DE2608082C2 - Electrophotographic recording material with a photoconductive layer - Google Patents

Description

50

The invention relates to an electrophotographic recording material having a photoconductive one Layer that acts as a photoconductor, a condensation product with formaldehyde * and amine <units and possibly optical or chemical sensitizers and possibly a binding agent contains.

- c,

C ₃

C ₂ -

contain, wherein Ct is a carbon atom on one

aromatic ring and Ci and Cj carbon atoms which form a hydrocarbon radical and form a bond orbit of the sp - type or sp ^J - type, have good photoconductivity, preferably when combined with a suitable sensitizer, ί Typical examples of such amines are N-substituted carbazoles and substituted aniline derivatives.

So far, the following three typical methods of forming electrophotographic photoconductive Recording materials using to of compounds with an aromatic tertiary Amine unit applied:

(I) A low molecular weight compound of defined structure, such as N-butylcarbazole, became uniform in a high molecular weight compound to form a photoconductive one Layer dissolved (see. US-PS 32 06 306).

(II) As in the case of the well-known poly-N-vinylcarbazoIs becomes a polymer with repeating Jn units of the form! (Ia) made from monomers, which contain a unit of the formula (la) or precursor units for this and the polymer is made into a thin film to form the photosensitive layer. :>

(III) As in the case of the reaction between polyepichlorohydrin and a carbazole alkali metal /. that in the Japanese Patent Publication 97540/73. becomes a polymer with a Low molecular weight compound for introducing a unit of formula (Ia) in the form implemented by bound groups of the polymer.

According to the method (I), a large amount of the η low molecular weight photoconductive material required to be sufficiently cheap Preserve sensitivity. However, it is very rare that the photoconductive material is of low Molecular weight a stable system in reciprocal -in Can form solution with the added binder polymer. Even if a stable system is formed it often phase separates or exudes and its quality changes when it does is not carefully stored 4> as recording material.

In the case of method (II), it is assumed that Poly-N-vinylcarbazole and its substituted derivatives have the best properties and some of them have been used technically, however, since polymers> n of this type are produced via two stages of monomer synthesis and polymerization and a strict one Purification of the product is required at each stage. to get good properties / u are the ones obtained Polymers are generally very expensive and can be 5ί can only be used to a very limited extent

In method (III), however, the polymer and the compound used in the polymer reaction are of low molecular weight are commercially available at low cost. So that the electrophotographic bo see photoconductive layer has sufficient sensitivity, but it is necessary that introduce photoconductive group in an amount above a certain limit. To this introduction without causing undesirable side reactions such as gelation, polymer and compounds must be achieved of low molecular weight react selectively with each other with good reactivity.

In fact, however, it is very difficult to find combinations that meet these requirements among the technical find useful low molecular weight polymers and compounds. Despite numerous No such material was technically available to date.

In DE-AS 11 97 325 is an electrophotographic Recording material described in which the photoconductive layer as a photoconductor is a condensation product from an aldehyde and an optionally substituted aromatic amine

The object of the present invention is to create an electrophotographic recording material with a photoconductive layer which, as a photoconductor, contains a condensation product with formaldehyde and amine units and optionally optical or chemical sensitizers and optionally a binder, the photoconductive layer being applied to a carrier material made of foils, paper may be, is easily produced, inexpensive and can be easily formed and a thin film by pulling up on the substrate and has a satisfactory sufficient sensitivity.

Research has found that soluble aromatic formaldehyde resins, the one electrophilic reactive group such as methylol or dimethylol ether group contain as typical Examples of xylene formaldehyde resins or resole resins, as Base polymer is readily available. Such resins are not polymers with high molecular weight chains, as used in the above-described method (III), but rather are Oligomers. It has also been found that low molecular weight compounds are aromatic Amine compounds represented by the following formula

Ar-H-N- \),

(1)

wherein A represents an aromatic group, the group

-H- N - Y).,

is bonded to the carbon atoms of the aromatic ring. η denotes the numbers I or 2 and Y denotes a hydrocarbon radical which, if desired, forms a ring with Ar either directly or via a nitrogen, oxygen or sulfur atom, with the proviso that. if η has the value 1. Y can be hydrogen, for example carbazole. Diphenylamine, aniline or methylaniline, are commercially available at a low cost, and that the hydrogen atom bonded to the nitrogen atom in the above compounds undergoes a substitution reaction with an electrophilic reactive group and can be substituted with a benzyl type group to form a condensation product with formaldehyde and amine units is formed.

Accordingly, the solution becomes the above specified object according to the invention with an electrophotographic recording material a photoconductive layer, which acts as a photoconductor Condensation product with formaldehyde and amine units and possibly optical or chemical sensitizers and optionally contains a binder, created that

is characterized by it. that it is a soluble reaction product as a photolciter

(A) a soluble polycondensation from residues of a benzene compound which has at least one free bond and at least one nitrogen-free bond. containing electrolytic substituents, where at least one of the radicals of the benzene compound contains a substitute of the formula —CH2X, where X is a haloalom or a hydroxyl, alkoxy or O-acyl group, and where the radicals of the benzene compound are replaced by a group of the formula - CHj (OCM) j) -m, wherein m is equal to 0.1,2,3 or 4, are connected, and

(b) contains from an amine, which from

(b-l) an aromatic amine of the formula

Il

Ar-f N-Y) ,,

where Ar is an optionally substituted aromatic group, π is I or 2 and Y is a hydrogen atom or a hydrocarbon group when η - 1 and Y is a hydrocarbon group when η = 2, or
(b-2) from a heterocyclic amine of the formula

H
N

Ar

Y '

where Ar is an optionally substituted aromatic group, η is 1 or 2 and Y 'is the atoms required to complete a heterocyclic ring which may contain another O, S or N atom.

The electrophotographic recording material according to the invention, which is that given above Having soluble condensation product as the photoconductive layer is particularly valuable.

The soluble aromatic tertiary amino group-containing photoconductive condensation product which is obtained from components (a) and (b), both of which are readily available industrially and after a simple processes can be produced, for example in the simplest case only by mixing the same and heating the mixture is therefore particularly advantageous. In addition, this has a condensation product superior properties as shown below and provides a photoconductive layer of excellent usability

In contrast to the compound used in the above method (I) of low Molecular weight, the condensation product used as a photoconductor is a glass-like transparent one Material with film-forming properties and can use the photosensitive photo-conductive layer without using it form a binder polymer. When a photoconductive layer with better flexibility if desired, a binder polymer can be added. The amount of binder polymer however, it may be very small compared to the method (I).

• In contrast to the one described above Process (II), which is the mutual dissolution of an aliphatic polymer of high molecular weight and a further polymer timfaßi, see according to FIG Invention of a very wide range of binder poly

1 »kidneys for complete mutual dissolution with the photoconductive condensation product available, since its molecular weight is about that of oligomers. although it represents a polycondensation. Therefore can according to the desired

r> End use / awaken a stable transparent thin film-like photosensitive photoconductive layer can be formed.

Furthermore, the condensation product used according to the invention has a better one

(1) J «Sensitivity as a model compound with a

defined structure despite the fact that due of the manufacturing process, its structure is not represented by defined, repeating units can be. It has already been confirmed experimentally.

2> as shown in the following comparative examples, that, for example, a reaction product from a polycondensation of a xylene polymer and carbazole. as a typical example of the photoconductive condensation product used according to the invention

ii) far higher sensitivity than a photoconductor N-ßenzylcarbazole, a model compound with the same photoconductive functional group, if the same sensitizer and the same

(2) binders are incorporated in the same amounts. The same result is obtained when the sensitivity a photoconductor composed of a polycondensate of a xylene polymer and aniline with that of a Dibenzylaniline photoconductor. a model compound of the former materials.

■ In view of the easy production of the invention photoconductive condensation product used, the breadth of additives for production the light-sensitive layers and their better sensitivity to the model compounds

-15 due to the special structure it is easy to see that the present invention provides an electrophotographic recording material of excellent quality Usability supplies.

The electrophotographic layer according to the invention may even consist of the photoconductive one Condensation product can be formed alone. Je ^ i For certain purposes of use, the sensitivity of such a layer and its flexibility are low is insufficient. It is therefore preferred to use suitable Amounts of sensitizers and binder polymers to add.

Because of their function, the sensitizers can be converted into optical sensitizers or dye sensitizers and chemical sensitizers.

If high sensitivity is required, Both types of sensitizers are often used together. In special cases a Substance that is used both as a binder and telpolymeres acts as a chemical sensitizer.

b5 The photoconductive condensation product, the sensitizers, the binders and the photoconductive Layer are explained in detail below on the basis of preferred examples.

230217/229

I. Photoconductive Konclensalionsproclukl

(a) Soluble polycondensation
of low molecular weight

The soluble low molecular weight polycondensate used to make the photoconductive condensation product can be used by Implementation of a benzene compound which has at least one nitrogen-free, electron-donating core substituent and at least two kcl'nsubstituierenden hydrogen atoms, which for the methylol substitution are capable of formaldehyde, contains, with formaldehyde and / or functional derivatives thereof in known Way can be obtained with the formation of an Addilionskondensaiion. The addition condensation should be in to such an extent that the resulting low molecular weight polycondensate Dissolve in solvents and preferably is also fusible.

Suitable compounds of the benzene type for the preparation of the soluble polycondensates of low Molecular weights can be represented by the following formula

(3)

where /, / 'and / ■ positive integers, where [/ + q x r] represent the numbers 1, 2, 3 or 4, /' denotes the number 0 or 1 and, if q has the value 0, the grouping

denotes a hydrogen atom and r denotes the number 0 or 1 and, if r has the value 0, the benzene ring C is bonded directly to the core carbon atom of the benzene ring B, while A and A 'can be identical or different, and at least one radical from the group of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups or halogen atoms with the proviso that if / or / 'has a value of 2 or more, A and A' can represent different groups from the above class and at least one of the radicals A and A ^{1 must represent} an electron-donating group from the above class.

Examples of such benzene type compounds include toluene, xylene, diphenyl ether. Butylphenyl ether, Phenol, CresoL xylene, tert-butylphenol, anisole Isopropylbenzene. Trimethylbenzene, ethylbenzene, 1-butylbenzene, p-phenylphenol, trimethylsilylbenzene, pseudocumene and DuroL of which xylene, diphenyl ether, Phenol or substituted phenols, for example halogen- or alkyl-substituted phenols, are preferred. m-XyloI is particularly preferred because it is practical The formaldehyde or its functional derivatives are mainly in the form of formalin used, but can also be in the form of p-formaldehyde. Trioxane or Chlormelhylmcthyläthcr can be used.

The conversion between the benzene-type compound and formaldehyde and / or its functional > nellcn derivatives is known according to a suitable Procedures performed according to the given combination of respondents. Of course it is not sufficient to merely obtain a polycondensation product, but must

'<> Care must be taken to ensure that one for A group capable of participating in a reaction with an aromatic amine compound of the formula (2), d. H a methylol group or functional derivatives thereof corresponding to the formula - CHjX in sufficient

ti amount must remain.

In the case of a benzene type compound which is mainly used as a difunctional compound in the iviemyioiicfürigsfciikiiCrfi Γ63§ίΕΓί. iViC Γίΐ-xyloi, pseudo Cumol or Durol can be a soluble condensate problem

- <> product, which has a methylol group or a dimethylol ether bond in addition to the methylene bond, can be obtained by adding the benzene compound and an excess amount of formaldehyde in the form of formalin or trioxane in an addition condensation

i'i the presence of an acidic catalyst. On the other hand, in the case of a benzene type compound which mainly reacts as a trifunctional compound in a methylolation reaction, such as phenol or cresol. a soluble condensation product

in having a reactive methylol group of the so-called resol type can be obtained by reacting the same with formaldehyde in the presence of an alkaline catalyst.

