DE2018038B2 - Process for the production of an electrophotographic recording material - Google Patents

Description

R :.

X '

z-

R ₂

35

40

wherein R ₁ and R ₂ each equal to a phenyl group or substituted phenyl group in which a substituent consists of an alkyl or alkoxy group having 1 to 6 carbon atoms, R ₃ being a phenyl group which is substituted by an alkylamino group having 1 to 6 carbon atoms in the alkyl group is, X is an oxygen or sulfur atom and Z ~ is an anion, is used.

4. The method according to claim 3, characterized in that a sensitizing dye 2,4,6-triphenylthiapyrylium dye salt used will.

5. The method according to claim 4, characterized in that the 2,4,6-triphenylthiapyrylium dye salt is 4- (4-dimethylaminophenyl) -2,6-diphenylthiapyrylium fluorate or 4- (4-dimethylaminophenyl) -2,6-diphenylthiapyrylium perchlorate is used. 6a

6. The method according to claims 1 and 2, characterized in that a halogenated solvent is used Alkane having 1 to 3 carbon atoms is used.

7. The method according to claim 6, characterized in that the solvent is dichlorometal is used.

8. The method according to claims 1 and 2, characterized

characterized in that the binder is a polycarbonate is used.

9. The method according to claim 2, characterized in that a di-, tri- or tetraarylalkane, in which at least one aryl group is substituted by an amino group and in which the aryl group is equal to a phenyl or naphthyl group, is a metaliorganic compound in the at least one aminoaryl group is bonded to a metal atom from group Ilia, IVa, or Va of the Periodic Table of the Elements, or a di- or triarylamine is used.

10. The method according to claim 9, characterized in that the photoconductor 4,4'-diethylamino-2,2'-dimethyltriphenylmethane, 4-diethylaminotetraphenylmethane, 4,4 ', 4 "-Tris- (diethylamino) - tetrapheny istannan, diphenyl - bis - (ρ - diethy 1-aminophenyl) -stannan or Tetra-p-diethylaminophenylgerman is used.

11. The method according to claim 2, characterized in that that for 100 parts by weight of solids in the coating solution, 0.5 to 30 parts by weight Sensitizing dye and 10 to 80 parts by weight of photoconductor can be used.

The invention relates to a method for producing an electrophotographic recording material of an electrically conductive substrate and at least one heterogeneous photoconductive layer, the of a continuous phase of a binder and a discontinuous phase with a content on at least one sensitizing dye, the aggregates recognizable at 2500x magnification consists in which a coating liquid containing sensitizing dye, binder and solvent applied to the support and the layer obtained is dried.

Electrophotographic recording materials and electrophotographic processes of various kinds Type are known and are described in numerous references, e.g. B. U.S. Patents 2 221776; 2,277,013; 2,297,691;

2,357,809; 2,551,582; 2,825,814; 2,833,648; 3,220,324;

3,220,831 and 3,220,833. For the production of images with the aid of electrophotography, as a rule an electrophotographic recording material having a normally insulating photoconductive one Layer imagewise exposed to electromagnetic radiation to form a latent electrostatic Charge image, whereupon the latent image obtained is converted into a visible, permanent image is transferred.

The use of an electrophotographic recording material has proven to be particularly advantageous proved to have a photoconductive layer made of an electrically insulating resinous substance having dispersed photoconductor. For the production of such an electrophotographic recording material is usually the photoconductive coating composition in the form of a layer on a Layer carrier applied, which was previously coated with a layer of an electrically conductive material had been, or directly on an electrically conductive substrate, e.g. B. on a layer support

3 4

made of an electrically conductive metal. It turned out to be noticeably improved, so it still exists that the electrophotographic properties, e.g. B. a need for methods of making electrodie Sensitivity and / or spectral characteristics of photographic recording materials with verder photoconductive layers of the electro- improved properties obtained, e.g. B. improved sensitivity photographic As a result, recording materials can be improved in the shoulder and sagging area are that the photoconductivity curve used, improved reproducibility Coating compounds one or more photographic shafts for full surfaces, rapid regeneration and sensitizing substances or additives incorporate advantageous electrophotographic sensitivity will. Typical suitable additives of this type are used for both positive and negative electroz. B. in U.S. Patents 3,250,615; 3,141,770 static charge.

and 2,987,395. Photosensitizing Processes are already known with the aid of which additives of the specified type advantageously effect a change in the sensitization or heterogeneous photoconductive sensitivity of the photoconductive layer, which incorporates most of the specified photoconductive layers, into the sensitization or dye aggregates containing and / or a change in their 15 disadvantages of known electrophotographic on-spectral characteristics. So z. B. with the help of drawing materials do not have, can be produced, such additives the sensitivity of an electro- So z. B. in the Belgian patent specification 705 117 photographic recording material compared to a process for the production of an electrophoto-radiation of a certain wavelength increased or graphic recording material is described in which a sensitizing dye and a polymeric area are effected with optionally opposite a broad wavelength. The mechanism causing such a sensitiser binder in a customary known solution has not yet been fully elucidated, in spite of being moderately dissolved, the coating composition obtained on the extremely great importance of this phenomenon, still applied to an electrically conductive layer support. The particular importance, the resulting layer 25 attaches dried and then the experts of the specified sensitizing with a solvent or solvent vapors, results in z. B. from the fact that a treatment is carried out in all of them in order to soften the layer and to aggregate the relevant specialist circles intensively for advantageous dye molecules present. Post-photosensitizing compounds for photoconductive part of this known process is, however, that capable coating compositions of the specified type are still being researched after the coating composition has been applied. ^ 30 an additional procedural stage, namely the

The way in which a change in the handling of a solvent is required. striving for electrophotographic properties. Furthermore, Belgian patent 705 118 usually depends on which club a method of making an electrophoto application the relevant electrophotographic recording material of the specified see recording material is intended. This should describe 35 type, with its hiUe the following z. B. in the document copying technology in that required for the coating of the substrate electrophotographic recording material prior to an additional process step avoided and the agglomeration Photoconductor a spectral sensitivity gregatbildung thereby causes the dye molecules have that reproduce the whole, in doing so, that the coating material from Sensibili-Question coming wide color range possible. 4 ° sizing dye and polymeric binder before If the photoconductor used does not correspond or does not correspond to the application on the layer support strong, at high completely the specified conditions, so speeds generated shear forces are subjected, whose spectral properties are advantageous in this known method, however, is by adding spectral sensitizing additives that also an additional one for its implementation of the specified type changed. For other procedural stages, namely the action of shear application purposes It turns out that the influencing forces on the coating compound are often required. electrophotographic properties other than there is also already known a method according to which advantageous to in this way z. B. electrophoto- electrophotographic recording materials with to achieve graphic recording materials, the higher sensitivity than after the one from the one Able to absorb high surface potential 5 ° Versind given Belgian patents and have further advantageous properties, can be produced. So z. B. in the Belgian z. B. a small charge drop in the dark, a patent specification 729 078 describes a method according to high one resulting from the sensitivity curve on the photoconductive layer one after the other Sensitivity, a low residual potential according to the known method produced by electrophotographic exposure and resistance to erratic recording material an additional one fatigue. Layer of a dye in the form of a dye

Often the sensitization is applied to the dissolution. However, this known method of making electrophotographic recording has the disadvantage that it requires an additional material-specific photoconductive coating-coating process,
masses with a content of photoconductors certain ^6o disadvantage of the specified known method type by the addition of certain dyes from the is that the photoconductive coating compounds used for the production of the heterogeneous large number of the dyes known at the moment causes photoconductive coating. However, it is disadvantageous that, as a result of the addition of these dyes, additives known to have different crystalline structures generally do not have any photoconductive properties. Depending on the type of crystalline coating material present, in which all the structure of the dye can be obtained comparatively easily or very easily, the formation of the properties indicated in the color, which only have an effect in their constituent aggregates when the indicated processes are used, to form high-quality electro-known processes lead, be difficult.

The object of the invention is to provide a method of oxide, if its discontinuous phase is given, with the help of which simply by producing a photoconductive coating solution optionally made of particles with a particle size and applying it outside the specified range,
The heterogeneous photoresponsive electrophotographic recording materials obtained according to the invention consist of dyes and materials with photoconductive layers, the multiphase sensitizing dyes containing the sen-polymer binders in the form of aggregates of organic solids. The polymeric binders hold, regardless of the type of the present, form an amorphous basic structure in the form of a crystalline structure of the dyes used, under continuous phase, which contains a separate dis-application of a single coating process io continuous phase, which makes the difference without additional, the formation of the Makes dye aggregates into a solution. The discontinuous intended process stages can be produced. Phase contains a substantial portion, as a rule

The invention is based on the knowledge that the majority of the existing sensitization

the stated object can be achieved in that the dye. It can be assumed that the

Dye present in the form of sensitizing dye, film-forming poly-continuous phase

There is more binding agent and solvent consisting of particles, but this must be discontinuous.

