DD154460A3 - TRANSPARENT PHOTOELITIC LAYER, ESPECIALLY FOR USE IN ELECTROPHOTOGRAPHIC RECORDING METHOD - Google Patents

Abstract

The invention relates to a photoconductive layer which consists of a polymer with aromatic amine units and is versatile sensitisable. The object of the invention is to provide an easily accessible photoconductive material, which forms transparent, pourable from solution, flexible, mechanically stable and well-conductive films on adherent films and is suitable for electrophotography. Erfindungsgemaess the object is achieved in that poly-beta-hydroxyalkylarylamine As photoconductive polymers are used, as they arise in great structural variability by polyaddition of diepoxides (diandiglycidyl ether) with disekundaeren aromatic diamines (N, N'-dibenzyl-4,4'-diaminodiphenylmethane and / or primary aromatic monoamines (aniline) by dye salts (malachite green picrate, (Ctief 23 H deep 25 N deep 2) high + (C deep 6 H deep 2 N deep 3 O deep 7) high - &, Broensted acids (picric acid), electron acceptors (2.4.7 - trinitrofluoreon), bis (cyanstyryl) arenes, positive and negative working layers for microfiches are exemplified be executed.

Description

The invention relates to a transparent photoconductive layer, which is particularly suitable for electrophotographic recording method and contains a soluble, pourable photoconductive polymer as a photoconductive, and at the same time! Converting component. The soluble photoconductive polymer is characterized essentially by the content of an aromatic tertiary amino group of the formula (1a) or (1b) as a photoconductive functional group

  Ψ

(1a) (1b)

wherein either two bonds from the N atom or from each of the aromatic group Ar and the U atom emanate a bond, by which this grouping is included in the polymer main chain.

Because of their transparency (homogeneity) and their good and easy film formation by conventional casting methods, the polymers of this class according to the invention are suitable as easily accessible photoconductive material which has satisfactory performance properties such as easy handling and low manufacturing costs in addition to good sensitivity and excellent mechanical properties. They can be used both as self-supporting films that are appropriately

clocked ν; It can be used as well as layers on rigid or flexible supports and for paper coating and sensitized if necessary in the ultraviolet and visible range, as it is most advantageous for the particular application. "Use as a low-cost electrophotographic tape-shaped data output material or microfiche or electrophotographic plate is particularly recommended because of its transparency and excellent mechanical properties." "Use for paper coating is particularly recommended because of the low manufacturing cost and good adhesion to virtually all common conductive substrates Of particular importance is also that the photoconductive material itself is thermoplastic and thus usable for combined electrophotographic-thermoplastic processes.

Characteristic of the known technical solutions

It is known that aromatic tertiary amines,

Ar - NC (1)

which contain a unit of the formula (1) have a good photoconductivity, which extends in an unsensitized manner to the ultraviolet and blue spectral range (transport polymers cf., M. Stolka and DM Pai, Advances in Polymer Science 2_9, 1-45 (1978)) , Typical examples of such amines are N-substituted carbazoles and substituted aniline derivatives. Using this photoconductive unit, transparent photoconductive layers have heretofore been prepared by four typical methods.

A. A low molecular weight compound of defined structure, such as N, U, Ψ , W -tetrabenzyl-1,3-phenylenediamine, W-alkylcarbazole or the like, became homogeneous in a high molecular weight compound (binder) to form a photosensitive layer embedded as disclosed in U.S. Patents 3,206,306, 3,265,496, 3,314,788, 3,615,404 and 3,767,393.

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B. Another approach which has been followed very often is the "attachment" of the tertiary amine moiety to a macromolecular backbone, which is the case with poly (N-vinylcarbazole), poly (N-vinyl = diphenylamine) (US Pat. No. 4,003,717, 4,038,468). , Poly (p-diphenylamino = styrene) (US 3265496), the reaction products of polyepi = chlorohydrin with Carbazolalkalisalz according to Jap.Pat. 97540/1973, polyvinyl esters of arylaminocarboxylic acids (US 3779750), polymethacrylates having arylaminoalkyl ester side groups (Stolka, Pai: Adv. Polym., Sci., 2.9, 1-45, 1978).

C. The incorporation of the tertiary aromatic amine unit by polycondensation processes has also been used for the preparation of photoconductive polymers and electrophotographic layers (US 3387973, Japanese Pat. No. 1735150 (1975), DOS 2608082). Further, reaction products of amino group-bearing photoconductors and at least one isocyanate or at least one epoxide according to DT 1216690 have been proposed as a photoconductive layer for an electrophotographic recording material.

D. Finally, DOS 2608082 has proposed the reaction of oligomeric formaldehyde resins (xylene-formaldehyde resins, resole resins) with mono- and bis-functional secondary aromatic amines to produce low cost, soluble photoconductor layers comprising tertiary aromatic amine units.