Benzene-type compounds that are relatively difficult

Jj are to be methylolated, such as diphenyl ether, with a mixture of hydrochloric acid and trioxane, a mixture of formalin, hydrochloric acid and sulfuric acid or chloromethyl ether is chloromethylated to form a polycondensate.

The chloromethyl group can be used in the form of a functional derivative of the methylol group. In general, however, it is preferred to pass them into a methylol group or dimethylol ether linkage Hydrolysis or to an alkoxymethyl group

-ti alcoholysis or to an acyloxymethyl group To convert esterification before the reaction with the aromatic amine compound of formula (2). this is preferred because no corrosive hydrogen chloride is formed during the reaction

Particularly preferred polycondensates are polyxylene condensates using m-xylene, modified polyxylene condensates, polydiphenyl ether condensates and resol type phenolic condensates. As a polyxylene condensate is a product with an oxygen content from 3 to 18% and a softening point (in the liquid state at room temperature) of up to 150 ° C or a modified polyxylene condensate Suitable Paint condensates that harden when heated can also be used as polyphenol condensates from Resole type can be used.

In general, these polycondensates preferably have a high content of methylol groups, Dimethylol ether groups and / or functional derivatives from this because they react with the aromatic amine compound to a large extent. But when If the content of these reactive groups becomes too high, a competing crosslinking reaction takes place at the time of implementation between the soluble

Ii

Low molecular weight polycondensate and of the aromatic amine compound and the product becomes insoluble. Therefore, in order to increase the solubility of the Photoconductive polycondensers according to the invention The content of these reactive substances must be maintained Groups within a suitable range corresponding to the aromatic amine compound of the formula (2) forming benzene nuclei or the soluble polycondensate can be adjusted. The polyxylene condensates are particularly preferred in this regard as they undergo essentially no crosslinking reaction, even if they have a large number of reactive groups

and because they are less colored than polyphenol condensates are.

In general, they have soluble polycondensates

of low molecular weight has a molecular weight

■> from 200 to 3000 and their content of methylol groups or Dimethyloläthergruppeh uhd / or functional derivatives thereof is 1 to 0.1 to 3 benzene nuclei.

As a dimethylolethcfgruppe with two groups Can react with HN, as shown schematically below in, its content is calculated as a methylol group, considered as 2:

-CH ₁ OCHj- + HN

- CH, N + HIGH ₂ - NII + HOCII ₃ - -> -ClI ₂ N + H ₂ O

(b) Aromatic amine compound

For the production of the photolite-capable polycondensate The aromatic amine compound used is represented by the formula (1). Preferably In the formula (1), the aromatic group Ar denotes 1 to 2 benzene or naphthalene nuclei with 6 to 15 Carbon atoms as an aromatic ring and consists especially of 1 to 2 such benzene groups. the carbon atoms of the aromatic ring can, for example, have 1 to 3 substituents. Preferred Substituents are alkyl groups with 1 to 3 carbon atoms, alkoxy groups with 1 to 3 carbon atoms. Aryloxy groups with 6 to 10 carbon atoms, N.N'-disubstituted amino groups and halogen groups. A part, preferably not more than 30 mol%, of residues Ar can have a strongly electron-withdrawing substituent. such as a nitro, cyano or alkoxycarbonyl group contain. However, if more of Ar has such a group, it affects detrimental to the photoconductivity of the obtained condensation product and therefore becomes such large content of substituents not preferred. If Y represents an aromatic group> E ', the same applies Requirements as for Ar, with the same examples given above being preferred.

As shown in the above formula (2), Ar and Y can be bonded to each other and 1 to 2 aromatic fused polynuclear rings

together with the group [[ form. Preferred

Examples of such heterocyclic amine compounds are carbazole, phenoxazine and indole.

When Y has a meaning other than an aromatic group, it preferably consists of one Hydrocarbon groups with 1 to 10 carbon atoms, which may contain the same substituents as indicated above with respect to Ar. As in the case des IndoHns, for example, Ar and Y 'can be fused together to form a multi-core ring be connected, as discussed above. Particularly preferred examples of Hydrocarbon groups are lower alkyl groups with 1 to 3 carbon atoms and benzyl groups.

Specific examples of preferred aromatic amine compounds are given below.

(a) If π = 1 and Y = H:

ΑπΠϊα, toluidine, xylydine, p-ethylaniline,
p-chloroaniline, p-bromoaniline,

2,4-DiehloraniÜn. p- Ankitlin. o-anise sirline,

NN-dimethyl-p-phenylenediamine and
in Λ- orSnaphthylamine.

(b) If η = 1 and Y is not an aromatic group and is not bonded to Ar:
N-methylaniline, N-ethylaniline,
N-propylaniline, N-benzylaniline,

2> N-methyltoluidine,

Ν.Ν, Ν'-trimelhyl-p-phenylenediamine,
N-cyclohexylaniline and
N-methyloc-naplv.hylamine.

(c) If η = 1 and Y is an aromatic group, but not bonded to Ar, then:

biphenylamine, phenylnaphthylamine,
Dinaphthylamine, Ditoluylamine and
4,4'-dichlorodiphenylamine.

(d) If η = 1 and Y is bound to Ar:
Carbazole, 3-chlorocarbazole,

3,6-dibromocarbazole, indole, isoindole,
Indoline, phenoxazine, phenothiazine and
2-phenylbenzimidazole.

(e) If η = 2:

4,4'-bis (monomethylamino) -diphenylme'.han,

4,4'-bis (monoethylamino) -dipheny! Methane,

l, l- [4,4'-bis (monomethylamino) -

diphenyl] ethane,

4.4'-bis (monobenzylamino) diphenylmethane,
4,4'-bis (phenylamino) diphenyl imethane,

4,4'-bis (methylamino) triphenylmethane,

N, N'-dimethyl] -p-phenylenediamine,

N, N'-diphenyl-p-phenylenediamine,

N, N '- (j3-naphthyl) -p-phenylenediamine and
Diindole.

Preferred aromatic amines are those which easily melt together with the soluble polycondensate and can be reacted in the molten state. However, so that they are easily available and photoconductive condensates of reduced coloring yeasts, especially those of the Formula (1) preferred, in which Y is selected from the group of hydrogen atoms, lower alkyl groups, benzyl groups and phenyl groups, in particular from at least one aniline, toluidine, N-methylaniline, N-ethylani-Hn, N-benzylaniline, carbazole, diphenylamine and 4,4'-bis (methylamino) diphenylmethane is chosen

The above aromatic amine compounds are limited to those in which 1 to 2 hydrogen atoms are bound to the nitrogen atom of the amino group. The reason is that if she has 3 more people containing such hydrogen atoms, easily with the

react reactive groups of the soluble polycondensation agent of low molecular weight and the reaction product undergoes gelation and becomes insoluble. However, some of the aromatic Arninverbindungcn provide improved sensitivity ouct Filmbil-> Manure capable wedge, if a portion (generally not more than 30 Mi) I ⁰ Zo) thereof by an aromatic Aminvcrbindung, wherein at least 3, preferably 3 to 4 VVasserstoffatome bound to the amino group are replaced. Examples of such aromatic amine compounds are 4,4'-diaminodiphenylmethane, 4,4'-diminodiphenyl ether and p- or m-l'henylene cliamine.

(c) Co-condensation component

The Uraudibarkeii of the photoconductive. a tertiary π Amino group-containing polycondensation product can sometimes continue to be used for certain applications by using a co-condensation component which is linked to the reactive groups of the Polycondensates to the same extent as the aromatic 2h • before the external connection reacts during the establishment of the Photoconductive polycondensation product described above be improved. The co-condensation component includes, for example, multi-core aromatic hydrocarbons and phenolic convolutions. The polynuclear aromatic hydrocarbons sometimes have an effect of increasing the sensitivity of the photoconductive folicondensation product. however, as they are for Are prone to discoloration. n. favorably chosen according to the desired use. Preferred Phenolic compounds are those with at least three aromatic rings, such as anthracene. Perylene end phenanthrene. where anthracene is particularly beneficial will.

The molar mixing ratio of polynuclear iromatic hydrocarbons to aromatic Amine compound is 0.1 to 3: 1. preferably 0.1 to 1: 1.

The phenolic compound as a co-condensation -to component sometimes has an effect on the Improvement of the film-forming suitability of the photoconductive polycondensation product and the compatibility the aromatic amine compound with the binder polymer. Preferred phenolic compounds are phenol. o-CresoI. m-cresol. p-cresol. Mixed cresol. 3.5-xylenol and terL-butylphenol. That molar mixing ratio of the phenolic compound to the aromatic amine compound is 0.1 to 3:!. Preferably 0.1 to 1: 1.

(d) Preparation of the photoconductive.

Polycondensation product containing tertiary amino groups

It is known that a polycondensation product containing tertiary amino groups is formed by condensation between a soluble low molecular weight polycondensation and an aromatic one Amine compound can be obtained, as in the case of the Conversion of aniline with a xylene-formaldehyde condensate, as for example in K. O. Kogyo Kagaku Zasshi, 58th page 520 (1955) and 62nd page 129 (1959) is specified. However, it was not known that the conversion of a soluble polycondensate of low Molecular weight with a secondary amine of the diarylamine type. such as carbazole or diphenylamine. preferably gives a tertiary amine and thus a polycondensation product containing this obtained can be.

The soluble and fusible aromatic polycondensation products containing tertiary amino groups according to the invention can be obtained by (I) a soluble polycondensai of low molecular weight as component (a) with the amine compound (b) umscut, wherein the an Carbon atom of the benzene ring bonded methylene group through the the amino group of the aromatic Amine compound (b) forming nitrogen atoms bonded hydrogen atom is substituted.

The ratio between the low molecular weight polycondensate (a) and that for preparation of the photoconductive polycondensation product used aromatic amine compound (b) is such that the Content of the dimethyl ether group. the methylol group and / or their functional derivatives of the polycondensate (a) Equivalenlgewichl equal to the content of those bonded to the nitrogen atom of the amino group Is water atoms, this ratio being preferred will. However, it is not necessary to set the ratio exactly to this standard, and it can be in Depending on the desired end use, the ratio can be varied. If you z. B. wishes the Amino group content of the photoconductive polycondensation product To increase, a method is sometimes used in which the aromatic amine compound (b) in excess of the dimethylol ether group. the methylol group and / or its functional Derivatives of the polycondensation product (a) are fed in and, after the reaction, the excess unreacted Amine (b) from the photoconductive polycondensation product obtained by distillation or Precipitation is removed. The amount of the aromatic amine compound (b) can generally be 20 Mol% to 300 equivalent% excess.

In some cases, the aromatic amine compound (b) is used in an amount less than the equivalent weight introduced so that a part of the Dimethyloiäthergruppen, the Methylo'jruppen and / or their functional Derivatives of the polycondensate (a) in the substitution reaction with the ring carbon atoms of the aromatic amine (b) is used, with or without the carbon atoms de, benzene ring of the polycondensate (a) is additionally used in the reaction with the amino group of the amine (b) so that the molecular weight of the photoconductive polycondensation product obtained is increased and its softening point or film-forming suitability is improved. However, if the crowd de ' supplied aromatic amine compound is too low, the proportion of photoconductive groups of the photoconductive polycondensation product and causes a decrease in sensitivity. As a result, there appears to be a tendency for the polycondensation product obtained to gel as a result of crosslinking to occur during the reaction. It is therefore generally preferred to use the aromatic amine compound to be used in an amount of at least half of the equivalent weight.

