. The layers were then covered with a transparent sheet that was opaque and translucent

Districts, and then with the light of an incandescent lamp with an exposure of about 807 lux exposed for 12 seconds. The electrostatic latent images obtained were then in Usually developed by cascade development. A mixture of negatively charged, black, thermoplastic toner particles and glass beads are used. In all Cases, excellent reproductions of the original were obtained.

Claims (6)

changed with the amount of external radiation incident in the case of image-wise exposure. To carry out electrophotographic processes 1. Electrophotographic recording material - such a photoconductive recording material rial of optionally a layer support and 5 usually initially uniformly charged, and a photoconductive layer with a metal - although usually in the dark after a certain organic photoconductor and optionally a dark adaptation. Thereafter, the recording sensitizing dye, thus identifying material exposed image-appropriately with actinic radiation, that there is a metalet as a photoconductor, which leads to the potential of the surface organic Connection with a metal atom of the io charge in relation to the amount of light irradiated Group IVa or Va of the periodic table which is reduced. Something latent remains on the surface Elements to which at least one aminoaryl radical has an electrostatic image, bound to its visible is, contains. making the surface of the recording material 2. Recording material according to claim 1, with so-called electroscopic development characterized in that it can be brought into contact with a 15 lung material as a photoconductor. That An organometallic compound with a metal developing material, also called a toner, can entatom of group IVa of the periodic table of neither in an insulating liquid nor on a Elements to which at least one aminoaryl radical is applied to the dry carrier and at least one hydrogen atom becomes an alkyl group. The toner particles are exposed on the or an aryl radical are bonded contains. 20 surface knocked down, whereupon sic permanently 3. Recording material according to claim 1, da- fixed, for. B. by the action of heat, pressure or characterized in that it acts as a photoconductor to a solvent vapors, or to an image-receiving organometallic Connection with a metal material on which they are transferred in entatom of group Va of the periodic system can be fixed in a speaking way. Possibly Elements to which at least one aminoaryl radical 25 can generate latent electrostatic images and at least one hydrogen atom, an acidic transferred to an image receiving material and on substance atom, an alkyl radical or an aryl radical bound to this are developed. are, contains. For making such electrophotographic 4. Recording material according to claim 1 recording materials are the most varied or 3, characterized in that the metal 30 photoconductive, insulating compounds use atom as an aminoaryl radical an aminophenyl radical and bar. So it is z. B. known, vapors of selenium or as an alkyl radical an alkyl radical with 1 to 8 carbon contains vapors of selenium alloys on suitable laminate atoms. to knock down carriers or photoconductive zinc 5. Recording material according to claim 4, oxide in the form of a dispersion in a resinous, characterized in that it can be used as a photoconductor 35 film-forming binder. It is further Tri-p-diethylaniinophenylbismuthin, triphenyl known, organic compounds of the most varied To use p-diethylaminophenylsilane, methyl-diphenyl-p-di-type as a photoconductor. Typical suitable äthylaminophenylsilan, triphenyl-p-diethylamino-organic photoconductors are z. B. triphenylamines and phenylgerman, triphenyl-p-dimethylaminophenyl-triarylmethane leuco bases. stannane, triphenyl-p-diethylaminophenylstannane, 40 Transparent ones have proven to be particularly advantageous Diphenyldi- (p-diethylaminophenyl) stannane, tri- or clear electrophotographic recording phenyl-p-diethylaminophenylplumban, tetra-p-di- materials with a content of photoconductors have been proven, äthylaminophenylplumban, Phenyldi- (p-diethyl- as these may be through the transparent aminophenyO-phosphine, bis- (p-diethylaminophe- layer support can be exposed through it, see above) nyl) -phosphine oxide, tri-p-dimethylaminophenyl- 45 that a high flexibility with regard to technical arsine, tri-p-diethylaminophenylarsine or 2-methane, e.g. B. copier is achieved. Also contains thyl-4-dimethylaminophenylarsine oxide in this way are electrophotographic 6. Recording material according to claim 1, since recording materials can be produced according to Gedurch marked that it can be reused as a sensitization consumption after removal of the dye a pyrylium, thiapyrylium or selenium 50 toner applied during development contains apyrylium salt. Transfer and / or purification. From the German patent specification 1 113 360 are already for electrophotographic and electroradio- recording material for specific graphic purposes 55 lines known whose photoconductors consist of organometallic compounds and which may have sensi- The invention relates to an electrophotographic containing bilizing dyes. Disadvantage of the However, recording material made of a known organometallic photoconductor is, if necessary, Layer support and a conductive layer with that they are only in the form of suspensions on layer an organometallic photoconductor and a given carrier can be applied, which is known to lead to if a sensitizing dye. that after evaporation of the It is known e.g. B. from the USA patent sion solvent used comparatively un- 297 691, for carrying out electrophotographic uniform, light-scattering, corpuscular photoconductive Procedure, e.g. B. so-called xerographic process-capable layers are obtained that have a comparative referring to photoconductive recording materials, they result in poor image resolution, turn, which consist of a substrate on which there is therefore a need for more than a layer of a normally insulating photoconductor which can be used organic compounds, Material is applied, the electrical resistance of which, however, complicates the fact that