According to the method (A), a high concentration of the low-molecular-weight photoconductive material is required in order to obtain a sufficient sensitivity. However, only a few tertiary aromatic amines can be combined in sufficiently high concentration to form stable homogeneous layers with binder polymers without phase separations, crystallizations, etc. occurring. Most binder polymers reduce the photoconductivity, which is often at the lower end of usability, even further. It was therefore necessary to use special binder polymers, such as poly (p-chlorophenyl acrylate), which cancel this negative effect. However, this considerably increases the cost of production.

In the case of process (B), the polymers can be obtained either via a mostly complicated monomer synthesis and a subsequent polymerization, or relatively complicated polymer-analogous reactions must be carried out. In order to obtain good properties, cleaning operations must be performed on both stages. Thus, the resulting polymers are generally very expensive and can only be used to a limited extent. In addition, there are serious problems with the mechanical properties (brittleness) and the adhesion of the layers thus produced to conductive substrates.

The polycondensation method of C is the same as that for B. Here, in addition, high molecular weights without crosslinking (gelling) are difficult to achieve, so that the effort of synthesizing a photoconductive soluble polymeric material is also considerable.

The prior art transparent type A, B or C photoconductive layers generally suffer from numerous disadvantages, such as difficult and costly manufacture, brittleness and poor adhesion to the substrate used as a support.

(D) Significant porting has evidently been achieved through the use of pormaldehyde resins or resole resins as readily available base resins and their reaction with industrially readily available secondary aromatic amines to produce a non-uniform, resinous, higher molecular weight photoconductive material which is a photoconductive transparent resin having a mushroom-forming property photosensitive layer with or without application of a binder polymer can form. Although the suggestion of a sensitized photoconductor of this kind per se seems to be economically viable, it nevertheless has the disadvantage that, due to the chemical nature of the non-uniform base resin, there are problems with the prevention of gelation when relatively high molecular weight aminopropene is used.

should be sought condensates or that the mechanical properties and the adhesion in the case of low molecular weight still need to be improved. Resins of this type are therefore often still used with binder polymers which are intended to reduce these disadvantages.

In most cases, the photosensitive layers A, B, C and D based on tertiary aromatic amines contain a sensitizer which improves the photosensitivity of the material. The sensitizers used are generally dyes which absorb light in such a region of the spectrum, which is optimal for the particular application, or such _; Additives that form charge-transfer complexes, which then have increased photoconductivity, ζ. B. 2,4,7-trinitro-9-fluorenone. The usual sensitisers of the triphenylmethane, pyrylium and trinitrofluorenone types achieve a substantial increase in photoconductivity, but have an increased dark conductivity for at least one polarity, or the photoconductivity for the two types of charge varies greatly.

Object of the invention

The object of the invention is therefore a transparent photoconductive polymer material which is therefore particularly suitable for electrophotographic recording processes which require high transparency, which is also highly abrasion resistant and flexible, has good thermal resistance, can be formed into self-supporting, binderless layers and ribbons and has good adhesion to common conductive substrates, such as metal, plastic, paper, special glass, and is sensitizable in wide ranges of the visible spectral range. At the same time, a positive and negative chargeability and a discharge rate of the charged layer which is approximately the same for both polarities are sought. Furthermore, the photoconductive polymer used should

, - 6 - 2 18 3 6 5

material be as simple and inexpensive synthetically accessible. This object is achieved by the invention.

Explanation of the essence of the invention

The invention relates to a transparent photoconductive layer, in particular for use in electrophotographic recording process, which contains a photoconductive polymer having aromatic amine units in the main chain and is optionally provided with the addition of plasticizers or other layer-improving additives, characterized in that the photoconductive layer consisting essentially of one or more photoconductive, higher molecular weight, (M _n - 2500), however, soluble, epoxide-.mu.min addition polymers (polyadducts) and that sensitizers are preferably contained for improving the photoconductive and electrophotographic properties.

The photoconductive epoxide-amine addition polymers (polyadducts) according to the invention are preferably poly-reaction products of a diepoxide or epoxy resin with a disecondary aromatic diamine or / and a primary aromatic monoamine. They are uncrosslinked aliphatic-aromatic polyamines having β-hydroxyalkylarylamine units in the main chain which have at least one of the following characteristic structural members:

Y Y

·· - CHCH ₂ ^ N-Ar - X - Ar - N-CH ₂ CH- - I

OH OH

, YY

--CHCH ₂ -N-Ar-N-CH ₂ CH--. Π

OH. OH

Ar ¹ Ar ¹ . ,

·· -CHCH ₂ -N-CH ₂ -R ^ Ch ₂ -N-CH ₂ CH- ΙΠOH OH

.-- CHCH ₂ -N-CH ₂ CH-- · TSL

OH OH j

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As Ar, X, Y, R 'and Ar are to be mentionedj