Depending on the kind of the aromatic amine compound and the reaction conditions, the difference between the substitution reactivity of the reactive groups of the polycondensate (a) with the hydrogen atom bonded to the nitrogen atom of the amino group and that with the to the core carbon atoms of the aromatic ring bonded hydrogen atoms sometimes low and it occurs

Tendency to gel.

The reaction between the polycondensate (a) and the aromatic amine compound (b) is through Use of a catalyst favors. An acidic catalyst such as m-xylene sulfonic acid, Methanesulfonic acid or toluenesulfonic acid can be used. The amount of the catalyst is 0.001 to 20%, preferably 0.1 to 3%, based on the weight of the soluble polycondensate of low Molecular weight (a).

The reaction can be carried out in the presence of an inert reaction solvent such as nitrobenzene or methyl benzoate are executed. However, since it is necessary. the photoconductive polycondensation product obtained to deposit from the solvent after the reaction, it is preferred to carry out the reaction in the molten state with evaporation of the water occurring as a by-product or optionally to be carried out with evaporation of the undesired unreacted reaction components. Preferably "· the reaction is carried out in an atmosphere of an inert gas such as nitrogen or argon, to prevent discoloration of the resulting polycondensation product due to oxidation. In some In some cases, the reaction can also be carried out under reduced pressure.

The reaction of the aromatic amine compound (b ^ with the polycondensate (a) with or without Co-condensation component is at a temperature from 50 to 300 ° C. preferably from 120 to 230 ° C. The response time varies accordingly however, the other conditions such as the reaction temperature is usually 0.2 to 10 hours. preferably Ibis 4 h.

The state of progress of the reaction can generally be determined by determining the NMR spectrum or IR spectrum of the reaction mixture can be followed. The disappearance of the absorption due to the proton NU in the aromatic amine (b) and that due to the proton of - CH2O - in the aromatic amine (b) Absorption can be determined in the course of the reaction. The IR spectrum can do that Progress of the reaction based on the reduction in the characteristic absorption, the binding of . "N-H can be traced. From the infrared absorption spectrum it can sometimes be seen that even after the reaction, a proton of the - NH type in small amount remains in the resulting polycondensation product. This is probably due to that the reaction of the melhylol group and / or its functional derivatives with the carbon atoms of the aromatic ring of the aromatic amine (b) competes with the reaction of these groups with of the - NH group takes place and consequently a group - NH- in the polycondensation product remains, or a group of the benzyl type from the formed tertiary amino group is rearranged

After the reaction, the polycondensation product formed can be used as a photo slider for a. electrophotography Phical recording material can be used without special cleaning, but if required Addition of a sensitizer or a binder of the types described above.

If desired, the polycondensation product obtained can for example by dissolving in a solvent such as MethyläthylkelörS ödeT Chlofbenzol and pouring the solution into a sewing solvent for the polycondensation product, such as methanol, to remove the unreacted material or through Comminution of the polycondensation product obtained to powder or granulate and extraction of the same with a substance that is a sewing solvent for the Represents a polycondensation product, but a solvent for the unreacted materials, for example methanol, can be purified to remove the unreacted materials.

It is also possible to include an appropriate amount of a halogen in the aromatic group of the recovered Polycondensation product by contacting the same with a halogenating agent for exchange of a halogen atom against the hydrogen atom on the aromatic ring, for example with bromine, chlorine, Introduce N-bromosuccinimide or sulfuryl chloride, or a sulfate group by reaction of the polycondensation product with oleum in part of the aromatic ring.

jo Polycondensation products subjected to these post-treatments can be used as a photoconductor according to the invention in the same way as the polycondensation products listed above.

(e) Properties of the photoconductors
according to the invention

The polycondensation used as a photoconductor

j (i product is a transparent amorphous solid material which is colorless. or is colored blue, green, yellow or brown It has a softening point of at least 50 ^° C. and can also be infusible, preferably it has a softening point of 70 to

ji 150 "C. The polycondensation product is in many Soluble in organic solvents and can be cast into films from solutions in these solvents will. The preferred solvents are those with a boiling point of 40 to 200 C. for example

4n ketones, such as methyl ethyl ketone. Acetone. Melhylisobutyl ketone and cyclohexanone and aromatic hydrocarbons such as toluene and xylene, halogenated Hydrocarbons such as diehlomethane. Tetrachloroethane and chlorobenzene. Ethers, such as tetrahydrofuran

ij dibutyl ether and anisole. Esters such as ethyl acetate and Butyl acetate and amides such as dimethyl formamide. Dirnethylacetamide and N methvlpvrrolidone

The photoconductors according to the invention have im generally a molecular weight, given as

in inherent viscosity and determined at 30 C for a solution of the polycondensation product in N methylpyrrolidor at a concentration of 0.5 g / 100 ml. from 0.03 to 0.80. preferably 0.07 to 0 50. The amount of amino groups hold of the polycondensation product is preferred

r, point 1 to 0.5 to 7 benzene nuclei. the soluble Form polycondensal (a), and in particular I to 0.6 bi: 4 benzene nuclei.

The amino group is attached to the benzene ring forming the skeleton of (a in the formula represented by the following

Ar

CH ₂

N —Y) "

indicated form, in which Af is an aromatic group and η denotes the numbers 1 or 2 and Y has the meaning given above.

230 217/29!

The amino group content can easily be derived from the nitrogen content of the photoconductive polycondensation product, determined by means of elemental analysis.

II. Sensitizers

In many cases it is preferred to have one To add sensitizer to the photoconductor layer according to the invention in order to reduce the sensitivity of the in to increase photoconductive polycondensation product containing tertiary amino groups. Such Sensitizers can be divided into optical sensitizers and chemical sensitizers. These Both types of sensitizers can alone produce an excellent sensitizing effect

are used, but are preferably used together

(a) Optical sensitizers

The optical sensitizers absorb light with a longer wavelength than the main photosensitizer, thereby increasing the overall sensitivity of the photosensitizer. Usually you can Dyes with an absorption in the visible range can be used as optical sensitizers. the optical sensitizers are effective even when added in very small amounts.

The known optical sensitizers for the organic photoconductors can be used. Examples of preferred optical sensitizers are discussed below.

Triarylmethane type compounds

Crystal violet

N® (CHj) j-Cl ^e

Victoria blue bra

N (CHj) ₂

N® (CH,) _r Cl °

Victoriii-Pure-ISiuc-BOII

C ₂ H ₅ -NH

N (C ₂ H ₅ ):

N ^e (CH,) i-Cl ^e

Methyl violet pure (CUj) ₂ N

Special

19th

Malachite green

20th

Dianix-Blue-EB-E

Diacryl-Turquoise-Biue-BG-E Dianix Brilliant Red BS E

Diaceiiiton-Fast-Pink-R

Acid Violet 5 B

C. I. Disperse Blue C.I. Basic Blue C. I. Disperse Red

Solar-Cyanine-6 B

Acid Violet 6B

brilliant green

O NH-,

/ VYVocH,

νγγ

O OH

HO ₃ S

HO ₃ S

OC ₂ II ₅

HOjS

VA

Meihyl violet

2! (CHibN

* (CH ₃ IrCI "

-Q-J /

NHCH,

Yicioria-Blue-oB

C. I. No 44 045, Basic Blue 26

Compounds of the anthraquinone type

4.5-Dinitrothr \ sa / m. 4.8-Diniirfjanthraehinrin. 1,5-diaminoanihrachinone. l-Amino ^ -pr ¹ iioxy ^ t-hydroxyanthrathinnn. and i- \ ielhviamin'j-t! nihrai_iimtjn

Connections from the ijyaninlyp

3.3'-DiethyI-2.2'-thia-oxac.arbr) tyaninj'jdid. 2-ip-DimethyIaminost> Tyl) -3-ethy! BenzothiazoIiumiodid, 1-Carboxymuth \ I-l'-earboxyäth> l-2.2'-chinrji.> Aninbromid and l.l'-diethyl ^^ '- quinocyanine iodide.

Compounds of rhodamine glyph

(C ₂ H ₅ J ₂ N

./v Vv

Rliodamine B

A- COOH

Rhodamine 6 G

COOC ₂ H ₅

Rhodafnin B Extra

f — COOC ₂ H ₅

Sulfo-rhodamine 13

Connections of the Xarithmic type

O Rose Ucngai

SO ₁ Na

ONa

CO ₂ Na

Cl

OH

Erythrosine

CO ₂ H

Thiazine type compounds

(CHj) ₂ N

Methylene blue

₃ ) Z-Ci ^e

Acridine-type compounds

H ₃ C Acridine Yellow

CH ₃

-HCI

Acridine Orange

(CH ₃ ^ N

NiCH ₁ J ₁

-HCI

Connections from the quinoline lymph

Gryplocyanin

Pinacyanol

Girbonyl-type compounds

O OH

alizarin

OiI

In terms of effectiveness, friarylniehant type dyes are preferred. Depending on the Absorption wavelengths of these dyes can linger at two or more of the optical sensitizers to expand the absorption range.

Blue to purple dyes have an absorption wavelength in the yellow to red areas and I are usually in terms of effectiveness and Appearance preferred. Examples of such sensitization are Cristal Violet, Kayaset-Blue 985 and Irictoria-Pure-Blue-BOH.

The amount of the optical sensitizer is actually 0.0001 to 20% by weight, preferably 0.01 Us 15% by weight, based on the weight of the Pfcoto leader.

(b) Chemical sensitizers

The chemical sensitizers increase the photo-sensitivity by chemical reaction with the ilau photoconductor.

The preferred chemical sensitizers are those used with the photoconductor according to the invention in FIG In an amount of at least 0.1% by weight, preferably at least 1% by weight can be mixed. These Connections can be roughly defined in connections with the properties of an electron acceptor and halogens classify organic compounds. The former include and are Lewis acids in the general sense preferably those that lead to the formation of a charge transfer complex with the aromatic amines (b) are capable. Therefore, connections are made based on aromatic compounds that contain an electron-withdrawing substituent, for example benzene, Naphthalene, anthracene, fluorene, fluorenone or biphenyl generally preferred Examples of electron-withdrawing groups are nitro groups and carboxyl groups or derivatives thereof, cyano groups, halogen groups, Sulfone groups, ketone groups, aldehyde groups and Sulfonic acid groups or their derivatives. Chemical sensitizers with at least one, preferably 2 up to 4 electron withdrawing groups are preferred.

Of the substituents listed above, the nitro group is chosen because of its high electron attracting ability preferred. Polynitro bonds

jo, however, are generally colored and numerous of these are strongly colored and can therefore only be used to a limited extent. The chemical sensitizers must of course be compatible with the photoconductor according to the invention. There will be particular

j5 aromatic nitro compounds, aromatic carboxylic acids or derivatives thereof and aromatic cyano compounds are used as chemical sensitizers. Examples of aromatic nitro compounds are trinitrofluorenone, tetranitrofluorenone, (2,4,7-trinitro-9-fluoreny! Iden) -maIonitriI, Nitroanthracene, dinitroanthracene, trinitroanthracene, nitroanthraquinone, dinitroanthraquinone, Trinitroanthraquinone, o- or m-dinitrobenzene, dinitronaphthalene, nitrophenol, dinitrophenol, Tri nitrophenol, mononitrocatechin, dinitrocatechin, monochior-mononitrophenol, monochloroditrophenol, Mononitrocresol and dinitrocresol.