Coating solution in a precisely defined way borrowed phase not completely made up of dye molecules

is provided. exist. Presumably in some cases

The invention relates to a process for the discontinuous phase from a cocrystalline production of an electrophotographic recording complex of dye and polymeric binder, voltage & material from an electrically conductive layer - but it is to be assumed that the dye aggregates that are carrier and at least one heterogeneous photoconductive according to the invention are not necessarily capable of being produced Layer consisting of a continuous phase of dye and polymer. Preferably from a binder and a discontinuous one is practically the entire existing phase with a content of at least one sensitizing »5 dye in the discontinuous phase,
If the process of magnification forms recognizable aggregates, there is a combination of a sensitizing dye, binder and nation with an organic photoconductor when using the process of enlargement which is applied to the layer substrate and the obtained 30 usually only two phases, since the photoconductor is dried with the layer, which is characterized in that the polymer consists of a continuous phase that usually forms a solid solution to produce the coating liquid. If, on the other hand, the sensitizing dye (s) are dissolved in the solution on the one hand, when the method of the invention is used, the binding agent is combined in combination with this solution and the resulting composition is mixed with a particulate photoconductor before application the substrate is intimately mixed. applies, there may be three phases,

The invention achieves that qualitatively namely a continuous polymer consisting of

high quality electrophotographic recording phase, also a sensitizing dye

materials with improved sensitivity and containing discontinuous phase of the specified

if desired, higher dye concentration and 40 type as well as another discontinuous one

with improved regenerability regardless of phase from the particulate photoconductor. Self-

the crystalline structure of the sensitivity used can be understood when using the method

sizing dyes in simple, easily controllable as well as the invention accruing multiphase coating

Can be produced in a time- and cost-saving manner. mass, if necessary, additional dis-

The continuous phases for carrying out the process of the Er- «5, z. B. from included

find usable heterogeneous coating impurities and the like, contain,

solutions act as both a photoconductor and another feature of when using the

Sensitizers for photoconductors. Method of the invention accruing Eeschichtungs-

According to the invention, the masses used are the fact that their absorption maximum dyes in an organic coating 50 is in a spectral range that is longer or solvent-soluble, before other additives are shorter-wave than that in which the ai are added to them. Only after the dyes have dissolved to a maximum of a practically homogeneous mass are the solutions obtained usually under dyes and polymers of the same type, if stirring is mixed with polymeric binders and these are in the form of a solid substance. Binder dissolved. In this way, heterogeneous, 55 How far the absorption maximum of such hetero-multiphase coating solutions are obtained, the generic coating masses of which on the basis of the formation of dye aggregates, discontinuous of dye aggregates in other wavelength phases, can be seen at 2500x magnification, whether areas are shifted, disgusts the coating solutions obtained up to which percentage of the pre-harder dye aggregate-unarmed eye, if necessary, practically optically you. In the case of using the method of appearing clearly. If necessary, however, a multiphase heterogeneous bemacroscopic heterogeneity arising from the invention can also be present. The dye aggregates which form the layering materials, the absorption maximum in the discontinuous phase, are generally shifted by at least about 10 μm and are expediently predominantly of a type that is comparable to that of homogeneous materials. Particle size from about 0.01 to 25 microns. 65 If mixtures of dyes are used, the heterogeneous coating obtained can be used, if necessary a dye, the location of the absorption solution for the sensitization of additional maximums for longer wavelengths and an existing particulate photoconductor, e.g. B. zinc- other dye the position of the absorption maximum

shift to shorter wavelengths. In such a case, do the positional shifts of the Absorption maximum more or less, so it is possible to demonstrate that a heterogeneous coating mass is present, possibly more easily by making the discontinuous phase visible corresponding magnification.

A variety of sensitizing dyes are used in practicing the method of the invention Type usable. Typical suitable sensitization iq dyes are z. B, pyrylium dyes, for example pyrylium, thiapyrylium and selenapyrylium dye salts the general formula:

X /

Table I.

link

description

4- [4-bis- (2-chloroethyl) aminophenyl] -

2,6-diphenylthiapyrylium perchlorate

4- (4-dimethylaminophenyl) -2,6-diphenyl-

thiapyrylium perchlorate

4- (4-dimethylaminophenyl) -2,6-diphenyl-

thiapyrylium fluoroborate

4- (4-dimethylamino-2-methylphenyl) -

2,6-diphenylpyrylium perchlorate link

No.

description

+ A ζ-

in which:

R ^a , R ^& , R ^c , K ^a and R ^e for themselves are hydrogen atoms, alkyl radicals with z. B. 1 to 15 carbon as atoms, for example methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, isoamyl, hexyl, octyl, nonyl, or dodecyl radicals, alkoxy radicals , e.g. B. methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy or octoxy radicals, or optionally substituted aryl radicals of the phenyl and naphthyl series, e.g. B. phenyl or 4-diphenyl radicals, or alkylphenyl radicals, e.g. B. 4-ethylphenyl or 4-propylphenyl, or alkoxyphenyl, z. B. 4-Äthoxyphenyl-, 4-Methoxypb.enyl-, 4-Amyloxyphenyl-, 2-Hexoxyphenyl-, 2-Methoxyphenyl- or 3,4-Dimethoxyphenylreste, or / J-Hydroxyalkoxyphenylreste, z. B. 2-Hydroxyäthoxyphenyl- or 3-Hydroxyäthoxyphenylreste, or 4-Hydroxyphenylreste or Halophenylreste, z. B. 2,4-dichlorophenyl, 3,4-dibromo- * o phenyl, 4-chlorophenyl or 3,4-dichlorophenyl, or azidophenyl, nitrophenyl or aminophenyl, z. B. 4-diethylaminophenyl or 4-dimethylaminophenyl radicals, or naphthyl radicals or vinyl-substituted aryl radicals, e.g. B. styryl, methoxystyryl, diethoxystyryl, dimethylaminostyryl, 1-butyl-4-p-dimethylaminophenyl-1,3-butadienyl or / S-ethyl-4-dimethylaminostyryl radicals or R ^a and R ⁶ or R ^d and R ^e together the atoms required to complete an aryl ring s «fused to the pyrylium nucleus, X a sulfur, oxygen or selenium atom and Z ^- an anion, ζ. B. a perchlorate, fluoroborate, iodide, chloride, bromide, sulfate, periodate or p-toluene sulfonate ion.

Typical suitable pyrylium dyes are listed in Table I below.

4- [4-bis (2-chloroethyl) aminoph.enyl] -2- (4-methoxyphenyl) -6-phenylthiapyrylium perchlorate
4- (4-dimethylaminophenyl) -2,6-diphenylthiapyrylium sulfate

4- (4-dimethylaminophenyl) -2,6-diphenyl-

thiapyrylium p-toluenesulfonate ; 4- (4-dimethylaminophenyl) -2,6-diphenylpyrylium-p-toluenesulfonate 2- (2,4-Dimethoxyphenyl) -4- (4-dimethylaminophenyl) benzo (b) pyrylium perchlorate 2,6-bis (4-ethylphenyl) -4- (4-dimethylaminophenyl) thiapyrylium perchlorate 4- (4-Dimethylaminophenyl) -2- (4-methoxyphenyl) -6-phenylthiapyrylium perchlorate 4- (4-dimethylaminophenyl) -2- (4-ethoxyphenyl) -6-phenylthiapyrylium perchlorate

ao 13 4- (4-Dimethylaminophenyl) -2- (4-methoxyphenyl) -6- (4-methylphenyl) pyrylium perchlorate

4- (4-Diphenylaminophenyl) -2,6-diphenylthiapyrylium perchlorate

2,4,6-triphenylpyrylium perchlorate 4- (4-methoxyphenyl) -2,6-diphenylpyrylium perchlorate

4- (2,4-dichlorophenyl) -2,6-diphenylpyrylium perchlorate

4- (3,4-dichlorophenyl) -2,6-diphenylpyrylium perchlorate

2,6-bis (4-methoxyphenyl) -4-phenylpyryben perchlorate

6- (4-methoxyphenyl) -2,4-diphenylpyrylium perchlorate

2- (3,4-dichlorophenyl) -4- (4-methoxyphenyl) -6-phenylpyrylium perchlorate 4- (4-amyloxyphenyl) -2,6-bis (4-ethylphenyi) pyrylium perchlorate

4- (4-amyloxyphenyl) -2,6-bis (4-methoxyphenyl) pyrylium perchlorate

2,4,6-triphenylpyrylium fluoroborate 2,6-bis (4-ethylphenyl) -4- (4-methoxyphenyl) pyrylium perchlorate

2,6-bis (4-ethylphenyl) -4- (4-methoxyphenyl) pyrylium fluoroborate

6- (3,4-diethoxystyryl) -2,4-diphenylpyrylium perchlorate

6- (3,4-diethoxy - /? - amy! Styryl) -2,4-diphenylpyrylium fluoroborate

6- (4-Dimethylamino - ^ - ethylstyryl) -2,4-dipheny] pyrylium fluoroborate

6- (1-n-Amyl-4-p-dimethylaminophenyl, 3-butadienyl) -2,4-diphenylpyrylium fluoroborate

6- (4-dimethylaminostyryl) -2,4-diphenylpyrylium fluoroborate

6 - [* - Ethyl- / 3, / S-bis (dimethylaminophenyl) vinylene] -2,4-diphenylpyrylium fluoroborate 33 6- (1-butyl-4-p-dimethylaminophenyl, 3-butadienyl) -2,4 -diphenylpyrylium fluoroborate
6- (4-dimethylaminostyryl) -2,4-diphenylpyrylium perchlorate
35 6-rj3, jö-bis (4-dimethylaminophenyl) vinylene] -2,4-diphenylpyrylium perchlorate 2,6-bis (4-dimethylaminostyryl) -4-phenylpyrylium perchlorate

409 514/3

3951

[•binding No.

