DE1772775C - Electrophotographic recording material - Google Patents

Description

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äthvlaminoprii'n-.Küan. Tnpheiv.l-p-diäihviaminophenvlgerrp n. Triphenvi-p-dimethvi-amuphenylstannane. ί'nphen>! - p-diäih \ i ^ minophenv ^ iannan. f) iphen> Idi- (p-uuV, h> lamini'phen \ l) -; iannar .. Tnphenvl-p-diaiir.bminnpnenvlplurnbun. Teira-n-dieth \ laminophen> lplumbap. Phen> .di (p-dieth \ i-.nninophenvli-pho-phi:!. His-ip-diethylarninuprien> l) -phosph'ine oxide. Tri-p-dirnethylaminophcnvlar-sin, Tri-p-diethylamine phenylarvn or 2-Nieth > l-4-dirr, e'hvlaminophen> lar5inoxid contains.

6. Auf / eichnung> material according to claim 1. thereby known / eichne :. that it is used as a sensitizing dye a pyrvlium. Thiapv rviium or Selenapyryhur malt contains.

The invention relates to an electrophotographic) Recording material optionally comprising a support and a photoconductive layer an organometallic film and optionally a sensitive dye.

It is known e.g. B. au-j of U.S. Patent 297,691 for performing electropholographic Procedure, e.g. B. so-called xerographic processes. to use photographic recording materials, which consist of a substrate on which a layer of a normally insulating Material is applied, the electrical resistance of which

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phuto'carjhigen. ! -. oliertiidcn compounds vcrAe ·· - .. ^ ar Sf; it e- /. iJ. known. Uanipie dts Se'eri ■■; ·· iJän ^ pfe son Se! En! Eg: find out on suitable St!:,.
hooligans down / u-chock or photo-conductive-j /; · ".
ο wc m form a dispersion in a har / arn / e. filrnbiidenden BmdemiUel / u serv.enden. I: s is fe ^r htkanni. organic compounds of the different ..
T \ p-. ah use photoconductor / u. Typical geig'- ··, organic photoconductors are /. H. I riphenylamine ■■. ■ : trivalent methane leuco bases.

ASs b-esunders advantageously have transparent. "· Or clear electrophotographic records. ·: -
materials with a content of photoconductors.
as these where appropriate d'irch the tran ^ PARL _L ■ · substrate werdei exposed through. be able. .. that a high degree of flexibility with regard to technical \. equipment, z. Ii. Copier., Achieved v. .r ·. ' Further, consumption are suitable for further use in this Wei> c clektrophotographi eiie-up / eichr.üP.gsmaierialien herstellbyr that rj by (d ^ after removal in the development of applied toner by the transfer and / or cleaning.

From the German patent specification 1 113 360 ^ ind also beiei'.s for electrop! .. biographical and electroradu graphic Purposes of certain recording mechanisms known whose Pholeiier consist of organometallic compounds and the optionally sensitizing dyes contain. However, there is a disadvantage with the known organometallic phctoconductors. that they: v.: r can be applied to the substrate in the form of suspensions, which is known to lead to that after evaporation of the to produce the suspension The solvent used is comparatively inconsistent, light-scattering, corpuscular photolei; -capable Layers are obtained which result in a comparatively poor image resolution.

There is therefore a need for further organic compounds that can be used as photoconductors, whereby, however, complicates the fact that

! \ oraiiv »agen läßl. ohome or ^ m 1 ler-ileiiiing elcktrop'ioii ».: Rap! ili can be used.

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V.ifgabe of the invention is e-. e .-e elektroiv.ot to be produced. . huungsiiimaterial with koniinuicrh ! u'.itei image resolution fiiiirendei : Ju to indicate, which is characterized by high PhoOenipfmd- ; r.ei: from / hnel and both poM! ". nk .mch nesiaaufladen lets, as well as further both to the Durehfüh- ■ • j '.on Rellex- as well as from Birc'icv. experience the-

f) a heterocyclic radical and

G! an organometallic radical with a metal aom from the G.-uppe IVa or Va des Periodisches System of elements.

Advantageous photo for the production of the photoconductive tool Recording material according to the invention can be seen again by the following structural formulas :

i> he invention is based on the knowledge that dali , .e specified task in particularly advantageous V · -. ■> e can thereby be solved. dali as photo egg metall-ο .;.,! Nice connections with a precisely defined structure \ _ ■ - ·. ·. will end.