Examples of aromatic carboxylic acids or their derivatives include phthalic acid, tetrachlorophthalic acid, Telrabromophthalic acid, trimellitic acid, pyromellitic acid, naphthalene-1,8- or -23-dicarboxylic acid, benzophenone tetracarboxylic acid, Anhydrides and esters of these acids, nitrobenzoic acid, dinitrobenzoic acid, trinitrobenzoic acid, Monochloro-mononitrobenzoic acid, monochloro-dinitrobenzoic acid and dir.itronaphthoic acid. In general, the sensitizing effect becomes greater in the Order of esters, acids and anhydrides and therefore the anhydrides are particularly preferred.

Examples of aromatic cyano compounds are isophthalonitrile, phthalonitrile, 4-nitrophthalonitrile, tetracyanobenzene and nitrobenzonitrile

Tetracyanoquinone dimethane, tetracyanoethylene, chloranil, dichloroacetic acid and maleic anhydride can also be used.
Particularly preferred chemical sensitizers are trinitrofluorenone. Nitrobenzoic acid. Nitrochlorobenzoic acid, nitrophenol, dinitrophenol, nitrochlorophenol. Phthalic anhydride, trimellitic anhydride, naphthalene-13-dicarboxylic acid anhydride, naphthalene

i, 4,5,8-telracarboxylic acid and naphthalene-1,4,5,8-letracarboxylic acid dianhydride.

Halogen containing compounds that act as sensitizers are usable and with the polycondensation product are compatible according to the invention, siiid z. D. -, aromatic halogen compounds, in particular halogcnicrtc Phenols and derivatives thereof, in which the ilalogen is preferably composed of chlorine, bromine or iodine Examples of these preferred types are halogenated bisphenols such as 2; 2'-methylenebis- (4-chloro- yne phenol), 2,2'-methylenebis (3.4,6-trichlorophenol), 4,4'-methylenebis (2-chlorophenol) and 4,4'-isopropylidenebis (2,6-dibromophenol), Mono-, di- or trichlorophenol, mono-, di- or tribromophenol, chlorocresol and halogenated phenol polycondensals, which are produced by implementation ι ν formation of phenols with formaldehyde.

Examples of further halogen-containing compounds which can be used in the context of the invention are polycarbonates or copolycarbonates which are derived from the halogenated bisphenols listed above, epoxy resins which contain the halogenated bisphenol units listed above, by addition of halogenated bisphenols to ethylene oxide or Products obtained from propylene oxide with the formation of glycols, polyesters derived therefrom, halogenated phenyl esters of polyacrylic acid or polymethacrylates, copolymers of such a unit with other vinyl monomers and hexachloro-p- or -m-xylene. Other useful halogen-containing compounds include, for example, polyvinylidene chloride, polyvinyl chloride. Polyvinyl bromide, copolymers containing this as a partially repeating unit, and halogenated paraffin compounds such as pentaery-yourityl bromide. _{) 5}

Of the compounds listed above, the polymers can also be used as binder polymers be used.

It has been found that polyarylmethane compounds represented by the following formula _4n

45

wherein the radicals R ₁ to R _{4 are the} same or different and are an alkyl group, alicyclic group or aralkyl group having 1 to 7 carbon atoms and R _{5 is} at least one alkyl group, alicyclic group, aryl group or aralkyl group having 1 to 7 carbon atoms or the grouping

60

wherein Ra and Rr are the same or different and are a lower alkyl group having 1 to 3 carbon atoms or a halogen atom and ρ ρ 'is an integer of 0 to 2, an excellent sensitizing effect

on photoleitfiShi ^! Polycondensation products that are a Carbazole or a ring-substituted derivative thereof contain.

These compounds become photoconductive when combined with the halogen-containing compounds listed above organic compounds can be combined. However, if they are capable of being used with a carbazole-containing phosphor Polycondensation products are combined, they show a very good sensitizing effect, even in complete absence of the halogen-containing organic compound as a sensitizer.

The chemical sensitizer must be added in a larger amount than the optical sensitizer. the The amount of the chemical sensitizer is generally 0.1 to 100% by weight, preferably 1 to 70% % By weight based on the weight of the photoconductive agent Polycondensation product.

When the amount of the chemical sensitizer is too low. its effect is reduced and on the other hand if it exceeds a certain limit, the effect does not increase any further. There continues to be the addition the chemical sensitizer generally worsens the properties of the photoconductive layer, it is preferred to use the most favorable amount experimentally according to the desired use to determine.

III. binder

The photoconductive polycondensation product used in the photoconductive layers according to the invention has film forming properties. however, its molecular weight is often insufficient is high. Therefore, in order to obtain photoconductive layers having superior flexibility, it is common necessary to add a binder.

In general, the binder takes at elevated amounts of the sensitivity of the photoconductive layer is from about ¹ decreases. The amount of binder should be kept as low as possible. In general, the amount of binder is 0.05 to 1.5 parts, preferably 0.1 to 1 part, based on the weight of the photoconductive polycondensation product.

Suitable binders are in at least one of the good solvents for the photoconductive polycondensation products, those described above are readily soluble. All polycondensates. Polymers of the polyaddition type. ring opening polymerized polymers and vinyl type polymers can be used provided they have a softening point of at least 60 ° C. Films with superior Can form flexibility and compatible with the photoconductive polycondensation product in one Degrees so that a translucent film is obtained.

Examples of suitable binders are polycondensates, for example amorphous saturated copolyesters an acid component such as terephthalic acid, isophthalic acid, phthalic acid or adipic acid and one Glycol component, such as ethylene glycol, propylene glycol, Neopentyl glycol or tetramethylene glycol, oil modified Alkyd resins, bisphenol A type polycarbonates and phenoxy resins and epoxy resins, polymers of the polyaddition type such as polyurethane resins with aliphatic polyesters as a soft segment, polyamide of the vinyl type, such as polystyrene, polyacrylates, polymethacrylates, Polyvinyl acetate, polyvinyl chloride and copolymers thereof, as well as polymerized by ring opening

Polymers such as polyepichlorohydrin. For certain applications it is necessary that the photoconductive Layer transparent isf. In these cases it is necessary to choose polycondensation products that have a particularly good tolerance.

IV. Preparation of the electrophotographic
Recording material according to the invention

The photoconductor layer according to the invention is usually by dissolving certain amounts of the photoconductive polycondensation products with or without a sensitizer and, if necessary, with a iindeniittel in an organic solvent, on · borrowed the solution obtained on a support and subsequent drying. For certain For example, finely divided silica is added for purposes of application in order to improve its graphic properties

do receive.

The itiiflösiing of the above components in The solvent can either be by dissolving a mixture of these components or by dissolving these components are dissolved in a desired order in a solvent or dissolution thereof and mixing the obtained solutions. The appropriate concentration of the The dissolved material of the solution varies depending on such factors as the type of dissolved components or method of coating, but is generally 5 to 80% by weight. preferably 10 to 60 Ge \ v%.

The coating of the resulting coating solution a carrier can be carried out in the usual way, for example by wire hanger covering, squeegee over-calibration. Roller coating, spray application or brush application.

If the solvent remains in the obtained photoconductive layer, trouble tends to occur Like decreased dark resistance, decreased photosensitivity or instability of the light conductivity. Therefore, the drying will be as complete as possible executed.

In general, the photoconductivity is better with smaller layer thicknesses of the photoconductive layer: however, if it is too low, there is a tendency that the charging voltage, for example, by means of a corona discharge becomes lower. The layer thickness that gives the optimal image is appropriate determined experimentally. The layer thickness of the photoconductive layer is usually from 2 to 30 μm. preferably 4 to 15 μm.

The carrier on which the photoconductor is to be applied can be a carrier made of aluminum, zinc, copper, nickel or iron, paper, plastic films or glass plates. If the substrate is a good electrical insulator, the surface on which the photoconductor layer is formed must be subjected to a treatment which makes it electrically conductive. This treatment should not ei preferably not share the carrier has a surface resistance of more than 10 ^IO Ohm / cm ^2, greater than 10 ⁹ Ohm / cm ^2.

According to the invention, photoconductors for light-sensitive layers to achieve transparent or sheer electrophotographs are produced and therefore are often used as supports Plastic sheeting, paper and glass sheets are used.

V. Properties and applicability of the

Electropholographic recording materials

according to the invention

The photoconductive polycondensation product is included of the invention can be obtained from commercially available raw materials very easily at a low cost and has a sensitivity similar to that of conventional low molecular weight photoconductors

Comparable in and polymeric organic conductors;: r isf. By combining the same with a suitable sensitizer and / or binder, electrophotographic Photolayer layers with superior utility in accordance with the genre

j, uses which form a superior flexibility or transparency or a superior light-permeable wedge in the near ultraviolet range in the production of a diazo double.
The electrophotographic recording material

2tr gCrnSu <jCr criiiTuürig ΚΰΠΠ ίΠΓϊί: Γιι3ΐυ ciPicS mustard wciicil can be used in areas of application. Beispeisweise a formed by coating the Photoieilerschicht on a plastic film electrophotographic recording material may be used as Mik ^r ofilm or as a second Vorlageblall. obtained by direct enlargement of a microfilm, can be used as a transparency for overhead projectors or as a slide for slide projectors. A recording material produced using paper as a support can be used as a coated paper copy for offices and as photosensitive paper for a second original

Further, when the photoconductive layer is formed on a metal plate, the image can be a Drawing can be formed thereon instead of lettering at the time of metal cutting.

Furthermore, an electrophotographic recording material for plain paper copying can be used by forming the photoconductive layer on a

Metal drum are formed. According to the invention can photoconductor layers with a sensitivity expressed as the half-dropout exposure amount Under white light from a tungsten filament lamp as a light source, it was preserved from 2000 to lOlux seconds will. This photosensitivity is completely sufficient if good sensitizers are chosen. the The following examples and comparative examples explain the invention in detail.

The materials and test methods used in the examples are illustrated below.

(I) Soluble polycondensate
of low molecular weight

(1) Xylene / formaldehyde polycondensation product Manufacturing

A reactor was coated with 106 g of m-xylene, 129 g of a 37% strength aqueous formaldehyde solution (formalin) and 98% by weight sulfuric acid and the reaction was started at 95 ° C. with stirring. The reaction was carried out for 6 hrs., And the temperature eventually rose to I04 ^c C After completion of the reaction the aqueous phase at the bottom (sulfuric acid phase) was separated and the resulting oil phase was dampfdesüiliert at 100 ⁰ C at atmospheric pressure. 107 g of a xylene / formaldehyde polycondensation product were obtained.

properties

Average molecular weight
Oxygen content
Acid number
viscosity

about 390

about 8.7% by weight

0.2

74 mPas

(intended for a

Toluene solution with a

Concentration of

Xylene condensation product

of 80% by weight)

Composition of the functional groups

The NMR spectrum of the xylene / formaldehyde polycondensation product was determined using deuterochloroform (CDCl ₃ ) as the solvent and the following peaks were observed:

Ü! Ar CH.

(2) Ar CIl-OCH;

(3) Ar-CH.-Ar

(4) Ar-CIUOCFM-.AM
Ar-CH.OII I

(5) phenyl proton

ppm

2.26! M) 3.32 (m) 3.84-, m)

4.5 (m)
7 (m)

Ar-CH.OH 2.2

Ar-CHOCII. 6.7

Ar-CH-Ar 4.2

Ar-CH.iOCH-hAr 9.8

(Mole each
funklionelleii group ie
Ben / nlringi

0.10
0.21
0.48
0.32

(2) Highly condensed
Xylene / formaldehyde polycondensation products

This polycondensation process was followed by others Condensation of the above xylene / formaldehyde polycondensation product (i) obtain.

