CH510900A - Organic metal complex photoconductor - Google Patents

Abstract

Photoconductor material for electrophotographic image prodn. comprises at least one metal-contg. organic complex cpd. of an aliphatic, aromatic or heterocyclic organic cpd. and metal, the organic cpd. having, in the spatial arrangement corresponding to the complex formation, at least one substituent capable of forming a principal valency to the metal, and an element capable of forming a secondary valency to the metal, and a non-metal of group IV, V or VI, having at least one free or uncoupled pair of electrons.

Description

  

  
 



  Electrophotographic imaging material
Electrophotographic material, which is suitable as a reproduction material for the known electrophotographic processes, which use the visualization of latent electrophotographic charge images with the aid of a triboelectric developer, usually consists of a carrier on which, optionally with the interposition of auxiliary or electrical barrier layers, an electrophotographic effective layer is located. This electrophotographic material is provided with an electrical charge in the dark and then exposed under an original using the projection and / or epidiascopic method. The result is a latent electrostatic charge image corresponding to the original, which is made visible by touching a triboelectric system.

  By heating and / or the action of solvent vapors, it is possible to anchor the developer used for image generation in a smudge-proof manner on the electrophotographic material.



   The electrophotographic layer, which is photosensitive after charging, of this electrophotographic mate rials contains certain substances which impart the electrophotographic effectiveness and which are referred to as photoconductors without restriction with regard to their mechanism of action.



   From the German Auslegeschrift 11all 015 Kl. 57 biO it is known that metal salts of 8-hydroxyquinoline and its substitution products with nonionic substituents are suitable as photoconductors. The German patent specification 1113 360 describes photoconductor layers which are wholly or partly composed of one or more compounds of the general formulas
EMI1.1
 consist, where X is one or more fused aromatic rings which can carry nonionic substituents which leave the electrical conductivity essentially unaffected, Y can be substituted, Me is a heavy metal and m is an integer identical to the valence of the heavy metal.



   The German Auslegeschrift 1192 044 teaches the use of photoconductors of the formula
EMI2.1
 where X is N or CH, R is H, OH, aryl or a single bond, together with the remainder of the same compound, A is a fused aromatic mononuclear or polynuclear radical which can be substituted with inert groups, Me is a metal and n is equal to the valence of Me, or of photoconductors of the formula
EMI2.2
 where Me is equal to a metal and A is equal to a fused aromatic mononuclear or polynuclear radical which may be substituted by inert groups, or of
Photoconductors made from a chelate compound on the basis of N, N'-DiX2-hydroxy-benzylidene) -dianisidine.



   The aforementioned patents, however, contain no indication of whether further organic compounds from the class of organic metal complex compounds could be suitable for producing photoconductors.



   Nor does it give any guidance as to the points of view according to which further organic compounds might have to be selected in order to produce usable photoconductors after conversion with metals. In contrast, the method according to the invention describes a number of different organic compounds which, in accordance with the definition according to the invention, can be used for complex formation with metals and which are also effective as photoconductors.



   It has now surprisingly been found that general compounds with metal secondary valence rings are formed from organic complex-forming molecules, in accordance with the definition according to the invention, and metals, especially those which are referred to as inner metal complexes, inner metal complex salts or metal chelate compounds , are suitable as photoconductors.



   Compounds in this sense are understood to be those in which the organic molecules used to form the complex contain groups that form true valence bonds with the metal atom and also have elements or groups that coordinate or secondary valence bonds with the same metal atom form.



   It can be regarded as certain that the inner metal complex salts consist of heterocyclic ring systems containing metal atoms, the metal atom being bonded by major and minor valences with ring closure, without, however, restricting the subject matter of the invention exclusively to the ring-shaped arrangement. In these inner metal complex salts, the metal atom can only belong to one ring system, but it can also be assigned to several ring systems, depending on the valency and, if the coordination number allows it.



   Organic metal complex compounds, such as phthalocyanines or hemin, which have heterocyclic, metal-containing minor valence rings, in which the major and minor valence bonds together belong to several heterocyclic, metal-containing minor valence rings and which also contain organic ring systems that are present in the heterocyclic metal-containing metal Minor valence ring are included and, moreover, are interconnected by conjugated systems that do not belong to the minor valence ring, show no effectiveness as photoconductors.



   Internal metal complex salts usually show less electrolytic dissociation than metal salts with an exclusively ionic bond. As a result of the different size of the inner complex rings, differences in the secondary valence binding energy, as well as the resonance energy and the mesomerism possibilities of the organic compounds used for complex formation, wide transitions exist. In addition, the atomic weight, the coordination number and the position of the metal atoms in the Periodic Table of the Elements are important.



   Heterocyclic secondary valence rings containing a metal atom of inner complex metal compounds with at least one main valence compound and one secondary valence bond on the metal atom, both of which belong to the ring system, can be characterized by the general formulas I and II. However, polymeric inner complex salts are also conceivable in which the groups X and Y are arranged in such a way that no inner molecular ring closure can be formed, for example X and Y belong to different identical or different organic molecules that produce an inner complex salt with the metal atom. The spatial position of the groups X and Y, the molecule size of the organic component, the coordination number and the valence of the metal atom are decisive for this.
EMI2.3


 

   Here, X denotes an organic grouping which is capable of forming a valence bond with the metal atom, such as, for example
EMI2.4
     -PH, -SO2H, -SO3H, -AsO (OH) 2, -As (OH) 2 or activated -H or H-ions.
EMI3.1
 means a secondary valence bond.



   Y denotes an element capable of forming at least one secondary valence bond to the metal atom, which element can also belong to an organic group and is made from a non-metal of IV., V. and VI. The main group of the periodic system consists, in particular, of oxygen, sulfur, selenium, nitrogen, phosphorus and carbon, and has a free electron pair suitable as a donor or decoupled.



   Me denotes a metal atom, n an integer from 1 to 8, or the valence of the
Metal atom.



   The connecting line between X and Y means further groupings that lead to the formation of 4-8 members
Rings are required, these members being aliphatic, aromatic or heterocyclic in nature or constituents of one or more aromatic, isocyclic or heterocyclic, optionally condensed ring systems.



     Rn denotes one or more substituents on X and Y or the groupings arranged between them, which can be different.



   The effectiveness of the inner metal complexes, created using organic complexing agents, is inherent in simple heterocyclic, metal-containing secondary valence rings. Even simple types, which consist practically only of the metal complex rings, already show a noticeable effectiveness as photoconductors. The simplest types without further conjugated systems belonging to substituents are: The Cu (II> inner complex salt of the glycocolla (formula 1.), the Ni (llp inner complex salt of the dicyanidiamidine (formula II.), As well as the Ni (IIt inner complex salt of the diacetyldioxime) (formula III.)
EMI3.2

These simple compounds show that the common major and minor valence bonds on the metal atom in conjunction with a non-metallic element of IV., V that acts as an electron donor.



  and VI. Main group of the periodic table, bound to an organic residue, which produce the effectiveness as photoconductor. However, the subject matter of the invention is not intended to be restricted to the examples given.



   If further aromatic, conjugated aliphatic or heterocyclic ring systems with aromatic properties or lone pairs of electrons are added to the inner complex rings or included in the inner complex rings, the effectiveness of such inner complex compounds as photoconductors increases.



  Ring systems that have a delocalized 71-electron bond system with electron pairs that cannot be permanently assigned and at the same time more than five possible boundary structures in the ring system, such as the anthracene, pentacene, phenanthrene or acridine ring, are also particularly valuable. The effectiveness as a photoconductor is increased if the substituents on the inner complex ring carry further groups that are capable of forming polar groups or of mesomerism.



   The accumulation of conjugated double bonds causes a shift in the light absorption towards longer-wave spectral ranges, whereby these conjugate systems can be interrupted by, for example, N-, -S-, i.e. groups that have free and easily mobile electron pairs, while the introduction of polarizable groups, like for example
EMI4.1
 -OH, -OR, -SR, halogen, 2NO, -NO2 and the like a. affects the effectiveness. The increase in the effectiveness as a photoconductor through the introduction of conjugated systems can be seen from the comparison of the Ni (IIS inner complex salt of diacetyldioxime (formula IV.) With that of benzil dioxime (formula V.), the latter being more easily electrostatically excitable and resulting in shorter exposure times.
EMI4.2




   The five-membered heterocyclic inner complex ring, which contains, for example, Cu (II) as a metal atom, experiences a considerable increase in its electrophotographic properties when it is linked to a conjugated system. If, for example, the inner complex ring of the Cu (III> inner complex salt of the glycocolla (formula I.) is compared with that of the Cu (IIt inner complex salt of 4-oxy-acridine (formula VI.) With regard to its effectiveness as a photoconductor, the effectiveness of the latter is several times greater .
EMI4.3




   A teaching for the production of electrophotographically active substances (photoconductors) can already be derived from these basic bodies.



   A large number of organic complex compounds according to the definition according to the invention and with electrophotographic activity are described in the literature.



   The table below in connection with the formulas gives, for example, a selection of X and Y and their arrangement that are capable of forming internal metal complexes and lists Rn substitutes and polarizable groups without, however, being limited to this selection or to the metals used .



     1st group: Oximes, aromatic o-nitroso-hydroxy compounds, for example compound class Effective Assumed formula designation Grouping inner complex ring image
EMI5.1


<tb> o <SEP> of <SEP> a-Dike- <SEP> 0 <SEP> inner complex salts <SEP> of <SEP> a-Ni
<tb> tone <SEP> and <SEP> aromat. <SEP> o-Ni- <SEP> C = N-OH <SEP> O <SEP> 1,2 <SEP> troso - naphthol, <SEP> des <SEP> zu
<tb> Zg, <SEP> a <SEP> = <SEP> a, <SEP> "<SEP> c = O <SEP> -oxims. <SEP> See <SEP> Sehultz color
<tb> as <SEP> Y <SEP>> <SEP> ^ <SEP> E <SEP> .5 <SEP> Q <SEP> c <SEP> r <SEP> 0 <SEP> material tables, <SEP> 7 . <SEP> edition, <SEP> 1.
<tb>



   <SEP> Bd. <SEP> 5. <SEP> d> <SEP> 5 <SEP> x <SEP> = <SEP> x <SEP> x <SEP> E <SEP> x <SEP> s <SEP> x <SEP>. = <SEP> x
<tb> <SEP> does <SEP> 0
<tb> S <SEP> m, <SEP>: P> <SEP> m <SEP> O <SEP> 3,4 <SEP> x
<tb> <SEP> C <SEP> o <SEP> Ó <SEP> = <SEP> Ge, <SEP> C <SEP> o- <SEP> tyldioxims, <SEP> z <SEP>, <<SEP> c
<tb> <SEP> c
<tb> <SEP> a <SEP> e <SEP>, <SEP> E <SEP>:

  :, <SEP> s <SEP> s <SEP> EOr
<tb> <SEP> H <SEP> OH
<tb> <SEP> IH <SEP> c
<tb> Hydroxyaldoxime <SEP> -C-C = N-OH <SEP> -c <SEP> ¸ <SEP> ÄAe <SEP> inner complex salts <SEP> of <SEP> zu
<tb> <SEP> -C-OH <SEP> ¯¯¯¯ <SEP> 7 <SEP> laldoxims
<tb> <SEP> 6N <SEP> 0M <SEP> F <SEP> F
<tb> Ketoxime <SEP> C = N-OH <SEP> -c <SEP> 6 <SEP> Inner complex salts <SEP> of <SEP> Ben
<tb> <SEP> CI <SEP> CI <SEP> zophenonoxims
<tb> cYes <SEP> containing <SEP> <) ¯ <SEP> o <SEP> AA <SEP> e <SEP> 7 <SEP> inner complex salts <SEP> des
<tb> <SEP> Oxims <SEP> des <SEP> / o- <SEP> zI <SEP> o
<tb> Oxime <SEP> 1.