Ar unsubstituted or substituted phenylene radicals, polynuclear aromatic difunctional radicals, arylene radicals;

X is CH ₂ , (CH ₂ ) J ₁ ,. C (alkyl) ₂ , C (aryl) ₂ , 0, S, -, SO ₂ , CO; Y is benzyl, phenylethyl, aralkyl, alkylj

R ^{1 is} unbranched or branched alkylene radicals, oxaalkylene radicals, 0, S, -, -CsC-, -CSC-, arylene radicals, bifunctional heterocycles;

Ar is phenyl, substituted phenyl, p-methoxyphenyl, p-chlorophenyl, baphthyl, anthryl or other aryl radical

The preparation of these polymers could be carried out in exceptional cases by other than by the amine-epoxide addition, .etvia by reaction of oi-chloro-ß-hydro ^ y-alkanes with said aromatic amines.

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o ·

- 9 - 21 83 6 5

According to a preferred embodiment, the transparent photoconductive layer contains an uncrosslinked, soluble, higher molecular weight epoxide-amine polyaddition product of the general formulas (2), (3), (4) or (5). Such epoxide-amine addition polymers can be obtained by reaction of diandiglycidyl ether with aromatic disecondary diamines of the formulas (6), (7), (8) or with a primary aromatic amine of the formula (9).

Y Y

H-N-Ar-X-Ar-H-H (6)

YY

H-N-Ar-N-H (7)

Ar ¹ Ar ¹

• H - N - CH ₂ - R ¹ - CH ₂ - 33 "- H (8)

Ar ¹

H - ir - H: (9)

Meaning of Ar, X, Y, Ar ¹ and R ^f in (2) to (9) as above

In addition to diandiglycidyl ether, it is also possible to use other diepoxides and epoxide resins such as dihydroxynaphthalene bis (glycidyl ether), hydrochi = non-bis (glycidyl ether), glycol bis (glycidyl ether) for the preparation of the soluble epoxide-amine addition polymers (polyadducts) according to the invention. , Dicarboxylic acid diglycidyl esters), bis (glycidyl) amines and the like. ä.

The production of higher molecular weight uncrosslinked aliphatic-aromatic polyamine compounds of the structure (2) and (3) according to the invention can advantageously be carried out according to DD 141 677 "Process for the preparation of high molecular weight, thermoplastic epoxide-amine polyadducts". Further representatives are also accessible according to DRP 676 117 or according to US 3,554,956.

Syntheses of epoxy-amine addition polymers of the types

(2) and (3) when Y = CH ₀ CH ^ is particularly important according to DD 141,677

ά o o

easy and inexpensive.

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For example, according to the invention can be a soluble epoxide-amine addition polymer of the general formula (2) by heating equivalent amounts 60stündiges Diandiglycidylether and N, N dibenzyl ^{t "f} 4,4-diamino-diphenylmethane 100 ⁰ O or with the addition of catalytic Amounts of an alcohol by heating for about 50 hours as a thermoplastic formula-pure adduct (formula (10))

(10) J η

obtained with a relative average molecular weight M - 4000. This aliphatic-aromatic polyamine according to the invention is a technically usable photoconductor (charge transport polymer). It dissolves in various solvents z. As 1,2-dichloroethane, chloroform-alcohol mixtures, toluene, toluene-cyclohexanone and the like and forms when applied by conventional casting methods, such as coating from a slot die, by roll coating or centrifugal casting, etc., excellent abrasion resistant, well adhering and flexible films that are transparent. Fibers, tapes and films made of this material can also by thermoplastic deformation can be manufactured without a solvent, and it is also possible for the film-forming solvent-free according to DD 141 on the surface to be coated by heating the coated component blend of Diandigl3 ^r cidylether and N, Ψ - Dibenzyl-4,4'-diaminodiphenylmethane make. The glass transition temperature Tp. This photoconductor material according to the invention is 87-93 C and by addition of plasticizers, eg. As Delor 106, adjusted to the intended use, ie, be degraded. Similarly, most polymers of the invention behave.

Photoconductive, soluble, film-forming epoxy-amine polyadducts useful for the purpose of the invention can be used

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However, even from technical epoxy resins, such as the epoxy resin EPILOX EG 34 of VEB Leuna-Werke Walter Ulbricht, produce (see Example 2).