Designation connection
No.

description

37 6 - (/? - methyl-4-dimethylaminostyryl) -2,4-diphenylpyrylium fluoroborate

38 6- [l-Ethyl-4- (4-dimethylaminophenyl) -1, 3-butadienyl] -2,4-diphenylpyrylium- fluoroborate

39 6-rj?, J3-bis (4-dimethylaminophenyl) vmylene] -2,4-diphenylpyrylium fluoroborate

40 6-11-Methyl-4- (4-dimethylaminophenyl) -1,3-butadienyl] -2,4-diphenylpyrylium fluoroborate

41 4- (4-Dimethylaminophenyl) -2,6-diphenylpyrylium perchlorate

42 2,6-bis (4-ethylphenyl) -4-phenylpyrylium perchlorate

43 2,6-bis (4-ethylphenyl) -4-methoxyphenylthiapyrylium fluoborate

44 2,4,6-triphenylthiapyrylium perchlorate

45 4- (4-methoxyphenyl) -2,6-diphenylthiapyrylium perchlorate

46 6- (4-methoxyphenyl) -2,4-diphenyithiapyrylium perchlorate

47 2,6-bis (4-methoxyphenyl) -4-phenylthiapyrylium perchlorate

48 4- (2,4-dichlorophenyl) -2,6-diphenylthiapyryli um perchlorate

49 2,4,6-tri (4-methoxyphenyl) thiapyrylium perchlon.t

50 2,6-bis (4-ethylphenyl) -4-phenylthiapyrylium perchlorate

51 4- (4-amyloxyphenyl) -2,6-bis (4-ethylphenyl) thiapyrylium perchlorate

52 6- (4-Dimethylaminostyryl) -2,4-diphenylthiapyrylium perchlorate

53 2,4,6-triphenylthiapyrylium fluoroborate

54 2,4,6-triphenylthiapyrylium sulfate

55 4- (4-methoxyphenyl) -2,6-diphenylthiapyr} 'lium fluoroborate

56 2,4,6-triphenylthiapyrylium chloride

57 2- (4-amyloxyphenyl) -4,6-diphenylthiapyrylium fluoroborate

58 4- (4-Amyloxyphenyl) -2.6-bis (4-methoxyphenyl) thiapyrylium perchlorate

59 2,6-bis (4-ethylphenyl) -4- (4-methoxyphenyl) thiapyrylium perchlorate

60 4-anisyl-2,6-bis (4-n-amyloxyphenyl) thiapyrylium chloride

61 2- [j?, ^ - bis (4-dimethylaminophenyl) vinylene] -4,6-diphenylthiapyrylium perchlorate

62 6 - () 3-Ethyl-4-dimethylaminostyryl) -2,4-diphenylthiapyrylium perchlorate

63 2- (3,4-dietiioxystyryl) -4,6-diphenylthiapyrylium perchlorate

64 2,4,6-trianisylthiapyrylium perchlorate

65 6-ethyl-2,4-diphenylpyrylium fluoroborate

66 2,6-bis (4-ethylphenyl) -4- (4-methoxyphenyl) thiapyrylium chloride

67 6-rjS, / 5-bis (4-dimethylaminophenyl) vinylene] -2,4-di (4-ethylphenyl) pyrylium perchlorate

68 2,6-bis (4-amyloxyphenyl) -4- (4-methoxyphenyl) thiapyrylium perchlorate

69 6- (3,4-diethoxy- / 8-ethylstyryl) -2,4-diphenylpyrylium fluorodorate

70 6- (4-methoxy - /? - ethylstyryl) -2,4-diphenylpyrylium fluoroborate

71 2- (4-Ethylphenyl) -4,6-diphenylthiapyrylium perchlorate 72 2,6-diphenyl-4- (4-methoxyphenyl) thiapyrylium-

perchlorate
S 73 2,6-diphenyl-4- (4-methoxyphenyl) thiapyrylium fluoroborate

74 2,6-bis (4-ethylphenyl) -4- (4-n-amyloxyphenyl) thiapyrylium perchlorate

75 2 _I 6-bis (4-methoxyphenyl) -4- (4-n-amyloxyphenyl) thiapyrylium perchlorate

76 2,4,6-tris (4-methoxyphenyl) thiapyrylium fluoroborate

77 2,4-Diphenyl-6- (3,4-diethoxystyryl) pyrylium perchlorate

78 4- (4-Dimethylaminophenyl) -2-phenylbenzo (b) selenapyrylium perchlorate

79 2- (2,4-Dimethoxyphenyl) -4- (4-dimethylaminophenyl) benzo (b) selenapyrylium perchlorate

80 4- (4-Dimethylaminophenyl) -2,6-diphenylselenaao pryrylium perchlorate

81 4- (4-Dimethylaminophenyl) -2- (4-ethoxyphenyl) 6-phenylselenapyrylium perchlorate

82 4- [4-bis (2-chloroethyl) aminophenyl] -2,6-diphenylselenapyrylium perchloral

»5 83 4- (4-dimethylaminophenyl) -2,6-bis (4-ethylphenyl) selenapyrylium perchlorate

84 4- (4-Dimethylamino-2-methylphenyl) -2,6-diphenylselenapyrylium perchlorate

85 3- (4-Dimethylaminophenyl) naphtho (2, l-b) selenapyrylium perchlorate

86 4- (4-DimethylaminostyryI) -2- (4-methoxyphenyl) benzo (b) selenapyrylium perchlorate

87 2,6-Di (4-diethylaminophenyl) -4-phenylselenapyrylium perchlorate and

88 4- (4-Dimethylaminophenyl) -2- (4-ethoxyphenyl) -6-phenylthiapyrylium fluoroborate

The use of pyrylium dye salts of the general formula has proven to be particularly advantageous:

R,

R ₁

R ₂

z-

proven, in which: R ₁ and R _{2 are} optionally substituted phenyl radicals which, if they are substituted, have at least one substituent consisting of an alkyl radical with 1 to 6 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms, R ₃ an alkylamino- substituted, optionally also dialkylamino or haloalkylamino substituted phenyl radical with an alkyl component having 1 to 6 carbon atoms, X is an oxygen or sulfur atom and Z "is an anion of the meaning given.

As already mentioned, the use of voi Pyrylium dyes have been found to be particularly advantageous, but others are also photographically spectral

sensitizing dyes which activate areas of photographic layers exposed to light, i Combination with an electrically insulating polymeric binder of the specified type can be used:

Various conventional known electrical means are used to carry out the method of the invention insulating, film-forming polymeric binders can be used, e.g. B. polycarbonates and polythiocarbonates, Polyvinyl ethers, polyesters, poly-a-olefins, phenolic resins Mixtures of such polymers can also be used, and the like. Suitable such polymers have a twofold function, namely they participate in the formation of the dye aggregates, and they also act as binders that allow adhesion between the photoconductive layers and the Effect layer carriers. Typical suitable polymeric binders are listed in Table II below.