  <SEP>> / <SEP> tons
<tb> <SEP> CS <SEP> I-U \ / 0 <SEP> 0
<tb> <SEP> L) '
<tb> <SEP> 7, '<SEP> inner complex salts <SEP> des
<tb> <SEP> C - N-OH <SEP> -c <SEP> 8 <SEP> oxime <SEP> of <SEP> phenyl-a-pyridyl containing N atoms <SEP>
<tb> Oxime <SEP> ¯¯¯¯¯¯ <SEP> ketones
<tb> <SEP> CNN <SEP> y
<tb> N-nitroso compounds <SEP> CNH <SEP> - <SEP> AA <SEP> e <SEP> inner complex salts <SEP> of <SEP> nitro
<tb> the <SEP> guanidines <SEP> in <SEP> the <SEP> N <SEP> 50-guanidines
<tb>:

  : C
<tb> <SEP> ¯ <SEP> Z <SEP> Z <SEP> X <SEP> o <SEP> Z <SEP> Z <SEP> Vt <SEP> Z <SEP> Z <SEP>% <SEP> X
<tb> <SEP> bO
<tb> <SEP>, <SEP> S <SEP> e, <SEP> <SEP> 2 <<SEP> M <SEP> <SEP> o <SEP> o
<tb>
EMI6.1


<tb> Nitroso-aryl-hydroxyla- <SEP>)> <SEP> N-N-OH <SEP> N <SEP> 10 <SEP> inner complex salts <SEP> of <SEP> Di
<tb> <SEP> in <SEP> of <SEP> 1! <SEP> nuethylamino-nitroso-phenylhydroxylamine
<tb> mmc <SEP> Oxmform <SEP> 0 <SEP> X <SEP> N <SEP> ¯¯¯¯¯¯ <SEP> 0 <SEP> and <SEP> of <SEP> nitroso-phenyl-hy
<tb> <SEP> II <SEP> N
<tb> <SEP> 0
<tb> <SEP> OR
<tb> X8 <SEP> R-C <SEP> / v1 <SEP> ii <SEP> tlny% okx3ml2läx5alze <SEP> der <SEP> Zim
<tb> <SEP> -OH
<tb> <SEP> R <SEP> alkyl, <SEP> aryl, <SEP> 0
<tb> <SEP> a-o <SEP> \ <SEP> /
<tb> <SEP> = <SEP> H, <SEP> Alkyf, <SEP> N
<tb> <SEP> acyl
<tb> 2.

  Group: Arylthiocarbazones, mono- and dihydrazides, biguanides, amidines, oxyamidines, azomethines, azo compounds, for example compound class Effective formula designation Grouping inner complex ring image
EMI6.2


<tb> Aryl-thioearbazone <SEP> -C-SH <SEP> - <SEP> c <SEP> 12 <SEP> inner complex salts <SEP> of <SEP> Di
<tb> prim. <SEP> and <SEP> sec. <SEP> Arylthio- <SEP> II <SEP> II <SEP> phenylthioearbazons, <SEP> Di-p-to
<tb> I <SEP> N-NH <SEP> N <SEP> N-H <SEP> lylthioearbazons, <SEP> Di-2,4-di
<tb> <SEP> methylphenyl-thiocarbazons,
<tb> <SEP> di-a-naphthylthiocarbazons,
<tb> <SEP> u, e.g.
<tb> <SEP> and <SEP> des <SEP> Di-p-biphenylthiocar- '
<tb> <SEP> bazons, <SEP> Ag inner complex salt
<tb> <SEP> of the <SEP> diphenylthiocarbazone.
<tb>



  Sulfhydrylhydrazones <SEP> -C-SH <SEP> c <SEP> s <SEP> inner complex salts <SEP> des
<tb> the <SEP> aldehydes <SEP> and <SEP> Ke- <SEP> AÄa <SEP> 2-M <SEP> ercaptobenzaldehyde-phenylhydrazone,
<tb> tone <SEP> -C-C - NN¸ <SEP> 13, <SEP> of the <SEP> 2-mereaptobenzaldazine,
<tb> <SEP> fH <SEP> 0 <SEP> ¯¯¯¯¯¯¯ <SEP> 14, <SEP> 15, <SEP> 16 <SEP> of <SEP> 1,2-mercaptonaphthalal
<tb> <SEP> H <SEP> N <SEP> dazins, <SEP> des <SEP> (4'-dimethylami
<tb> <SEP> / <SEP> \ <SEP> nophenyl) 3-mereaptonaphthyl ketone (2)
<tb> <SEP> C-SH <SEP> HSC- <SEP> -phenylhydrazone.
<tb>



   <SEP> 1 <SEP> e.g.
<tb>
EMI7.1

  <SEP> Biguanide, <SEP> also <SEP> 1- <SEP> or <SEP> H (R) <SEP> 1.2 <SEP> inner complex salt <SEP> of <SEP> o-To <SEP> 1.5 -mono- <SEP> and <SEP> di-, <SEP> sym- <SEP> N <SEP> c <SEP> ¯¯¯¯¯¯ <SEP> NH <SEP> 17 <SEP> lylbiguanids
<tb> <SEP> metric <SEP> and <SEP> asymmetrical <SEP> tric <SEP> substituted <SEP> C - NH <SEP> N
<tb> <SEP> NH <SEP> cag <SEP> H
<tb> <SEP> = Z = az <SEP> 0 =
<tb> <SEP> V <SEP> N <SEP> = <SEP> = <SEP> C <SEP> Y <SEP> V
<tb> <SEP> N3C13 <SEP> N '
<tb> <SEP> x <SEP> a: <SEP> x <SEP>.

  <SEP> 4 <SEP> N
<tb> <SEP> Azomethine, <SEP> die <SEP> U <SEP> against <SEP> = <SEP> e <SEP> tS <SEP> O <SEP> = <SEP> = <SEP> =
<tb> <SEP> if necessary <SEP> next to <SEP> Z <SEP> Sehiff's see <SEP> bases <SEP> from: <SEP> Y <SEP> o <SEP> o
<tb> <SEP> ren <SEP> substituents <SEP> on <SEP> - <SEP> l-naphthaldehyde <SEP> and <SEP> Z <SEP> oK
<tb> <SEP> aromatic <SEP> ring <SEP> in <SEP> 18 <SEP> methyl-p-phenylenediamine, <SEP> from
<tb> <SEP> o-position <SEP> or <SEP> on <SEP> -CH = <SEP> 2-mereaptobenzaldehyde <SEP> and
<tb> <SEP> heterocyclic <SEP> ring <SEP> 5, <SEP> ethylenediamine, <SEP> made of <SEP> 2-Mereap
<tb> <SEP> in <SEP> a-position <SEP> to <SEP> Alde- <SEP> X <SEP> to-5-nitro-benzaldehyde <SEP> and
<tb> <SEP> II <SEP> a <SEP> CN <SEP> ethylenediamine.
<tb>



   Wear <SEP> b, <SEP>. <SEP> CH-N \ <SEP> H
<tb> <SEP> \ -SH <SEP> HS <SEP> s <SEP> inner complex salts <SEP> of <SEP> bis <SEP> azomethine <SEP> from <SEP> 2-Mereapto
<tb> <SEP> I <SEP> O'I <SEP>> <SEP> 4O <SEP> I
<tb> <SEP> c <SEP> 19 <SEP> nitro-benzaldehyde <SEP> or
<tb> <SEP> N <SEP> R-N <SEP> thio-a-naphthaldehyde <SEP> with
<tb> <SEP> R <SEP> = <SEP> aryl, <SEP> alkyl <SEP> or <SEP> H <SEP> H <SEP> ethylenediamine.
<tb>



  I <SEP> Z <SEP> F <SEP> YI
<tb> <SEP> w <SEP> cn <SEP> o
<tb> <SEP> uD <SEP> &verbar; <SEP> I <SEP> 11
<tb> <SEP> I <SEP> z <SEP> I <SEP> ev
<tb> <SEP> Z <SEP> 11 <SEP> <SEP> -o
<tb> <SEP> II <SEP> Z <SEP>>
<tb> <SEP> I <SEP> I <SEP> t <SEP> I <SEP> I <SEP> 11 <SEP> ç
<tb> <SEP> D <SEP>; t <SEP> g <SEP> zv <SEP> =
<tb> <SEP> Uv <SEP> Y <SEP> e) <SEP> Z <SEP> Y <SEP> C <SEP> cX
<tb> <SEP> -v <SEP> v <SEP> V <SEP> .SX <SEP> = <SEP> C <SEP> Q <SEP> = <SEP> N <SEP> g <SEP> w
<tb> <SEP> C <SEP> C <SEP> m <SEP> C <SEP> o <SEP> O <SEP> m;
<tb> <SEP> N <SEP> C <SEP> C <SEP> o <SEP> C <SEP> C <SEP>: t
<tb> <SEP> w <SEP> <¯O <SEP> X <SEP> Y <SEP> O <SEP> t.¯ <SEP> <<SEP> I
<tb>
EMI8.1

 aromatic <SEP> or <SEP> hete- <SEP> 3 <SEP> 20 <SEP> inner complex salt <SEP> of <SEP> l2-pyroeyclic <SEP> ringsy- <SEP> -x <SEP> ndylazoY2-thionaphthol.
<tb>



  stems containing <SEP>
<tb> Azo compounds, <SEP> the <SEP> N = N <SEP> inner complex salts <SEP> des
<tb> in <SEP> 0- <SEP> or <SEP> a-position <SEP> 21 <SEP> 2 ', 2'-dimereapto-azobenzene,
<tb> to <SEP> azo group <SEP> little- <SEP> more <SEP> see <SEP> C <SEP> z <SEP> ") <SEP> C
<tb> at least <SEP> a <SEP> substituent <SEP> or <SEP> U <SEP> U <SEP> U <SEP> E <SEP> the <SEP> azo
<tb> th <SEP> X, <SEP> especially <SEP> -x <SEP> x <SEP> series, <SEP> for example <SEP> 2-Thio
<tb> cc <SEP> -SO3H, <SEP> or <SEP> o, Ct <SEP> naphthyl-14'-nitro-1'-azoben
<tb> next to <SEP> X'Oc = <SEP> Substi- <SEP> 22 <SEP> red <SEP> R <SEP> Sehultz dye table
Wear <tb> oC <SEP>. <SEP> Me <SEP> inner complex salt <SEP> of <SEP> C: O
<tb> -SH, <SEP> if necessary <SEP> C: <SEP> zol)
<tb> <SEP> E <SEP> len, <SEP> 7th <SEP> edition <SEP> 1931, <SEP> No.

