DE2608082A1 - ELECTROPHOTOGRAPHIC SENSITIVE LAYER AND METHOD FOR MANUFACTURING IT - Google Patents

Description

PATENT LAWYERS

DR. EWiEGAND DiFL-ING. Vv. NiErMNN 26 0 8 08 2

DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 555476 8000 MONTHS 2,

TELEGRAMS: KARPATENT MATH I LU E N ST RAS S E TELEX: 5 29 068 KARP D

W 42 495/76 - Ko / Ja 27-February 1976

Teigin Limited, Osaka (Japan)

Electrophotographically sensitive layer and process for its manufacture

The invention relates to a very valuable electrophotographic sensitive layer containing eixi soluble photoconductive resin as a photoconductive material.

The soluble photoconductive resin is represented by the content of an aromatic tertiary amino group of the following formula characterized as a photoconductive functional group

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ORIGINAL INSPECTED

CH ₂ (1)

\ / K ^ - ^C 1 ^C 2 ^

wherein 0 is a benzene nucleus with at least one nitrogen-free electron-donating nuclear substituent, C _{1 is} a carbon atom of the aromatic ring and Cp is a carbon atom which forms a hydrocarbon radical and a bond

2 ^ 5

Orbit of the sp type or sp type assumes, and the benzene nuclei represented by 0 with one another via a methylene group to the extent that the solubility of the resin is maintained.

Copying in the office using electrophotographic methods gained widespread use in recent years and, on the other hand, various attempts have been made to help others Develop uses that depend on various properties of the electrophotographic process. Some These tests already resulted in technically applicable applications, such as microfilms, micro-clichés, matrices for construction drawings, transparent sheets for overhead projectors, slides for slide projectors and radiography.

The usual electrophotographic processes used for office copying can be roughly converted into a copying process with coated paper (abbreviated CPC) and a copying process with plain paper (abbreviated PPC). The former involves the formation of a toner image directly on a paper coated with a photoconductor and the same As such, fixation and the latter method involves the formation of a toner image on the first Surface of a photoconductor, subsequent transfer of the same to a plain paper and fixing of the transferred

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Image. In general, the CPC method has an advantage that a copying machine of simple structure can be used and the image obtained 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 that is expensive. However, since If copying can be done on plain paper, the resulting copy has a very similar appearance to a printed material and thereby gains a wide acceptance of consumption. Because of this, the PPC process became predominant.

In the other applications listed above, however, the CPC method is often cheap or carefree from the viewpoints of the quality of the images obtained, the desired size of the images, and the cost of the image forming machines. In addition, in many cases it is necessary to use plastic film bases instead of paper, and plastic films and paper bases for these purposes often need to be transparent or translucent. The zinc oxide that has hitherto been mainly used in the CPC process is not transparent and cannot be used for such purposes. It can be concluded that in order to apply electrophotography to such uses other than office copying, a photoconductive composition having transparency and flexibility and useful as a thin photosensitive layer on paper or film is a very important key material.

Inorganic photoconductors are unsuitable for this purpose and organic photoconductors are becoming absolutely necessary. Investigations have become active in the art with both low molecular weight compounds and compounds carried out of high molecular weight, however, have so far proven unsuitable to use photoconductors entirely

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satisfactory performance properties, such as easy handling and cost in addition to good sensitivity.

It is therefore an object of the invention to provide an electrophotographically sensitive layer which is an organic Contains photoconductor which is suitable for use as a photoconductive layer on a basis such as film or paper is, is very easy to manufacture, is inexpensive and easy to be based on a thin film by peeling is malleable and has sufficient sensitivity.

It is known that aromatic tertiary amines, which are a unit of the formula

contain, in which C, a carbon atom on an aromatic ring and C ₀ and C, carbon atoms that form a hydrocarbon

2 form a residue and a bond orbit of the sp type or

sp type, mean to have good photoconductivity, preferably when combined with a suitable sensitizer be combined. Typical examples of such amines are N-substituted carbazoles and substituted aniline derivatives .

Heretofore, the following three typical methods of forming electrophotographic photoconductive layers have been used using compounds with an aromatic tertiary amine inheii. applied:

(I) A low molecular weight compound of defined structure such as n-butylcarbazole has been uniformly identified in a high molecular weight compound to form a photosensitive layer as disclosed in U.S. Patent 3 206 306 specified.

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2608032

(II) As in the case of the known poly-N-vinylcarbazole is, a polymer having repeating units of the formula (Ia) produced from monomers which contain a unit of the formula (Ia) or precursor units for this and that Polymer is processed into a thin film form to form the photosensitive layer.

(III) As in the case of the reaction between polyepichlorohydrin and a carbazole alkali salt used in Japanese Patent Publication 97540/73 discloses a low molecular weight compound polymer implemented to introduce a unit of the formula (Ia) as a bonded group of the polymer.

According to the method (I), a large amount of the low molecular weight photoconductive material is required to obtain sufficiently favorable sensitivity. It is very rare, however, _a ß ^ £ _as photoconductive material may form, with an added on the issue of film formation suitability binder polymers of low molecular weight, a stable mutually dissolved system. Even if a stable system can be formed, it often shows phase separation or blooming and its quality changes if it is not carefully stored as a photosensitive material.

In the case of the method (II), it is assumed that poly-N-vinylcarbazole and its substituted derivatives have the best properties, and some of them have achieved technical Use. However, since polymers of this type are produced through two stages of monomer synthesis and polymerization cleaning of the product is strictly necessary at every stage in order to obtain good properties the polymers obtained are generally very expensive and can only be used in very limited applications.

In process (III), however, the polymer and the compound used in the polymer reaction are of low mo-

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Cell weights are both technically available at low cost. If in a photoconductive polymer with good properties Could be transferred by means of a simple reaction, it goes without saying that this is a means of delivery an electrophotographically sensitive layer with excellent utility would be that of the method (I) and (II) own errors listed above would be free.

In order for the electrophotographically sensitive layer to have sufficient sensitivity, it is necessary to have a photoconductive group in an amount above a certain one To introduce limit. In order to achieve this introduction without causing undesirable side reactions such as gelation, must Polymer and low molecular weight compounds selectively react with each other with good reactivity. Indeed, it is very difficult to find combinations which meet these requirements among the technically useful polymers and compounds of low molecular weight. Despite numerous attempts, no such material has been technically available to date.

Investigations have now been made to find photoconductive resins containing units of type (Ia), which can be obtained by a method corresponding to the above-described method (III) and which have excellent usability. These investigations led to the finding that the foregoing Resins containing the unit of formula (1) meet these requirements.