The structural variability of the poly-β-hydroxyalkylarylamines suitable as polymeric photoconductive material according to the invention is extremely great. To illustrate the scope of the invention, for example polyadducts of Diandiglycidylether with EF were, N'-di (p-methoxyphenyl) ethylene di = amine, Ii, EP-diphenylethylene diamine, aniline, anisidine, N, N ¹ -Diphenylxylylendiamin, Ή, Ψ - Mbenzyl-1,3-phenylenediamine, U, N- ¹ -dibenzyl-4,4'-diaminodiphenyl ether, F, Ψ -dibenzyl-4,4'-diaminodiphenyl sulfide and other similar aromatic amines were prepared and examined for their photoelectric conductivity and electrophotographic sensitivity , Thereafter, polymers with the structural members (11) to (17) are particularly suitable as transparent photoconductive layers, which can be applied from solutions to conductive substrates. Due to different glass transition temperatures of the various polymers having the structural elements (10) to (17), the photoconductive layer can be adapted to specific methods of electrophotography or special thermal requirements of the device variant by appropriate selection of the photoconductor material.

OCH ₃ .

OCH ₃

1-CH ₂ -CH-CH ₂ -N-CH ₂ -CH ₂ -N-CH ₂ -CH-CH ₂ -OH OH

CH ₃

CH ₃

CH ₃ _

VO-CH ₂ -CH-CH ₂ -N-CH ₂ -Ch ₂ -N-CH ₂ -CH-CH ₂ -

CH ₃ OH OH

KCH ₂ -Ch-CH ₂ -N-CH ₂ -CH-CH ₂ ^ OH

OH

OCH ₃

'L-CH ₂ -CH-CH ₂ -N-CH ₂ -CH-CH ₂ -CH ₃ OH OH

(12)

(13)

(U)

ro I

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.to

\\ /)

Ι -O OJ I O ί ο- L j: CM O X I ο- -2

- 14 - 2 18 3 6 5

Further, it is possible to use instead of the homopolymers of the formula (2) to (5) also copolymers having at least two different structural members of the formulas (2) to (5) and (10) to (17). Furthermore, mixtures (blends) of the homopolymers can be used.

The polymers of the invention differ from the usual crosslinked, cured with aromatic diamines epoxy resins by their thermoplasticity and solubility in the usual organic solvents, which makes the very advantageous processing and diverse sensitization after conventional thermoplastic or solution technologies possible. They are comparable in this respect with the phenoxy resins. This also applies to their excellent mechanical properties and their adhesion to many documents. However, they are distinguished from the phenoxy resins in the point essential to the invention in that they themselves are photoconductive by their content of aliphatic-aromatic amine units, while the phenoxy = polymers themselves have no photoconductive properties (see, DOS 1 522 679).

Although such polymers have just sufficient photoconductivity for electrophotography, they are preferably sensitized.

Sensitization of the photoconductive material according to the invention is possible by a multiplicity of known sensitizers-dye sensitizers, electron acceptors, carbonyl compounds, preferably by addition of 2,4,7-trinitro-fluorenone or other nitrated aromatics or by bis (cyansyryl) arenes.

Is understood by those skilled in the art that in order to sensitize the films of the invention all low- other or high molecular weight aromatic amine photoconductors such as', N ^f -Tetrabenzyl-1,3-phenylenediamine especially poly-N-vinylcarbazole, N, Ή, N, N-alkylcarbazole, etc. used

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Sensitisers are applicable. Preference is given here electron acceptors, Triplettsensibilisatoren, Lewis acids, carbonyl and azo dyes, tyrylium salts, dye salts, such as cyanine dyes, triphenylmethane dyes, thiazine dyes, also picric acid, salicylic acid, naphthalene-1,4,5,8-tetracarboxylic u. a. ,

As very advantageous for obtaining transparent sensitized photoconductive layers for the various applications of electrophotography, novel additions of dye salars possessing bulky organic counterions have been found. Preference is given to those counterions which are themselves dyeing ions. Very good results are obtained using the following dye or sensitizer salts, which are homogeneously incorporated in amounts of 0.05 to 20% by weight, with suitable choice of photoconductive matrix according to the invention, and corresponding to high sensitization in the ultraviolet range and in absorption of the dye ion cause visible area!

Malachite green-t etraphenylboranate [ ^C 23 ^H 25 ^N 2] ⁺ [ ^σ 24 ^Η 20 ^Β ] ~

Malachite green pikrat Crystal violet picrate Methylene blue picrate Tris (4-methoxyphenyl) methyl picrate

The production of the dyeing pikraten mentioned takes place, as described in DD 146 112, by double reaction of corresponding dye salts, eg. B, of commercially available malachite green salts and sodium picrate in aqueous solution, or by precipitating the sparingly water-soluble sensitizing salts from the corresponding dyeing solutions. Picric acid.

Malachite green tetraphenylboranate can be prepared analogously by reacting the aqueous solution of commercially available malachite green salts with sodium tetraphenylboranate ("Kalignost").

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With appropriate selection of the sensitizing salt, specific sensitization for specific wavelength ranges, e.g. Example, the range of 630 - 660 nm for the use of argon laser light sources possible.