  <SEP> 219
<tb> o <SEP> less- <SEP> Cu, <SEP> Ni inner complex salts <SEP> der
<tb> <SEP> sr <SEP> with <SEP> g <SEP> triphenylformazan-2'-earbon
<tb> at least <SEP> one <SEP> to <SEP> format- <SEP> N <SEP> - <SEP> - <SEP> H <SEP> N <SEP> acid
<tb> zankette <SEP> orthoständi- <SEP> R-07 <SEP> - /
<tb> gen <SEP> -OH, <SEP> -SH <SEP> or <SEP> MNll <SEP> ¯¯¯ <SEP> In
<tb> -COOH group <SEP> on <SEP> 11 <SEP> N
<tb> aryl
<tb> <SEP> R ', <SEP> R' <SEP> aryl <SEP> R <SEP> alkyl, <SEP> carboxo-al
<tb> <SEP> O
<tb> <SEP> F <SEP> X
<tb> <SEP> X <SEP> Z <SEP> Z <SEP> Zo
<tb> <SEP> Z <SEP> XU
<tb> <SEP>, <SEP> v <SEP> bO <SEP> = <SEP> 5 <SEP> O <SEP> ÏD
<tb> <SEP> ev <SEP>> <SEP> v <SEP> = <SEP> ¯ <SEP> 3 <SEP> uz <SEP>; <SEP> 3 <SEP> o <SEP> = <SEP> to
<tb> <SEP> D <SEP> c <SEP> c <SEP> t:

  <SEP> ¯ <SEP>> <SEP> O <SEP> s <SEP> <SEP> c <SEP> c <SEP> É <SEP> <SEP> c>
<tb> <SEP> 2 <SEP> K <SEP> E <SEP> o <SEP> o <SEP> <<SEP> c <SEP>> <<SEP> <SEP> = <SEP> c <SEP> c <SEP> <SEP> j <SEP> <<SEP> c <SEP> <SEP>>>
<tb> 3rd group: amino acids, pyridine, quinoxaline, quinzaolin, phenazine and quinoline + except the compounds derived from 8-oxyquinoline, acridines, acridones, oxy-quinacridines, indoles, pyrazines,

   Murexide for example Compound class Effective Assumed formula designation Grouping Inner complex ring image
EMI8.2

  <SEP> Y
<tb> <SEP> X
<tb> <SEP> 0
<tb> <SEP> N <SEP> =
<tb> <SEP> C3, n
<tb> <SEP> Nc
<tb> <SEP> ma
<tb> <SEP> X
<tb> <SEP> rzC
<tb> <SEP> fv,
<tb> <SEP> / <SEP> \ <SEP>
<tb> <SEP> EO
<tb> <SEP> i <SEP> i
<tb> <SEP> M
<tb> <SEP> 1
<tb> <SEP> 1 <SEP> Cl '<SEP> O) <SEP> AZ <SEP> inner complex salt <SEP> of the <SEP> glyco
<tb> a-amino acids <SEP> C - OH <SEP> - <SEP> ¯¯¯¯¯¯ <SEP> n <SEP> 23 <SEP> kolls, <SEP> of <SEP> histidine
<tb> <SEP> O <SEP> Z
<tb> <SEP> 0m <SEP> UU
<tb> <SEP> C
<tb> <SEP> I
<tb> <SEP> C
<tb>
EMI9.1

  <SEP> aromatic <SEP> or <SEP> hete- <SEP> 0 <SEP> 0 <SEP> inner complex salts <SEP> of <SEP> an <SEP> rocyelisehe <SEP> Cl '<SEP> ii <SEP> thranilic acid ,

   <SEP> the <SEP> o-amino <SEP> o <1, -2-amino carboxylic acids, <SEP>
<tb> <SEP> also <SEP> substituted, <SEP> or <SEP> -o <SEP> 0 <SEP> 0 <SEP> naphthalenedic acid, <SEP> inner
<tb> <SEP> Q <SEP> V <SEP> | <SEP> c <SEP> o <SEP> N <SEP> tk2 <SEP> x <SEP> 24 <SEP> complex salts <SEP> of <SEP> a-pyridine Me <SEP> carboxylic acid, <SEP> of <SEP >% <SEP> 0
<tb> <SEP> b¯ <SEP> the <SEP> in <SEP> to <SEP> 77 <SEP> G <SEP> linearboxylic acid, <SEP> the <SEP> quinoline-8
<tb> "'E12v15-, <SEP> 0-11 <SEP> carboxylic acid.
<tb>



   <SEP> or <SEP> for <SEP> quinoline <SEP> in <SEP> 0 <SEP> H2
<tb> a. <SEP> a <SEP> Carbo- <SEP> II
<tb> <SEP> have xyl group <SEP>. <SEP> H <SEP> E <SEP> 8 <SEP> "
<tb> <SEP> N <SEP> Åa <SEP> C <SEP> C <SEP> E <SEP> 0
<tb> <SEP> n
<tb> N /)
<tb> <SEP> 0 = 0
<tb> <SEP> O = C \ oH
<tb> <SEP> -coln <SEP> des
<tb> <SEP> 2 <SEP> <<SEP> or <SEP> Chinal- <SEP> t <SEP> F
<tb> <SEP> dine, <SEP> the <SEP> given
<tb> <SEP> if <SEP> in addition to <SEP> other <SEP> 26 <SEP> 5,7-dibromo-8-mereaptochinolins,
<tb> <SEP> Substituents <SEP> in <SEP> place- <SEP> N <SEP> N <SEP> 27 <SEP> of <SEP> 4-styryl-8-mereaptochino
<tb> <SEP> lung <SEP> 8 <SEP> a <SEP> / vie <SEP> lins
Wear <tb> <SEP> / I <SEP>.

  <SEP> 7s <SEP> - · ¸-xs
<tb> <SEP> 0 <SEP> the <SEP> in <SEP> place <SEP> - \ <SEP> OH <SEP> (-sH
<tb> <SEP> treatment <SEP> 4 <SEP> and / or <SEP> 5 <SEP> a <SEP> 28 <SEP> inner complex salt <SEP> of the <SEP> 4-Oxy
<tb> <SEP> -OH <SEP> or <SEP> aeridins
<tb> <SEP> given in <SEP>- <SEP> N
<tb> <SEP> or <SEP> next to <SEP> other <SEP> -.
<tb>



   = C) <SEP> Z <SEP> <SEP> V <SEP> ¯
<tb> <SEP> c
<tb> 3 <SEP> c <SEP> i; <SEP> a <SEP> t <SEP> s <SEP>;
<tb>
EMI10.1

 Indoles, <SEP> the <SEP> in the <SEP> position <SEP> (= <SEP> s, <SEP> = <SEP> H) <SEP> inner complex salts <SEP> of the <SEP> isatin
<tb> <SEP> aa <SEP> next to <SEP> 0
<tb> a <SEP> Substituents <SEP> II <SEP> p) = I
<tb> a <SEP> = 0, <SEP> = NH,
<tb> = S group <SEP> included.
<tb>



  Connections, <SEP> the
<tb> <SEP> Inner <SEP> pseudoacido complexes
<tb> a <SEP> pyridine <SEP> or <SEP> R <SEP> hydrates <SEP> of <SEP> picolinaldehyde, <SEP> of <SEP> Uc
<tb> a <SEP> pyrazine ring <SEP> ent- <SEP> aryl,
<tb> hold <SEP> and <SEP> on <SEP> this <SEP> C = ö <SEP> Oxalkyl) <SEP> HO \ <SEP> nyl-a-pyridylketons <SEP> after <SEP> Hy
<tb> for the <SEP> pyridine ring <SEP> in <SEP> a- <SEP> C¯¯¯¯¯ <SEP> 0 <SEP> dratisation <SEP> of the <SEP> q <SEP> .U
<tb> one, <SEP> or <SEP> with <SEP> Pyra- <SEP>
<tb> C <SEP> in <SEP> 2,3 position <SEP> 11 <SEP> ¯¯¯¯¯
<tb> one <SEP> or <SEP> two <SEP> Alde- <SEP> N <SEP> 30
<tb> hyd-, <SEP> keto-, <SEP> carboxylic acid <SEP> -¯
<tb> <SEP> o
<tb> <SEP> or <SEP> i <SEP> n
<tb> drazid groups,

   <SEP> given
<tb> at least <SEP> alongside <SEP> others
<tb> selected <SEP> substitu
<tb> ducks <SEP> wear <SEP> and <SEP> the
<tb> t) <SEP> s
<tb> <SEP> II <SEP> in <SEP> der
<tb> C) - <SEP> rca
<tb> II <SEP> (- <SEP> 11- <SEP> H <SEP>) <SEP> NH <SEP> (= <SEP> N-N) <SEP> Inner complexes <SEP> of <SEP> quinoline-2
<tb> <SEP> 3 <SEP> cL. <SEP> II <SEP> carboximide, <SEP> des <SEP> chino <SEP> C
<tb> <SEP> lin-2-carboxylic acid hydrazide,
<tb> <SEP> 11 <SEP> des <SEP> pyrazine-2,3-diacid
<tb> <SEP> - <SEP> Me <SEP> reimids <SEP> or <SEP> -hydrazids, <SEP> ins
<tb> <SEP> N <SEP> special <SEP> under <SEP> o / <SEP> \\
<tb> <SEP> from <SEP> Cu.
<tb>



   <SEP> 6
<tb> <SEP> 6 <SEP> 6 <SEP> Q <SEP> 6 <SEP> 6 <SEP> 3 <SEP> 3 <SEP> e <SEP> 6 <SEP> 6; <SEP> i <SEP> u <SEP> S <SEP> =
<tb> 4th group: Oxyketones, also produced by enol bonds, naphtho- and anthraquinones, flavones, for example, class of compounds, effective formula designation, grouping, inner complex ring image
EMI11.1


<tb> S¯i <SEP> X <SEP> 0 <SEP> = <SEP> o <SEP> - <SEP> of the <SEP> .Ci
<tb> <SEP> HC <SEP> Essigesters, <SEP> des <SEP> 0 <SEP> o
<tb> <SEP> 1 <SEP> Q <SEP> nitro-anilides, <SEP> o <SEP> Ï <SEP> i <SEP> C <SEP> C <SEP> Co <SEP> X <SEP> Ï <SEP> Xdes <SEP> acetic acid-4
<tb> <SEP> ¯¯¯¯¯ <SEP> 32 <SEP> x;

  <SEP> Y <SEP> N <SEP> 5 <SEP> <
<tb> <SEP> E <SEP> Ï = <SEP> E <SEP> S <SEP> E <SEP> = <SEP> <<SEP> <<SEP> = <SEP> 2 <SEP> == < SEP> E
<tb> <SEP> 0-OH
<tb> <SEP> CH
<tb> LC <SEP> e <SEP> aCI <SEP> an <SEP> aro- <SEP> 01 = 0
<tb> aa <SEP> or <SEP> hetero- <SEP> inner complex salts <SEP> of <SEP> Ther
<tb> c <SEP> rings <SEP> in <SEP> 33 <SEP> ephthalyl-1 <SEP>, 4-di-aeetons
<tb> the <SEP> 5:

  :
<tb> <SEP> i
<tb> <SEP> OH
<tb> <SEP> 0-OH
<tb> <SEP> R
<tb> <SEP> R <SEP> = <SEP> alkyl
<tb> <SEP> o <SEP> o <SEP> also <SEP> O <SEP> l <SEP> l
<tb> 11 <SEP> especially- <SEP> X <SEP> vv <SEP>, 2-di-oxanthraquinone <SEP> (Aliza
<tb> special <SEP> polynuclear, <SEP> = 0 <SEP> rin), <SEP> of <SEP> alizarin orange, <SEP> Ali
<tb> the <SEP> in the <SEP> neighboring position <SEP> 35 <SEP> zarin blue, <SEP> alizarin bordeaux
<tb> a <SEP> substituent <SEP> X, <SEP> -SH) <SEP> 36 <SEP> shaped <SEP> inner complex bil
<tb> to <SEP> = 0 grouping <SEP> -OH <SEP> M /, '/,', '- O <SEP> and <SEP> quinizarin <SEP> under <SEP> chain
<tb> especially <SEP> -OH <SEP> u. <SEP> dung <SEP> with <SEP> Me = 2, <SEP> more spatial
Wear <tb> -SH <SEP>.