Table II
Compound Name of the polymer

1 polystyrene

2 polyvinyl toluene

3 polyvinyl anisole

4 polychlorostyrene

5 poly-α-methylstyrene

6 polyacenaphthalene

7 poly (vinyl isobutyl ether)

8 poly (vinyl cinnamate)

9 poly (vinyl benzoate)

10 poly (vinyl naphthoate)

11 polyvinyl carbazole

12 poly (vinylene carbonate)

13 polyvinyl pyridine

14 poly (vinyl acetal)

15 r- * lv (vinyl butyral)

16 Pol (ethyl methacrylate)

17 poly (butyl methacrylate)

18 poly (styrene-co-butadiene)

19 polyistyrene-co-methyl methacrylate)

20 polyistyrene-co-ethyl acrylate)

21 polyistyrene-co-acrylonitrile)

22 polyvinyl chloride-co-vinyl acetate)

23 polyvinylidene chloride-co-vinyl acetate)

24 poly (4,4'-isopropylidenediphenyl-co-4,4'-isopropylidene-dicyclohexyl carbonate)

25 poly [4,4'-isopropylidenebis (2,6-dibromophenyl) carbonate]

26 poly [4,4'-isopropylidene bis (2,6-dichlorophenyl) carbonate]

27 poly [4,4'-isopropylidene bis (2,6-dimethylphenyl) carbonate]

28 Polyi-i ^ '- Isopropylidenediphenyl-co-l ^ Cyclohexyldimethylcarbonat)

29 poly (4,4'-isopropylidenediphenyl terephthalate co-isophthalate)

30 poly (3,3'-ethylenedioxyphenylthiocarbonate)

31 poly (4,4'-isopropylidenediphenyl carbonate co-terephthalate)

32 poly (4,4-isopropylidenediphenyl carbonate)

33 Poly (4,4'-Isopropyh'dendiphenylthiocarbonat)

34 poly (2,2-butane-bis-4-phenyl carbonate)

35 poly (4,4'-isopropylidenediphenyl carbonate block ethylene oxide)

36 poly (4,4'-isopropylidenediphenyl carbonate block tetramethylene oxide)

37 poly [4,4'-isopropylidene bis (2-methylphenyl) carbonate]

38 poly (4,4'-isopropylidenediphenylco-1,4-phenylene carbonate)

39 poly (4,4'-isopropylidenediphenylco-1,3-phenylene carbonate)

link

No.

Name of the polymers

40 poly (4,4'-isopropylidenediphenyl-co-4,4'-diphenyl carbonate)

S 41 poly (4,4'-isopropylidenediphenyl-co-4,4'-oxydiphenyl carbonate)

42 poly (4,4'-isopropylidenediphenyl-co-4,4'-carbonyldiphenyl carbonate)

43 poly (4,4'-isopropylidenediphenyl-co-4,4'-ethylenediphenyl carbonate)

44 poly [4,4'-methylene bis (2-methylphenyl) carbonate]

45 poly [1,1 - (p-bromophenylethane) bis (4-phenyl) carbonate]

46 poly [4,4'-isopropylidenediphenyl-co »sulfonyl bis (4-phenyl) carbonate]

47 poly [1,1-cyclohexanebis (4-phenyl) carbonate]

48 poly (4,4'-isopropylidenediphenoxydimethylsilane

49 poly [4,4'-isopropylidene bis (2-chlorophenyl) carbonate]

50 Polyfj *, <x, * ', o (' - Tetramethyl-p-xy] ylolbis (4-phenyl carbonate)]

51 poly (hexafiuoroisopropylidene-di-4-f) henyl carbonate)

»5 52 PolylDichlorotetrafluoioisopropylidendi-4 ^ phenylcarbonat)

53 poly (4,4'-isopropylidenediphenyl-4,4'-isopropylidenedibenzoate)

54 poly (4,4'-isopropylidene dibenzyl-4,4'-isopropylidene dibenzoate)

55 poly (4,4'-isopropylidene-di-1-napthyl carbonate)

56 poly [4,4'-isopropylidene-bis (phenoxy-4-phenylsulfonate)]

57 acetophenone formaldehyde resin

58 poly [4,4'-isopropylidene-bis (phenoxyethyl) -co-ethylene terephthalate]

59 phenol-formaldehyde resin

60 polyvinyl acetophenone

61 chlorinated polypropylene
62 chlorinated polyethylene

63 poly (2,6-dimethylphenylene oxide)

64 poly (neopentyl-2,6-naphthalenedicarboxylate)

65 poly (ethylene terephthalate-co-isophthalate)

66 Polyil ^ phenylene-co-l ^ -PheRylene succinate) 67 poly (4,4'-isopropylidenediphenylphenylphosphonate)

68 poly (m-phenyl carboxylate)

69 poly (1,4-cyclohexanedimethyl terephthalate co-isophthalate)

70 poly (tetramethylene succinate)

71 poly (phenolphthalein carbonate)

72 poly (4-chloro-1,3-phenylene carbonate)

73 poly (2-methyl-1,3-phenylene carbonate)

74 poly (l, l-bi-2-naphthylthiocarbonate)

75 poly (diphenylmethane-bis-4-phenyl carbonate)

76 Poly [2,2- (3-methylbutane) bis -4-phenyl carbonate

77 poly [2,2- (3,3-dimethylbutane) bis-4-phenyl carbonate]

78 poly {l, l- [l- (l-naphthyl)] bis-4-phenylcarbonai 79 Poly [2,2- (4-methylpentane) bis -4-phenyl carbonate]

80 poly [4,4 '- (2-norbornylidene) diphenyl carbonate]

81 poly [4,4 '- (hexahydro-4,7-methanoindan-5-ylidene) diphenyl carbonate] and

82 poly (4,4'-isopropylidenediphenylcarbonate block-oxytetramethylene)

Compounds No. 28, 30 to 47, 49, 51, 53, and 76 to 82 of Table II given have si

: Proven to be> particularly advantageous for carrying out the method of the invention.

Polymeric binders used with preference are:. B. also linear polymers or copolymers With repeating structural units of the general formula:

R »

R ₇

■ .— C

R ₅

-R.

in which:

R ₄ and R ₆ alone are hydrogen atoms, optionally substituted alkyl radicals, for example methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl or trifluoromethyl radicals, or optionally substituted aryl radicals of the phenyl and naphthyl series, the substituents which may be present, e.g. B. consist of halogen atoms or alkyl radicals with 1 to 5 carbon atoms, or together to complete a cyclic hydrocarbon radical, z. B. a cycloalkane radical, for example

ι? a cyclohexyl radical, or a polycycloalkane radical, for example a norbornyl radical, required atoms, where the radicals R ₄ and R ₅ together have up to 19 carbon atoms, R ₆ and R ₇ hydrogen or halogen atoms, for example chlorine, bromine or iodine atoms, or alkyl radicals with 1 to 5 carbon atoms and R _{8 is} a divalent radical of the formulas

O SOO

O —C —O—, —O —C —O—, —C —Ο—, -CO-CH ₂

CH.

- C - O - CH-, - CH ₁ - O - C - O - or - O - P - O -

O -

If the linear polymers are hydrophobic polycarbonates, then the use has been made of polymers with recurring structural units of the following formula:

R ₄ O

ι '

—R — C-R-Ο — C-O-

j i

R _s

in which R ₄ and R _{5 have} the meaning given and the radicals R are phenylene radicals which can be substituted by halogen atoms or alkyl radicals.

Compounds of the specified type are z. See U.S. Patents 3,028,365 and 3,317,466 described. The use of polycarbonates has proven to be particularly advantageous repeating structural unit an alkylidene diarylene component included, e.g. B. polycarbonates made using bisphenol A, ζ. Β. those obtained by ester exchange between diphenyl carbonate and 2,2-bis-4-hydroxyphenylpropane will. Compounds of the specified type are z. B. in U.S. Patents 2,999,750, 3 038 874, 3 038 879, 3 038 880, 3106 544, 3106 545 and 3,106,546 and also in published Australian patent application no. 19 575/56.

To carry out the method of the invention has the use of film-forming polycarbonate of various types has proven to be expedient, where particularly advantageous results can be achieved with such commercially available polycarbonates, whose inherent viscosity is 0.5 to 0.6. Furthermore, there has also been the use of high molecular weight Polymers, e.g. B. of high molecular weight bisphenol A polycarbonates have been shown to be advantageous. Such high molecular weight polymers are preferably those with a inherent viscosity of over 1, measured in 1,2-dichloroethane at a concentration of 0.25 g / 100 ml and a temperature of about 25 ° C. So z. B. the use of high molecular weight Polycarbonates advantageously help that in coating compositions with a comparatively high Content of sensitizer dye facilitates the formation of dye aggregates and a photoconductive one Mass with increased sensitivity is obtained.

The coating compositions obtained using the process of the invention are more suitable Way to increase the sensitivity and widen the spectral sensitivity range the most varied of organic and inorganic

So photoconductors that are both η-type and p-type can belong. A typical suitable inorganic photoconductor is e.g. B. zinc oxide. Suitable are also numerous organic, z. B. also organometallic photoconductors that only have a low or have practically no photoconductivity persistence at all. Typical suitable such organometallic Connections are e.g. B. organic derivatives of metals of groups HIa, IVa and Va des Periodic table, e.g. B. those which have at least one aminoaryl radical bonded to the metal atom. Typical suitable such organometallic compounds are, for. B. triphenyl-p-dialkylaminophenyl derivatives of silicon, germanium, tin and lead as well as tri-p-dialkylaminophenyl derivatives of arsenic, Antimony, phosphorus, bismuth, boron, aluminum, gallium, thallium and indium. Suitable photoconductors of the specified type are z. B. in the German Auslegeschriften 1 772 775 and 1 943 387 described.