It has first been found that soluble aromatic formaldehyde resins containing an electrophilic reactive group such as methylol or dimethylol ether group are _{readily available as typical examples of xylene-formaldehyde resins or ReSOLIERZe 7} as the base polymer. Such resins are not high molecular weight chain polymers,

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as they are used in the usual method (III), but rather oligomers. It has also been found that, as low molecular weight compounds, aromatic amine compounds the following formula

H
Ar-f- N - Y) _n (2)

where Ar represents an aromatic group, the group • fN - Y) _n is bonded to the carbon atoms of the aromatic ring, η the numbers 1 or 2 and Y a hydrocarbon radical, which, if desired, forms a ring with Ar either directly or via a nitrogen, Forms oxygen or sulfur atom, with the proviso that, if η has the value 1, Y can be a hydrogen,

for example carbazole, diphenylamine, aniline or methylaniline / are technically available at low cost and that the hydrogen atom bonded to the nitrogen atom in the above compounds undergoes a substitution reaction with a enters into an electrophilic reactive group and is substituted by a group of the benzyl type so that a unit of the formulas (Ia) introduced into the polymer.

The invention results in an electrophotographically sensitive layer which has at least one soluble, contains an aromatic tertiary amine group-containing resin as a photoconductive material, this soluble, a aromatic tertiary amine group-containing resin by reaction

(1) a soluble polycondensate of low molecular weight, which is residues of a benzene compound of the following formula

0 (1-A)

wherein 0 is a benzene compound radical with a valence of at least 1 and at least one nitrogen-free electron

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supplying core substituents contains, the Carbon atoms of these benzene compound residues through a linking group represented by the following formula

-CH ₂ (OCH ₂ ^ (1-B)

in which m is the number 0 or a positive number from 1 to 4, are bonded and at least one of these benzene compound radicals at least one linked (pendant) group of the following formula

-CH ₂ X. (1-C)

contains, wherein X is a hydroxyl group, an alkoxy group, a O-acyl group or a halogen atom as a substituent on the carbon atoms of the aromatic ring in principle

(2) an aromatic amine compound represented by the following formula

H
Ar ■ £ N - Y) _n (2)

,H . where Ar is an aromatic group, the group T ^- NY) _n ^ar * the carbon atoms of the aromatic ring is bonded, η the numbers 1 or 2 and Y a hydrocarbon radical, which optionally forms a ring with Ar either directly or via a nitrogen, oxygen or forms sulfur atom, with the proviso that if η has the ¥ ert 1, Y can be a hydrogen atom,

was prepared so that the methylene group bonded to the carbon atom of the benzene compound residue for the on which the amino group of the aromatic amine compound (2) forming nitrogen atom bonded hydrogen atom was substituted.

Photoconductive ones containing the soluble aromatic tertiary amine Resin, which is used as the photoconductive material of the

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photosensitive layer used according to the invention can be made from the polycondensate (1) and the aromatic amine compound (2), both of which are readily available industrially are, are produced by a simple process, for example in the simplest case only by mixing same and heating the mixture. Since this photoconductive resin has superior properties as shown below, it provides a photoconductive layer of excellent utility.

Unlike the low molecular weight compound used in the above method (I), that is photoconductive Resin is a vitreous transparent resin having a film-forming property and can be the photosensitive layer form without using a binder polymer. If a If a photoconductive layer having better flexibility is desired, a binder polymer can be added. The amount however, the binder polymer may be very small compared to the method (I). Furthermore stands in contrast to the case of the method (II), which is the mutual dissolution of an aliphatic high molecular weight polymer and a further polymers includes a very wide range of binder polymers for complete mutual dissolution with available to the photoconductive resin because its molecular weight is about that of oligomers, although it is a polycondensate represents. Therefore, according to the desired end use, a stable transparent thin film-like can be produced photosensitive layer are formed.

Furthermore, the photoconductive resin used in the invention has a better sensitivity than a model compound with a defined structure in spite of the fact that, due to the manufacturing process, its structure is not represented by defined, repeating units can be. It has already been confirmed experimentally, as shown in the following comparative examples, that example

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wise a mass of a polycondensate of a xylene resin and carbazole, as a typical example of the invention photoconductive resin used, has a much higher sensitivity than a mass of N-benzylcarbazole, a model compound with the same photoconductive functional group when the same sensitizer and the same binder be incorporated in the same quantities. The same result is obtained when the sensitivity of a mass of a polycondensate of a xylene resin and aniline with that of a mass of dibenzylaniline, a model compound of the former material.

In view of the ease of manufacture of the photoconductive resin used in the present invention, the breadth of compounding approaches for the production of the photosensitive layers and their better sensitivity to the Model compounds due to the specific structure, it is readily apparent that the present invention is an electrophotographic Delicate layer of excellent usability provides.

The electrophotographically sensitive layer according to FIG Invention can even be formed from the photoconductive resin alone. However, for certain purposes, the Sensitivity of such a sensitive layer is low and its flexibility is insufficient. In numerous In some cases it is therefore preferred to add appropriate amounts of sensitizers and binder polymers.

From the point of view of their function, the sensitizers can be classified into optical sensitizers or dye sensitizers and chemical sensitizers. If high sensitivity is required, both will Types of sensitizers often used together. In special cases, a substance can be used at the same time both acts as a binder polymer as well as a chemical sensitizer.

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The photoconductive resin, the sensitizers, the binder polymers and the photoconductive layer are explained in detail below with reference to preferred examples.

I. Photoconductive resin

(1-1) Soluble low molecular weight polycondensate

The soluble low molecular weight polycondensate used in the manufacture of the photoconductive resin is, can by reacting a compound of the benzene type, which at least one nitrogen-free electron donating Nuclear substituents and at least two nuclear-substituting hydrogen atoms which are used for methylol substitution are capable of formaldehyde, contains, with formaldehyde and / or functional derivatives thereof in a manner known per se be obtained with the formation of an addition condensation. The addition condensation should be carried out to such an extent that the resulting low molecular weight polycondensate is soluble in solvents and preferably is also fusible.