  <SEP> Flavones <SEP> three-dimensional <SEP> with <SEP> Me
<tb> <SEP> v,
<tb> <SEP> I
<tb> <SEP> UX <SEP> V <SEP>, ° <SEP> O <SEP> X <SEP> I <SEP>
<tb> <SEP> <SEP> 9 <SEP> v <SEP> c <SEP> 3 <SEP> uz <SEP> m3 <SEP> b
<tb> <SEP> x <SEP> c <SEP>. <SEP> z <SEP>. [Li <SEP> c <SEP> FS <SEP> r <SEP> .5 <SEP> 11 <SEP> C <SEP> D
<tb> <SEP> O <SEP> wi <SEP> U <SEP> c <SEP> X <SEP> r <SEP> s <SEP> e.5
<tb> 5.

  Group: imidazoles, thiazoles, thiocyanuric acids, for example, class of compound effective Assumed formula designation grouping inner complex ring image
EMI12.1


<tb> <SEP> X <SEP> boE
<tb> <SEP> v <SEP> uz <SEP> r <SEP> v <SEP> cx <SEP> 3
<tb> <SEP> m¯a <SEP> imidazoles <SEP> s <SEP> inner complex salts <SEP> of <SEP> N.t '
<tb> <SEP> with <SEP> a <SEP> x <SEP> s <SEP> Y <SEP> c <SEP> droxy-benzimidazoles
<tb> <SEP> th <SEP> X <SEP> in <SEP> 2 position, <SEP> ins- <SEP> 2
<tb> <SEP> C <SEP> C <SEP> o, <SEP> -COOH, <SEP> CX
<tb> <SEP> -OH, <SEP> -SO3H, <SEP> o "<SEP> -c
<tb> <SEP> not <SEP> x <SEP> Q <SEP> x <SEP> the <SEP> ducks <SEP> ii
<tb> <SEP> the <SEP> to <SEP> the <SEP>> <SEP> =
<tb> <SEP> N <SEP> 00
<tb> <SEP> o,

   <SEP> orthocondes
<tb> <SEP> set <SEP> are <SEP> or <SEP> in <SEP> position
<tb> <SEP> I <SEP> 6,
<tb> cal <SEP> or <SEP> heterocyeli- <SEP>
<tb> see <SEP> substituents <SEP> tra
<tb> gen. <SEP> y
<tb> Thiazoles <SEP> corresponding to <SEP> II <SEP> 38 <SEP> inner complex salts <SEP> of <SEP> 2-Hy
<tb> The above <SEP> C <SEP> droxy-benzothiazols
<tb> <SEP> 5
<tb> <SEP> u <SEP> e.g.
<tb> <SEP> v
<tb> <SEP> A
<tb> ehe, <SEP> the <SEP> 1 <SEP> or <SEP> 2 <SEP> N <SEP> N <SEP> lent <SEP> arranged.
<tb>

 

   <SEP> To <SEP> and <SEP> there
<tb> next to 2oderl
<tb> -OH groups <SEP> contain- <SEP> S'H <SEP> (-OH)
<tb> ten. <SEP> Teehn. <SEP> mixtures
<tb> en <SEP> o
<tb> c-z <SEP> v
<tb> Z <SEP> O-CI)
<tb> <SEP> Z = <SEP> O \ <SEP> 2 = <SEP> k
<tb> <SEP> -z = <SEP> I <SEP> \ n <SEP> 0 <SEP> 1
<tb> <SEP> 3 <SEP> E <SEP> e <SEP> g <SEP> <SEP> <SEP> e <SEP> ¯ <SEP> ¯ <SEP> E <SEP> e <SEP> Z < SEP>> <SEP> 0
<tb>
The metal inner complex compounds, which are also referred to as metal inner complex salts or metal chelate compounds, are distinguished in many cases by an increased bathochromic effect compared with the organic components and the corresponding metal ions.

  Colorless or only weakly colored inner metal complexes are particularly valuable for special purposes when white surfaces are required, for example in the case of coated papers, or the photoconductors according to the invention are embedded or applied in transparent materials.



   Usually, elements of the alkaline earth, earth, noble or heavy metals are used to produce intrinsically complex metal compounds, with heterocyclic intrinsically complex ring systems that either occupy the entire metal atom or those of the spirane type in which the metal atom consists of several ring systems, depending on the valency and coordination number listened together. However, it is also possible that trivalent and polyvalent metal atoms in particular, as a result of steric hindrance, still saturate free major and minor valences through other bonds that do not belong to a heterocyclic ring system, with those that are not worthwhile; but have a homeopolar bond of the free valences, are particularly valuable.

  Furthermore, bi- or polyfunctional arrangements of X and Y, in the necessary spatial position relative to one another, can be converted to intrinsically complex metal compounds that represent linear polymers or three-dimensionally crosslinked macromolecules. For example, linear polymers form terephthalylacetone after reaction with Me = 2 with the coordination number 4, which obtain additional solubility in solvents if, instead of the terminal methyl groups, longer-chain aliphatic or aromatic groups, such as n-octyl, are inserted, which have additional solubility-increasing and adhesion-improving substituents , such as alkyl ethers, -OH groups, dialkylamino groups and the like. a. can carry.



  These connections have their own adhesive effect and are self-adhesive photoconductors.



   Spatially cross-linked macromolecules, produced by the formation of intrinsically complex secondary valence rings, form a large number of so-called metallic lacquer or chromating dyes.



   Furthermore, those dyes are particularly valuable for producing the photoconductors according to the invention, which can be fixed on textile fibers by metal stains during the dyeing process. This class mainly includes the oxyquinone, oxyketone and flavone dyes, which in particular contain the ring systems of naphthoquinone, anthraquinone, anthraquinonequinoline, phenanthrenequinone, flavone and, at the same time, substituents X adjacent to the carboxyl group in the positions on the ring system, which are due to their spatial arrangement allow the formation of internal metal complex compounds.



  For example, the metal inner complex compounds of alizarin or morine are effective photoconductors.



  Those mono- or polyazo dyes which carry substituents which allow the formation of internal complexes with metals are also valuable as photoconductors.



   A selection is mentioned in Ullmann, Enzyklopadie der technischen Chemie, 4th volume (1953), pp. 154 to 163 under body colors of the Azo series. These azo dyes contain an —OH, —SH, —COOH or —SO3H group on the aromatic radical in the o-position or on the heterocyclic ring system in the a-position to the azo nitrogen. These color bodies are particularly valuable if apart from the substituent X they have no other groups that dissociate H ions or have been used with alkalis to form salts. The selection is therefore preferably restricted to the ring systems with the chromophoric and complex-forming groups.

  The color lakes have been found to be particularly suitable, the organic components of which are produced by coupling diazo compounds with β-naphtholes or 5-oxy-phenyl-pyrazolones and then reacted with metals to form inner complexes.



  The barium and lead inner complex salts of Litholred-RS, Litholred-R or Litholrubin-BK are photoconductors of very high light sensitivity.



   Furthermore, azomethine dyes, which can be lacquered with metals to form inner complexes, are particularly valuable as photoconductors. For example, the Perlon yellow RS (Formula 8) and Zaponechtgelb (Formula 7) described in the above encyclopedia p. 164 are valuable photoconductors.



   A large number of organic internal metal complexes are characterized by their poor solubility in polar ones
Solvents, especially water, while ver different of them in non-polar solvents arelös Lich. These solvent-soluble inner metal complex compounds are particularly valuable for producing homogeneous layers when they are processed together with solvent-soluble binders or are anchored or embedded by swelling a solvent-soluble film on the surface of the same or in this through the film material. They are also valuable for producing self-adhesive photoconductors by reacting with epoxies and / or isocyanates in a homogeneous phase. A considerable number of them are used for analytical characterization and are described in the relevant literature.

  A limited one
The number is given in Feigl, Tüpfelanalyse, Vols. I and II
1960 / Frankfurt called.



   To produce the electrophotographic layer, either photoconductors are used alone or in combination with a binder, or they are converted into self-adhesive photoconductors with molecular magnification. Self-adhesive photoconductors are reaction products which contain components in a molecule that bring about both electrophotographic effectiveness and adhesion to a substrate. They can also be designed so that they are able to form a film themselves. Self-adhesive photoconductors with excellent properties are obtained if substitutents that are reactive with epoxies and / or isocyanates are added to the organic complex-forming components to impart the electrophotographic effectiveness
Reacts epoxies and / or isocyanates.

  These reaction products can be adapted to desired application purposes by adding further compounds that carry substituents that react with epoxides and / or isocyanates to increase the size of the molecule, but are not photoconductors, in the reaction to create - using epoxies and / or isocyanates generated - includes self-adhesive photoconductors.

 

   Reactive with isocyanates and / or epoxides
Groupings are in particular -NH2, -NHR, = NH, -COOH, CONH2, -CONHR, -SO3H, -SO2NH2, -SO2NHR, -OH, -SH and the activated hydrogen atom, for example in an ionized state. Furthermore, self-adhesive photoconductors can be produced in that when heterocyclic secondary valence rings of polyfunctional, complex-forming organic components are produced, molecules with their own adhesive effect are already formed.



   It is also possible to produce electrophotographic layers with the formation of self-adhesive photoconductors in that the metal atom belongs, on the one hand, to the inner complex ring of the electrophotographically active component and, on the other hand, with further valences of the substance that promotes the adhesion.



   In addition, photoconductors according to the inventive method can also be designed to be self-adhesive if the organic component is such that it is able to adhere to the substrate itself or are converted into linear polymers by forming several heterocyclic secondary valence rings which contain a metal atom together. Another form of
The electrophotographic layer is produced by embedding the photoconductors according to the invention in the carrier material.