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The use of organic photoconductors of the so-called "Organic amine type" have been shown to have at least one amino group as a common structural feature. Typical suitable spectrally sensitizable using the method of the invention organic photoconductors of the specified type are e.g. B. Arylarainverbindungen, for example (1) Diarylamine, such as B. diphenylamine, dinaphthylamine, N, N'- diphenylbenzidine, N - phenyl -1 - naphthylamine, N-Phenyi-I-naphthylamine jN.N'-Diphenyl-p-phenylenediamine, 2-carboxy-5-chloro-4'-methoxydiphenylatnia. p-anilinophenol, N, N'-di-2.-naphthyl-p-phenylenediamine, those described in U.S. Patent 3,240,597 Compounds and (2) triarylantines, e.g. B. (a) non-polymeric triarylamines such. B. triphenylamine, Ν, Ν, Ν ', Ν' -Tetraphenyl-m-phenylenediamine, 4-acetyltriphenylamine, 4-hexanoytriphenylamine, 4-lauroyltriphenylamine, 4-hexyltriphenylamine, 4 - Dodecyl triphenylamine, 4,4'-bis (diphenylamine) benzil, 4,4'-bis- (diphenylamino) -benzophenone and (b) polymeric triarylamines, such as. B. Poly [N, 4 "- (N, N \ N'-triphenylibenzidine)], polyadipyltriphenylamine, polysebacyltriphenylamine, Polydecamethylene triphenylamine, poly-N- (4-vinylphenyl) <liphenylamine or poly-N- (vinylphenyl) - *, * '- dinaphthylamine. Further suitable PN conductors are of the organic amine type z. In U.S. Patent 3,180,730.

Also suitable photoconductors that can be sensitized according to the invention are those from the USA patent 3,265,496 known compounds of the following general formula:

R- [N-T -] "Q

proven in the mean:

T a mononuclear or polynuclear, either condensed or linear divalent aromatic radical, e.g. B. a phenyl, naphthyl, biphenyl or binaphthyl radical, or a substituted one divalent aromatic radical of the specified type, the substituent of which is e.g. B. from a Acyl radical with 1 to about 6 carbon atoms, for example an acetyl, propionyl or butyryl radical, an alkyl radical having 1 to about 6 carbon atoms, for example a methyl, ethyl, propyl or Butyl radical, an alkoxy radical with 1 to about 6 carbon atoms, for example a methoxy, ethoxy, Propoxy or pentoxy radical, or consists of a nitro group,

M a mononuclear or polynuclear, either condensed or linear monovalent aromatic radical, e.g. B. a phenyl, naphthyl or biphenyl radical, or a substituted monovalent aromatic radical of the specified type, the substituent of which is e.g. B. from an acyl radical with 1 to about 6 carbon atoms, for example an acetyl, propionyl or butyryl radical, from an alkyl radical with 1 to about 6 carbon atoms, for example a methyl, ethyl, propyl or butyl radical, an alkoxy radical with 1 to about 6 carbon atoms, for example a methoxy, propoxy or pentoxy radical, or consists of a nitro group,

Q represents a hydrogen or halogen atom or an aromatic amino radical, e.g. B. one of the general ones Formula MNH -,

b = an integer from 1 to 12 and

R is a hydrogen atom or a mononuclear or polyuclear, either condensed or linear aromatic radical, for example a phenyl, naphthyl or biphenyl radical, a substituted one aromatic radical of the specified type, whose substituent consists of an alkyl, alkoxy, acyl or nitro radical, or from a poly (4'-vinylphenyl) radical which has a carbon atom of the phenyl radical is bound to the nitrogen atom.

ίο The use has proven to be particularly advantageous of photoconductors consisting of polyarylalkanes, the z. From U.S. Pat. No. 3,274,000 and U.S. Pat French patent 1,383,461 are known.

Such photoconductors can, for. B. from leuco bases of diaryl or triarylmethane dye salts or 1,1,1-triarylalkanes, the alkane radical of which has at least two carbon atoms, and tetraarylmethanes, in which at least one of the aryl radicals bonded to the alkane radical or Methanresi is substituted by an amino group. The last two photoconductor classes mentioned are not leuco bases.
The use has proven to be particularly advantageous

as of photoconductors consisting of polyarylalkanes proven by the following general formula:

J - C - E

in which:

D, E and G aryl radicals of the phenyl and naphthyl series, where at least one of the radicals D, E and G is substituted by an amino group, and

J represents a hydrogen atom, an alkyl radical or an aryl radical from the phenyl and naphthyl series.

The aryl radicals bonded to the central carbon atom are preferably Phenyl radicals, but it can also be naphthyl radicals. The aryl radicals can also be used in ortho-, Meta- or para-position may be substituted, e.g. B. by Alkyl or alkoxy radicals usually having 1 to 8 carbon atoms, hydroxy radicals or halogen atoms. Phenyl radicals substituted in the ortho position have proven to be particularly advantageous substituted aryl radicals. The aryl radicals present can also be linked to one another or cyclized. z. More colorful Formation of a fluorene ring.

The amino substituents present in at least one of the aryl radicals can be represented by the formula

-NC

are reproduced, where L alone is an alkyl radical with usually 1 to 8 carbon atoms, a hydrogen atom or an aryl radical, or both radicals L together to complete one heterocyclic amine radicals with usually 5 to 6 Pvingatomen, z. B. a morpholino, pyridyl or Pyrrylrestes required atoms mean.

Polyarylalkanes of the formula given in which at least one of the radicals D, E or G is a p-dialkylamino-

represents phenyl radical. If J stands for an alkyl radical in the formula given, this can, for. B. in advantageous Way to be an alkyl radical with 1 to 7 carbon atoms. Typical suitable poly (ylalkane) photoconductors are z. B. the compounds listed in the following Table IH.

link

No.

Table III

description

10

1 4,4'-benzylidene-bisCN, N-diethyl-m-toluidine)

2 4 ', 4 "-Diamino-4-dimethylamino-2', 2" -dimethyItriphenylmethane

3 4 ', 4 "-bis (diethylamino) -2,6-dichloro-2', 2" -dimethyltriphenylmethane

4 4 ', 4 "-bis (diethylamino) -2', 2" -dimethyldiphenylnaphthylmethane

5 2 ', 2 "-Dimethyl-4,4', 4" -tris (dimethylamino) triphenylmethane

6 4 ', 4 "-bis (diethylamino) -4-dimethylamino- so 2 \ 2 "-dimethyltriphenylmethane

7 4 ', 4 "-bis (diethylamino) -2-chloro-2', 2" -dimethyl-4-dimethylaminotriphenylmethane

8 4,4 "-bis (dietbylamino) -4-dimethylamino-2,2 ', 2" -trimethyltriphenylmethane as

9 4 \ 4 "-bis (dimethylamino) -2-chloro-2 ', 2" -limethyltriphenylmethane

10 4 ', 4 "-bis (dimethylamino) -2', 2" -dimethyl-4-methoxytriphenylmethane

11 bis (4-diethylamino) -l, l, l-triphenylethane

12 bis (4-diethylamino) tetraphenylmethane

13 4 ', 4 "-bis (benzylethylamino) -2', 2" -dimethyltriphenylmethane

14 4 ', 4 "-bis (diethylamino) -2', 2" -diethoxytriphenylmethane

15 4,4'-bis (dimethylamino) -l, l, l-triphenylethane

16 l- (4-N, N-dimethylaminophenyl) -l, l-diphehylethane

17 4-dimethylaminotetraphenylmethane and

18 4-Diethylaminotetraphenyimethane

Photoconductors which can be used using the method of the invention are also the 4-diarylafnino-substituted ones Chalkohe. Typical suitable compounds of this type are non-polymeric ketones low molecular weight of the following formula:

R ₁ .

R ₁

N-

- CH = CH - C - R

2

in which R ₁ and R _{2 are} optionally substituted phenyl radicals and where R _{2 is} advantageously a phenyl radical of the formula

60

represents, in which R ₃ and R ₄ aryl radicals, aliphatic radicals with 1 to 12 carbon atoms, ζ. B. alkyl radicals preferably having 1 to 4 carbon atoms, or hydrogen atoms.

The use of compounds of the given general formula in which the radicals R _{1 is} optionally substituted phenyl radicals and R _{2 is} a diphenyl group has proven particularly advantageous.

aminophenyl, dimethylaminophenyl or phenyl radical

mean. ,., ._. , ._,

Other suitable photoconductors when performing of the process of the invention are incorporated into the coating compositions containing dye aggregates can, are z. B. Rhodamine B, malachite green, crystal violet, phenosafranine, cadmium sulfide, cadmium selenide, Parachloronil, benzil, trinitrofluorenone and tetranitrofluorenone.