Composition animal functional üruppön

Funlumnelle groups

Ar-CH ₁ -Ar
Ar-CHJ (OCH,) - Ar

In (I) to (4), Ar represents an aromatic ring

In the above peak according to (4), the peaks of ArCH ₂ (OCH ₂ J _n Ar and Ar-CH ₂ OH overlap and are broad. Thus, Ar-CH ₂ OH was acetylated to Ar-CH ₂ OOCCH _3. The determination of the NMR spectrum showed that Ar-CH ₂ OOCCHs was 1.8 ppm (Ar-CH ₂ OOCCH ₂ 4.8 ppm). These peaks were separated from the peak of Ar-CH ₂ (OCH ₂ J _n Ar 'and the composition of the functional groups calculated for each peak were as follows:

properties Average 1300 weight-wise below 7 Molecular weight Acid number 105 to 125 ° C Ring softening point and ball method)

MoI more functional Groups per benzene ring

0.70 0.17

(3) Resole condensation product

This polycondensation product was obtained by condensing a mixed cresol (m to ρ = b: 4) and formaldehyde using sodium hydroxide ι -, as a catalyst.

properties 270 Weight through 0.045 Pa s _ '[) Cut molecular weight viscosity 55% (135 ^C C Content of non- volatile substances 1.020 specific weight r »(25'C)

Composition of the functional groups

Functional ·: Groups

Ar-CH, -Ar
Ar-CH.OH

Moles of each functional group per benzene ring

0.4 0.5

(II) Binder (a) Vinyl acetate polymer

This polymer was obtained by polymerizing prior to vinyl acetate.

properties

Weight average 4 · average molecular weight
Volatile material
viscosity

transparency

1050

below 3% by weight

120OmPas

(determined at 30 ^ C with

a solution with

50% by weight of the

Resin in methanol)

95%

(associated with a

IO ⁿ / nigen solution

480 um)

Apparent density 0.78 C. specific weight (25'C) 1.20 UP Softening point 55 C Melting point 87 ms 88 Melt viscosity (170 C) 1.47 χ 10 (b) acrylic polymer

This polymer was obtained by polymerizing voi Methyl acrylate, butyl methacrylate and acrylic acid ii obtained in a weight ratio of 20: 778: 1.

230 217/23

properties

Acid number 3.7
Weight average molecular weight 2500 solids content 49.8% by weight

(c) polycarbonate polymer

This was a commercially available polycarbonate obtained from bisphenol A (4,4'-dihydroxydipheny! -2 ^ -propane) and phosgene.

properties

Weight average molecular weight about 35,000, specific gravity 1.4

Oxidation initiation temperature ^{300 0 C}

(d) polyester

This polymer was obtained by copolycondensation of an acid component from 46 mol% terephthalic acid and 54 mol% of isophthalic acid and a glycol component obtained from 45 mol% ethylene glycol and 55 mol% neopentyl glycol.

properties

Weight average molecular weight about 1700

Specific gravity 1.26

Intrinsic viscosity 0.053 Pa · s

determined at 30 ⁰ C for a solution with 0.5 g of the polyester, dissolved in 100 ml of a mixture of phenol and tetrachloroethane (6: 4)

Softening point 163 ° C

(e) polystyrene

This consisted of a commercially available polystyrene, which was obtained by polymerizing Slyrolmonomerem and a weight average molecular weight of about 100,000 and one Had a density of 1.045.

(f) vinyl chloride copolymer

This polymer was obtained by copolymerizing 91 mol% vinyl chloride, 3 mol% vinyl acetate and 6 Obtained mole percent vinyl alcohol.

properties

Weight average extent of the

Polymerization about 420

Apparent density 0.65

Volatile content

Fabrics 3%

Solution viscosity 220 mPa s

determined with a 20% solution in a 1: 1 mixture from methyl isobutyl ketone and toluene at 25 ° C

(g) alkyd resin

It became a commercially available modified alkyd resin used, which by implementation of glycerin and

, Coconut oil with the formation of a monoglyceride, which was then reacted with phthalic anhydride, was prepared. A 60% solution of this Resin in xylene had a specific gravity of 1.02, an acid number of 3 and a viscosity (Gardner) of

id V-Y.

(III) carrier

The following materials were used as the support on which the photoconductive slide was formed was det.

(a) aluminum plate

An aluminum plate with a thickness of 300 μm, the surface of which was polished with emerald of a fineness of 1000> o.

(b) Drawing paper made electrically conductive

A sheet of general engineering drawing paper was immersed in a 10% aqueous solution of polyvinylbenzyltrimethylammonium chloride and dried. Both surfaces of the drawing paper were thus coated with polyvinylbenzyltrimethylammonium chloride in an amount of 2 g / m ² . This paper is known as "T-paper".

(c) Made electrically conductive
Polyethylene terephthalate film

A ΙΟΟμπι thick biaxially oriented polyethylene terephthalate film was immersed in a 10% aqueous solution of polyvinyltrimethylammonium chloride and dried. Both surfaces of the film thus had a coating of polyvinylbenzyltriniethylammonium chloride in an amount of 2 g / tn ² . This film is known as "PET film".

(d) Foil with metal deposition

Metallic indium was deposited in a vacuum on a 75 μm thick biaxially oriented polyethylene terephthalate film and then oxidized in air to form a transparent coating. This had a transmittance at 480 nm of 80% and a surface resistance of about 400 ohm / cm ² .

(IV) Production of the test pieces / for determination
the photosensitive properties

The soluble low molecular weight polycondensate, binder, and chemical sensitizer as indicated in each example were dissolved in the amounts indicated in each of the solvents listed in the examples. Was a solution containing 1% by weight of the sensitizer? in dimethylformamide and mixed with the above solution and then stirred well. The solution obtained was applied to a support by means of a conventional flask, for example a wire hanger coater, and heated at 70 ° C for 15 hours to form a photoconductive layer with a thickness of about 7 μιτι dried on the carrier.

(V) Method of Determination
the photosensitive properties

A voltage of -6 kV was applied to a square test piece measuring one side

of 10 cm using a corona discharge device at a speed of 5 m / min. The surface potential of the specimen was then measured by a high level surface potentiometer. The high level surface potentiometer was connected to a recorder, which determined the measured potential. The light source used was a 30 W tungsten filament lamp, if any nothing else is stated. It was spaced 49 cm from the specimen. The illumination intensity of the lamp in this position was 50 lux.

The half-fall exposure was made according to the following Calculated equation:

Half waste exposure (E ₅₀ ) = L χ f (lux sec)

An electric charge was applied to the test piece by corona discharge in the dark room, and its potential (Va) was read after the lapse of 35 seconds. At the end of this 35 sec period, light with an illuminance of L lux was irradiated onto the specimen from a tungsten filament lamp. The time (t sec) until the potential (V _n ) had reached the value V ₀ H was read off.

(VI) Method of Determination
the playback images

After measuring the half-decay exposure time (Eio) in the dark room, a corona discharge with -6 kV was applied to the entire surface of the test piece at a speed of 5 m '.nin. The specimen was exposed imagewise using a test card to light from a 30 W tungsten filament lamp which had an amount of illumination 4 times that of the semi-waste exposure. The exposed sample was developed with liquid development or dry development as indicated below.

(1) Liquid development

The exposed sample was a few seconds in a dispersion of a toner (particle size 0.1 to 1.0 µm) immersed. The toner dispersion was through good kneading of a mixture of 15 g of a phenol-modified pentaerythritic agent from rosin (with an acid number of 10, a specific gravity at 20 ° C of 1.09 and a melting point from 110 to 120 ° C. 15 g of a copolymer of lauryl methacrylate and styrene (molar ratio 95: 5. weight average molecular weight about 10,000). 150 g of carbon black and 15 g of xylene and dispersion of the mixture in 5 l isoparaffin (Cq to Cn mixture) using ultrasonic oscillation.

(2) dry development
(Magnetic brush development)

200 points by weight of reduced iron powder with a particle size corresponding to a sieve with a clear mesh size of 0.1 to 0.04 mm with 5 parts by weight of a toner from 1 part by weight of a Styrene / butadiene copolymers, 0.05 parts by weight polystyrene, 0.1 part by weight of carbon black and 0.18 part by weight of oil black, which had been melt blended, blended, cooled and reduced to an average particle size of 10 μm pulverized. The toner you are using is holding a Particle size from 5 to 25 μm. The resulting mixture was adhered to a bar magnet and closed by friction with the exposed specimen whose development contacts.

The images obtained were rated on the following scale:
' Excellent:

Very rare copies have been preserved.
Good:

Despite a few mistakes, the copies were practically satisfactory,
ι «Bad:

There was heavy fog and the copies were unclear or no copies were observed.

example 1

(1) Production of the soluble aromatic

tertiary amine-containing resin

A 100 ml three-necked flask was filled with 17 g of des Xylene / formaldehyde polycondensate, 16.7 g (0.1 mol)

jo carbazole and 0.17 g of 2,5-Dimethyibenzoisuifonsäure which is hereinafter referred to as m-xylene sulfonic acid, as a catalyst and reacting the materials at 200 ⁰ C in a nitrogen stream. The reaction product was dissolved in 50 ml of toluene at room temperature.

2'j The solution was added to 1000 ml of methanol in a mixer with stirring. The resulting precipitate was filtered off and at 70 ^° C. and 1 mm Hg abs. Dried for 15 hours and yielded 25 g of a pale green-white polythene containing tertiary amino groups

jo condensation product. which has the following properties would have:

Melting point 135 ⁰ C Inherent viscosity 0.26 N content 4.16% by weight More aromatic Amine group content 0.70 per benzene ring NMR spectrum Peak ('2J ppm) the base of -NH des Carbazole was not observed

(2) Formation of the photoconductive layer
and determination of the property

2 g of the polycondensation product containing tertiary amino groups obtained in (1) above were formed in 10 ml of chlorobenzene at 20 ° C dissolved in a solution.

On the other hand, metallic indium was vacuumed on the surface of a polyethylene terephthalate film mi. a thickness of 75 µm and an area of 10 cm ' deposited and then exposed to air to form a transparent conductive layer with a resistor of 400 ohm / cm 'oxidized.

The resulting solution was applied to the surface of this layer using a conventional coating. ventilation device and at 70 "C for 15 hours. to form a photoconductive layer mn a thickness of 7 μπι dried.

The half-waste exposure (Ej ₀ ) of this photoconductive layer, determined using light with an illumination intensity of 10000 lux from a 300 W tungsten filament lamp, was 1.8 10 ⁴ lux · sec. After a month, this layer was still adhering of the polyethylene terephthalate film and no precipitate appeared on the surface was visible, and the photoconductive layer had a transparency of more than 70%.

Comparative example 1

10 g of polyvinyl carbazole was pulverized and dissolved in 100 ml of methylene chloride and again with 1000 ml precipitated purified methanol and then dried. This procedure was carried out three times for Purification of the polyvinyl carbazole carried out. 1 g of the purified polyvinyl carbazole was dissolved in 10 ml of chlorobenzene dissolved to form a 10% solution.

In the same manner as in Example 1, the solution was coated on the aluminum plate to form a layer. The half dropout exposure (Em) of this layer, determined in the same manner as in Example 1, was 1. Gx 10 ⁴ IuX · sec.

The obtained layer had numerous scratches and was prone to breakage.

When the polyvinyl carbazole solution on the transparent conductive polyethylene terephthalate film in the in the same manner as in Example 1, the photoconductive layer peeled off and it was impossible to determine the photosensitive properties of the layer and to evaluate the copies.

Table I.