   If a combination of binders and the photoconductors according to the invention is used to produce the electrophotographic layer, a large number of natural or synthetic materials can be used as binders for this purpose. Particularly suitable are alkyd resins made from phthalic acid and / or maleic acid and polyalcohols and natural resins, rubbers, including degraded or cyclized phenolic resins, resorcinol resins, styrenated alkyd resins, purified Manilakopal, light-colored bammar resins, cellodammar, shellac resins, aniline resins made from polyesters, and polyalcoholic silicone resins, polyesters , Pentaerythrite resins, reaction products of ureas and / or aminotriazines with aldehydes, epoxy resins, high molecular weight resinous hydrocarbons of aliphatic or aromatic nature, cellulose esters such as cellulose acetate, etherified with alcohols or partially esterified with alkyd resins,

   Cellulose butyrate or cellulose acetobutyrate, cellulose ethers such as esters of cellulose glycolic acid, methyl celluloses, ethyl celluloses, benzyl celluloses, Ke tonharze, such as cyclohexanone or methylcyclohexanone resins, coumarone resins, u. a., sulfonamide resins, resins made from heterocyclic nitrogen compounds, such as carbazole resins, polyvinyl compounds such as polyvinyl acetals, polyvinyl esters, polyvinyl chloride, polyvinylidene chloride, copolymerization resins made from vinyl compounds with other polymerizable unsaturated compounds, such as copolymers made from vinyl chloride and / or maleic acid and / or vinyl acetals and / or vinyl acetals and / or / or vinyl idene chloride and / or styrene, unsaturated hydrocarbons and the like. a.

   or also polymerization products such as polyacrylonitrile, polystyrene and polymeric hydrocarbons, as well as aldehyde resins, superpolyamides, polyurethanes, polycarbonates and the like. a. proven more.



   These binders can either be dissolved or used as dispersions, depending on their properties, in combination with one or more of the photoconductors according to the invention, optionally with the addition of sensitizing dyes, to produce the electrophotographic layer.



   The quantitative ratio of the photoconductors to the binders can be varied within wide limits, it being possible to change both the charging time and the photosensitivity. The ability to store latent electrostatic charge images over a longer period of time is also influenced by this ratio. A ratio of the photoconductor to the binder of from 3: 1 to 1: 3 is preferably used.



   A large number of the photoconductors according to the invention are strongly colored as a result of the bathochromic effect which the inner complex formation produces. This deepening of color occurs particularly in the case of already colored organic complex-forming components, in particular those with a dye character, or if the metal atom is capable of forming colored ions. A large number of these already have good photosensitivity in incandescent lamp light. A selection of them are so highly photosensitive that they can be used as sensitizers for other photoconductors, for example zinc oxide. For example, the inner complex salts of xorin or those of the lithol dyes known as a commercial product class are particularly sensitive to light.

  Colored photoconductors are particularly valuable for making electrophotographic materials that can be converted into printing forms, as they can be used to easily assess the degree of delamination.



   The colorless to yellow-colored photoconductors according to the invention generally show a photosensitivity in the range from 3000 to 4200. With these, it is useful for many forms of application to make them sensitive to the spectrum of the light used for exposure by adding known and customary sensitizers, unless arc or mercury vapor lamps are used as the light source. Usually 0.3 to 3 / o of the sensitizers are added to the electrophotographic layer. Photographs are used as sensitizers. There are z. B. The following dyes are suitable, for their identification the numbers given in Schultz Dye Tables, 7th Edition, Leipzig 1931, are used. Triarylmethane dyes, such as brilliant green (No. 760), crystal violet (No.

  785), methyl violet (no.783), Victoria blue base (no.822), midnight blue (no.823), acid violet (no.824/831), cyanine B (no.829), xanthene dyes such as rhodamine B (no . 864), rhodamine 5 G (no. 862), rhodamine 3 g (no. 868), aeridin red B (no. Methylene red (no. 856), real acid eosine G (no. 870), oxyfluorenone dyes such as fluoresoein (no. 880 ), Eosin 8 (no. 883), rose bengale (no. 889), acridine dyes such as acridine yellow (no. 901), acridine orange 2 G (no. 902), euchrysin (no.



  914), quinoline dyes such as quinoline red (No. 920), quinoline blue (No. 921), ethyl red (No. 923), pinacyanol blue (No.



  926), pinachrome blue (No. 924), thiazine dyes such as methylene blue (No. 1038), quinone and ketone dyes such as Alzarin (No. 1141), alizarin garnet (No. 1144), quinizarine (No.



  1148).



   Both electrically conductive and non-conductive materials such as: metal plates or foils, coated with metals or vacuum-deposited plastic foils, papers, fiber or fabric nonwovens, glasses, ceramic products, as well as papers, fiber nonwovens, plastic foils, in particular, can be used as carriers for the production of electrophotographic reproduction materials those made of polycarbonates or cellulose esters, glasses, wood and ceramic products are used.

 

   The preparations used to produce the electrophotographic layer are applied to this carrier material by known processes and they are dried. Layer thicknesses between 0.003 and 0.03 mm are usually particularly valuable. This electrophotographic layer can be additionally protected against harmful effects by covering it with a thin plastic layer on the surface.



   If absorbent supports are used to produce electrophotographic material, such as papers, for example, it is advisable to pretreat them with substances which prevent the penetration of the electrophotographic preparation before the electrophotographic layer is applied.



   For this purpose, preferably water-soluble colloids such as polyvinyl alcohols, methyl celluloses, cellulose glycolates, alginates, reaction products of carbohydrates with epoxides, polymethacrylic acid amides and the like are used. a.



   Flat-shaped bodies made of aluminum are preferably particularly valuable as supports for the electrophotographic layer if they have a layer of γ-aluminum oxide on their surface, which is produced thereon by the known anodizing process. If the carrier is to be suitable for printing purposes, a spongy anodized layer is used, preferably on a brushed or etched aluminum foil. For electrophotographic reproduction materials for image transfer, re-compacted anodized layers on galvanized aluminum are particularly valuable.



  The anodized layer can also contain dyes or iron oxide.



   A particular embodiment consists in converting the electrophotographic material into printing forms, in particular for the offset process. For this purpose, either surface roughened metal sheets or foils are used as a carrier, for example produced by brushing or galvanic treatment, or those made of aluminum and its alloys, which ren by anodizing or phosphating with a water-absorbent
Layer were provided.



   Furthermore, papers can be used for this purpose which are provided with a known hydrophilic layer which is customary for printing purposes and / or which have been vapor-deposited with metals, onto which the electrophotographic layer is applied. The electrophotographic material is charged by known means.



  After exposure, it is developed with a triboelectric toner system, which consists of a toner carrier and a toner. Either metals, ceramics, glass or synthetic resins are used as toner carriers. It can furthermore be expedient to produce toner carriers by coating ceramic materials or glasses with plastics which have a suitable dielectric constant. The, preferably colored, thermoplastic toner usually has a particle size of 5 to 100 μl.



   The toner and the carrier must have a significant difference in their dielectric constants.



  By selecting appropriate toner systems or changing the polarity of the charging field of the electrophotographic plate, it is possible to produce both positive and negative reproductions from the same original.



   In addition to dry development, electrophotographic images can also be produced by liquid triboelectric systems. For this purpose, use is made of a toner which is optionally dispersed in a solvent or solvent mixture which is slightly or not dissociated into ions and which contains one or more soluble or dispersed plastics.



   The developed electrophotographic images are fixed in the powder process either by heating and / or solvent vapors, while in the liquid development the toner is anchored by the binder or by itself.



   On electrophotographic plates which are to be converted into printing forms, a particle image is produced by known measures using a toner suitable for printing purposes and this is fixed. The electrophotographic layer is then removed, preferably by dissolving or heating, and the printing substrate is exposed, while the particle image remains on the printing plate. Solvents are used for decoating which dissolve the electrophotographic layer but not the toner. On the other hand, such substances can be used for decoating, the non-water-soluble electrophotographic layer.



  converted into a water-soluble state, for example by chemical reaction, and then washed off the converted electrophotographic layer. The washing process can optionally be carried out on the printing machine itself.



   The printing forms created in this way are treated with aqueous wetting agents according to the known measures of the offset printing process, which may already be contained in the solvents used for stripping, and then colored with a fat printing ink on an offset printing machine with the addition of water. They allow a large number of copies.



   example 1
For the production of the internally complex barium-8-mercaptoquinolate, according to formula 25, are
25 g barium chloride 2 H2O and
65 g ammonium acetate dissolved in 100 cm3 water. To this heated to 50 "C
Solution
30 g of 8-mereaptoquinoline, dissolved in 150 cm3 of ethanol, are added. The pale yellow colored precipitate of the
Barium mercapto quinolates is heated to 80 ° C., separated off, washed and dried.



  18 g of barium-8-mercaptoquinol are in one
Varnish, consisting of
5 g ester-soluble, highly viscous collodion wool,
6 g of a ketone-formaldehyde resin (example, the commercial product synthetic resin AP),
12 cm3 of ethanol, 75 cm3 of ethyl acetate and 20 cm3 of butyl acetate are finely dispersed on the vibrating mill.



   A 60 gram cellulose paper, which may have been protected against the penetration of the above preparation by known measures, is coated with this by machine and dried. This paper is suitable for the direct production of reproductions by the electrophotographic process. After the action of a coronary discharge, the paper is exposed to a high-pressure mercury lamp or UV fluorescent tubes under a template, and developed with a developer system consisting of a toner carrier and a toner (for example, commercial product Graph-O-Fax-Toner 39/50 and glass spheres) fixed by heating. The electrophotographic reproduction is rich in contrast and shows a high resolution.

 

   Example 2
10.25 g of diphenylthiocarbazone are dissolved in 200 cm3 of chloroform and a solution consisting of
76 g lead acetate,
20 g ammonium citrate and 300 cm3 water, added and shaken, whereby the PbADiphenylthiocarbazone) 2 formed, according to formula 12, is absorbed by the chloroform. The chloroform solution is dried and concentrated in vacuo.



  100 cm3 of this chloroform solution that
Contains 13.8 g of lead diphenyl thiocarbazonate and to the
25 cm3 of dioxane were added with
11.8 g of a modified triisocyanate with three free -CNO groups in the molecule, prepared by reacting 1 mole of trimethylolpropane with 3 moles of 2,4 (or 2,6) -tolylene diisocyanate,
75% in ethyl acetate, added and five
Heated to reflux for minutes.



   The reaction solution is applied to an aluminum foil roughened by brushing and dried. The electrophotographic material is ready for use for making reproductions.



   Briefly charged with a negative 6-10 kV under a spray electrode arrangement, exposed under a template for 15 seconds with UV fluorescent lamps and with a tribo-lectric system, for example consisting of a highly dried, crushed condensate of aminoplasts or glass beads and a toner, the thermoplastics, dyes and / or contains soot, develops a high-contrast electrophotographic image. This is fixed by heating or solvent vapors.

  The unfixed powder image is for transfer to other sheet-like materials, such as paper, plastic films and the like. a. suitable in the electric field
Example 3
The lead (-8-mercaptoquinoline) finer complex salt, according to formula 25, is produced by precipitating a weakly ammoniacal lead acetate solution with alcoholic 8-mercaptoquinoline solution as an intense yellow pigment. To produce the electrophotographic layer, which is particularly suitable for conversion into printing forms, are
50 g ethyl cellulose N 100 in
130 g of ethanol and
200 g of ethyl acetate dissolved.

  To do this, a solution is made
120 g of a hydrogenated rosin ester resin (commercial product Staybelite ester 10 der
Hercules Powder) 1500 g ethyl acetate and
200 g of butyl acetate added and then with
360 g of lead di (-8-mercaptoquinolate) on the
Finely ground the vibrating mill.



   A commercially available offset printing stencil made of aluminum that has been pretreated for printing by anodizing, phosphating or brushing is coated with the above solution in an even layer: thick and dried briefly at 100 to 120 ° C. The electrophotographic material is ready for use to create reproductions this is briefly charged under a corona discharge with 5 to 10 kV, exposed to a high pressure mercury or UV fluorescent lamp under a template in the projection or epidiascopic process and then with a toner suitable for printing purposes (for example the commercial product Graph-O-Fax-Toner No. . 39/50 of the Philip A. Hunt Company) and glass balls.