These sensitizing salts are outstandingly suitable for the sensitization of the soluble, higher molecular weight epoxy-amine polyaddition products according to the invention, because they allow the high charge of the layers both negative and positive with the addition of effective concentrations. They lead to an extension of the photosensitivity up to the red region of the spectrum and give an approximately similar photoconductivity for the integral light of a WoIframlampe for both polarities. The photosensitivities, expressed as half-value exposure Hw ₂ in lxs, are predominantly in the range of 200 to 1000 lxs. Such combinations are a valuable electrophotographic recording material because it is generally considered difficult in the art to provide a bipolar chargeable and bipolar approximately equally sensitive photoconductive material. This feature is particularly suitable for the application of the layers in copiers, which can optionally process positive and negative originals to positive copies.

Since only low concentrations of the latter are required for effective sensitization of the inventive polymeric photoconductors with the sensitizing salts mentioned, transparent electrophotographic layers can be produced which are also sensitive in the red spectral range and have a low visual optical density (-0.2). Such layers are applicable to suitable transparent and conductive substrates as a microfiche material. By suitable choice of the sensitizing salt, the optical density in the range of 360 to 420 nm can be kept so low that a second copy with Diazof! Immaterial is possible. This is given, for example, when using 0.5% by mass malachite green picrate as a sensitizer for (10) (see Example 1).

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By the invention it is further achieved that sufficient photosensitive layers are obtained for electrophotographic recording, which have high mechanical stability without additional binder and can be arranged for example on a cylindrical drum or circulate as an endless belt, without showing any signs of wear, and Accordingly, they are very suitable for use in electrophotographic copying machines or electrophotographic data output devices.

The good solubility in easy-to-evaporate solvents and the good adhesion to paper and plastic fibers also allows the use as a paper coating for electrophotographic copy paper. Here the low visual color density, the cost-effective production and the low specific weight of effective layers according to the invention benefit the application.

In another context, it is essential that also usual photoconductive pigments, for. As zinc oxide, organic dyes, insoluble polymers can be dispersed in the layer-forming polyimine, so that non-transparent photoconductor layers formed.

In this sense, an additional use of the transparent photoconductor according to the invention in general as a special photoconductive binder or as a charge transport layer for other photoconductors and photoconductor combinations, for example in multi-layer systems, possible, in particular the charge transport property and the excellent mechanical properties and the excellent adhesion reach the application ,

As with all combinations of low or high molecular weight aromatic amines with electron acceptors also arises in the novel polymers, especially with the addition of

τ 18-218365

2,4,7-trinitrofluorenone (TUP), aromatic Garbonylverbindungen, unsaturated nitriles, especially Bis (cyanogen tyryl ^, re- _t nen, etc., an increase in photosensitivity.

This addition may occasionally be beneficial in setting a desired magnitude of photosensitivity. It is very favored by the excellent binder property of the photoconductors according to the invention.

It should be emphasized that the combination of the photoconductive polymers according to the invention with TNP or other nitroaromatics and the special triphenylmethane dye prepolymer particulate sensitizers represents a preferred embodiment insofar as different from the conventional aromatic amine / TNP / triphenylmethane dye combinations by the action of the special Paraffin sensitizers bipolar chargeability and photoconductivity is present and high photosensitivity is achieved.

The class of bis (cyanstyryl) arenes (compare DD 114 874) has proved to be a further additive which significantly increases the photoconductivity of the layers. For example, 1,4-bis (2-cyanstyryl) -2,5-dimethoxybenzene in proportions of 1 to 10 percent by mass can be distributed homogeneously in photoconductive material according to the invention and already at the addition of 1 percent by mass leads to an increase in the photoconductivity of corresponding layers.

For panchromatic sensitization of the polymeric photoconductor of structure (2) according to the present invention, a combination of 0.5% by mass of malachite green picrate, 0.5% by weight of puchsine picrate and 1% by weight of 1,4-bis (2-cyansyryl) -2,5-dimethoxybenzene proves to be suitable (see Photoleitspektrum Fig. 2).

As a further photoconductivity of the layers substantially increasing additive has proven the class of Brönstedt acids and here preferably the addition of picric acid. Pur the Pail, that only one mode of operation with negative loading

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In addition, since depolarity is required and, moreover, no rapid repetition of exposure is required, a sensitive electrophotographic layer can be advantageously obtained by the combined addition of a dyeing pentate (eg, 0.5 to 2 mass% malachite green picrate) and 2 to 10 mass% picric acid to the photoconductive material of the present invention ,

example 1

According to DD 141 677 molar amounts of N, N'-dibenzyl-4,4'-diaminodiphenylmethane and pure diandiglycidyl ether (DDGE) by melt polymerization at 100 - 110 ⁰ C over 60 hrs. Implemented. This produces a homogeneous polyadduct of the formula 10 which is soluble in (toluene, chloroform, dichloroethane, chloroform-methanol mixtures (4: 1) and the like.) The vapor pressure osmometric molecular weight determination gives a number average of 1 = 5000-6000.