Typical suitable photoconductors and photoconductive ones Masses whose sensitivity * -, sensitization and / or regeneration properties with the aid of the heterogeneous masses accruing according to the invention can be improved, z. B. in the USA. Patents listed in the following Table IV.

Table IV

U.S. Patent No. 3,158,475 3 041 165 3 163 505 3 037 861 3 163 530 3 072 479 3 163 531 3 066 023 3 163 532 3 112197 3 169 060 3,047,095 3,174,854 3 144 633 3 180 729 3 133 022 3 180 730 3 127 266 3 189 447 3 122 435 3 206 306 3 131 ObO 3 240 597 3 130 046 3,257,202 3 139 339 3 257 203 3 139 338 3,257,204 3 141 770 3 265 496 3 140 946 3,265,497 3 155 503 3 274,000 3 148 982

When the coating compositions obtained using the method of the invention become photoconductors added, so has the use of organic, z. B. organometallic photoconductors in Concentrations of at least about 0.5 percent by weight based on the total amount of the coating solvent added solids, proven to be useful. The upper limit of the concentration range the photoconductor present can vary widely and can be up to 99 percent by weight, based on on the total amount of solids. When using a photoconductor, it has proven to be * Proven to be particularly advantageous to use this in concentrations of about 10 to 80 percent by weight. Of course, however, as already mentions the dye-containing aggregates obtained using the process of the invention heterogeneous coating compositions even without the addition of a photoconductor for the production of photoconductive ones Layers are used.

A variety of organic coating solvents can be used in practicing the method of the invention, e.g. B. liquid coals' hydrogen, which may be substituted, halogenated hydrocarbon solvents in a particularly advantageous manner. Coating solvents have proven to be suitable which are capable of dissolving the sensitizing dye used and dissolving or at least swelling the polymeric binder used to a high degree. Furthermore, it has proven useful if the solvents used are volatile, preferably if they have a boiling point of below about 200 ^° C. The use of solvents made from halogenated short-chain alkanes having 1 to 3 carbon atoms has proven to be particularly advantageous be available, for example the use of dichloromethane, dichloroethane, dichloropropane, trichloromethane, trichloroethane, tribromomethane, trichloromono fluoromethane, trichlorotrifluoroethane and the like, far away:

AA

19 20

of halogenated benzene compounds, e.g. Chloro- 750μ. However, useful results are

benzene, bromobenzo !, dichlorobenzene and the like can also be achieved outside the specified range.

Mixtures of solvents can also be used. To carry out the method of the invention

Various conventional known electrical means are used to carry out the method of the invention the concentration of sensitizing dye, 5 conductive support can be used, e.g. B. Layer of initially practically completely in an orgaiii- carrier made of paper with a relative humidity of See coating solvent is dissolved, very over 20%, from aluminum foils and paper on different levels his, depending on the solubility built laminates, made of metal foils, beispie'isdes used dye in the way used aluminum foils and zinc foils, from metal solvents as well as of the desired dye iti plates, for example aluminum, copper ^ zinc, concentration in the coating compound to be formed. Brass and galvanized plates, made on paper Comparatively high dye concentrations result in vapor-deposited metal layers made of z. B. silver, nickel, usually to photoconductive coating compositions aluminum and the like, or from customary known ones with a comparatively high electrophotographic photographic support based on see sensitivity. It has proven to be useful 15 cellulose acetate, polystyrene, poly (ethylene terephthalate) have been shown to use the sensitizing dyes in concentrates and the like trations of about 0.5 to 30 percent by weight, be ζ. B. Nickel, drawn in a vacuum on a transparent layer vapor-deposited onto the total amount of the coating carrier in the form of such thin layers masses of added solids to be used. that electrophotographic recording

In order to carry out the process of the invention 20 materials can be produced which can optionally be exposed to at least one sensitizing dye from each of the two sides. A BE coating solvent is mixed in and the particularly advantageous electrically conductive layer-containing mixture can be produced at about room temperature. B. for example at 20 "C, stirred until the dye poly (ethylene terephthalate) existing substrate is completely dissolved. As a rule, it turns out to be provided with a photo-sensitive layer, which is sufficient, the mixture of dye and a semiconductor dispersed in a resin, e.g., solvent for up to about 2 to 3 hours to form copper (I) iodide Touch the conductive layers to obtain a practically complete solution of the given type, optionally in combination with dye For reasons of convenience, insulating barrier layers are, for example, in the USA.-The dye is usually described in about Zimmer- 30 patents 3,245,833 and 3,428,451, temperature-dissolved, but electrically conductive layers can be used to increase the suitable If, for example, the rate of dissolution is increased, the sodium salt of a carboxy ester lactone can also be used, but Von Malei Nsäureanhydrid and a Vinylacetatpoly-use of elevated temperatures, care should be taken to produce merisat. Conductive layers of the "are not to use temperatures that are higher than the given type, as well as advantageous processes for their being than the boiling point of the solution used. Manufacture are, for example, in the USA patents by means of. The period of time during which stirring is carried out , 3 007 901 and 3 267 807,
can be very different and depends on the solution to be prepared. After the solvent is practically completely dissolved before the dye is dissolved, the solution obtained is ttlit the binder and optionally a photoconductor added to the polymeric binder and added, has, in addition to the numerous stirred, which usually takes 2 to 3 hours the advantages already listed also the over-stirring has proven to be sufficient. Then there is a surprising advantage that with its help, if necessary, a photoconductor is added to only one and the solution containing the coating process electrophotographic components is briefly stirred - drawing materials with photoconductive layers. The products obtained in this way can be produced which have a higher dye concentration coating composition than comparable layers which can be used according to conventionally known methods and which can be used for coating layer supports without further additional treatment. The in is applied to a suitable substrate. 5. The photoconductive layer obtained according to the invention is then dried in the usual manner, which leads to a higher dye concentration leading to the known manner. The drying can e.g. B. advantageously to a higher electrophotoin in such a way that the solvent at graphic sensitivity. So shows z. B. that room temperature and normal pressure is simply left to vaporize the producible by the process of the invention. Furthermore, the resulting electrophotographic perforated recording materials with a layer can be dried with the aid of circulating air or by only one dye-containing photoconductive layer, whereby this is practically as sensitive as known ones, care must be taken to avoid damage caused by heat using electrophotographic recording materials will. The dye aggregation obtained in this way by simply several dye-containing layers for their coating and drying, e.g. B. after the specified known gate-containing photoconductive layer requires no process (see. Belgian patent 729 078) for further post-treatment. a first dye-containing photoconductive layer still

A further dye layer is applied to the layer according to the method of the invention. from Photoconductive layers applied to a carrier can also have the advantage that according to the method of harvesting have the most varied of strengths. In the 65th high-sensitivity electrophotographic controller photoconductive layers have proven to be useful drawing materials can be produced without a It has been moderately proven that a starch second coating operation is required before drying, as well from about 10 to 1250 μ, preferably from about 50 to that the quality and sensitivity of the

Tbsp

21 ²²

making recording materials in particularly wraps. In the so-called liquid development are advantageously controllable. After the treatment, the developer particles graze on the electrophoto-bearing surface that can be produced using the method of the invention. exposed electrophotographic recording materials are characterized by graphic recording materials in the form of improved electrical behavior. standing carrier material incorporated smd, applied and cleared. Further development processes of the specified type to be achieved according to the invention have their advantages, e.g. B. the possibility of high-sensitivity known and are described in numerous literatures. B. in the USA.-patent step I yO7 67 ^ depending on the crystalline structure of the for Her and the Australian patent step ZIl JlX
Setting of the coating materials used Sensi- When using dry development agents

To produce bilizing dyes in a simple manner, a visible, permanent image is usually mn have already been mentioned. With the help of an electrostatically attractable particle

The 15 holding developers which can be produced by the method of the invention, one component of which is composed of electrophotographic recording materials consists of a low-melting resin, produced, are to carry out the usual known, If this is verelectrically with such a developer powder Conductive layers, which require an electro-visual image, are heated, so it melts or softens suitable for photographic processes. So they are resin, if necessary with indentation into the film. B. to carry out the so-called forex ao surface, so that in this way a permanent graphic process can be used in which an adhesion of the developer powder on the surface of the electrophotographic recording material is effected in the photoconductive layer. Possibly Keep in the dark and use an electrostatic that is formed on the photoconductive layer Surface charge is provided by applying a charge image to a second carrier material, e.g. B. a Corona discharge is exposed. Which in this way as such on paper basis, transferred to what in this uniform image-receiving material imparted to the photoconductive layer by development under Because of the practically iso-melts of the developer, surface charge remains in the finished copy properties of this layer in the dark. Processes of the type indicated are known d. H. because of the low conductivity of this layer and are described in numerous literature references, in the dark, received. The on the surface of the 30 z. In U.S. Patents 2,297,691 and photoconductive layer formed electrostatic 2,551,582 as well as in "RCA Review", Vol. 15 (1954), Charge is then determined by imagewise exposure pp. 469 to 484.