  With negative charging, a positive, high-contrast image of the original with high resolution and intense line sharpness is created. This is fixed by heating to 140 "C.



   To convert it into a printing form, the electrophotographic layer is removed by decoating with ethanol to which 5% phosphoric acid has been added. Wiped over with a cotton ball soaked in aqueous triethanolamine solution, this is colored on an offset printing machine with the addition of water.



  It allows an exact print reproduction with high print runs.



   Example 4
19.6 g of 4-oxy-acridine are dissolved in 200 cm3 of hot ethanol and a solution of 20 g of lead acetate 3 H2O dissolved in 100 cm3 of water is added with stirring, the lead inner complex salt of 4-oxyacridine precipitating according to formula 28. This is separated off, washed again with water and dried
16 g of the above complex compound are finely dispersed in 100 g of the binder combination described in Example 3 and placed on an electroplated anodized aluminum foil with a 4 F anodized layer or on an anodized, brushed lithography film made of aluminum with an anodized layer 1.5 to 3 lt thick, which is not electroplated , machine applied and dried.



   Charged with 6 to 10 kV under a coronary discharge, exposed under an original with a high pressure mercury lamp, after development with a toner consisting of polystyrene, maleinate resins and carbon black or dyes, and a toner carrier, such as glass beads, a high-contrast image is created Template.



   Example 5
21.2 g of o-oxybenzalphenylhydrazone are suspended in 120 cm3 of water and then poured through
adding
17.2 g sodium hydroxide solution, 24% strength by weight and
60 cm3 of water dissolved. This solution is on
90-100 "C heated and stirring a
Solution of
10 g of CdCl2 - 1 H2O are added dropwise to 100 cm3 of water, and after a short time
Boil the Cd inner complex salt of the o-oxybenzal-phenylhydrazone, accordingly
Formula 13, fails in the form of a yellow precipitate. This is slurried several times, filtered off and then dried.



   2.5 g ethyl cellulose N 100
7 g of a modified fuel-soluble, non-curable phenolic resin from the Novo lacquer range (for example commercial product
Alnovol 229 k) are in
20 g ethanol,
70 g of ethyl acetate as well
20 g butyl acetate dissolved,
14 g of the above-described inner cadmium complex compound added and ground up.



   To produce an electrophotographic plate, which is particularly suitable for converting into a printing form, an aluminum sheet pretreated by anodizing or brushing for printing purposes is coated evenly with the dispersion described above and dried at 100 to 120 ° C. in a stream of hot air.



   The image generation and the conversion into a print carrier are carried out according to Example 3. The printing form is characterized by high contrast and exact reproduction of the line image.



   Example 6
15 g of 2-hydroxybenzimidazole are dissolved under He warm in 200 cm3 of ethanol and with a solution, existing from
25 g lead acetate - 3 H2O
3 cm3 conc. aqueous ammonia and 200 cm3 water are added while stirring. A precipitate of the lead (-2-hydroxybenzi midazole), - inner complex salt, forms accordingly
Formula picture 37. This is shown several times with
Water and then washed with methanol and dried
16 g of the above photoconductor are slurried in 100 cm3 of the binder combination specified in Example 5 and finely dispersed on the vibrating mill.

  With cyclohexanone im
Diluted ratio 1: 1, the so obtained is
The preparation was applied by machine to 80 gram cellulose paper and dried
The electrophotographic paper produced in this way for reproduction purposes with a white layer is briefly charged under a spray electrode arrangement with negative 6 to 8 kV, exposed under a template with a high-pressure mercury lamp and then according to known measures, for example with the commercial product Graph-O-Fax toner and glass balls, developed and fixed. This electrophotographic material has a high resolution and enables a high-contrast reproduction of a black line image, for example, on a white background.



   0.8 g of Rhodamine-B-Extra are added to the preparation of 16 g of photoconductor and 100 cm3 of the binder combination described in Example 5 and used to coat an aluminum foil suitable for printing purposes. With a corona discharge negatively charged with 8 kV, exposed with a 100 W incandescent lamp at a distance of 10 cm under an original for 5 seconds, a high-contrast image is created after development and fixing, which can be converted into a printing form using known measures.



   Example 7
33 g of 2-hydroxybenzothiazole are dissolved in 200 cm3 of ethanol. This solution is poured into 300 cm3 of a 16.7% strength by weight aqueous lead acetate solution which had previously been made so weakly alkaline by adding aqueous ammonia that no cloudiness occurred.



   The inner complex salt of lead (-2-hydroxy benzothiazole) 2, according to formula 38, precipitates out as a precipitate, which several times with
Water is washed and dried.



   16 g of the lead compounds described above are used in
100 cm3 of the paint described in Example 5 finely dispersed
An aluminum foil suitable for printing purposes (for example the commercial product Rotaprint Rotablatt E) is coated with the above preparation with a layer thickness of 0.006 mm on the centrifuge and dried. Negatively charged under a corona discharge and exposed through an original with a high-pressure mercury lamp, a high-contrast electrophotographic image of high resolution and the finest reproduction of the detail is created after development. To convert into a printing form, the procedure is as in Example 3. It allows a large print run and is characterized by a high-contrast line image when reproducing the finest lines.



   Example 8
The known commercial product Litholrot RB extra BASF, which represents the Ba inner complex salt of Litholrot RS, analogous to Formula 22, is slurried five times in hot water for the purpose of cleaning and then dried.



   16 g of purified Lithol Red RS are introduced into 100 cm3 of the lacquer formulation described in Example 5 and finely dispersed in a vibratory mill. A deep red colored, well-flowing lacquer is formed, which is used to generate the electrophotographic
Layer is used.



   A commercially available aluminum printing stencil for the offset process is evenly coated on the centrifuge with a layer thickness of 0.005 mm and dried. Negatively charged for 3 seconds under a spray electrode arrangement and then exposed for 2 seconds under a template with UV fluorescent tubes, then developed according to known measures, a high-contrast electrophotographic image is created.



   The compound is also highly sensitive to light in the spectral range of tungsten wire lamps.



   The above preparation for creating the electrophotographic layer is applied by machine to a commercially available paper printing stencil for offset printing, which has a hydrophilic intermediate layer, and then dried. Negative is charged with a 150 W incandescent lamp at a distance of 10 cm through a microfilm with the aid of a projection device If exposed for 5 seconds, a high-contrast electrophotographic image is created after development, which can be converted into a printing form according to known measures.



   Example 9
15 g of 3,5,7,2 ', 4'-pentahydroxyflavone (Morin) are dissolved in 200 cm3 of ethanol and converted into a solution consisting of
50 g of lead acetate and 250 cm3 of water are allowed to flow in while stirring. A deep orange precipitate forms, which is washed several times with water and then dried.

 

   16 g of the lead morinate inner complex salt, corresponding to Formula 36, are added to 100 cm3 of the paint described in Example 5 and dispersed on the vibrating mill. A well flowing one forms
Preparation for the production of the electrophotographic layer, which is on an aluminum plate suitable for printing purposes, on a shiny anodized aluminum sheet or on a
Paper is applied with a layer thickness of approx. 0.006 mm and dried.



   This electrophotographic material is highly sensitive to light in both UV and incandescent light.



  A commercially available aluminum foil pretreated for printing purposes by anodizing (for example that known as Rotaprint Rotablatt E) is sensitized with the above dispersion to produce the electrophotographic layer and dried. Charged with negative 6 to 10 kV under a coronary discharge, exposed for 2 seconds under a template with UV fluorescent tubes, a high-contrast image is created after development with a triboelectric system (for example the commercial product Graph-O-Fax-Toner 39/50 and glass spheres), which is also suitable for reproducing large areas.



   For conversion into a printing form, especially for the offset process, the above-described electrophotographic plate, the powder image of which was fixed by heating to 140 "C, is decoated with a mixture of 90 vol. 0/0 technical ethanol and 10 vol.% Formic acid and the hydrophilic plate The printing plate is uncovered in the areas that do not carry any toner. Wiped over with an aqueous wetting agent, the printing plate is inked with printing ink on an offset printing machine with the addition of water. It allows a large print run with precise printing.



   In order to produce an electrophotographic plate, which is particularly suitable for transfer purposes, an electrolytically gloss-treated aluminum or copper foil is sensitized in accordance with the above. When charged with a negative 8-10 kV and exposed in a magnifying apparatus with a 150 W incandescent lamp through a lens with an aperture ratio of 1: 4.5 at a distance of the incandescent lamp to the image plane of 80 cm for 10 seconds, a high-contrast reproduction of the original is created known measures is developed.



   The electrophotographic plate provided with the unfixed powder image is covered with a sheet of paper or a plastic film and then placed in an electric field in such a way that the negative electrode is arranged on the back of the transfer sheet. The result is a legible transfer of the powder image, which is fixed by heating and / or solvent vapors.



   To create a printing stencil from paper, the procedure described above is analogous.



   Example 10 12 g of 1,2-dioxyanthraquinone (alizarin) are dissolved in 200 cm3 of ethanol and 50 cm3 of acetone. 12 g of chromium (III-sulfate - 5 H2O dissolved in 100 cm3 of water) are poured into this solution. The deep yellow precipitate which forms immediately is filtered off, slurried several times in water and, after separation, dried.



  16 g of the chromium inner complex salt of alizarin, analogous to formula 35, are finely dispersed in 100 cm3 of the paint described in Example 5 and used to coat an electroplated aluminum sheet, a commercially available aluminum printing stencil (commercial product Rotaprint Rota sheet E) and one pretreated against the penetration of solvents
80 gram cellulose paper is used.



   The electrophotographic material produced from this is highly sensitive to light in the spectral range of the mercury vapor lamp. According to known measures, high-contrast reproductions can be produced from this, which can be converted into a printing form or transferred to other sheet-like materials in an electric field.



   Example 11
45 g - of the phenylhydrazone of 4'-dimethylamino phenyl-3-oxynaphthyl ketone (2) are dissolved in 500 cm3 of warm ethanol and a weakly ammoniacal solution of
24 g lead acetate - 3 H2O added to 300 cm3 water.



   A greenish-gray amorphous precipitate is formed, which consists of the lead inner complex salt of the phenylhydrazone of 4'-dimethylaminophenyl-3-oxynaphthyl ketone2), according to formula 16. Washed Pb-ion-free with water and then dried, 6 g of the inner complex salt are finely dispersed in 80 cm3 of the paint described in Example 5. A finely grained, roughened aluminum foil suitable for printing is coated evenly with the above preparation, which gives the electrophotographic layer, and dried. The electrophotographic material is already highly sensitive to light in the long-wave UV spectral range.

  According to the measures described in the above examples, an image is then generated, fixed and then optionally converted into a printing form.



   EXAMPLE 12 9 g of phenylthienyl ketoxime are dissolved in 150 cm3 of ethanol and a weakly ammoniacal solution of 20 g of lead acetate-3 H2O in 150 cm3 of water is allowed to flow in with stirring at 20 ° C. A white precipitate is formed, which is several times with Wash out water and then dried.



  12 g of the lead inner complex salt of phenyl thienyl ketoxime according to formula 7 are finely dispersed in 75 cm3 of the binder combination described in Example 5 on the vibrating mill.