The subject matter of the invention is a clektrophototpiiisches AufnahmiHing ^ matenal from optionally e '.-' Vi layer support and a bioconductive layer ^ u r. an organometallic photographic egg and sie'oet i.ills a sensitizing dye, which thereby; is drawn. As photo conductor, it is a metallic compound with a metal atom of the (ippe IVa or Va of the Periodic System of the Elements, to which at least one Ammoarvir residue is attached).

The group ^ denoting corresponds to the eriodic system of the 1 leinei.ie. like it for example in the »Handbook of C'neniistry and Physics ··. : io ν output. Pp. 394 and 395 is indicated.

Metals of groups IVa and especially of the periodic '.stems of the elements are thus silicon. Germanium. 'mn and lead from group IVa and phosphorus. \ rsen. Antimony and bismuth from group Va.

The invention achieves that electro-miolographic recording materials are available which are characterized by versatility, high photoconductivity and ease of manufacture and / u lead to a high image resolution, since their photoconductive layers are very uniform and not corpuscular are due to the fact that they can be produced from photoconductor solutions.

The organometallic compounds that can be used Photoconductors can be substituted on the metal atom by a wide variety of substituents, however should at least one of the Siibstiiuenlen an Aniinoary'rest being.

The Atnmoresl can be in any position of the 5 » aromatic ring or nucleus. Particularly good results are obtained when the aryl radical is a phenyl radical and if there is also the amino radical 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 substances:

Ar

T-Ar- M, _1: D

T Ar NU,

(It

(2)

(3)

Ar

M .. M

Ar

(4)

T Ar M ,.

Jl

T Ar M "

M ".

a) a hydrogen, sulfur or oxygen atom,

b) an alkyl radical.

e) an optionally substituted aryl radical, /. B. an aminoaryl, alkylaryl or (lalogenaryl radical,

d) an oxygen-containing residue, /. 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,

(M, Herein mean:

E. Ci. E and Q a) each represent a hydrogen atom.

b) in each case an optionally substituted aryl radical. /. B. each one Phenyl radical, a naphthsyresi. a dialkylaminonaphthyl radical or a dialkylaminonaphthyl radical. each having preferably I to 8 carbon atoms in the alkyl groups,

c) in each case one alkyl radical with 8 carbon atoms,

d) each an alkoxy resl with 1 hi ¹ S carbon atoms.

e) one aryloxy radical each. z. H a phenoxy radical.

Π each one amino residue of the enormous

wherein R, and R., hydrogen atom

are or alkyl mil I to S carbon atoms, or g) each have a hcierocveliselien radical having 5 to (ι Ringalomen which at least one is a nitrogen atom lsi ie for example, a triazolyl or a Pyridylresi:... ^T a Aminore.st / B. a.. Alkylaminores! With 1 to 5 carbon atoms or an Arvlamino radical, 7. a Phonvlaminoresi: Ar an aromatic radical. /. B. a

Phenyl or Niiphlhylresi: M ₀ , and Ma. same oiler different metals the

Group IVa of the Periodic Table of the Elements:

Mb a metal from group Vn of the Periodic Table of the Elements; D a radical of the meaning given for F. (i. L and Q sovv'e also an organometallic radical with a metal atom from group IVa of the Periodic Table of Elements or, together with F., an oxygen or sulfur atom and J a radical the meaning given for E, G. L and Q sou ie additionally together with E an oxygen or sulfur atom.

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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-diethvlaminophenylsilane.

Triphei.yl-p-diethylaminophenylgerman.

Triphenyl-p-dimethylaminophenylstannane,

Triphenyl-p-diethylaminophenylstane,

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

Triphenyl-p-diälhy la minopheny IpIu mban.

Tctra-p-diethylaminophenylplumban.

Phenyi-di- (p-diethylaminophynyl! -Phosphine.

Bis-ip-diethylaminophcnyD-phosphinoxide.

Tri-p-dimethylaminopheny larsine. ⁴ "

Tri-p diet hy laminrnheny larsine,

2-methyl-4-dimethylaminophenylarsine oxide.

Tri-p-diethylami.iophcnylbismuthin,

Methyl-di- (p-diethylaminophynyl) arsine,

Methyl-di- (p-diethylaminophenyl (-phosphine.