Examples 2 to 18

600 mg of the polycondensation products containing tertiary amino groups, which according to Example i (1) was obtained and is referred to below in the tables with PKP for short, binder and chemical sensitizers as listed in Table I were used with each of those listed in Table 1 Solvents mixed to form a solution.

The solution was made with a separately prepared solution of each of the sensitizers listed in Table I. mixed with 1% by weight in dimethylformamide with stirring at room temperature. The mixture obtained was drawn down onto each of the slides shown in Table I using a spin coater and dried, so that a photoconductive layer with a thickness of 7 μm was obtained.

The semi-waste exposure (Ε · ο) the photoconductive Layer and copy quality were determined and the results are shown in Table I.

example
2 3 4th PKP (mg)
Solvent (ml) 600
N-methylpyrrolidone (3) 600
Meth> ethyl ketone (3) 600
Methyl ethyl ketone (3) Binder (mg)
Solvent (ml) Polyester (400)
N-methylpyrrolidone (2.0) Polyester (100)
Methyl ethyl ketone (0.50) Polyester (100)
Methyl ethyl ketone (0.50) Chemical sensitiv
Sator (mg)
Solvent (ml) 1,4,5,8-naphthaIintetra-
carboric acid (300)
N-methylpyrrolidone (3.0) Bis- (4-dimethylamino-
phenyl) methane (200)
Methyl ethyl ketone (1.0) Bis- (4-dimethylamino-3-
bromophenyD methane (200)
Methyl ethyl ketone (1.0) Optical sensibili
Sator (mg) - Crystal violet (0.5) Crystal violet (0.5) carrier Al T-paper Al 1 IaIh-AbMI-
exposure (E _4n )
(lu \ ■ sec) 80 163 1.1 (1 Evaluation of the copies excellent excellent excellent

Table I (Forlsct / ung)

Gouge

PKP (mg)
Solvent (ml)

Binder (mg)
I (isiingsmilicl (ml)

C hcmischcr Scrisibilr *
Sator (mg)

Solvent (ml)

Optical sensitizer (mg)

600
Methyl ethyl kelon (3)

Polyester (100)
(hlorben / ol (0.50)

"l-ühlofO-nitrobenzoic acid (100)
Methyl ethyl ketone (1.0)

Crystal Violet (0.5)

6 (10
Methyl ethyl kelon (3)

Polyester (100)
Methylethylkefn (0.50)

Trimellitic anhydride (100)
Methyl ethyl ketone (1.0)

Crystal violet (O /)

600
Methyl ethyl ketone (3)

Polyester (100)
Methyl ethyl kelon (0.50)

Tris44-dimelhylaminophenylmetban (200)
Chlorobenzene (1.0)

Crystal violet (0.5)

a
ί carrier 26th
39 08 082 40 j MaIb-AbPaII-
illumination (Ε, »)
(lux sec) example
5 (1 7th Evaluation of the copies Ai Al Al Table I (continued) 360 290 98 I. excellent excellent excellent ύ
ι PKP (mg)
Solvent (ml) Binder (mg)
Solvent (ml) example
S. 9 10 Chemical sensitiv
Sator (mg)
Solvent (ml) 600
Methyl ethyl ketone (3) 600
Melhyläthyikclön (3) 600
Methyl ethyl ketone (2) I.
1 Optical sensibili
Sator (mg) Polyester (100)
Methyl ethyl ketone (0.50) Polyester (100)
Methyl ethyl ketone (0.50) Polyester (100)
Methyl ethyl ketone (0.50) 1 carrier l, l-bis- (4-N, N'-dibenzyl-
aminophenyl) butane (200)
Chlorobenzene (1.0) (M) (200)
Chlorobenzene (1.0) 2,2'-methylenebis (4-chloro
phenol) (200)
Chlorobenzene (1.0) * HaIb-WpaIl-
exposure (E < ₀ )
(lux sec) Crystal violet (0.5t Crystal violet (0.5) Crystal violet (0.5) i Evaluation of the copies Al Al Al Table Γ (continued) 228 455 553 excellent excellent excellent PKP (mg)
I solvent (ml) Binder (mg)
Solvent (ml) example
H 12th 13th !
[Chemical Sensibill ·
i sator (mg)
Solvent (ml) 600
Methyl ethyl ketone (3) 600
Chlorobenzene (3) 600
Methyl ethyl ketone (3) Optical sensibili
Sator (mg) Polystyrene (100)
Methyl ethyl ketone (0.50) Polystyrene (100)
Methyl ethyl ketone (0.50) Polycarbonate (100)
Methylene chloride (0.50) I - carrier Bis- (4-dimethylamino-
phenyO-methane (200)
Chlorobenzene (1.0) Bis- (4-dimethyiamino-
phenyO-methane (200)
Chlorobenzene (1.0) Bis- (4-dimethylamino-
phenyD methane (200)
Methyiethyiketone (LO) Half-waste
I exposure (E ₅₀ )
I (Iux ■ sec) Crystal violet (OS) Crystal violet (OS) Crystal violet (OS) I Evaluation of the copies T-paper Al Ai 163 104 169 excellent excellent excellent

41

42

Table I (continued)

example
M. 600
Methyl ethyl ketone (3) 16 Solvent (ml) 600
Methyl ethyl ketone (3) Polyester (100)
Methylilhyiketone (0.50) 600
Methyl ethyl ketone (3) Binder (mg)
Solvent (ml) Polyester Π00)
Methyl Ethyl Keton (0.50) 2,4-dinilrobenzoic acid
(200)
Methylilhyiketone (1.0) - Chemical sensitiv
Sator (mg)
Solvents (ml) 4-nitrophthalic acid (200)
Methyl ethyl ketone (1.0) Crystal violet (0.5) 2,4,7-Tfiiiilfofiuofenori
(300)
Methylilhyiketone (6) Optical sensitivity Krislall violet (0.5) AI KfisUillviölett (0.5) Carrier Al 480 Al HaIb-AbIaIl-
exposure (E ₅₀ )
(lux sec) 620 excellent 14th Evaluation of the copies excellent excellent

Table I (continued)

Example 17

19th

PKP (mg) solvent (ml)

Binder (mg) Solvent (ml)

Chemical Sensitizer (mg) Solvent (ml)

Optical sensitizer (mg)

carrier

Ualb waste exposure (E ₅₀ ) (lux - sec)

600 methyl ethyl ketone (3)

') (300)

Methyl ethyl tint (1.5) crystal violet (0.5)

AI 870

Excellent evaluation of the copies

600
Methyl ethyl ketone (3)

² Y (300)

Tetrahydrofuran (6.0) crystal violet (0.5)

excellent

500 N-methylpyrrolidone (5)

1,4,5,8-naphthalene tetracarboxylic acid (100) N-methylpyrrolidone (1.0)

AI 400

excellent

Br

(n is average T)

Copolymer of vinylidene chloride and vinyl chloride f 1: 1) with a molecular weight by weight of about 100,000 and a melting point of S5 ° C.

Example 20and
Comparative example 2

A 100 ml three-necked flask was filled with 10 g of des high-condensation xylene / formaldehyde condensate, 6.8 (0.04! Mol) carbcizole and 0.10 g m-xylene sulfonic acid charged and the reaction carried out for 4 hours at 200 ° C. in a nitrogen atmosphere Product was dissolved in 25 ml of toluene at room temperature and the solution in 800 ml of methanol in one Wiper added while stirring. The precipitate received was filtered off and at 70 * C and Ϊ mm Hg abs. • Dried for 15 hours and gave 9.5 g of one »Tear polycondensation product containing tertiary amino groups mild following properties:

Melting point
Fig viscosity

I15 ° C
0.12

The photosensitive properties of the obtained polycondensation product became the same as a pure mixture of Bcfizyleafbazol of the following formet

in

A peak (12.3 ppm) due to: = NH des Carbazole was not observed in the NMR spectrum analysis.

and the highly condensed xyloi / formaldehyde Kondcrrsn'icp.sprcd'jki yergüche (see example! 2), which has the same nitrogen content as the above polycondensation product containing tertiary amino groups would have. The results are shown in Table II.

Table II Example 20

Comparative example 2

Photoconductor (mg)

Solvent (ml)
Binder (mg)
Solvent (ml)
Chemical sensitizer
(mg)

Solvent (ml)
Optical sensitizer
carrier

Half waste exposure (E ₅₀ )
| lux sec)

Evaluation of the copies

Polycondensation product containing tertiary amino groups

Chlorobenzene (3)

Polyester (100)

Chlorobenzene (0.5)

Bis- (4-dimelhyIaminophenyI) -

methane (200)

Chlorobenzene (1.0)

Crystal vio fat

Aluminum plate

330

excellent

Mixture of benzyl carbazole (259)
and the highly condensed xylene /
Formaldehyde condensate (300)
Chlorobenzene (3)
Polyester (100)
Chlorobenzene (0.5)

Bis (4-dimethylaminophenyl) methane (200)

Chlorobenzene (1.0)

Crystal violet

Atuminium plate

not sensitive even if that
Light source made 5 times as bright
became
bad

Examples 21-31

In the same manner as in Example 1 (1), the reaction was carried out in those shown in Table III Temperatures and times using the various aromatics listed in Table III Amines instead of the carbazole carried out yield, melting point, inherent viscosity and N content of the Polycondensation products obtained containing tertiary amino groups were determined; the results are listed in Table III

0.6 g of each of the polycondensation products obtained were dissolved in 3 ml of methyl ethyl ketone 0,! g of a polyester were dissolved in 0.5 ml of methyl ethyl ketone. Furthermore, 0.2 g of 2 ^ '- methylenebis (4-chlorophenol) was dissolved in 1 ml of methyl ethyl ketone. Further, 0.5 mg of crystal violet was dissolved in 50 ml of dimethylformamide. These solutions were at room temperature while stirring, and the mixture was mounted on each of the carriers listed in Table III using a disc coating apparatus and at 70 ⁰ C for 15 hours. to form a photoconductive layer with a thickness of about 7 μπι dried

e ~ The half-waste exposure of each of the samples obtained was determined and the copies were evaluated The results are shown in Table III

Title III

example 22nd 23 24 25th 21 20th 5 10 20th Xylene / formaldehyde poly-
conclusion (g) 10 aniline
(26.7) Benzyl
iinilin (4.4) methyl
aniline (10.28) ö-naphthyl-
amiri (9.2) Aromatic amine (g) Diphenyl
amine (10) 0.2 0.05 0.1 0.2 X> lnkulfon <; acid fg) 0.1 200 200 '200 200 Reaction temperature (C) 200 3 2 3 2 Response time fh.) 2 24 6th 10 18th Yield igj 10.7 128 30th 65 59-61 Melting point (C) 68-70 0.13 0.08 0.10 0.07 r. intrinsic viscosity 0.09 4.29 3.75 4.69 2.60 Nitrogen content (%) 3.75 T-paper Al Al Al carrier Al 390 293 293 780 Ilcilb-Atinilibelichlung (E ₅₀ )
flux sec) 228
C ⁺ ) the end
drawn the end
drawn the end
drawn the end
drawn Evaluation of the copies the end
drawn

When only the xylene / formaldehyde polycondensate was used, this value was 3.5 × 0 * (determined by the same method as in Example 1).

table III (description)

example 27 28 29 30th 26th 10 10 20th 20th Xylene / formaldehyde poly- 20th condensal (g) N, N'-Di- Pheno- N, N'-Dt- o-v'iluidin Aromatic amine (g) Indole (7.5) phenyl-p- thiazine (12.8) amino-di- (6.85) phenylene phenyl diamine (12.5) methane (5.1) Carbazole (17.1) 0.1 0.1 0.2 0.2 m-xylenesulfonic acid (g) 0.1 200 200 200 200 Friction temperature ('C) 200 2 2 2 2 Response time (hours) 2 12.9 15.6 36 18.5 Yield (g) 12.3 80-82 100 73-75 96-98 Melting point (C) 74 above 0.07 0.10 0.07 0.10 Inherent viscosity 0.08 5.58 4.26 5.03 3.68 Nitrogen content (%) 5.13 AI Al Al Al carrier Al Half waste exposure (E ₅₀ ) 1120 1900 *) 970 1200 9/5 (lux - sec) Well the end the end the end Evaluation of the copies the end drawn drawn drawn drawn

*) Bis- <4-d! Methylammophenyl) methane was used as a chemical sensitizer

Comparative example 3

Example 22 was repeated, but only a mixture of dibenzylaniline of the formula

CH ₂ -

CH, -

and the highly condensed xylene / formaldehyde polycondensate, which had the same nitrogen content, instead of the tertiary used in Example 22 Amino group-containing polycondensation products was used. The photosensitive properties of the photoconductive layer obtained were determined, but they did not show any sensitivity. When a tungsten filament lamp with an illumination intensity 5 times as large as the above is applied the layer also showed no sensitivity whatsoever.