   To produce a printing plate, the above-described electrophotographic lacquer is applied to a roughened aluminum sheet and then dried.This electrophotographic material is sensitive in the spectrum of the high-pressure mercury lamp and can be made photosensitive to the spectrum of the incandescent lamp by adding 2% rhodamine B, brilliant green or ethyl red will.

 

  Charged under a negative corona discharge of 6-8 kV and exposed through an original under a high-pressure mercury lamp without the addition of sensitizers to the electrophotographic layer, arises after
Develop an electrophotographic reproduction with toner and glass balls, which is fixed by heating. The conversion into a printing form takes place according to example 3 or 9.



   Example 13
29.4 g of isatin are in
8 g sodium hydroxide and
500 cm3 of water are dissolved into this solution
38 g lead acetate - 3 H2O, dissolved in
200 cm3 of water, allowed to flow in while stirring.



   The lead (isatin) 2 inner complex salt is formed as an orange precipitate according to formula 29. This is washed several times with water, filtered off with suction and dried
16 g of the isatin lead compound are added to 100 cm3 of the paint described in Example 5
Dispersed with the aid of a vibrating mill; and then a galvanically polished aluminum foil is coated on the centrifuge and dried.



   The material provided with the electrophotographic layer with a layer thickness of 0.005 mm is light-sensitive both in long-wave UV and in incandescent lamp light.



   To produce reproductions, this electrophotographic material is charged under a negative spray electrode assembly with about 8 kV and exposed for 5 seconds under an original with a high-pressure mercury lamp. After development with the commercial product Graph-O-Fax-Toner 39/50 and glass spheres, a high-contrast powder image is created, which is fixed by heating. The unfixed powder image is suitable for transferring to flat materials, such as paper or plastic films, in an electric field.



   Example 14
17.3 g of a-nitroso-ss-naphthol are in
Dissolved 300 cm of ethanol and this with stirring
Solution
29 g cobalt nitrate - 6H2O and
150 cm of water at 50 "C were added dropwise.



   Red-brown crystals form, which are separated, washed several times with water and then dried. The Cobalt-3
Inner complex salt of a-nitroso-P-naphthol, according to formula 2, is in non-polar solvents, such as
Chloroform, esters of acetic acid, dioxane, aliphatic ketones, cyclohexanone and others, soluble in red color.



   2 g Co (-a-nitroso-ss-naphthol) 3
6 g of a hydrogenated resin acid (for example the commercial product Staybelite Resin) and
4 g of a ketone resin (for example the
Commercial product synthetic resin AP) are sold in
30 cm3 of cyclohexanone dissolved and after dissolution and
cooling down
100 cm of ethyl acetate added.



   A cleaned sheet of copper is coated with the above solution by machine so that a layer thickness of 0.003 mm is formed. In addition, the same solution is used to coat an aluminum foil that has been phosphated for printing purposes and also a 60 gram cellulose paper that has been pretreated to prevent the penetration of the coating solution.



   The electrophotographic material is sensitive to both longer-wave UV and incandescent light. If, for example, the electrophotographic material produced using a copper foil is charged under a corona discharge with a negative 6-10 kV and then exposed for 10 seconds with UV fluorescent tubes under a template, a high-contrast electrophotographic image is created after development, which is fixed by heating.



   If a 100 W incandescent lamp is used at a distance of 10 cm and the electrophotographic material, which has a paper carrier, is exposed for 20 seconds, a clearly visible image is also produced after development.



   The electrophotographic material is suitable for conversion into a printing form or can be used for image transfer.



   Example 15 Bis-N, N'-2oxynaphthalethylenediamine, prepared by reacting 2 moles of 2-oxynaphthalaldehyde A1) with one mole of ethylenediamine, F => 280 "C, are added to 500 cm3 of dimethylformamide under refluxing
Boiling dissolved.



   Get into the hot solution
12 g nickel chloride - 6 H2O, dissolved hot in 100 cm3 dimethylformamide, added and afterwards
Combination briefly boiled on the reflux condenser.



   It is allowed to cool and the reaction product is poured into
5 liters of water, after which the Niekel inner complex salt of bis-N, N'-2-oxynaphthalene-ethylenediamine, analogous to Formula 13, is deposited as a yellow-brown precipitate. After separation, this is washed several times with water and dried.



   8 g of the photoconductor described above are in
70 cm3 of the binder combination described in Example 5 was finely dispersed on the vibrating mill.



   To produce the electrophotographic material, this preparation is applied to a 110 gram cellulose paper, a 60 gram cellulose paper vapor-deposited with aluminum in a vacuum, an aluminum foil that has been pretreated for printing purposes and an aluminum sheet that has been subjected to an electrolytic gloss treatment. The well adhering electrophotographic layer is used for image formation in accordance with the above examples. The compound is highly sensitive to light in both the ultraviolet and incandescent light. The corresponding electrophotographic materials can be converted into printing forms according to known measures described above or are used for image transfer.



   Example 16
According to known methods, the nickel Innerkom plexsalz of diacetyldioxime is produced. To produce an electrophotographic layer
23 g ethyl cellulose N 100,
160 g ethanol, 3400 g ethyl acetate,
60 g of a hydrogenated rosin acid ester, vornehm Lich from hydrogenated abietic acid ester be standing (for example the commercial product
Staybeliteester 10),
150 g isopropanol,
310 g of butyl acetate and
180 g Ni inner complex salt of diacetyldioxime, corresponding to formula 3, ground on a vibrating mill for one hour.



   A carrier suitable for printing purposes (for example the commercial product Rotaprint Rotablatt E) is coated with the above preparation on the spinner in such a way that a layer thickness of 0.025 mm is formed.



   By reacting excess ammoniacal nickel chloride solution with an alcoholic solution of benzil dioxime, the nickel inner complex salt of benzil dioxime, according to formula 4, is produced. Corresponding to the above approach for producing the electrophotographic layer, the nickel inner complex salt of diacetyl dioxime is replaced by the nickel inner complex salt of benzil dioxime, and an electrophotographic plate is produced by the same methods and on the same support.



   In comparison, both electrophotographic plates suitable for conversion into printing forms are charged for 5 seconds with a negative 10 kV under a spray electrode arrangement and exposed to UV fluorescent tubes under the same original. While the electrophotographic plate, which was produced using the Ni inner complex salt of diacetyl dioxime, requires an exposure time of 35 seconds, the one produced using the Ni inner complex salt of benzil dioxime requires an exposure time of 20 seconds. The commercial product Graph-O- was used for development. Fax toner 39/50 and glass beads used. Both materials are suitable for creating reproductions, converting them into printing forms or for transferring images.



   Example 17
According to Beilstein Vol. 26, page 256, triethiocyanuric acid is obtained by reacting
61 g of cyanuric chloride and 100 g of sodium sulfide - 9 H2O produced in the ball mill for 6 hours. The reaction product is taken up with 11 water, filtered off with suction, several times with
Water washed and dried.



   16 g of triethiocyanuric acid are dissolved in 100 cm3 of dimethylformamide with moderate heating. For this purpose, a solution consisting of is added at 30 ° C. with stirring
50 g lead acetate 3 H2O and 100 cm3 water, which until the alkaline reaction with
Ammonia was added and then filtered, added, the lead complex of trithiocyanuric acid immediately separating out as a green-yellow precipitate. This is filtered off, repeatedly slurried in water and dried. The inner lead complex compound of triethiocyanuric acid contains 25.2% sulfur and 54.8% lead.



   19 g of the above photoconductor are in 100 g of a binder combination, consisting of:
60 g of ethyl cellulose N 100, 120 g of a hydrogenated rosin ester resin (for example the commercial product
Staybelite ester 10), 700 g of ethyl acetate, 220 g of isopropanol, 150 g of butyl acetate and
50 g of cyclohexanone finely dispersed in a vibrating mill and used to produce the electrophotographic layers.



   These are produced by machine on a glossy anodized aluminum foil, an 80 gram cellulose paper vaporized with aluminum in a vacuum or on a commercially available printing template made of metal or paper (for example, commercial product Rotaprint Rotablatt E).



   The electrophotographic material is charged under a coronary discharge with a negative 8 kV and then exposed to a 500 W nitraphot lamp at a distance of 20 cm for 3-5 seconds, depending on the substrate, and with a triboelectric system (for example commercial product Graph-O-Fax-Toner 39/50 and glass balls). In a separate approach, AO rhodamine B is added to the electrophotographic layer 1 as a sensitizer and the electrophotographic layer is produced on the above supports.



   The exposure times are reduced to 0.5-2 seconds with the same light source by adding Rhodamine B.



   The electrophotographic material can be converted into a printing form according to known and above-described measures, is used to create reproductions or to transfer images in an electric field.



   Example 18
According to Example 3, instead of 360 g of lead diX8-mercaptoquinolate) a mixture consisting of 220 g of leadA8-mercaptoquinolate) 2 and 120 g of the commercial product Litholrot RB extra is dispersed on the vibratory mill using the same combination of binders and for coating a substrate suitable for printing purposes (For example, commercial product Rotaprint-Rotablatt E) is used.



   Charged according to Example 3 and exposed for 3 seconds with a 500 W nitraphoto lamp at a distance of 20 cm under an original, a high-contrast electrophotographic image is produced after development, which can be converted into a printing form by known measures. This electrophotographic material has good sensitivity to incandescent light.



   Example 19
5 g of the cobalt inner complex salt of α-nitroso-ss- naphthol turn into a deep red color
Solution in 75 g of cyclohexanone and 50 g of acetone dissolved warm and filtered and used for
Generation of the electrophotographic
Layer used in and on a plastic film.



   For this purpose, the above solution of the photoconductor is applied to a 0.05-0.1 mm thick film made of cellulose acetate containing plasticizers from the range of phthalic acid esters (for example the commercial product Ultraphan from Lonza AG) and then wiped off with an air knife and dried The photoconductor is embedded evenly in the surface of the film. The material sensitized in this way is colored red and clearly transparent.



   This electrophotographic film is placed on a metal plate and then charged negatively or positively under a corona discharge with 5-10 kV, exposed under a template with UV fluorescent tubes or in a projection process with incandescent lamp light. The electrophotographic film is then separated from the conductive substrate and developed with a triboelectric system (for example the commercial product Graph O-Fax toner and glass spheres). The resulting image is either fixed by heating to 120 "C or transferred to other sheet-like materials in an electric field. Image generation and transfer can be carried out continuously and automatically.

 

   If the sensitized side of the film is placed on the metal plate, positively charged and, after exposure, developed as above, a negative image is created from a positive original. After image formation, this film can be laminated to a support such as paper by heating.



   Example 20
10 g of 4-nitro-2 ', 4'-dioxy-azobenzene are in
Dissolve 200 cm3 of ethanol with the addition of one equivalent of aqueous ammonia at 40 ° C. For this purpose, a
Solution
15 g of nickel chloride hexahydrate and
100 cm3 of water were added dropwise. The inner complex salt of the nickel-diA4-nitro-2 ', 4'-dioxy-azobenzene) precipitates out as a brown-black precipitate, which is dried after washing several times with water.



   11 g of the above Ni inner complex salt becomes that described in Example 3 in 75 g
Binder combination finely dispersed and thus one by etching and subsequent
Application of an anodized layer made of absorbent aluminum foil coated.



   Negatively charged with 8 kV under a corona discharge and under a template with UV fluorescent tubes.