Diphenyl-p-diethylaminophenylsilane,

p-diethylaminophynylarsiri,

Telrakis- [diphcnyl- (p-diethy la minopheny I) -

pltimbylj-methane,
Tetrakis- [diphenyl- (p-diethylaminophenyl) -

stannylj-stannan.

Bis- [phenyl- (p-diethylaminophynyl)] - dibismuthin Tri-ip-diäthylaminophcnyll-phosphinsuHid and Di-tp-diethylaminophenyO-thioxotin.

The organometallic photoconductors required for the production of an electrophotographic recording material according to the invention can be produced by known processes. For example, the aminoaryl bond compounds and the aminoaryltin compounds according to the )? JACS. 54, 3726 9 (1932), or according to the method described in J. Org. Chcm. 15, p. 994 (1950). described procedure

55

60 can be made. The aminoarylgcrmanium compounds can be prepared according to the method described in CA. 60. p. 395d, described method .-> be aesthetized. The production of Ammoarylbismuthinen is for example in JACS. 03. pp. 207 to 211 (1941). Amiiioarylderi'.atc des .Arsens can after the in J. Indi.'n Uiemical Soc. 10. pp. 515 to 518 (1939), described methods can be synthesized. Phosphorus and antimony contained compounds with Aminoarylresicn can in turn, for example, according to the in CA. 28, pp. 3392 ³ , and CA. 40, p. 46S9 ⁶ , processes described.

The electrophotographic recording materials of the invention can be known in a conventional manner t: r \ Vci..e be made, d. h .. for example through Mixing a dispersion or solution of a photoconductor with a binder, if this is necessary or desirable, and applying the obtained Dispersion or the Beschiciunngsmasse on a layer support or optionally shaping the Coating compound for a self-supporting carrier For the production of the photoconductive recording material After the discovery, a mixture of L can also be used. the photokiter is used. Furthermore, you can ;: the photoconductors used as required, if applicable be mixed with other known photoconductors.

The clektrophotographischc recording maieria: according to the invention may also contain customary additives, such as in particular compounds, which change the spectral sensitivity of the material, especially sensitizers or Sensitizers for the photoconductor.

To sensitize those used as intended A wide variety of known sensitizers are suitable for photoconductors. As particularly beneficial Sensitizers have been shown to be derived from pyryliuin-. Consist of thiapyrylium or selenapyrylium salts, as described, for example, in U.S. Patent 3,250,615.

Other suitable sensitizers are, for example, fluorenes, e.g. 13. 7,12-dioxo-13-dibenzo (a, h) fluorene: 5,10-dioxo-4a, l-diazaben / o (b) fluorene; 3,13-dioxo-7-oxadibenzo (bg) fluorene; Trinitrofluorcnon, Telranitrofluorenon 11. The like. Further suitable sensitizers are, for example, aromatic nitro compounds, such as are used, for example, in US Pat. In U.S. Patent 2,610,120, anthrones, e.g. B. the from US ^{Pat. No. 2,670 2. r} t5 known anthrones, quinones, wiv. : .ic are known from U.S. Pat. No. 2,670,286, for example. Benzophenones. Compounds known from U.S. Patent 2,670,287. Thiazoles, e.g. B. of the type described in USA.-Palentschrift 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. Triphenylmcthan-, Diarvimclhan-, thiazine, azine, oxazine, xanthene, phthalein, acridine, azo, anthraquinone dyes and the like.

Except pyrylium, tliapyrylium and selenapyrylium salts in particular fluorenes and carboxylic acids and triphenylmethane dyes have proven themselves as proved particularly advantageous sensitizers.

If a sensitizer is used to produce the electrophotographic recording material, in the usual way this can be

mass or those used to make rinrs

Element used mass are incorporated. To prepare an electrophotographic Aufzeichniingsmatcrials after ^Q: However, the use of a sensitizer is * not essential .rlindung. However, since even small amounts of sensitizer generally lead to a substantial increase in electrophotographic sensitivity, it is preferred to use sensitizers. The optimal amount of a sensitizer in individual cases can vary widely. It depends on the particular sensitizer used and on the photoliter to be sensitized. In general, it has been found to be expedient to use the sensitizers in concentrations of from about 0.0001 to about 30 percent by weight, based on the weight of the film-forming coating composition. The sensitizers are preferably used in concentrations of from about 0.005 to about 5 percent by weight, based on the total weight of the coating composition.