Suitable compounds of the benzene type for the preparation of the soluble polycondensates of low molecular weight can be expressed by the following formula

(A)

(O)

(3)

wherein 1, I ¹ and ± - positive integers, where [1 + qxr] represent the numbers 1, 2, 3 or 4, I ¹ -the number 0 or 1 and, if q has the value 0, the grouping

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denotes a hydrogen atom and r denotes the number 0 or 1 and, if r has the ¥ ert 0, the benzene ring C is bonded directly to the core carbon atom of the benzene ring B, while A and A ^{1 are} identical or different and have at least one group of alkyl groups 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, hydroxyl groups or halogen atoms with the proviso that if 1 or I ^{1 has} a value of 2 or more, A and A ¹ can represent different groups from the above class and at least one of the A and A 'radicals 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, xylenol, tert-butylphenol, anisole, isopropylbenzene, Trimethylbenzene, ethylbenzene, 1-butylbenzene, p-phenylphenol, Trimethylsilylbenzene, pseudocumene and durene. Of this Xylene, diphenyl ether, phenol or substituted phenols, for example halogen- or alkyl-substituted phenols, are preferred. m-Xylene is particularly preferred because it is practically colorless is. Formaldehyde or its functional derivatives are mainly used in the form of formalin but also in the form of p-formaldehyde, trioxane or chloromethyl methyl ether be used.

The implementation between the benzene type compound and Formaldehyde and / or its functional derivatives is given by a suitable known method according to the given Combination of respondents carried out. Self-

not
it is understandable / sufficient to only obtain a polycondensation product, but careful attention must be paid to the fact that a reactive group capable of participating in a reaction with an aromatic amine compound of the formula (2), ie a methylol group or a functional

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tional derivatives thereof corresponding to the formula (1-C) or represented by the formula (1-B) wherein m represents a value not lower than 1 must remain in a sufficient amount.

In the case of a benzene type compound, mainly used as a difunctional compound in the methylolation reaction reacts like m-xylene, pseudocumene or durol can a soluble resin which has a methylol group, a dimethylol ether linkage and the like. In addition to the methylene bond, can be obtained by using the benzene compound and an excess amount of formaldehyde in the form of formalin or trioxane of an addition condensation in the presence of a acidic catalyst is subjected.

On the other hand, in the case of a benzene type compound, which mainly acts as a trifunctional compound In a methylolation reaction, like phenol or cresol, a soluble resin reacts with a reactive methylol group of the so-called resol type obtained by reacting the same with formaldehyde in the presence of an alkaline catalyst will.

Benzene-type compounds which are relatively difficult to methylolate, such as diphenyl ether, are mixed with a mixture of hydrochloric acid and trioxane, a mixture of formalin, hydrochloric acid and sulfuric acid or chloromethyl ether with formation of a resinous product chloromethylated.

The chloromethyl group can be used as a kind of functional derivative of the methylol group. In general however, it is preferred to convert them into a methylol group or dimethylol ether linkage by hydrolysis or to a Alkoxymethyl group by alcoholysis or to an acyloxymethyl group by esterification before reaction with the aromatic To convert amine compound of formula (2). This is preferred because there is no corrosive hydrogen chloride forms during the reaction.

Particularly preferred polycondensates are xylene resins and

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ter use of m-xylene, modified xylene resins, diphenyl ether resins, and resol type phenolic resins. Nicanol (name of a product of Mitsubishi Gas Chemical Co. Ltd.). with an oxygen content of 3 to 18% and a softening point (in the liquid state at room temperature) of up to 150 ⁰ G is suitable as a xylene resin or modified xylene resin. On the other hand, paint resins which harden upon baking are also suitable as resol type phenolic resins.

In general, these resins preferably have a high content of methylol groups, dimethylol ether groups and / or functional derivatives thereof because they react with the aromatic amine compound in a large ratio. However, if the content of these reactive groups is too large, a crosslinking reaction takes place competitively Time of reaction between the soluble low molecular weight polycondensate and the aromatic amine compound and the product becomes insoluble. Therefore, in order to maintain the solubility of the photoconductive resin according to the invention, The content of these reactive groups must be within a suitable range corresponding to that of the aromatic ones Amine compound of the formula (2) forming benzene nuclei or the soluble resin. The xylene resins are particularly preferred from this point of view because they undergo essentially no crosslinking reaction by themselves when they contain a large number of reactive groups and they are less colored than phenolic resins.

In general, the soluble low molecular weight polycondensates have a molecular weight of from 200 to 3000 and their content of methylol groups or dimethylol ether groups and / or functional derivatives thereof is 1 on 0.1 to 3 benzene nuclei.

Since a dimethylol ether group with two groups C

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can react, as shown schematically below their content, "calculated as the mathylene group, considered to be 2:

- CH ₂ OCH ₂ - + HN <* -CH ₂ NC + HOCH ₂ -

> NH + HIGH ₂ - »-CH ₂ NC + H ₂ O

(1-2) Aromatic amine compound

The aromatic amine compound used to prepare the photoconductive resin is represented by the formula (2). In the formula, the aromatic group Ar preferably contains 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 having 6 to 10 carbon atoms, Ν, Ν'-disubstituted amino groups and halogen groups. A part, preferably not more than 30 mol%, of Ar can contain a strongly electron-withdrawing substituent such as a nitro, cyano or alkoxycarbonyl group. If, however a greater part of Ar has such a group, it adversely affects the photoconductivity of the obtained Resin and therefore such a large content of the substituent is not preferred. If Y is an aromatic group represents, the same requirements for Ar and the same preferred examples as given above are applicable.

Ar and Y can be bound to each other, and 1 to 2 forming aromatic fused polynuclear rings together with -N-. Preferred examples are carbazole and phenoxazine and indole.

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If Y has a different meaning than an aromatic group, it preferably consists of a hydrocarbon group with 1 to 10 carbon atoms that have the same substituents, as indicated above with respect to Ar. As in the case of the indoline, for example, Ar and Y can interact with each other .be connected to form a fused multi-core ring, as discussed above. Particularly preferred Examples of hydrocarbon groupings are lower alkyl groups having 1 to 3 carbon atoms and benzyl groups.

Specific examples of preferred aromatic amine compounds are given below.

(a) If n = 1 and Y = H:

Aniline, toluidine, xylydine, p-ethylaniline, p-chloroaniline, p-bromoaniline, 2,4-dichloroaniline, p-anisidine, o-anisidine, N, N-dimethyl-p-phenylenediamine and <x- or ß-naphthylamine.

(b) If n = 1 and ':' is not an aromatic group and is not bonded to Ar:

N-methylaniline, N-ethylaniline, N-propylaniline, N-benzylaniline, N-methyltoluidine, N, N, N ^f -trimethyl-p-phenylenediamine, N-cyclohexylaniline and N-methyl-a-naphthylamine.

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

Diphenylamine, phenylnaphthylamine, dinaphthylamine, ditoluylamine and 4,4 ^f -dichlorodiphenylamine.