according to customary known exposure methods, the following examples are intended to illustrate the invention in greater detail

explain, for example, with the help of a contact printing technique.

or by lens projection of an image, selectively 35 B e i s ρ i e 1 1

dissipated from the surface of the layer so that in. ,,. . ,. · · _N

the photoconductive layer a latent electro- (comparative example)

static image is generated. By the after a For the production of a serving as a comparison sample

The exposure of the electrophotographic recording material was carried out using the specified methods Electro mixer for 2 hours at 20 ⁰ C stirred rapidly until static charge in the resin hit by the light was completely dissolved. The solution obtained was proportional to the intensity of the incident areas with 6 parts by weight of the photoconductor 4,4'-Di radiation is removed from the film surface. 45 ethylamino-2,2'-dimethyltriphenylmethane added,

The charge pattern formed during the exposure, which ^{is then further stirred at about 20 °} C. for 30 minutes, is then developed or a surface has been applied. Thereafter, 0.3 weight receiving material was transferred to the mixture and developed there. parts 4- (4-DimethylaminophenyI) -2,6-diphenylthiapyry-The development takes place by visualization. liumfluoroborat added, whereupon the resulting either the charged or the uncharged area 50 solution was stirred for 2 hours. The latent image obtained by treatment with a coating compound was then coated with an optically dense particle known as an electrostatically attractable, optically dense particle called "Fulflo cartridge". The electrostatically attractable 5 ^ fiber filter cartridge filters.
Developer particles can be in the form of a dust, The filtered solution was applied to one of a

z. B. powder, or in the form of a resinous 55 poly (ethylene terephthalate) film existing layer carrier incorporated pigment, ie toner, carrier, which are electrically present with a vapor-deposited thin. Such a toner is applied to the conductive nickel layer, developing latent electrostatic image preferentially in such a way that the measured after drying is applied with the aid of a magnetic brush, to thickness of the layer obtained about 10 to 12 microns the development of full areas to ensure. 60 was. The optical density of the er method for producing and using available electrophotographic recording directions on the basis of magnetic brushes to the material was then measured at 600 and 690 μm. Thereafter, application of toners was z. B. in the USA - the recording material under a Coronaent patent specification 2 786 439, 2 786 440, 2 786 441, charge electrostatically charged until the 2 811 465, 2 874 063, 2 984 163, 3 040 704, 3 117 884 S ₅ with the help of an electrometer sample and the Reissue-Fatentschrift 25 779 described. surface potential was about 600 volts. The charged one

The electrostatic latent image can then be given a recording material if also with the help of liquid developers

23 24

Short-wavelength radiation was rapidly stirred. A shear treatment was the reference filter with 30% permeability at 600 ηΐμ of the solution, but not subjected. 3000 ° K tungsten light source exposed. The coating material obtained was then such exposure applied the surface potential according to the method described in Example 1 to the recording material under each step of the 5 a support of the specified type, gray wedge from its original potential V _0, whereupon the resulting electrophotographic increase to a lower potential V The drawing material of which, as described in Example 1, was tested for the exact value of the optical density and sensitivity for the area concerned, actually measured for the amount of exposure imposed. The results obtained are dependent on the meter-candle-seconds indicated below. Table V lists the potentials. The results show that both the optical density and the electrical density of the exposed recording material were measured, and the results obtained were graphically improved compared to an evaluation by calculating the surface potential V versus log exposure for each exposure step in the upper electrophotographic recording material was applied according to customary known methods in compliance. The actual positive or negative sensitivity of the tested electrophotographic component was produced in the usual order of addition. The resulting electrophotographic record can then be expressed as the reciprocal value of the exposure that the recording material could advantageously be required to reduce the surface potential to a charged, exposed and arbitrarily set value using liquid. In the pre-ao developers of the in-USA. Patent 2907674 case, if nothing else indicated type described for the production of high, the positive high-quality visible images determined in the manner indicated to be developed or negative sensitivity expressed as the . . Value 10 * divided by the exposure in meter-B e 1 s ρ 1 e 1 4 candle-seconds, which was used to reduce the applied surface potential from 600 V to 50 V from 600 V to 50 V. The procedure described in Example 3 was required is. Those determined in this manner repeatedly with the exception that first the poly-sensitivities are referred to as positive or negative meric binders to the coating solvent SO-V sag sensitivities. The photographic material was added at and the resulting mixture was stirred for 2 hours of testing of the photographic material as indicated, whereupon the sensitizing dye provided, serving as a comparative sample, and again stirred for 2 hours. The resulting solution was then obtained with the photo results, namely its optical density and clek- ladder added, whereupon the resulting mixture again trophotographic sensitivity, was stirred for 30 minutes below. In this way, Table V is shown in the table below. 35 obtained a coating solution which, according to the im. · 1 ? Example 1 described method on a layer example .. carrier of the specified type was applied (comparative example) whereupon the electrophotographic image obtained

Following the procedure given in Example 1, draw material in the manner indicated a coating compound was prepared with the 4 "electrical sensitivity and optical density exception, that 10% of the obtained was tested before filtering.

Solution in a high-speed seer-mixer Following the specified procedure, several

and for 20 minutes a Scherbean electrophotographic recording material

interruption. The one of the shear effect, the sensitivity of which was measured in each case,

The subject portion of the solution was then given a value of 45. The results obtained deviated very greatly from-

the remaining 90% of the untreated solution from each other and revealed that some of the

reunited. The obtained electrophotographic obtained electrophotographic recording

According to the materials in Example 1, the recording material had a very much lower sensitivity

methods described on optical density and than others, produced by the same method

electrophotographic sensitivity tested. The 50 had recording materials. This results in,

The results obtained are in that given below that it is not sufficient to use one in a conventionally known manner

Table V listed. The results show that by solving the sensitizing dye and polymer

the shear treatment to establish both the optical density and the binder before the photoconductor is in the dei

also the electrophotographic sensitivity obtained solution is dissolved, but that only after

be raised. 55 the method of the invention in compliance with dei

_R. IT precisely defined order of addition of the

^{exp l e} individual components coating compositions herstellbai

Using those given in Example 1, the electrophotographic recording

Components were made according to the method of materials with improved sensitivity unc

Ending in such a way as to produce a coating mass of optical density,

put that first the sensitizing dye. -ic

added to the coating solvent and Example 5

the mixture obtained until the dye dissolves (comparative example)

was stirred for about 2 hours. Thereafter, according to the procedure described in Example 1]

the resulting solution with the polymeric binder 65 was using twice the amount of Sensi

added, followed by stirring for a further 2 hours. bilizing dye herge a coating mass

Finally, the solution was added to the and to an electrophotographic assembly

Photoconductor added, whereupon drawing material is processed again for about an hour. The result

of the electrophotographic tests are listed in Table V below. The results show that the optical density and electrical sensitivity compared to that prepared according to Example 1 electrophotographic recording material are only slightly increased, from what shows that when using the specified method hardly more dye is dissolved than when using the procedure described in Example 1.

■■ · Examples

(Comparative example)

Using a coating solution prepared according to Example 5, the procedure described in Example 2 was repeated. The electrophotographic recording material obtained using a coating material from which 10 % of a shear stress had been applied was tested for optical density and electrical sensitivity according to the method described in Example I. The results obtained are shown in Table V below. The results show that the optical density and electrophotographic sensitivity are only slightly greater than in the electrophotographic recording material prepared according to Example 2 using only half the amount of sensitizing dye. It can also be seen that the electrophotographic recording material prepared using the pre-shear coating material has an optical density and electrical sensitivity which are not greater than those of the electrophotographic recording material prepared by the method of the invention according to Example 3 using only half the amount of sensitizing dye.

Example 7

Following the procedure described in Example 3, using twice the amount Sensitizing dye prepared a coating compound and applied to a support, whereupon the obtained electrophotographic recording material for optical density and electrical Sensitivity has been tested. The results obtained are shown in Table V below. The results show that, according to the method of the invention, using twice the amount Sensitizing dye almost twice as high an electrophotographic sensitivity is achieved.

The electrophotographic obtained in the investigation of Examples 1 to 3 and 5 to 7 The results obtained from recording materials are listed in Table V below:

Table V

Optical density Photo sensitive example exposure
by an interference 600 πιμ 690 ΐπμ filter on a lower one No. 0.52 0.50 Potential of -50 V 1 0.85 1.24 <50 2 0.91 1.55 800 3 0.58 0.52 900 5 0.87 1.57 <50 6th 1.08 > 4.00 900 7th 1600

Example 8

The procedure described in Example 3 was repeated except that the sensitizing dye was used 4 - (4 - Dimethylaminopheny 1) - 2,6 - diphenylthiapyrylium perchlorate was used. There was a spontaneous formation of dye aggregates, which was complete after the addition of the polymeric binder was. The obtained electrophotographic recording material was made in the above manner tested. Advantageous results as in Example 3 were obtained accordingly.