El ement ar analyzes e j

^C 48 ^H 50 ^N 2 ° 4 ⁽⁷¹⁸ ' ⁹⁾

Ber. C 80.19 H 7.01 U 3.90

Gef. 79 C 79.98 H 7.10 N 4.24

A solution of 85 mg of the polyadduct 10 in 1 ml of dichloroethane with 0.42 mg Malachitgrünpikrat ΟρςΗργΝ ^ Ο, (prepared according to Example 1 DD 146 112), dissolved in 0.05 ml of dichloroethane, added. It forms a homogeneous, green-colored coating solution. From this coating solution

are applied 17.2 / Ul per cm on an aluminum foil. After slow evaporation of the solvent at room temperature results in a homogeneous, slightly green colored layer of a thickness of about 10 / tun and a visual optical density ^ O, 25o The layer is dried for 5 to 10 hours at 50 ⁰ C (atmospheric pressure). It adheres perfectly to metallic substrates, glass and plastic films.

The photoconductivity spectrum is shown in Fig. 1. The

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Layer can be charged both positive and negative high. With a corotron voltage of +8 kV, a charge of +1000 V is achieved. By exposure to 950 lxs (light of a tungsten lamp), the layer is discharged to half the value of its initial potential.

For a -750 V charge, 790 Ixs are needed to drop to half the value of the initial potential.

Example 2

6,027 g Epilox EC 34 having an epoxide number of 198 (VEB Leuna Werke Walter Ulbricht) and 5.753 g N, U ^t dibenzyl-4,4 -di ^t = aminodipheny be methane 60 hrs at 100 -. 105 ⁰ O reacted in melt. The result is a glassy mass, which "contains structural units according to formula 10, has a molecular weight M _n = 2500 and is soluble in dichloroethane and similar solvents.

A coating solution in dichloroethane is prepared by dissolving 100 parts of the polyadduct and 2 parts of malachite green picrate. From this, photoconductive layers are cast analogously to Example 1. Fig. 2 shows the photoconductive spectrum of such a layer.

Example 3

Polyadduct 10 prepared according to Example 1 is used to prepare a coating solution in dichloroethane containing 100 parts of polyadduct 10, 20 parts of 2,4,7-trinitrofluorenone and 2 parts of malachite green picrate. From this solution can be prepared in a conventional manner, a homogeneous layer. Their photoconductive spectrum is shown in Fig. 2.

Example 4

With the polyadduct 10, prepared according to Example 1, a coating solution in dichloromethane / dioxane mixture

2 18 3 6 5

which contains 100 parts of polyadduct 10, 0.5 part of malachite green picrate, 0.5 part of fuchsin picrate and 1 part of 1,4-bis (2-cyanstyryl) -2,5-dimethoxybenzene. From this solution can be prepared in a conventional manner, a homogeneous layer having a panchromatic photosensitivity. The photoconductive spectrum of such a layer is shown in FIG.

Example 5

With the polyadduct 10 prepared according to Example 1, a coating solution is prepared in dichloroethane / dioxane mixture containing 100 parts of polyadduct 10, 0.5 parts Malachitgrünpikrat and 0.5 parts Fuchsinpikrat. It can be with this coating solution, a homogeneous layer (thickness 10 / am) produced by conventional Begießverfahren, compared to Example 1 has an increased sensitivity in the wavelength range of 500-600 nm. The layer can be charged both positively and negatively high (about + 1000 V). For the drop to half the value of the initial potential 450 lxs are required for a positive charging polarity, 380 lxs for a negative charging polarity. The light source was a tungsten lamp.

Example 6

Polyadduct 10 prepared according to Example i is used to prepare a coating solution in dichloroethane containing 100 parts of polyadduct 10, 10 parts of picric acid and 2 parts of malachite green picrate. From this solution, it is usually possible to produce a homogeneous layer (thickness 10 μm) which has an increased photosensitivity in the case of a negative charging pole. owns. The layer can be charged to -650 V and requires an exposure of 240 lxs for the drop to half the initial potential.

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Example 7

Wach DD 141 677 are molar amounts of Έ, W -dibenzyl-4,4 ¹ -diaminodiphenylsulfid and pure diandiglycidyl ether (DDGE) by melt polymerization at 120 C for 1id5.Stdn. This produces a homogeneous polyadduct of formula 17, which is soluble in dichloroethane and has a number average molecular weight M _n ^ 10 000 (vapor pressure osmometry).

As of the supernatant temperature 92 ⁰ C. · elemental analysis; ^C 47 ^H 48 ^N 2 ° 4 ^S (736.9) ·

Ber. {C 76.60 H 6.57 N 3.80 Found: C 76.50 H 6.72 N 4.08

With the polyadduct 17, a solution is prepared in dichloroethane containing 100 parts of polyadduct 17 and 2 parts Malachitgrünpikrat. From this solution can be prepared in the usual way a homogeneous layer which adheres extremely well to aluminum. Their photoconductivity spectrum is shown in Fig. 3.