(d) If n = 1 and Y is bound to Ar:

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

(e) If n = 2:

^F 4,4-Bis (monomethylamino) -diphenylmeths.n, 4,4'-bis (monoäthylamino) diphenylmethane, 1,1- [4,4-bis ^f (monomethylamino) diphenyl] -ethane, 4 , 4 · bis (monobenzylamino) diphenylmethane, 4,4'-bis (phenylamino) -dipheny! methane, 4,4 · bis- (methylamino) triphenylmethane, N, N-dimethyl-p-phenylenediamine ^f , N, N ^f -diphenyl - ^ - phenylenediamine, N, N '- (ß-naphthyl) -p-phenylenediamine and diindole.

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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 readily available and provide photoconductive resins of reduced color, particularly those of the formula (2) are preferred in which Y is selected from the group of hydrogen atoms, lower alkyl groups, benzyl groups and phenyl groups, in particular at least one of aniline, toluidine, N -Methylaniline, N-ethylaniline, N-benzylaniline, carbazole, diphenylamine and 4.4 ^l -bis- (methyamino) -diphenylmethane is selected.

The above aromatic amine compounds are limited to those in which 1 to 2 hydrogen atoms are bonded to the nitrogen atom of the amino group. The reason is that if they contain 3 or more such hydrogen atoms, they easily react with the reactive groups of the soluble low molecular weight polycondensate, and the reaction product suffers from gelation and becomes insoluble. However, some of the aromatic amine compounds result in improved sensitivity or film-forming suitability if a part (generally not more than 30 ¥ iol%) thereof by * an aromatic amine compound in which at least 3, preferably 3 to 4 hydrogen atoms are bonded to the amino group

is replaced,
are, / Examples of such aromatic.amine compounds are 4.4 ^! -Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and p- or m-phenylenediamine.
(1-3) Co-condensation component

The usefulness of the phatoconductive, a tertiary amine containing resin can sometimes continue for certain applications by using a co-condensation component, which with the reactive groups of the polycondensate in the to the same extent as the aromatic amine compound reacts in producing the above photoconductive resin be improved. The co-condensation component comprises

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for example polynuclear aromatic hydrocarbons and phenolic compounds. The polynuclear aromatic hydrocarbons sometimes have an effect of increasing the sensitivity of the photoconductive resin, but will do so they are prone to discoloration, suitably chosen according to the desired use. Preferred phenolic Compounds are those with at least three aromatic rings, such as anthracene, perylene and phenanthrene. That Anthracene is particularly preferred.

The molar mixing ratio of polynuclear aromatic hydrocarbon to aromatic amine compound is generally 0.1 to 3: 1, preferably 0.1 to 1: 1.

The phenolic compound as a co-condensation component sometimes has an effect of improving the film-forming suitability of the photoconductive resin and the compatibility of the aromatic amine compound with the binding polymer. Preferred phenolic compounds are phenol, o-cresol _y m-cresol, p-cresol, Mischcresol, 3,5-xylenol, and tert-butylphenol. The molar mixing ratio of the phenolic compound to the aromatic amine compound is generally 0.1 to 3: 1, preferably 0.1 to 1: 1.

(1-4) Preparation of the photoconductive _/ tertiary amine-containing resin

It is known, for example, that a tertiary amine-containing resin by condensation between a soluble polycondensate of low molecular weight and an aromatic amine compound can be obtained, as in the case of reacting aniline with a xylene-formaldehyde resin, such as, for example in K.O. Kogyo Kagaku Zasshi, 5jB, page 520 (1955) and 62, page 129 (1959). However, it is actually unknown that the implementation of a soluble polycondensate vora low molecular weight with a diarylamine type secondary amine such as carbazole or diphenylamine is preferred tertiary amine and thus a resin, which this ent-

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holds, yields.

The new soluble and meltable aromatic tertiary amine-containing resins according to the invention are obtained by reaction (1) a soluble low molecular weight polycondensate obtained by addition condensation of a benzene compound with at least one nitrogen-free, electron-donating core substituent and at least two core-substituting ones Hydrogen atoms responsible for methylol substitution by formaldehyde, with formaldehyde or its functional derivatives are capable of being obtained, wherein at least one of the benzene compound residues is a bonded group represented by the following formula

-CH ₂ X (1-C)

contains wherein X is a hydroxyl group, an alkoxy group, a O-acyl group or a halogen atom as substituents on the carbon atoms of the benzene ring principally with (2) an aromatic amine compound of the following formula

H
Ar ■ £ N - Y) _n (2)

where Ar is an aromatic group and the group • fN-Y) on the core carbon atoms of the aromatic group is bonded, η the numbers 1 or 2 and Y is an aromatic group which is the same or different from Ar or optionally forms a ring either directly or through a nitrogen, oxygen or sulfur atom, so that the methylene group bonded to a carbon atom of the benzene ring through that of the amino group of the aromatic amine compound (2) forming nitrogen atom, bonded hydrogen atom is substituted and good photoconductivity owns, received.

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The ratio between the low molecular weight polycondensate (1) and that for producing the photoconductive one The aromatic amine compound (2) used in the resin is in principle such that the content of the dimethyl ether group, the methylol group and / or its functional derivatives of the polycondensate (1) equal in equivalent weight to the content the hydrogen atoms bonded to the nitrogen atom of the amino group is and in many cases this ratio is preferred. However, it is not necessary to have the ratio to be set exactly to this standard, but the ratio can also be different according to the desired purposes be. For example, if one wishes to increase the amine group content of the photoconductive resin as much as possible, it will sometimes preferred to employ a method in which the aromatic amine compound (2) is in excess of that of Dimethylolethergruppe, the methylolgruppe and / or their functional derivatives of the polycondensate (1) in the reaction with the amino group of the aromatic amine compound (2) is fed in as completely as possible and, after the reaction, the excess unreacted amine (2) from the resulting photoconductive resin is removed by distillation or precipitation. In this case, the amount of aromatic Amine compound (2) generally 20 Mo1% to 300 equivalent% Excess.

In some cases, the aromatic amine compound (2) is incorporated in an amount less than the equivalent weight, thus some of the dimethylol ether groups, the methylol groups and / or their functional derivatives of the polycondensate (1) in the event of a substitution reaction with the ring carbon atoms of the aromatic amine (2) is used, with or without the carbon atoms of the benzene ring of the polycondensate (1) can also be used in the reaction with the amino group of the amine (2), so that the molecular weight of the photoconductive resin obtained

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and its softening point or suitability for film formation is improved. However, if the amount of the aromatic amine compound fed is too small, the proportion will increase of the photoconductive groups of the photoconductive resin and causes a decrease in sensitivity. Through this Furthermore, there appears to be a tendency for the resin obtained to gel by crosslinking during the reaction. Generally therefore, it is preferred to use the aromatic amine compound in an amount of at least half the equivalent weight to use.