For the production of the electrophotographic recording materials the invention, the customary known film-forming, polymeric binders are suitable, which have a suitable dielectric strength and which are good electrically insulating, film-forming Are carriers or binders. Suitable binders consist, for example, of Slyrol-Buladien-Mischpoiymerisaten, Siiiconharzen, Siyroi-Aikydiiärzeü, SiIicon-Alkydharzen, Soy alkyd resins, polyvinyl chloride, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, polyvinyl acetate, copolymers of vinyl acetate and vinyl chloride, polyvinyl acetate «!, z. B. polyvinyl butyral, polyacrylic and methacrylic esters ^ z. B. Polymethylmethacrylatcn, Poly-n-butyl methacrylates, poly (isobutyl methacrylates) and the like, polystyrenes, nitrided polystyrenes, polymethylstyrenes. Isobutylene polymer, polyesters, z. B. Polyäthyienalkaryloxyalkyleneterephthalaten, phenol-formaldehyde resins. Ketone resins, polyamides, polycarbonates, polythiocarbonates, polyethylene glycol bishydroxyethoxyphenylpropane terephthalates), Copolymers of vinyl haloarylates and vinyl acetate, e.g. B. copolymers of vinyl m-bromobenzoate and vinyl acetate, and the like. Methods of making such binders are known in numerous Patent specifications described. For example, the production of styrene-alkyd resins can be found in the USA patents 2 361019 and 2 258 423 are known. Other types of suitable binders that can be used Making use of the photoconductive recording materials according to the invention are for example Paraffin and mineral waxes.

For the production of the electropholographic recording materials According to the invention, a wide variety of customary known solvents can also be used used, such as benzene, toluene, acetone, 2-butanone, chlorinated hydrocarbons, z. B. methylene chloride and ethylene chloride, also ether, z. B. tetrahydrofuran, and mixtures this solvent.

In the production of the electrophotographic recording materials, the proportion of photoconductor should be at least about 1 percent by weight, based on the coating compound or the layer. the upper concentration limit of the photoconductor can be very different. Used to make the photoconductive Material of the invention uses a binding agent, the proportion of the conductive agent in the photoconductive layer can be about 1 to about 99 percent by weight. The proportion is preferably Photoconductors on the sealing ground or on the photoconductive layer 10 to about 60 percent by weight.

The photoconductive layers can have the usual thickness. Usually they have photo-sharing capabilities Layers on supports a thickness of about 0.00254 to about 0.0254 cm, measured before drying. The layer thicknesses are preferably about 0.005 to about 0.015 cm, measured before drying, although of course also photoconductive recording materials with photoconductive layers other strengths may be beneficial.

The support of the electro-holographic recording material of the invention may consist of any of the conventional for making photoconductive Recording materials consist of known substrates, d. H. from any of the familiar usual electrically conductive carrier, for example made of paper at a relative humidity above 20% Aluminum paper laminates, metal foils, e.g. B. aluminum and zinc foils, Metallplattcn, for example Aluminum, copper, / ink. Brass and galvanized plates or made of layers by deposition generated by metal vapors, such as silver and aluminum vapors.

As a particularly advantageous! Eitep.de carrier have those proven to consist of a carrier such as a polyethylene terephthalate film with one thereon layered layer with a semiconductor dispersed in a binder. Such conductive Layers with and without an insulating separating layer are described, for example, in the USA patent 3,245,833.

Other particularly advantageous conductive layers can be made from the sodium salts of carboxy ester lactones of polymers made from maleic anhydride and vinyl acetate. Method of manufacture such conductive layers are described, for example, in U.S. Patents 3,007,901 and 3,267,807.

The electrophotographic recording materials according to the invention may experience within the übl'chen known electrophotographic ^v, are required for their implementation photoconductive layers may be used. One such method is the well-known xerographic method.