Example 8

A glassy amorphous polyadduct of formula 11, M _n 6500, Tg 64 ⁰ C, which dissolves in chloroform / methanol (20: 1), dichloroethane and the like, is prepared from chloroform / methanol (20: 1) together with malachite green picrate cast as Example 1 au a layer containing 100 parts of polyadduct 11 and '2 parts Malachitgrünpikrat. Their photoconductive spectrum is shown in Fig. 3.

Example 9

A glassy amorphous polyadduct of Formula 14, IL 12000, Tg "89 ° C, is dissolved in chloroform / methanol (4: 1) and made into a homogenous layer along with malachite green picrate

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potted containing 100 parts polyadduct 14 and 2 parts Malachitgrünpikrat. Their photoconductive electricity is shown in Fig. 3.

Example 10

A Copolyaddukt with the same proportions of structural units of the formulas 12 and 13 (corresponding · £ 12} _& ... ^ -f 13, asb), I _n 2600, Tg 72 ⁰ G, is dissolved in chloroform / methanol (4: 1) or Dissolved dichloroethane.

Analogously to Example 1, a layer is produced from this copolyadduct which contains 2 parts of malachite green picrate per 100 parts of copolyadduct. It has excellent adhesion to glass, aluminum and plastic films. Their photoconductive spectrum is shown in Fig. 3.

Example 11

A glassy amorphous polyadduct of the formula 16, Tl 10 200, Tg 84.5 ⁰ C, prepared according to DD 141 677 from N, F-dibenzylm-phenylenediamine and diandiglycidyl ether, is dissolved in dichloroethane and, together with 2,4, 7-trinitrofluorenone cast to form a homogeneous layer containing 2.4 _S 7-trinitrofluorenone contains 100 parts polyadduct 16 and 10 parts. The photoconductive spectrum is shown in FIG.

Example 12

100 parts of a glassy-amorphous polyadduct of formula 16, I _n 10 200, Tg 84.5 ° C, are dissolved in dichloroethane and mixed with 0.5 parts Malachitgrünpikrat (dissolved in dichloroethane). This solution is potted to a 15 μm thick layer on a conductive substrate. The layer is transparent and has a visual optical density of -0.3.

The layer can be charged both positively and negatively.

- 24 - 2 18 3 6 5

At a corotron voltage of +8 kV, a charge of 800 V is obtained. By exposure to 1400 lxs (light of a tungsten lamp), the layer is discharged to half the value of the initial potential. For a -950 V charge, 1200 lxs are needed to drop to half the value of the initial potential. The photoconductive spectrum is shown in FIG.

Claims (19)