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 (1) with that on the nitrogen atom of the amino group bonded hydrogen atom and the one with the to the core carbon atoms of the aromatic ring bonded hydrogen atoms sometimes small, and the above gelation tends to occur. That is why care is often required required when selecting the amount of the aromatic amine compound (2) and the reaction conditions.

The reaction between the polycondensate (1) and the aromatic amine compound (2) is promoted by using a catalyst. In general, the catalyst preferably consists of an acidic catalyst such as m-xylenesulfonic acid, methanesulfonic acid or toluenesulfonic acid. The amount of catalyst is generally from 0.001 to 20%, preferably 0.1 to 3% _f based on the weight of the soluble polycondensate of low molecular weight (2).

The reaction can be carried out in the presence of an inert reaction solvent such as nitrobenzene or methyl benzoate will. However, since it is necessary to deposit the obtained photoconductive resin from the solvent after the reaction, it is generally advantageous to carry out the reaction in the molten state with evaporation of the secondary

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occurring water or possibly with evaporation carry out the undesired unreacted reaction components. Preferably the reaction is in an atmosphere an inert gas such as nitrogen or argon to prevent the resulting resin from being discolored by oxidation. In some cases, the reaction can also be carried out under reduced pressure.

The reaction of the aromatic amine compound (2) with the polycondensate (1) with or without co-condensation component is generally carried out at a temperature of 50 to 30O ⁰ G, preferably 120-230 ^0C. The reaction time varies according to other conditions such as reaction temperature, but it is generally 0.2 to 10 hours, preferably 1 to 4 hours.

The state of progress of the reaction can generally be determined by determining the NMR spectrum or IR spectrum of the reaction mixture to be tracked. In the case of the NMR spectrum can be determined by the state of disappearance of the proton in the aromatic amine (2) and one due to the proton of -CHpO- in the aromatic amine (2) this can be confirmed in the course of the reaction. In the case of the IR spectrum, this can be done by reducing the characteristic Absorption attributable to the stretching vibration of the bond of> N-H can be confirmed. Sometimes For example, it can be seen from the infrared absorption spectrum that there is a proton even after the reaction } NH type remains slightly in the obtained resin. This is probably due to the fact that the reaction of the methylol group and / or its functional derivatives with the carbon atoms of the aromatic ring of the aromatic amine (2) competitively with the implementation of these Groups with the -NH group takes place and as a result a group -NH- remains in the resin or a group from Ben-

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zyltyp rearranged from the tertiary amino group formed will.

After the reaction, the resin formed can be used as a photoconductive resin composition for an electrophotographically sensitive one Layer can be used without special cleaning, but if desired after adding a sensitizer or one Binder resin of the types already described.

If desired, the resin obtained can, for example, by dissolving in a solvent such as methyl ethyl ketone or chlorobenzene / and pouring the solution into a nonsolvent for the resin, such as methanol, to remove the unreacted Material or by comminuting the resin obtained into powder or granules and extracting the same with a substance that is a non-solvent for the resin, but a solvent for the unreacted materials, for example methanol, can be purified to remove the unreacted materials.

It is also possible to add an appropriate amount of a halogen to the aromatic group of the obtained resin by contacting the same with a halogenating agent to replace halogen atoms for the hydrogen atom or the aromatic one Ring, for example bromine, chlorine, N-bromosuccinimide or sulfuryl chloride or by reacting the same with oleum for Introduction of a nitro group in part of the aromatic groups.

These resins, which have been subjected to post-treatment, can be used in the same The manner in which the resins listed above are used and are in the definition given according to the invention of the photoconductive tertiary amine-containing resins.

(1-5) Properties of the photoconductive tertiary amine-containing resins

The photoconductive resin obtained by the above method is a transparent amorphous solid Resin which is colorless or generally colored blue, green, yellow or brown. It has a softening point of

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5C ⁰ C to a point where it is said to be infusible. Preferably it has a softening point of 70 to 15 OPC. The resin is soluble in a wide variety of organic solvents and can be cast into films from solutions in these solvents. The preferred solvents are those with a boiling point of 40 to 20O = C, for example ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone and aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, tetrachloroethane and chlorobenzene, ethers such as tetrahydrofuran, Dibutyl ether and anisole, esters such as ethyl acetate and butyl acetate and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

The photo-conductive resins used in the invention generally have a molecular weight, stated as inherent viscosity and determined at 30 ⁰ C for a solution of the resin in N-methylpyrrolidone at a concentration of 0.5 g / 100 ml, 0.03 to 0 , 80, preferably 0.07 to 0.50. The amino group content of the resin is preferably 1 to 0.5 to 7 benzene nuclei which form the soluble polycondensate (1), and in particular 1 to 0.6 to 4 benzene nuclei.

The amino group is on those forming the backbone of (1) Benzene ring in the by the following formula

CH ₂
Ar -4- N - Y) _n (4)

given form, in which Ar is an aromatic group, the group C

N-Y)

is bonded to carbon atoms of the aromatic ring, η denotes the numbers 1 or 2 and Y denotes a hydrocarbon radical or a hydrogen atom, which is optionally a ring

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together with Ar either directly or via a nitrogen, Oxygen or sulfur atom or optionally to the benzene ring 3 or C in the formula (3) through a methylene group are bound.

The amino group content can generally be easily calculated by calculating calculated from the nitrogen content of the photoconductive resin according to the invention determined by elemental analysis will.

Sometimes amino groups other than tertiary amino groups are mixed in the photoconductive resin. As above carried out, the amount of these other amino groups can be determined by, for example, infrared absorption spectrum or NMR spectrum can be determined. Since the photoconductive resin according to the invention has various kinds of tertiary amino groups contains, it is difficult to determine the nature of the tertiary amino groups directly. For example, that's through an NMR spectrum found proton in

an effective measure of determination. An appropriate method such as an infrared absorption spectrum or a mass spectrum must be selected in accordance with the photoconductive resin obtained. In general, the elemental analysis-based method is simple and convenient and widely applicable. An ultraviolet absorption spectrum and a fluorescence spectrum acting in the visible ultraviolet can also provide effective means of identifying the compounds.
(2) sensitizers

In many cases it is preferred to add a sensitizer to the electrophotographically sensitive layer according to the invention to add to the sensitivity of the photoconductive amine-containing resin as a photoconductive material

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to increase. Such sensitizers can be divided into optical sensitizers and chemical sensitizers. These two types of sensitizers alone can produce an excellent sensitizing effect are used, but are preferably used together. (2-1) Optical sensitizers

The optical sensitizers absorb and transmit light with a longer wavelength than the sensitive wavelength limit of the main photosensitizer Energy on the photosensitizer while energizing the photosensitizer. This becomes the sensitive 'wavelength range of the photosensitizer while increasing the ratio that portion of the light from a light source which is used for sensitization, so that the overall sensitivity of the photosensitizer is increased. Usually dyes with an absorption can be used as optical sensitizers in the visible range. In numerous cases these are optical sensitizers effective even when added in very small amounts.