  If exposed for 5 sec., After development with a toner and toner carrier, for example the commercial product Graph-O-Fax-Toner 39/50 and glass spheres, a high-contrast positive image of the original is created. The development is also successful with polystyrene powder with a particle size of 0.1-50 liters and glass spheres, whereby a white image is created on a dark background. This is particularly suitable for printing purposes. The powder image is fixed by heating.



  The electrophotographic material can be converted into a printing form by known measures of decoating. It allows a high circulation.



  Formula picture 1
EMI21.1
   Me (II) = Pb
UO2
Cu formula picture 2
EMI21.2
   Me (III) = Co
Fe formula picture 3
EMI22.1
 Me = Ni formula 4
EMI22.2
 Me = Ni formula picture 5
EMI22.3
 Me = Cu formula 6
EMI22.4
 Me = Pb formula 7
EMI22.5
 Me = Pb formula picture 8
EMI23.1
 Me = Ni
Pb
Co
Pt formula picture 9
EMI23.2
 Me = Pd formula picture 10
EMI23.3
 Me = Ni
Co
Fe
Ba
Pb
Cu formula picture 11
EMI23.4
 Me = Cu, Ni, Co, Cd Formula 12
EMI23.5
 Me = dithizone metals according to G. Iwantscheff The dithizone and its application in micro- and trace analysis, Weinheim (1958).
EMI23.6
  



  Formula picture 13
EMI24.1
   Me = Cu, Ni, Pb, Co, Cd Formula 14
EMI24.2
 Me = Cu, Ni, Co, Pb, Cd Formula 15
EMI24.3


<tb> <SEP> CHN <SEP> - <SEP> N <SEP> CH
<tb> <SEP> 7 <SEP> \ 4 <SEP> / <SEP> \ <SEP> Mc <SEP> = <SEP> Cu, <SEP> Ni, <SEP> Co, <SEP> Pb, <SEP > Cd, <SEP> Zn
<tb> ;;

  ; o / xo
<tb> <SEP> 1 <SEP> yI
<tb> Formula picture 16
EMI24.4


<tb> <SEP> C <SEP> = <SEP> Pb
<tb> <SEP> 7
<tb> <SEP> OH3
<tb> <SEP> 1 <SEP> e <SEP> ¸ <SEP> hL <SEP> H3
<tb> <SEP> HNffi
<tb> O <SEP> H <SEP> Me <SEP> H <SEP> <
<tb> <SEP> II
<tb> H, C / <SEP>
<tb> Formula picture 17
EMI25.1
 Me = Cu formula picture 18
EMI25.2
   Me = Cu, Co, Pb, Cr, Cd Formula picture 19
EMI25.3
 Me = Cu, Co, Ni, Pb, Fe, Cd Formula 20
EMI26.1


<tb> A <SEP> Mc <SEP> = <SEP> Zn, <SEP> Cu, <SEP> Cd, <SEP> Co, <SEP> Pb, <SEP> Fe, <SEP> Bi, <SEP> Ba
<tb> <SEP> N
<tb> <SEP> N <SEP> 0
<tb> <SEP> YMYi <SEP> N
<tb> Formula image 21
EMI26.2
 Me = Cu, Ni, Pb, Co, Cd, Ba Formula picture 22
EMI26.3


<tb> o
<tb> Mc <SEP> Q <SEP> o <SEP> mm <SEP> = <SEP> Ba, <SEP> Ca, <SEP> Ni, <SEP> Cu, <SEP> Pb, <SEP> Cd,

   <SEP> Co
<tb> X <SEP> N <SEP> ¯ <SEP> N <SEP> X
<tb> Formula picture 23
EMI26.4
 Me = Cu, Au, formula 24
EMI27.1
   Me = Zn, Cd, Cu, Ni, Co, Pb, Hg Formula picture 25
EMI27.2
   Me = Ag, Cu (I) Formula 26
EMI27.3
   Me = Ba, Zn, Cd, Pb, Cu (II), Ni,
Sn4 Al, Mn, Fe Formula 27
EMI27.4
 Me = Al, Cr (III),
Bi, Fe (III) formula 28
EMI27.5
 Me = Zn, Cd, Pb, Ni, Cu Me3 = ring systems analogous to formula 27 with Co (III),
Al,
Fe (III),
Cr (III) formula picture 29
EMI28.1
   Me = Pb, Ni, Cu Formula 30
EMI28.2
 Me = Cu, Co, Ni Formula 30
EMI28.3
 Me = Cu, Co, Ni Formula picture 31
EMI28.4
 Me = Cu formula picture 32
EMI29.1
 Me = Cu, Ni,

   Co
EMI29.2


<tb> <SEP> H
<tb> <SEP> g, /,
<tb> <SEP> O <SEP> O
<tb> <SEP> S <SEP> /
<tb> <SEP> e
<tb> Formula image <SEP> 33 <SEP> <SEP> l <SEP> kl
<tb> <SEP> 70
<tb> <SEP> c / <SEP> -1 <SEP> / <SEP> ss-R
<tb> <SEP> II
<tb> <SEP> H <SEP> O \ / O
<tb> <SEP> tte
<tb> <SEP> J
<tb> <SEP> R0yx07O) x
<tb> <SEP> H
<tb> Me = Cu, Ni, Zn, Co, Fe, Mn, Ba, Cd, Pb Formula 34
EMI30.1


<tb> <SEP> 0
<tb> HO
<tb> <SEP> 0
<tb> <SEP> \ <SEP> 7 <SEP> Formula image <SEP> for <SEP> Me2 <SEP> = <SEP> Ni, <SEP> Mn, <SEP> Co, <SEP> Be, <SEP> Pb,

   <SEP> Cd
<tb> <SEP> Me
<tb> <SEP> M <SEP> for <SEP> Me3 <SEP> = <SEP> analogue <SEP> 35
<tb> <SEP> O <SEP> O
<tb> <SEP> C
<tb> <SEP> o
<tb> Formula picture 35
EMI30.2


<tb> <SEP> HO <SEP> N1Oz
<tb> 02 <SEP> 7 /
<tb> <SEP> - <SEP>
<tb> <SEP> HO <SEP> 0
<tb> <SEP> yÜ
<tb> <SEP> oH
<tb> <SEP> X <SEP> S
<tb> <SEP> O <SEP> Formula image <SEP> for <SEP> Me3 <SEP> = <SEP> Al, <SEP> Cr, <SEP> Fe, <SEP> W
<tb> <SEP> for <SEP> Me2 <SEP> = <SEP> analogue <SEP> 31
<tb> Formula picture 36
EMI31.1


<tb> <SEP> HO
<tb> <SEP> 0
<tb> <SEP> \ -OH
<tb> <SEP> 11 <SEP> 11 <SEP> v
<tb> <SEP> OH
<tb> <SEP> 4 \ 0, <SEP> 3
<tb> with <SEP> Me4 <SEP> o <SEP> \ <SEP> <= <SEP> with <SEP> Me3
<tb> <SEP> c
<tb> <SEP> HO <SEP> H / <SEP> to <SEP> Me2 <SEP> = <SEP> Pb, <SEP> Cd, <SEP> Ni, <SEP> Mn, <SEP> Be, < SEP> Zn, <SEP> Cu
<tb> <SEP> Me3 <SEP> = <SEP> Al, <SEP> Cr,

   <SEP> l <SEP> Me3 = Al, Cr, WW
<tb> <SEP> HOXYHÖ <SEP> 7 <SEP> -Me4 <SEP> Me4 <SEP> = <SEP> Zr, <SEP> Sn
<tb> Formula picture 37
EMI31.2
   Me1 = Ag Me2 = Zn, Cd, Pb, Cu Formula 38
EMI31.3

 NY <SEP> MeN¯
<tb> <SEP> Me <SEP> = <SEP> divalent <SEP> metals <SEP> Pb, <SEP> Tl, <SEP> Cu, <SEP> Cd
<tb>

 

Claims (1)

PATENT CLAIM Material for electrophotographic imaging, which has a support and a photoconductive layer, characterized in that the photoconductive layer contains at least one metal-containing, organic complex compound of aliphatic, aromatic or heterocyclic organic compound and metal, the organic compound in which the complex formation corresponding spatial arrangement has at least one substituent X, which is capable of forming a major valence to the metal, and at least one element Y, which is capable of forming a minor valence to the metal and a non-metal of IV., V. or VI. The main group of the periodic table is where the non-metal has at least one free or decoupled electron pair. SUBCLAIMS 1. Material according to claim, characterized in that the metal is an alkaline earth, earth, noble or heavy metal. 2. Material according to claim and dependent claim 1, characterized in that the metal-containing, organic complex compound has a heterocyclic, metal-containing secondary valence ring. 3. Material according to claim, characterized in that the photoconductive layer consists of the organic, metal-containing complex compound alone or of a mixture of these with natural or synthetic binder. 4. Material according to claim, characterized in that the organic, metal-containing complex compound contains groups which are reacted with epoxy and / or isocyanate to enlarge the molecule, so that the organic metal-containing complex compound can adhere to the carrier without a binder. 5. Material according to claim and dependent claim 4, characterized in that the metal atom in the molecule of the organic metal-containing complex compound jointly belongs to both the photoconductivity and the group that promotes adhesion. 6. Material according to claim and the dependent claims 4 and 5, characterized in that part of the valences of the complex-forming metal atom is involved in the organic complex compound in the form of an inner metal complex and the remaining part of the valences of the metal atom is saturated by further inorganic or organic groups . 7. Material according to claim, characterized in that it has a flat material made of metal, plastic film, paper, glass or ceramic material as the carrier, the carrier containing an additional, conductivity-increasing layer or conductivity-increasing additives, such as by vapor deposition Metal layers produced with metals in a vacuum, on or in which the photoconductor and / or the photoconductive layer is applied or embedded. 8. Material according to claim, characterized in that the photoconductive layer contains at least one sensitizer for shifting the spectral photosensitivity. 9. Material according to claim, characterized in that the photoconductive layer is applied directly or via an intermediate layer which increases the electrical conductivity to a support suitable for printing purposes, so that the electrophotographic material can be converted into a printing form after image generation. 10. Material according to claim, characterized in that it is suitable for the transfer of electrophotographic images to other materials, preferably under the action of an electric field or by pressing. 11. Material according to claim, characterized in that the metal-containing organic complex compound is an internal metal complex, an internal metal complex salt or a metal chelate compound. 12. Material according to claim, characterized in that X is an active hydrogen-containing or hydrogen ion-supplying group. 13. Material according to claim, characterized in that X is one of the following groups: -OH, -SH, = N-OH, EMI32.1 = NH, -NH2, = CH2, -COOH, EMI32.2 EMI32.3 = PH, -S02H, -SO3H, - AsO (OH) 2 or -As (OH) 2. 14. Material according to claim, characterized in that Y is oxygen, sulfur, selenium, nitrogen, phosphorus or carbon. 15. Material according to claim, characterized in that the organic compound, in addition to the substituent X, has at least one substituent Rn, which is preferably one of the following groups: N (R1) R2, -COOR1, EMI32.4 = 0, = S, EMI32.5 -CN, -SR1, -OR1, -NO, -NO2, or a halogen atom, where R 'and R2 are identical or different and are hydrogen atoms or optionally substituted aliphatic or aromatic hydrocarbon radicals and Ar is aryl or conjugated unsaturated aralkyl.