As already stated, in such a xerographic process the electrophotographic Material is first electrostatically charged by passing it through a corona discharge will. The charge is on the photoconductive layer due to the insulating properties of the layer, d. H. the low conductivity of the layer in the dark. The electrostatic charge on the Surface of the photoconductive layer is then selectively derived by passing the surface through a Slide is exposed, for example by the known contact copying process or by lens projection, thereby forming a latent image on the photoconductive layer. Because of the exposure of the surface of the photoconductive recording material * in this way, the charge becomes the photoconductive Layer derived in relation to the intensity of the irradiated amount of Liclit. That on the Charging pattern remaining in the phospholite-capable layer or latent image can then be developed, i.e. i.e., visible

309 618/228

can be made by applying electrostatic to the layer attractable particles of optical density are applied. The / ur development used, electrostatic Attached particles can be in the form of a dust * ·, /. B. a powder. Pigment in a resinous form Binder, d. H. a toner or a liquid developer, wherein the developer particles are in a liquid, electrically insulating binder. Development process of this type are known and are described, for example, in U.S. Pat. No. 2,297,691 and in Australian Patent 212,315.

In electrophotographic reproduction processes, e.g. B. xerographic processes in which to Development particles are used, one of which is a component from a low melting point Resin or plastic, it is possible for the developed, photoconductive material to be exposed to Exposing heat and thereby making the developer powder permanent on the surface of the photoconductive Fix layer. In other cases there may be a transfer of the developed image from the photoconductive Layer made on a second receiving layer, the one used in the transfer Recording material is the final copy. Such processes are known and are exemplified see in U.S. Patents 2,297,691 and 2,551,582 and in the journal "RCA Review", Volume 15 (1954), pp. 469 to 4S4.

The electrophotographic recording material of the invention can be used in reproduction processes can be used in which various kinds of radiation are used, i. H., electromagnetic radiation as well as nuclear radiation. This means that the photoconductive recording material of the invention, for example, not only in the context of xerographic processes, but can also be used in the context of xeroradiographic processes.

The following first describes the production of some for the production of an electrophotographic recording material photoconductors suitable according to the invention are described.

A) Preparation of triphenyl-p-dimethylaminophenylstannar.

A solution of 26 g (0.13 mol) of p-bromo-N, N -dimethylanitine added in 1000 ml of dry ether. The resulting mixture was then heated on a steam bath for 15 minutes. About 1 g of a lithium dispersion was then added and the mixture was heated to reflux temperature. The mixture was then concentrated to V _{3 of} its original volume on a steam bath. At this point the reaction began and the reaction mixture was refluxed for about 30 minutes without the application of external heat. The brown mixture was then n 'I about 1 ¹ I ₁ hours at Rückflußteinperatur heated and then filtered through glass wool into a vigorously imigcrühiic mixture of 44.6 g (0.116 mol) Triphenvizinnchlorid and 200 ml of ether. The reaction mixture was stirred at room temperature for 3 hours and then allowed to stand overnight. It was then stirred into a cold ammonium chloride solution. The resulting dark red ethereal layer was dried over anhydrous sodium sulfate. The blue residue obtained after removal of the solvent was dissolved in 20 ml of chloroform, and 400 ml of boiling absolute alcohol was added to the solution. The total volume was reduced to about 300 ml in a rotating vacuum reactor, whereupon the solid lower

u) blow filtered off, washed and in the air at room temperature was dried. 18.4 g of a solid white mass were obtained. The reaction product was first recrystallized from 45OmI ligroin and then again from 425 ml ligroin. There were 10.8 g of reaction product in the form of a solid white mass with a melting point of 132 to 134.5 C.

B) Production of Triphenyi-p-diethylaminophenyl _ao stannane

A mixture of 1.44 g (0.06 mol) of magnesium turnings, 30 ml of distilled tetrahydrofuran and 4.6 g (0.02MoI) distilled p-bromo-N, N-diethylaniline heated to reflux temperature for 15 minutes. The volume of the Reaction mixture was then made using a water aspirator reduced to about half, whereupon the mixture is heated to reflux temperature for 1 hour would. The temperature was then reduced to »p The reflux temperature is reduced, whereupon the mixture rapidly with a solution of 7.7 g (0.02 mol) Triphenyltin chloride in 50 ml of distilled tetrahydrofuran was added. The obtained mixture became then heated to reflux temperature for 1 hour and then left to stand overnight. Thereupon was in 1 liter of a stirred mixture of ice and Ammonium chloride filtered. The deposited precipitate was dissolved in 320 ml of absolute alcohol, whereupon the solution was cooled to room temperature and filtered. The filtrate was in a refrigerator cooled, whereupon it was filtered and the deposited precipitate was dried in air at room temperature. 4.4 g of white crystals were obtained. The crystals were recrystallized from 125 ml of absolute alcohol.