In the context of the invention, the known optical Sensitizers for the organic photoconductor are used. Specific examples of preferred optical sensitizers are dealt with below.

(a) Compounds of the triarylmethane type crystal violet, Victoria blue BH, Victoria pure blue

BOH, Methyl Violet Pure Special, Malachite Green, Dianix Blue EB-E, Diaryl-Turquoise-Blue-BG - E, Dianix-Brilliant-Red-BS-E, Diacelliton-Fast-Pink-R, Acid-Violet-5B, Solar-Cyanine-6B, Acid-Violet-6B, rsrilliant-Green, Methylviolet, Victoria-Blue-6B and Victoria Blue are examples.

(b) Compounds of the anthraquinone type 4,5-dinitrochrysazine, 4,8-dinitroanthraquinone, 1,5-di-

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aminoanthraquinone, 1-amino ^ -phenoxy ^ -hydroxyanthraquinone, 1-methylamino-anthraquinone, Turquoise-Blue-776, Kayaset-Blue-985 and Kayaset-Blue-020.

(c) Cyanine type compounds

3.3 ^! -Diethyl-2,2 * -thia-oxacarbocyanine iodide, 2- (p-dimethylaminostyryl) -3-ethylbenzothiazolium iodide, 1-carboxymethyl-1 ^f -carboxyethyl-2,2- ^t -quinocyanine bromide and 1,1'-diethyl-2,4 '-quinocyanine iodide.

(d) Rhodamine-type compounds

Rhodamin B, Rhodamin 6G, Rhodamin B Extra and SuIfo-Rhodamin B.

(e) Rose Bengal xanthene-type compounds and erythrosine.

(f) Thiazine-type compounds, methylene blue.

(g) Acridine-type compounds Acridine Yellow and Acridine Orange. (h) Quinoline-type compounds, cryptcyanine and pinacyanol.

(i) Carbonyl-type compounds Alizarin and Solway Ultrablue B.

Triarylmethane type dyes are preferred from the viewpoint of effectiveness. Depending on the absorption wavelengths of these dyes, two or more of the optical sensitizers can be used to to expand the absorption range.

Some specific colors are undesirable in certain applications of the photosensitive layer. In general blue to purple dyes have an absorption wavelength in the yellow to red regions and are commonly used applied from the point of view of effectiveness and appearance. Examples of such sensitizers are Cristal Violet, Kayaset-Blue-985 and Victoria-Pure-Blue-BOH.

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The amount of the optical sensitizer is usually 0.0001 to 20% by weight, preferably 0.01 to 15 % by weight based on the weight of the photoconductive resin.

(2-2) Chemical sensitizers

The chemical sensitizers increase the photoconductivity by chemical reaction with the main photosensitizer during non-exposure and / or during exposure, in which they cause the generation of carriers by light or facilitate the movement of such carriers.

The compounds previously known to be effective for photoconductors contain a tertiary amine unit of the formula (Ia) and can, for example, generally be used as chemical sensitizers according to the invention. The preferred chemical sensitizers are those which can be mixed with the photoconductive resin as the main photosensitizer to an extent of at least 0.1 % by weight, preferably at least 1% by weight. These compounds can be roughly divided into compounds with the properties of an electron acceptor and halogen-containing organic compounds. The former include Lewis acids in the broader sense and are preferably those capable of forming a charge transfer complex with the aromatic amines (2). For this reason, compounds based on aromatic compounds which contain an electron-withdrawing substituent, for example benzene, naphthalene, anthracene, fluorene, fluorenone or bipheriyl, are generally preferred. Examples of electron-attracting groups are nitro groups, carboxyl groups or derivatives thereof, cyano groups, halogen groups, sulfonic groups, ketone groups, aldehyde groups and sulfonic acid groups or their derivatives. Chemical sensitizers with at least one, preferably 2 to 4, electron withdrawing groups are preferred.

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

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preferred. However, polynitro compounds are generally colored and many of them are strongly colored, especially If you. form a charge transfer complex. This coloring can be a problem in certain applications. In these cases, a carboxyl group or derivatives thereof such as anhydride groups or ester groups and Cyano groups preferred. These compounds of either high or low molecular weight can be used if they only meet the requirement of "compatibility with the photoconductive resin. Thus, aromatic Nitro compounds, aromatic carboxylic acids or derivatives thereof and aromatic cyano compounds as chemical sensitizers be used. Thus, in particular aromatic nitro compounds, aromatic carboxylic acids or derivatives of these and aromatic cyano compounds are used as chemical sensitizers.

Examples of aromatic nitro compounds are trinitrofluorenone, Tetranitrofluorenone, (2,4,7-trinitro-9-fluorenylidene) ~ malonitrile, Nitroanthracene, dinitroanthracene, trinitroanthracene, nitroanthraquinone, dinitroanthraquinone, trinitroanthraquinone, o- or m-dinitrobenzene, dinitronaphthalene, nitrophenol, dinitrophenol, trinitrophenol, mononitrocatechin, Dinitrocatechin, honochloromononitrophenol, monochloroditrophenol, Mononitrocresol and dinitrocresol;

Examples of aromatic carboxylic acids or their derivatives include phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, Trimellitic acid, pyromellitic acid, naphthalene-1,8- or-2,3-dicarboxylic acid, benzophenone tetracarboxylic acid, Anhydrides and esters of these acids, nitrobenzoic acid, dinitrobenzoic acid, trinitrobenzoic acid, monochloro-mononitrobenzoic acid, Monochloroditrobenzoic acid and dinitronaphthoic acid. In general, the sensitizing effect will be greater in the order of esters, acids and anhydrides and therefore

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the anhydrides are most preferred.

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

Tetracyanoquinone dimethane, tetracyanoethylene, chloranil, Dichloroacetic acid and maleic anhydride are also worth mentioning.

Particularly preferred chemical sensitizers are trinitrofluorenone, Nitrobenzoic acid, nitrochlorobenzoic acid, nitrophenol, Dinitrophenol, nitrochlorophenol, phthalic anhydride, trimellitic anhydride, naphthalene-1,8-dicarboxylic anhydride, Naphthalene-1,4,5,8-tetracarboxylic acid and naphthalene-1,4,5,8-tetracarboxylic acid dianhydride.