Example 9
(Comparative example)

The procedure described in Example 4 was repeated using twice the amount Sensitizing dye. The obtained electrophotographic recording material was tested for sensitivity and optical density tested. No clear results were obtained, so not It could be determined with certainty whether at least doubling the dye concentration

as a small increase in sensitivity and optical Density is achievable.

Example 10

The procedure described in Example 3 was repeated except that 4-diethylaminotetraphenylmethane was used as the photoconductor and 4- (4-dimethylaminophenyl) -2,6-diphenylthiapyrylium perchlorate as the sensitizing dye. Based on solids, 2 percent by weight of dye and about 37 percent by weight of photoconductor and an amount of 100 percent by weight missing binder of the type described in Example 1 were added to the solution. It was first, followed by dissolution of the dye, the binder and the photoconductor, and the resulting coating solution was coated on a support of the type specified by the process described in Example 1 at a coating block temperature of about 15 "C. The electrophotographic recording material obtained was applied to electrical sensitivity The 100 V negative sag sensitivity was found to be about 1100. Thereafter, the recording material was tested for regeneration using 100 cycles.

So properties tested. To conduct this test the film sample was subjected to a corona discharge according to the method described in Example 1 and then exposed, whereupon it is subjected to a flood or erase exposure with the entire cycle being completed within 3 seconds. The specified The treatment cycle was repeated 100 times, whereupon the one examined in the measurement of the surface charge of the The results obtained with the recording material after the first and the 100th cycle were compared with one another became. It was found that the maximum surface charge of the photoconductive layer after the 100th cycle had not fallen compared to the first cycle.

The obtained electrophotographic recording material was then used to produce a visible image charged, exposed and developed by the method described in Example 3.

27 28

Example 11 Example 1 consisted of the type described. The application the coating compound on the substrate

Following the procedure described in Example 10 was conducted at a coating block temperature of two photoconductive coating compositions were about made 15 ⁰ C. The obtained electrophotographic wherein as photoconductors for preparing the 5 recording material was after the first in the Example 10 coating composition 4,4 ', 4 "- Tris (diethylamino) - method described was tested and it was found tetraphenylstannane and used to make the second that the negative 100 volt sag sensitivity coating composition was diphenyl-bis- (p-diethyiaminophe-1800. To produce a visible image, nyl) stannane was used The first coating consisted of 2 parts of drawing material, based on solids, of drawing material in the specified manner by weight percent of dye, loaded to about 60% by weight, exposed and developed.
Percent from photoconductor and the remainder from binder,. 114
and the second coating consisted of 2 Ge Example 14
weight percent from dye, about 53% from photo After the method described in Example 3 head and the remainder of the binder in Example 1 15 were initially 0.375 g of sensitizing dye of the type described. type described in Example 3 in 42.5 g of methylene

Each of the two coating compounds obtained chloride dissolved with stirring for about 2 hours,

were according to the method described in Example 1. After dissolving the dye, the resulting solution was

drive at a coating block temperature of 4.5 g of poly (4,4'-isopropylidene diphenyl carbonate

about 18 ⁰ C applied to a layer support. The 20 block oxytetramethylene) are added with stirring and

obtained two electrophotographic recordings for about 2 hours until the poly-

Application materials 1 and 2 were then stirred after the merisate. After that became the sublime solution

Method described in Example 10 to electrical with 3 g photoconductor of the method described in Example 1

Sensitivity tested. Type added, whereupon the resulting mixture a

The results obtained showed that the sample 35 more Z ¹ was stirred for ₂ hour. The received

No. 1, a 100 volt negative sag sensitive coating, was then applied to an electrically

speed of about 3500 and sample no. 2 has a negative conductive layer support of the one described in example 1

100 volt sag sensitivity of about 1700 benen type applied to what the layer obtained

exhibited. The two recording materials were left to dry.

the then described in Example 1 30 The electrophotographic record obtained

Process charged, exposed and developed. It was recorded in the dark on a surface

clearly visible images were obtained. potential of 600 V and after the im

Example 1 described method exposed, whereupon

If ρ ie 1 12 ^{it has been} tested for sensitivity. The received

35 positive or negative sensitivities were made

According to the method described in Example 10, expressed as the value 10 ⁴ divided by the was an electrophotographic recording exposure in meter-candle-seconds, the material produced using a reduction of the 600 V amounting to the surface potential of the layer mass, based on Solids content, to a potential of 500 V (100 volt Schuiter to 2 percent by weight of dye of the sensitivity in Example 10 40) or to a potential of 100 V, to about 62 percent by weight (100 volt sag sensitivity) is required . p-Diethylaminophenylgerman as a photoconductor and the results obtained showed that the positive to the remaining portion consisted of binder of the 3200 shoulder sensitivity in Example 1, the positive type written through. The application of the slope sensitivity 320, the negative shoulder tempering coating compound on a layer 4500 sensitivity and the negative sag sensitivity support was carried out according to the sensitivity 500 described in Example 1. After Auslöschbelichtung method at a coating block temperature of the electrophotographic Aufetwa obtained was 15 ⁰ C. The obtained electrophotographic drawing material to produce a visible recording material was prepared by the in Example 1 of the image according to the method described in Example 3. The method described charge to electrical sensitivity 50, expose and develop imagewise,
fceit tested. The results showed that the neeative. .
100 volt sag sensitivity was about 480. Example 15
With the aid of the recording medium obtained. This example shows that clearly visible images according to the invention were obtained when it was charged, exposed and developed using a coating according to the method described in Example 1 for an electrophotographic recording material. solution that only has a sensitizing dye and

contains a binder and is free of photoconductor

B e i s ρ i e 1 13 For the preparation of the coating solution were

initially 0.16 g 4- (4-dimethylaminophenyl) -2,6-di-

According to the method described in Example 10, 60 phenyl thiapyrylium fluoroborate in 18.2 g of dichloro

an electrophotographic recording methane was dissolved with stirring for about 3 hours. the

material prepared using a solution obtained was with 4.0 g of a bisphenol

coating compound, which, based on the addition of the A polycarbonate, whereupon the resulting color

Solids added to stratification solvent, stir to fabric-binder solution for about 18 hours)

2 percent by weight of the dye in Example 10 65 was.

type described and about 40 percent by weight The resulting coating solution was thenr

«.Us photoconductor of the type described in Example 1 at 18.3 ⁰ C on a polyethylene terephthalate ·

consisted, with the remainder of the binder of the existing film in the substrate, with a

q 5 1

Vaporized conductive nickel layer was applied. The layer thickness of the dry photoconductive Layer was about 12-14 microns. See a sample section of the obtained electrophotograph Recording material was charged under a corona discharge until that was achieved with the aid of an electrometer probe measured surface potential reached about 600 volts. The charged recording material was then exposed to a 3000 ° K tungsten light source and the loss of surface potential was measured as a function of exposure. The sensitivity measurement was carried out according to the im Example 1 described procedure, but with the exception that the sensitivity determination on a 100 volt shoulder sensitivity instead of, as in the Example 1, on a 50 volt shoulder sensitivity based.

The obtained results, which were obtained both in the positive as well as negative charge, are in the following table as a shoulder sensitivities (K ₀ -100 volts) and 100 volts slack sensitivities reproduced.

The optical density was measured on another section of the recording material obtained, and the results obtained are also shown in the following table.

Table VI

Electrical H and D rec. (Shoulder / 100 volt
Passage) pos.
360/9 neg.
360/16

Optical density

600 nm
2.10

685 nm
3.35

The results show that the dye aggregates obtained according to the invention act as photoconductors, so that for the production of an electrophotographic recording material according to the invention Do not use a separate photoconductor

ao is necessary. The high light absorption found at 685 nm and a microscopic one Examination of the recording material obtained revealed an extensive conversion of the material used Dye and binder in the invention

»5 photoconductive dye-binder combinations that can be produced recognize.

Claims (3)

Patent claims: 1. Method of making an electrophotographic Recording material composed of an electrically conductive layer support and at least a heterogeneous photoconductive layer composed of a continuous phase of a binder and a discontinuous phase containing at least one sensitizing dye, which forms recognizable aggregates at 2500x magnification, consists of a sensitizing dye, binder and coating liquid containing solvent is applied to the support and the layer obtained is dried thereby characterized in that, for the preparation of the coating liquid, the sensitizing dye (s) dissolved in the solvent, the binder added to this solution and the obtained ao The mass is intimately mixed before application to the substrate. 2. The method according to claim 1, characterized in that that a coating liquid is used which additionally contains a photoconductor, wherein the photoconductor is added to the coating liquid after the addition of the binder will. 3. Process according to Claims 1 and 2, characterized in that the sensitizing dye is used a selenapyrylium dye salt or a pyrylium or thiapyrylium dye salt of the formula