- 29 - 218 3 6 5 1 to 50% by mass is included. 1 -OCH ₂ -CHCH ₂ -N-CH ₂ CH ₂ -N-CH ₂ CH-CH ₂ -J- I 1 Jn OH OH 1. Transparent photoconductive layer, in particular for use for electrophotographic recording method, comprising a photöleitfähigen polymer having aromatic amine units in the main chain and optionally sensitizers, and optionally a plasticizer, characterized in that the photoconductive layer consists essentially of one or more photoconductive higher molecular weight OL ₁ - 2500), soluble epoxide-amine addition polymers is that ß-hydroxyalkylaryl = amine groups of the types I - IV alone or in combination Y Y "--CHCH ₂ -N-Ar-X-Ar-N-CH ₂ CH -" - I OH OH. YY
II --CHCH ₂ -N-Ar-N-CH ₂ CH-- Π OH OH Ar ¹ Ar ¹ --CHCH ₂ -N-CH ₂ -R'-CH ₂ -N-CH ₂ CH- • OH OH -CHCH ₂ -N-CH ₂ CH-- EZ OH OH contains nation, where mean Ar unsubstituted or substituted phenylene radicals, polynuclear aromatic difunctional radicals, arylene reste; Y is benzyl, phenylethyl, aralkyl, methyl, ethyl, alkyl Z is CH ₂ , (CH ₂ ) J ₁ , C (alkyl) ₂ , C (aryl) ₂ , 0, S, -, SO ₂ , CO; R ¹ unbranched or branched alkylene radicals, Oxaalky = lenreste, 0, S, -, ^ C = CC, -C = G, arylene radicals, bifunctional Heterocyclenf Ar is phenyl, substituted phenyl, p-methoxyphenyl, p-chlorophenyl, 2183 65 and that to improve the photoconductive and electrophotographic properties as sensitizers, triarylmethane dye-type dye salts having large-volume organic counterions, dye-dye combinations in which both anion and cation are dye ions, electron acceptors, aromatic nitro compounds, aromatic carbonyl compounds, bis (cyanstyryl) arenes, Brönstedt acids or mixtures of Farbstoffsalζen and electron acceptors and / or Bronsted acids are included. '. 2 18365 2 18365 2. Transparent photoconductive layer according to item 1, characterized in that mixtures (blends) of epoxy-amine addition polymers are used. 3. A transparent photoconductive layer according to item 1, characterized in that the photoconductive epoxy-amine addition polymer contains structural members of the type Ia - IVa. T- OCH ₂ -CHCH ₂ -N-Ar-X-Ar-N-CH ₂ CH Oh oh HCH ₂ -J- ^{f /} ^ -OCH ₂ -CHCH ₂ -N-Ar-N-CH ₂ CH-CH ₂ J- OH OH L \ = r OCH ₂ -CHCH ₂ -N-CH ₂ CH-Ch ₂ -I- Oh oh 4. Transparent photpleitfähige layer according to item 1, 2, 3, characterized in that the photoconductive epoxy-amine addition polymer contains structural members of the type Ib and Hb. CH ₂ C ₆ H ₅ CH ₂ C ₆ H ₅ -O- / VC- / V-OCH ₂ -CHCH ₂ -N-Ar-X-Ar-N-CH ₂ CH-CH ₂ J-CH ₃ OH OH ib with Ar = X = CH ₂ 10.sup.s, -O SO ₂ . CO CH ₃ CH ₂ C ₆ H ₅ CH ₂ C ₆ H ₅ Ό- <f3 "- ^C - / 3-0CH ₂ -CHCH ₂ -N-Ar - N-CH ₂ CH-CH ₂ -L CH ₃ OH OH with Ar - ^ v> 5. Transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the structure: OH CH ₂ C ₆ H ₅ CH ₂ C ₅ H ₅ -CH ₂ - / yN-CH ₂ CH-CH ₂ 4 \ = z / i J! OH 6. Transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the structure: CH ₂ C ₆ H ₅ . CH ₂ C ₆ H ₅ XH ₂ -CHCH ₂ -NZ ^- VS-Zy-N-CH ₂ CH-CH ₂ ^ OH 7. Transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the following structure? CH ₂ C ₆ H ₅ CH ₂ C ₆ H ₅ I! CH ₃ OH 8. Transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the structure: OCH ₃ OCH ₃ 9. Transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the structure: -OCH ₂ -CHCH ₂ -N-CH ₂ CH-CH ₂ - OH OH - 33 - 2 18 3 6 5 10. A transparent photoconductive layer according to item 1, characterized in that the soluble photoconductive polymer has the structure: CHCH ₂ -N-CH ₂ CH ₂ -N-CH ₂ CH-CH ₂ - - · Oh, ^{yes, yes} 11. A transparent photoconductive layer according to item 1, characterized in that as sensitizer one or more dye salts of triarylmethane dye type are used which have a large volume organic counterion, preferably crystal violet, malachite green pikrat, fuchsin pikrat, Malachitgrüntetraphenylboranat, preferably in a proportion of 0.01 to 20% by mass. 12. A transparent photoconductive layer according to item 1, characterized in that are used as the sensitizer 0.01 to 20 percent by mass of a dyeing salt in which both anion and cation are dye ions, such as preferably methylene blue picrate and the like. Transparent, photoconductive layer according to item 1, characterized in that it comprises a soluble polyaddition product of structure (10) having a relative average molecular weight IL - 4000 and an addition of 0.1 to 1% by mass of crystal violet picrate and / or malachite green picrate contains. - 34 - · 218365 14. Transparent phot o l EIT capable layer according to item 1, characterized in that as the sensitizer an electron acceptor, preferably an aromatic Hitroverbindung and / or an aromatic carbonyl compound, especially 2,4,7-trinitrofluorenone, in a mass fraction of 15. Transparent photoconductive layer according to item 1, characterized in that a bis (cyanstyryl) arene, preferably in a proportion of 1 to 20 percent by mass, is contained as a sensitizer. 16. A transparent photoconductive layer according to item 1, characterized in that a Brb'nstedt acid, preferably picric acid, is contained as a sensitizer. 17.- Transparent photoconductive layer according to item 1, characterized in that a mixture of a dye salt and an electron acceptor according to 14 or 15 and / or a Brönsted acid is used as the sensitizer. 18. Use of the transparent photoconductive layer according to items 1 to 17, characterized in that it is used as a photoconductive insulating layer for charge transport with organic or inorganic photoconductor second layers in multi-layer systems. 19. Use of the transparent photoconductive layer-forming polymers according to item 1 to 10, characterized in that they are used as a special flexible, adhesive and photoconductive binder for per se known pigment photoconductors such as ZnO, insoluble dyes or insoluble polymers.