In this way, 2.7 g of the reaction product having a melting point of 100.5 to 102 ° C. was obtained.

C) Preparation of Tetra-p-diethylaminoplumban Fine mixture of 6.5 g (0.27 mol) of magnesium,

20.5 g (0.09 mol) of distilled p-bromo-NN-diethylaniline and 90 ml! Distilled tetrahydrofuran was heated to reflux temperature for 45 minutes with vigorous stirring and then treated with a mixture of 11.1 g (0 The reaction mass was left to stand overnight and then filtered. White crystals separated from the filtrate after standing for about 15 to 20 minutes. The crystals were filtered off, whereupon the filirate was converted into a mixture of 3 liters of an F ^: is ammonium The mixture was then extracted with 300 ml of chloroform at room temperature. The chloroform extract was dried over anhydrous: ¹ . ) soiutein Mkiilii'i stirred in, whereupon filtered, with

Acetone washed and recrystallized from 45 ml of acetone would. 0.35 g of white crystals with a melting point of 220.5 to 221.5 ° C. were obtained.

D) Preparation of tri-p-dimelhylaminophynylarsine

Line mixture of 26.8 g (0.222 mol) of N ₁ N-dimethylaniline and 50 g (0.276 mol) Arscntriehlorid was heated for 2 hours on a steam bath and then poured into 800 ml of water with stirring. The resulting mixture was then liltriert and the filtrate by the addition of about 350 ml of an IO ° _'o sodium hydroxide solution was made alkaline. The gummy precipitate that separated out was washed with ligroin and then dissolved in 2 (X) ml of methylene chloride. The solution was dried over anhydrous sodium sulfate and the solvent was removed in vacuo. The residue was recrystallized from a mixture of 50 ml of absolute alcohol and 20 ml of chloroform. The recrystallized reaction product was then dried in air at room temperature. In this way, 0.94 g of white crystals having a melting point of 237 to 240 ° C were obtained.

L) Production of tri-p-diethylaminophenylarsine

With stirring, a mixture consisting of 8.64 g (0.36 mol) of magnesium, 27.6 g (0.12 mol) of distilled p-Bromo-N, N-diethylaniline and 120 ml of distilled tetrahydrofuran, reflux for 1 hour heated. The resulting brown mixture was then added dropwise over 10 minutes a solution of 7.3 g (0.04 mol) of arsenic trichloride in 70 ml of distilled tetrahydrofuran, so that the mixture continued to reflux. Then was still?. Heated for hours, after which the mixture was filtered into a stirred mixture of ice and an ammonium chloride solution. the precipitated yellow precipitate was dried in air at room temperature and then from a Mixture of 500 ml of absolute alcohol and 300 ml of chloroform recrystallized. There was 11.1 g of one yellow solid precipitate obtained. By a second recrystallization from a mixture of 600ml Alcohol and 300 ml of chloroform were 7.6 g of a white crystalline reaction product with a Melting point of 211.5 to 214 ° C obtained.

F) Preparation of 2-methyl-4-dimethylaminophenylarsine oxide

A mixture consisting of 20.3 g (0.15 mol) of NN-dimethyl-m-loliiidine and 27.0 g (0.15 mol) of arsenic trithloride was heated on the steam bath for 20 minutes, after which the reaction mixture was poured into 1 liter of water with stirring . The solution obtained was then made alkaline by adding 180 ml of a 10 ^N sodium hydroxide solution. The deposited precipitate was then washed with ligroin gel and then dissolved in a boiling mixture of 50 ml ligroin and 17 ml chloroform, whereupon the total volume was reduced by concentrating to 1 ml. A gel-solid precipitate separated out overnight, which was dried in air at Raimileinpera-S-, door. In this way I). 17} · Reaction products with a melting point of 1 \ \ to 21 / C are obtained.

(i) Preparation of Uis- (p-Diälhylaminophenyl) -phosphinoxyd

Fine homogeneous mixture of 37.5 g (0.276 mol) Phosphorus trichloride and 33.1 g (0.222 moles) of N.N-diethylaniline was heated on a steam bath for 2.5 hours, after which the reaction mixture was allowed to return to room temperature cooled and slowly poured into 1 liter of water with stirring. The solution obtained

ίο was then made alkaline by the addition of 300 ml l () ° / _o sodium Natriunihydroxydlösung and extracted with two U) 0-ml portions of methylene chloride. The combined extracts were dried over anhydrous sodium sulfate and the solvent removed on a steam bath. The remaining oil was stirred into 200 ml of boiling ligroin, whereupon it was filtered while still hot and the filtrate was cooled to room temperature. In this way, 0.34 g of white crystals with a melting point of 126.5 to 128 ° C. were obtained.