Example 31

500 mg of the polycondensation product containing tertiary amino groups, which between the Xylene / formaldehyde polycondensate and diphenylamine had been formed according to Example 21, and 500 mg of the polycondensation product containing tertiary amino groups, which between xylene / formaldehyde polycondensate and Ν, Ν'-diphenyl-p-phenylenediamine according to Example 27 was formed. were each in 6 ml of methyl ethyl ketone with a Content of 100 mg of trinitrofluorenone dissolved. Each solution obtained was placed on an aluminum plate under Application of a disc coater applied and dried. The measured half-waste exposure was 350 lux · sec and 600 lux · sec. The copies were excellent in both cases

B e i s ρ i e I e 32 to 37

Various co-condensation components are used in these examples used

The xylene / formaldehyde condensation product that aromatic amine compound, the co-condensation component and the catalyst (m-xylene sulfonic acid) were in the ratios listed in Table IV at the temperatures and specified in Table IV Periods implemented yield, melting point intrinsic viscosity and nitrogen content of the obtained tertiary Polycondensation products containing amino groups were determined; the results are in the table IV listed.

Using each of the obtained polycondensation products, photoconductive layers in the same way as in Example 1 (unsensitized) and the half-waste exposure and the The quality of the copies was evaluated.

On the other hand, using each of the dei polycondensation products obtained photoconductive layers according to the approach of Example 19 (in Case of Examples 32 to 35) and the batch according to Example 10 (in the case of Examples 36 and 37) and the half-waste exposure and the quality of the copies were determined.

The results are shown in Table IV in each case.

1 Table IV example 20th 34 35 36 37 230 217/29! 32 40 20th 10 10 • 400 Carbazole j
I xylene / formaldehyde (20) Carbazole Carbazole Benzyl methyl j polycondensate (g) Carbazole Tetra (20) (20) aniline (8.8) aniline (10.2) \ Aromatic amine (200) chloroxylene Anthracene tert-butyl p-chlorine p-chlorine Anthracene (1) (10) phenol (5) phenol (7.5) phenol (6.8) Co-condensation (200) lert.-butyl- component (g) 0.2 phenol (10) 0.4 0.2 0.1 0.1 4th 200 m-xylene sulfone 200 170 200 200 acid (g) 200 4th Reaction 29.2 4th 4th 2 2 temperature (C ") 2 151 62 22.9 16.3 144 Response time (hours) 644 0.08 130 154 46 52-53 Yield (g) 129-133 4.14 0.07 O ₁ (J ⁷ 0.08 0.07 Melting point (C) 0.12 1.90 3.68 4.98 5.79 Inherent viscosity 2.27 I nitrogen content (%) I semi-waste 9000 i exposure
(lux sec) 120 1.6 x I0 ⁴ 1.4 x 10 ⁴ 1.8XlO ⁴ 1.7 x OK ⁴ i not sensitized 1.4 X 10 ⁴ 150 210 780 488 sensibilisicrl 200

I. (j ; I. I. 26 08 082 49 i, chemical sensitizers 50 each of the in Table V . 40 I. i \ and optical sensitizers in the form shown in Table V specified carrier mounted and dried. the 600 1 ! I B ejspie ι e jo pisdd example listed ratios mixed. The received j photosensitive properties of the obtained photo- Methyl ethyl ketone (3) excellent I. ! The tertiary amino group obtained in Example 32 3S Mixtures were on Conductive layers were determined; the results Polyester (200 ^ containing polycondensation product (co-condensate 600 are included in Table V. Methyl ethyl ketone (1.0) from xylene / formaldehyde polycondensate, carbazole and Methyl ethyl ketone (3) 4-chloro-3-nitrobenzoic acid 46 Antracen) was tested with all of the in Table V Polyester (400) (100) 600 listed binder no Methyl ethyl ketone (2.0) 39 Methyl ethyl ketone (0.50) Methyl ethyl ketone (3.0) Table V 2,4,7-trinitrofluorenone 600 Crystal violet (0.5) Acrylic resin (200)! (400) Methyl ethyl ketone (3) Methyl ethyl ketone (1.0) Methyl ethyl ketone (2.0) Polyester (200) Al Trimellitic anhydride PKP (mg) Crystal violet (0.5) Methyl ethyl ketone (1.0) 90 (100) Solvent (ml) Trimellitic anhydride Binder (mg) Al (100) excellent Solvent (ml) 130 Methyl ethyl ketone (0.50) Chemical sensi- Crystal violet (0.5) I bilizer (mg) excellent 43 Solvent (ml) Al 600 Optical sensi example 90 Methylene chloride (3.0) bilizer (mg) 41 Polycarbonate (100) carrier 600 excellent Methyl tertiary chloride (1.0) Half-waste exposure Chlorobenzene (3) Bis- (4-dimethylamino- (lux ■ sec) Polyester (200) phenylVmethane (200) Evaluation of the copies Methyl ethyl ketone (1.0) 42 Methyl ethyl ketone (1.0) Table V (continued) p-bromophenol (100) 600 Crystal violet (0.5) Chlorobenzene (3) Methyl ethyl ketone (0.50) Polystyrene (100) Al PKP (mg) Crystal violet (0.5) Chlorobenzene (0.5) 169 Solvent (ml) Bis- (4-dimethylamino- Binder (mg) Al phenyD methane (100) Solvent (ml) 120 Methyl ethyl ketone (1.0) Chemical Sensi Crystal violet (0.5) bilizer (mg) Solvent (ml) excellent Al Optical sensi 104 bilizer (mg) example carrier 44 Half-waste 600 excellent exposure Methyl ethyl ketone (3.0) (lux sec) Alkyd resin (100) Evaluation of the copies Methyl ethyl ketone (0 * 50) 4 < Table V (continued) Bis- (4-dimethylaniino- 600 phctiyl) * methane (200) Methyl ethyl ketone (3.0) Polyvinyl acetate (100) PKP (mg) Methyl ethyl ketone (0.50) Solvent (ml) 4-ChloN3 ⁱ tiitröbenzoe ⁱ Binder (mg) acid (50) Solvent (ml) Chemical Sensi * bilisatof (mg)

i
I.
I. 26 08 082 51 45 52 1 Methyl ethyl ketone (1.0) I,. 44 Crystal violet (0.5) 46 1 Methyl ethyl ketone (1.0) Methyl ethyl ketone (1.0) I solvent (ml) Crystal violet (0.5) PET-RIm Crystal violet (0.5) I optical sensi- 390 I bilizer (mg) Al T-paper I carrier 176 165 1 half waste excellent 1 exposure I ₄ (lux sec) excellent excellent j Evaluation of the copies 4S ί Table V (continued)
5 example 600 S.
ι
S. 47 Methyl ethyl ketone (3.0) 49 ! 600 Polyester (100) 600 j PKP (mg) Methyl ethyl ketone (3.0) Methyl ethyl ketone (0.5) Methyl ethyl ketone (3.0) j solvent (ml) Polyester (100) - Polyester (100) j binder (mg) Methyl ethyl ketone (0.5) Methyl ethyl ketone (0.5) I solvent (ml) - - - I chemical sensi- Victoria-Pure Blue BOH ί bilizer (mg) - (0.5) - j solvent (ml) Kayawt-Blue BOH (0.5) Al Turquioise Blue 776 (0.5) Optical sensi- 800 I bilizer (mg) Al Al I carrier 860 860 ^! Semi-waste excellent exposure (lux sec) excellent excellent I Evaluation of the copies 51 ί Table V (continued) example 600 50 Methyl ethyl ketone (5.0) 52 600 - 600 PKP (mg) Methyl ethyl ketone (3.0) - Methyl ethyl ketone (3.0) Solvent (ml) Polyester (100) 2,4,7-trinitrofluorenone Polyester (400) '' Binder (mg) Methyl ethyl ketone (0.5) Methyl ethyl ketone (2.0) j solvent (ml) - 4-chloro-3-nitrobenzoic Chemical Sensi seure (100) bilizer (mg) Methyl ethyl ketone (2.0) Trimellitic anhydride - (100> - Methyl ethyl ketone (1.0) Solvent (ml) Methyl pure pure special Al Crystal violet (0.5) I optical sensi- (0.5) 200 I bilizer (mg)
I carrier Al Al I half-a-full 890 146 1 exposure excellent I (lux sec) I Evaluation of the copies excellent excellent

26th 53 08 082 54 Table V (continued) example 5.1 55 6QÜ 54 600 PKP (mg) Methyl ethyl ketone (3.0) 600 Tetrahydrofuran (3.0) Solvent (ml) Polyester (40 (H. Chlorobenzene (3.0) Polyester (400) BindemitH (mg) Methyl ethyl ketone (2.0) Polyester (400) Tetrahydrofuran (2.0) Solvent (ml) m-nitrobenzoic acid (200) Methyl ethyl ketone (2.0) I 2,4,6-trichlorophenol (200) Chemical Sensi Phthalic Anhydride (200) bilizer (mg) Methyl ethyl ketone (1.0) Methyl ethyl ketone (1.0) Solvent (ml) Crystal violet (0.5) Methyl ethyl ketone (1.0) Crystal violet (0.5) Optical sensi Crystal violet (0.5) bilizer (mg) ΛI Al carrier 260 Al ISO HaIh-AhPaII- 195 exposure (do \ sck) excellent l excellent Evaluation of the copies Example 56 excellent ter »polycondensation product with the following

500 mg of the polycondensation product containing tertiary amino groups used in Example 35 (Co-condensate from xylene / formaldehyde polycondensate, Carbazole, anthracene and tert-butylphenol) and 100 mg of 2,4,7-trinitrofluorenone were dissolved in 6 ml of methyl ethyl ketone solved. The obtained solution was applied to the aluminum plate using a wire plating machine raised and dried. Calf waste exposure amount of the obtained photoconductive layer was 95 lux ■ sec. The copies were of excellent quality.

Example 57 and 58

10 g of the same polycondensation product containing tertiary amino groups as in Example 1 (1) obtained were dissolved in 50 ml of chloroform and the solution with a solution of 8 g of bromine in 80 ml Contacted chloroform for bromination of the polycondensation product. 8.6 g of a modified

Melting point

in inherent viscosity
Bromine content
Nitrogen content
Ratio of aromatic amine groups

r> per benzene nucleus

175 to 178 ° C

0.09

28.84 wt%

2.89% by weight

0.78

The polycondensation product obtained containing tertiary amino groups was mixed with the binder, the chemical sensitizer and the optical sensitizer set forth in Table VI Formation of the coating solution mixed. The coating solution was drawn up on the aluminum plate and dried. The semi-waste exposure of the obtained photoconductive layers and the quality of the copies were determined; the results are in Table VI contain.