The mechanism of sensitization of the halogen-containing compounds is not clear, but it is believed that a halogen residue dissociated by direct or indirect exposure to light plays an important role. Compounds with at least one carbon-halogen bond in the molecule that meet the requirements of compatibility are chemically stable in the dark at room temperature, regardless of whether they are present alone or in the presence of the photoconductive resin or binder polymers. If these compounds can generate halogen radicals on exposure, they can be used as chemical sensitizers in the context of the invention, regardless of their molecular weight. The halogen in these compounds preferably consists of chlorine, bromine or iodine. Chlorine and bromine are particularly preferred. In view of the compatibility with the photoconductive resin and the sensitizing effect, aromatic halogen compounds, particularly halogenated phenols and derivatives thereof are preferred. Examples of these preferred types are halogenated bisphenols such as 2,2'-methylenebis (4-chlorophenol), 2,2'-methylenebis (3,4,6-trichlorophenol), 4,4'-methylenebis (2-chlorophenol) ) and 4.4 ^l -Isopropylidenebis (2,6-dibromophenol), mono-, di- or trichlorophenol, mono-, di- or tribromophenol, chlorocresol and halogenated phenolic resins, which are between halo-

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Generated phenols and formaldehyde are formed.

Examples of further halogen-containing compounds which can be used in the context of the invention are polycarbonates or copolycarbonates derived from the halogenated bisphenols listed above, epoxy resins, the halogenated bisphenol units listed above th contain, by addition of halogenated bisphenols to ethylene oxide or propylene oxide with the formation of glycols products obtained, polyesters derived therefrom, halogenated phenyl esters of polyacrylic acid or polymethacrylic acid, Copolymers of such a unit with other vinyl monomers and hexachloro-p- or -m-xylene. Others useful halogen-containing compounds include, for example, polyvinylidene chloride, polyvinyl chloride, polyvinyl bromide, copolymers, which contain this as a partially recurring unit, and halogenated paraffin compounds such as pentaerythrityl bromide.

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

It has been found that polyarylmethane compounds of following formula

wherein the radicals R-. to R ^ are the same or different and an alkyl group, alicyclic group or aralkyl group having 1 to 7 carbon atoms and R ^ are at least one Alkyl group, alicyclic group, aryl group or aralkyl group having 1 to 7 carbon atoms or the moiety

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^R 1

wherein Rg and R ^ are the same or different and are a lower alkyl group having 1 to 3 carbon atoms or a halogen group and ρ and p ^{1 are} an integer of O to 2, an excellent sensitizing effect on photoconductive resins containing a carbazole or a nucleus-substituted derivative thereof contain, although their sensitization mechanism is not fully understood.

These compounds themselves contain a unit of the formula (Ia) and become photoconductive when combined with the above listed halogen-containing organic compounds are combined. However, when using a carbazole-containing photoconductive Resin combined, they show a very good sensitizing effect, even in the 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 in view of its effect v / earth. The amount of the chemical sensitizer therefore differs according to, for example, The ratio of the photoconductive group of type (Ia) in the photoconductive resin or the molecular weight of the sensitizer, however, is generally 0.1 to 100% by weight, preferably 1 to 70% by weight, based on the weight of the photoconductive Resin.

If the level of the chemical sensitizer is too low, its effect is reduced and, on the other hand, it decreases if it exceeds a certain limit, the effect ceases to apply. Since the addition of the chemical sensitization

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tor generally deteriorates the properties of the photoconductive layer as a coating, it is preferred to determine the most favorable amount experimentally according to the intended use.

(iii) binder polymers

The photoconductive resin used in the photosensitive layers according to the invention has a film-forming property, but its molecular weight is not so high in many cases. Therefore, in order to obtain photosensitive layers with superior flexibility, it is often necessary to add a binder polymer.

In general, as the amount of the binder resin increases, the sensitivity of the photosensitive layer decreases numerous cases. The amount of the binder should desirably be as little as necessary. In general the amount of the binder polymer is 0.05 to 1.5 parts, preferably 0.1 to 1 part, based on the weight of the photoconductive one Resin.

The polymers preferably used for this purpose are readily soluble in at least one of the good solvents for the photoconductive resins described above. Any of the polycondensates, polyaddition type polymers, ring opening polymerized polymers, and vinyl type polymers can be used for this purpose so long as they have a softening point of at least SCFG , can form films with superior flexibility, and are compatible with the photoconductive resin to an extent such that the result is a shimmering film.

Examples of suitable binder polymers are polycondensates, for example amorphous saturated copolyesters from a Acid component such as terephthalic acid, isophthalic acid, phthalic acid or adipic acid and a glycol component such as ethylene glycol, Propylene glycol, neopentyl glycol or tetramethylene

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glycol, oil-modified alkyd resins, polycarbonates of the bisphenol A type and phenoxy resins and epoxy resins, polyaddition type polymers such as polyurethane resins with aliphatic polyesters as the soft segment, vinyl type polymers such as polystyrene, polyacrylates, polymethacrylates, polyvinyl acetate, polyvinyl chloride and copolymers comprising any of these materials- ·. s contained as a component, as well as polymerized by ring opening Polymers such as polyepichlorohydrin. For certain applications it is necessary that the photosensitive layer is transparent. In these cases it is necessary to choose resins which are particularly well tolerated. As noted above, some of the halogen-containing polymers act as sensitizers. These binder polymers can also can be used in combination of two or more.

(iv) Preparation of the electrophotographically sensitive layer

In general, the electrophotographically sensitive layer according to the invention is made by dissolving certain amounts the photoconductive resin with or without a sensitizer and the binder polymer in an organic solvent, absorption the resulting solution on a carrier and then dried the same. For certain applications, For example, finely divided silica added to give graphic properties or a matte finish to the photosensitive Layer to yield.

The dissolution of the above components in the solvent can be carried out either by dissolving a mixture of them Components or dissolving these components in a solvent in a desired order or dissolving them carried out separately and mixing of the solutions obtained will. The appropriate concentration of the dissolved material of the solution differs depending on such factors, such as the type of the dissolved components or the method of drawing up, but is generally 5 to 80% by weight, preferably 10 to 60% by weight.

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The method of coating the obtained coating solution on a support may be any method which results in the formation of a uniform photosensitive layer. In general, a support bracket overdraft, a Aufstreichblattüberziehung, a curtain overdraft, a roll overdraft, a Sprühüberziehung or Pinselüber- is applied ¹ draw.

If the solvent remains in the obtained photoconductive layer, inconveniences often arise in a decreased dark resistance, decreased photosensitivity or instability of the photoconductivity to reveal. Therefore, it is preferred to carry out the drying as completely as possible.