The following examples are intended to illustrate the invention in more detail.

example 1

Coating compounds were produced from the following components:

Photoconductor 0.15 g

Binder 0.50 g

Sensitizer 0.002 g

Methyl chloride 5 ml

The resulting coating compositions were then applied by hand to a conductive layer of the sodium salt of a carboxy ester lactone. ; ellt, as described in LJSA. Patent 3,120,028, which again on a conventional cellulose acetate film support, applied in such a way that layers of a Thickness, measured wet, was obtained from 0.010 cm. The obtained elements were then kept at a temperature kept at 32.2 C.

The finished elements were then passed through a positive or negative corona discharge, until the surface potential c. as shown by measurement with an electrometer, for example 600 V reached.

The resulting photoconductive recording materials were then exposed to light through a gray scale tablet using a 3 (MK) K Wolfrani light source. The exposure caused a reduction in the surface potential of the recording material below each step of the gray scale from the original potential l '" to a lower potential V, the exact value of which depends on the irradiated amount of light in lux.

The results of the measurements carried out were plotted in a diagram in which the surface potentials V for each exposure level were plotted against the logarithm of the exposure.

The so-called shoulder uniqueness is the numerical expression of H) ¹ , multiplied by the university distance of the exposure in Meler-Caiuile seconds. die eifordeilkh! ·>'. around the Oberlachenpotenti.il .im (il) UV around HX) V,; i u-rniinderii.

Dio lmpliudluhKt.it im DiirclihaiiglK-ieicli tlei

! 772

The swelling curve is the numerical pressure of A K) ¹ , multiplied by the conversion of the exposure B in Mctcr-C'anillc-Secimdcn. which is necessary to reduce the WX) V st; irkc surface potential to 100 V / u. 5 C

The severity of the appearances produced result in photoconductive cut-off materials can be found in 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-amyloxyphenyl) -thiapyrylium perchloral was used as a sensitizer \ orwcndct;

as a sensitizer, 2,4-bis- (4-ethylphen1) -6- (4-slyrylsylryl) -pyryliiimpcrchlorat used.

The binder consisted of ^ / T-isopropylidenebis-tphenyloxyethyO-co-ethylenetcrcphthalate].

table example

! 'waveguide

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
4ÖÖ 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)
c)
d)

e)
f)
G)

Ii)

i)
j)

Methyl-diphenyl-p-diethylaminophenylsilane. Triphenyl-p-dimethylaminophynylslannane .. Triphenyl-p-diethylamirto-phenylstarmaii .. .. Diphenyl-di- (p-diethylaminophenyl) -stannane

Triplienyl (p-diethylaminophenyl) plumban.

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 sealing compounds were composed as follows:

Phoconductor: 0.97 · 10 ³ mol per g of solid in the coating mixture, sensitizer: 2 ° / “. based on the amount by weight of the coating compound 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 dihydroxydiarylaican or prepared by ester exchange between diphenyl carbonate and 2,2-bis-4-hydroxyphenyl propane.

The sensitivities obtained are shown in Table II below.

Table!!

example Photolcitcr 100 volts, sensitivity in
Slack area of the blackening curve c
Positive j Negative 950
1100
3400
2000
630 a)
b)
<■■)
d)
c)
f) Mclhyldiphenyl-p-diethylaminophenylsilane
Triphynyl-p-dimclhvlaininophcnvlstannan
TriphcnNl-p-difiihyl-ainophenylstannane
Diphenyldi- (p-di; ithyl-aminophenyl) -stannane
Triphynyl-p-diethylaminophenylplumban
Tri-p-iliälhylaminophynylarsine 120
150
250
1400
380
230

Example 3

With the Be? Described in Examples 1 and 2? Sealants became more supple supports. as described in Example 1, coated. In a darkened room, the surfaces were the photoconductive layer charged to a potential \ on about 4-60OV 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. To develop 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 (1)

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