Table VI example 58 57 600 600 Chlorobenzene (3.0) PKP (mg) Methyl ethyl ketone (3.0) Polyester (100) Solvent (ml) Polyester (100) Chlorobenzene (0.5) Binder (mg) Methyl ethyl ketone (0.5) 4-Ch! Or-3-nitrobenzoic acid (200) Solvent (ml) Bis- (4-dinielhylaminophenyD- Chemical sensitizer methane (200) Chlorobenzene (1.0) Methyl ethyl ketone (1.0) Crystal violet (0.5) Solvent (ml) Crystal violet (0.5) '10 Optical sensitizer (mg) 98 Semi-waste exposure excellent (lux sec) excellent Evaluation of the copies

R e i s ρ ι c I 59

ViO ιημ of the bromicrtcn used in Example 58 polycondensation product containing tertiary amino groups. 300 mg of 2,4,7-trinitrofluorenone and 50 nip KnMallviolett were in 10 ml of Methyläthylkcton The solution obtained was dissolved on an aluminum plate under \ n \ vendting of a disk transfer noise absorbed and dried. The semi-waste exposure boy of the photoconductive layer obtained was 14 Iu <sck. w ^ is means very high sensitivity. The quality of the copy obtained was excellent.

Example 60

A lOOml-Drcihalskolben was stirred mil 23.5 g (non-volatile content 52%) of a Resolpolykondensals, 16.7 g of carbazole and 0.2 g of m-xylene sulphonic acid were charged and at 80 ⁰ C during 1 in Sticksloffatmosphäre to the in Resolpolykondensat contained volatile components to distill off. The reaction was continued for a further 2 hours at 230 ^° C. and gave 22 g of a black-brown polycondensation product containing tertiary amino groups. The determination of the NMR spectrum showed no peak (12.3 ppm) which could be attributed to the —NH group of the carbazole. This confirmed that all of the starting carbazole had reacted with the resol polycondensate.

The obtained polycondensation product containing tertiary amino groups had the following properties:

Aromatic Amitrol ·, .ill
each Ben / olkern

1.41

Melting point

Inherent viscosity

Nitrogen content

above 300 "C

0.274

5.79 wt%

The product obtained was in N-methylpyrrolidor dissolved to form a 10% solution was on the aluminum plate by means of a washer Soaked up overmgsgerates and in a vacuum dryer (! mm Hg abs.) at 70 C for 12 hours dried, tier half waste exposure amount of he holding photoconductive layer, determined using a 100 W tungsten filament lamp of 300 lux was 7500 lux sec.

Comparative example 4

10.7 g (0.10 mol) of N-monomethylaniline. § 7.5 (0.10 mol) of 37 ° / cent formaldehyde (formalin) and 12 m of concentrated hydrochloric acid were placed in a three-lÖOml corn cobs and at 100 ⁰ C for 8 h implemented. The keaclion product was neutralized to pH 7 using a sodium carbonate solution. The solid was filtered, washed with water and dried at 50 ° C. and 1 mm Hg for 12 hours, yielding 10.8 g (melting point 8 ° to 86 ° C.) of a black solid. From the fact that the nitrogen content of the product, determined by elemental analysis, was 11.63% by weight, it is concluded that there is a condensate in a molar ratio of 1: 1 between N-monoethylaniline and formalin.

The coating was prepared in the same manner as in Example 20 using the obtained condensate tries to apply the product. He had any a poor solubility in common solvents and a uniform coating could not be obtained will.

Claims (15)

Patent claims: 1. Electrophotographic recording material having a photoconductive layer, which as Photoconductor a product of compensation with formaldehyde and amine units and optionally optical or chemical sensitizers and optionally a binder contains, characterized in that it is a soluble reaction product from in as a photoconductor (A) a soluble polycondensate of radicals of a benzene compound which contain at least one free bond and at least one nitrogen-free, electron-donating substituent, η where at least one of the radicals of the benzene compound has a substituent of the formula - CH2X, where X is a halogen atom or a Is hydroxyl, alkoxy or O-acyl group, and wherein the radicals of the benzene compound are linked by a group of the formula -CH ₂ (OCH ₂ ) - ^, wherein m is 0, 1, 2, 3 or 4 , and
from an amine that contains from
(b-1) an aromatic amine of the formula Ar-H-N-Y), 30th where Ar is an optionally substituted aromatic group, π is 1 or 2 and Y is a hydrogen atom or a hydrocarbon group y, pe if / 7 = 1. and Y is a hydrocarbon group when π = 2. or
(b-2) from a heterocyclic amine of the formula Ar ¹ Y ' where Ar is an optionally substituted aromatic group, η is 1 or 2 and Y 'is the atoms required to complete a heterocyclic ring which may contain another O, S or 5ί N atom. consists. 2. Electropholographic recording material according to claim 1, characterized in that it is a soluble reaction product incorporating an aromatic amine of claim 1 given formula (b-1) contains, wherein Y equals an optionally substituted by halogen Is phenyl or naphthyl. 3, electrophotographic recording material according to claim 1, characterized in that it is a soluble reaction product with units 65 of a heterocyclic amine of the formula (b-2) given in Claim 1, in which the ring of the heterocyclic amine is substituted by a phenylene or naphthene ring which is optionally substituted by halogen. 4. Electrophotographic recording material according to claim 1, characterized in that it is a soluble reaction product with units of an aromatic amine of claim 1 given formula (b-1), wherein Ar has one or two benzene or naphthalene nuclei, the benzene or Naphthalene nucleus optionally I to 3 substituents from the group of alkyl groups with 1 to 3 Carbon atoms, alkoxy groups with 1 to 3 carbon atoms, aryloxy groups with 6 to 10 Carbon atoms, Ν, Ν-dialkyl-substituted amino groups with 1 to 2 carbon atoms in the. alkyl group or contains halogen atoms, and Y is an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, Ar or a hydrogen atom, or with units of an aromatic amine in Claim 1 given formula (b-2) from the group of carbazole, 3-chlorocarbazole, 3,6-dibromocarbazole, Indole. Isoindole. Indoline. Phenoxazine. Phenothiazine and contains 2-phenylbenzimidazole. 5. Electrophotographic recording material according to claim 1, characterized in that it is a soluble reaction product with incorporation of an aromatic amine of claim 1 given formulas (b-1) and (b-2), those of aniline. Toluidine. N-methylaniline, N-ethylaniline, N-benzylaniline, Carbazole or D-phenylamine derived contains. 6. Electrophotographic recording material according to one of claims 1 to 5. dadurc " ^1, characterized in that it is a soluble reaction product." (a) A soluble polycondensate with units derived from a benzene compound of the formula (A) (AV are derived, where [/ + q . ·. · r] has the value 1.2, 3 or 4. / equal to 0,1.2.3 or 4 and around q are each equal to 0 or 1, and A and A 'are the same or different and at least one alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a hydroxyl group or a Halogen atom, where at least one of the groups A or A is a substituent of the 1 ormel - CHjX. wherein X is a * halogen atom or a hydroxyl. Alkoxy or O-acyl group isi, and if / or / 'is 2.3 or 4, A or A' can mean different groups, where at least one of the groups A or A 'must be an electron-donating group, where im Polycondensate that is linked to benz oil flanges B or C via a methylene group, and an amine of the formulas (b · 1) and (b-2) given in claim 1. 7. Electrophotographic recording material according to claim 1 or 6, characterized in that it is a soluble reaction product with Contains units of benzene compounds derived from m-xyloI 8. Electrophotographic recording material according to Claim 1 to 7, characterized in that that it contains a soluble reaction product which additionally contains units of a polynuclear organic Hydrocarbon as comonomer in a molar mixing ratio 7U the units of aromatic amine compound from 0.1 to 3: 1 9. Electrophotographic ¹ recording material according to claim 8, characterized in that the units of the polynuclear organic hydrocarbon are derived from anthracene, perylene or phenanthrene. 10. Electrographic recording material according to one of claims 1 to 8, characterized characterized in that it contains a soluble reaction product which additionally contains units of a phenolijchen Compound as a comonomer in a molar mixing ratio to the units of aromatic amine compound from 0.1 to 3: 1. 11. Electrophotographic recording material according to claim 10, characterized in that the units of the organic phenol compound of phenol. o-cresol. m-cresol, p-cresol. Mixed cresol. 3,5-xylenul or tert-butylphenol derived »Ind. 12 Flektrophotogranhi>! Rs Xuf.'eichnunesmaterial according to claim 1 to ll.dadur ii, that it contains a soluble reaction product with a solubility of 0.03 to 0.8, which at 30 ⁰ C in a solution of 03 g of the reaction product in 100 ml of N-methylpyrrolidone has been determined. 13. Electrophotographic recording material according to any one of claims 1 to 12, characterized in that it is a soluble reaction product contains, in which the amine group content is 1 to 0.5 to 7 benzene nuclei. 14. Electrophotographic recording material according to claim 1, characterized in that the soluble polycondensate with at least one optical and / or chemical sensitizer and at least one solvent-soluble and is mixed with the polycondensate compatible binder. 15. Electrophotographic recording material according to claim 14, characterized in that the chemical sensitizer consists of a halogemerten Phenol or a derivative thereof. lh flexrophotographic recording material according to claim 14, characterized in that the optical sensitizer is composed of a triarylmethane type compound. 45 Office electrophotographic copying has become widespread in recent years. Electrophotographic recording is also used for the production of microfilms, micro clichés, matrices for construction drawings, transparent sheets for overhead projectors, slides for slide projectors and radiographs. The usual electrophotographic methods can be roughly divided into a copying process using coated paper (abbreviated to CPC) and a copying process using plain paper (abbreviated to PPC). In the former method, a toner image is formed directly on a coated with a photoconductor paper and fixed thereon, while in the latter method, first forming a toner image on the surface of a photoconductor and this wi subsequently transferred to a plain paper and fixed ^r d. The CPC method has the advantage that a copying machine of simple construction can be used and the obtained image is of good quality. However, since the copy paper is coated with zinc oxide as a photoconductor, it is inconvenient to handle and the copy obtained is difficult. On the other hand, the PPC method requires an apparatus of complicated structure which is expensive. However, since copying can be done on plain paper, the resulting copy has a very similar appearance to a printed material and thereby gains an advantage; wide consumer acceptance In the other applications listed above, however, the CPC process is often more favorable Regarding the quality of the images received, the desired size of the images and the cost J ?: Copy machine. It is also often necessary. Use plastic backing instead of paper and the supports for these purposes often have to be transparent or translucent. That so far However, zinc oxide mainly used in the CPC process is not transparent and can be used for such Purposes of use are not used. To use electrophotography for such other uses than to make it applicable to office copying, there is therefore great technical interest for a photoconductive composition having transparency and flexibility and applicability in the form of a thin light-sensitive layer on paper or a plastic layer support. Inorganic photoconductors are unsuitable for this purpose, and so organic photoconductors have become examined. Studies have been carried out with both low molecular weight compounds and with Compounds of high molecular weight Runaway, which, however, were not found to be suitable to Photoconductor with completely satisfactory usage properties such as ease of use and cost in addition to good sensitivity. It is known that aromatic ten are Amir ν. ·, which is a unit of the formula