In general, the photoconductivity is better with smaller thicknesses of the photoconductive layer, but if this is too low there is a tendency that the electrification voltage caused by, for example, corona discharge becomes, becomes lower. Therefore, in general, the strength that gives the best image is determined experimentally. Usually the thickness of the photoconductive layer is 2 to 30 μ, preferably 4 to 15 μ.

The support for forming the photosensitive layer is usually selected from metal plates, for example made from aluminum, zinc, copper, nickel or iron, sheets of paper, plastic films or glass plates. If the support is a good electrical insulator, the surface on which the photosensitive layer is formed must be subjected to a treatment which makes it electrically conductive. All methods of such treatments can be used as long as they do not adversely affect the photoconductive sensitive layer and result in a surface ^{resistance of not more than 10 10} ohm / cm, preferably not more than 10 ohm / cm.

As stated above, the application is more organic

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Photoconductors according to the invention are suitable for light-sensitive layers for obtaining transparent or translucent electrophotographs and consequently plastic films, paper sheets and glass plates are often used as bases . Therefore, in many cases, these principles require treatment to form a transparent ^managerial: the layer thereon. For example, this treatment can be carried out by a method which consists in drawing up or impregnating a polymeric electrolyte such as poly-N-trimethylbenzylammonium chloride or polysodium styrene sulfonate on or in the surface of the base material with the formation of a conductive layer, a method which consists in the vacuum deposition of a metal such as aluminum, copper, gold or palladium in a thin layer on the base surface, a method which consists of applying an oxide, for example indium oxide, on the base surface by vacuum vapor deposition or spraying and then increasing the transparency, for example by oxidation, or a method where a vacuum deposited layer of copper is formed and it is converted into a copper iodide layer using iodine. The formation of a conductive layer using an electrolyte is very cheap and the transparency of the layer is good. However, since there is ionizing conduction, the resistance value of the conductive layer varies according to the degree of moisture absorption. The indium oxide layer or the copper iodide layer has good transparency and conductivity, but it requires a complicated process for production and the cost of production is high. An ultra-thin metal coating is cheaper than an indiurium oxide layer or copper iodide layer because no post-treatment is required, but it has the defect of reduced transparency. According to the desired purpose, an appropriate method is made

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selected.

(ν) Properties and usefulness of the electrophotographically.sensitive layer

That used as the photoconductive base material of the electrophotographically sensitive layer according to the invention amine-containing photoconductive resin can be obtained from commercially available raw materials materials can be obtained very easily at low cost through a simple reaction and has one with the usual ladders of low molecular weight and polymeric organic conductors comparable sensitivity. By combining the same With a suitable sensitizer and / or binder polymer, electrophotographically sensitive layers with superior Usability can be obtained according to the requirements of the end use purposes, having a superior flexibility or transparency or superior near-ultraviolet light transmission in making a diazo duplicate own as a second master image.

Therefore, the electrophotographically sensitive layer according to the invention can be used within a very wide range of the applications are used. For example, by forming a photosensitive layer on a A light-sensitive sheet formed from a plastic film as a microfilm, microfish or as a second master image sheet, which is produced by direct Enlargement of a microfilm was obtained, as a transparency sheet for overhead projectors or as a slide for slide projectors be used. A photosensitive paper made using paper as a base can be used as coated paper copy for business offices and as photosensitive Paper for second master images can be used.

Further, when the photosensitive layer is formed on a metal plate, the image can be a drawing be formed thereon in place of the applied lettering at the time of metal cutting.

Furthermore, a photosensitive transfer drum for plain paper copying by forming the photosensitive layer on the metal drum.

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According to the invention, electrophotographically sensitive Layers having a sensitivity expressed as a half-fall exposure amount under white light from a tungsten filament lamp as a light source, from 2000 to 10 lux-sec can be easily obtained. This sensitivity is perfectly adequate if it is good Sensitizers are chosen. The following examples and comparative examples illustrate the invention in detail.

Before the examples, a description of the materials and test methods used in the examples is given. (I) Soluble low molecular weight polycondensate (1) Xylene / formaldehyde resin
Manufacturing

A reactor was charged with 106 g m-xylene, 129 g of a 37 & lgen aqueous formaldehyde solution (formalin) and 98 wt.% Sulfuric acid were charged and the reaction started at 95 ⁰ G with stirring. The reaction was carried out for 6 hrs., And the temperature eventually rose to 104 ⁰ C. After the reaction, the aqueous phase at the bottom (sulfuric acid phase) was separated and the oil phase obtained was steam-distilled at 10O ⁰ C at atmospheric pressure. 107 g of a xylene / formaldehyde resin were obtained.
Properties

Average molecular weight about 390

Oxygen content about 8.7% wt.

Acid number 0.2

Viscosity 74 cP (determined

for a toluene solution with a xylene resin concentration of 80 wt

Composition of the functional groups

The NMR spectrum of the xylene / formaldehyde resin was below Use of de ^ terochloroform (CDCX *) as a solvent and the following peaks were noted:

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ppm

(1) Ar-CTi ₃ 2.26 (m)

(2) Ar-CH ₂ OCH ₃ 3.32 (m)

(3) Ar-CH ₂ -Ar 3.84 (m)

(4) Ar-CH ₂ (OCH ₂ ^ Ar | _{4> 5 (ffi)} Ar-CH ₂ OH J

( ⁺ In (1) to (4) Ar means an aromatic ring)

(5) phenyl proton 7 (m)

In the above peak according to (4), the peaks of ArCH ₂ (OCH ₂ - ^ 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 OOCCH _{3 was} 1.8 ppm (Ar-CH ₂ OOCCH ₃ 4.8 ppm). These peaks were separate from the peak of Ar-CH ₂ (OCH ₂ -) - Ar ¹ and the functional group composition calculated for each peak was as follows:

% (Moles of each functional group per benzene ring)

Ar-CH ₂ OH 2.2 0.10 Ar-CH ₂ OCH ₃ 6.7 0.21 Ar-CH ₂ -Ar 4.2 0.48 Ar-CH ₂ (OCH ₂ - ^ Ar 9.8 0.32

(2) Highly condensed xylene / formaldehyde resin

This resin was obtained by further condensing the above xylene / formaldehyde resin (1). properties

Weight average molecular weight. 1300

Acid number. below

Softening point (ring and ball method) 105 to 125 ⁰ C

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Composition of the functional groups

Functional groups moles of functional groups

Ar-CH ₂ -Ar 0.70

Ar-CH ₂ (OCH ₂ ^ -Ar 0.17

(3) Resole resin

This resin was obtained by condensing a mixed cresol

(m: p = 6: 4) and formaldehyde using sodium hydroxide

obtained as a catalyst.

properties

Weight average molecular weight 270

Viscosity 0.45 poises

Content of non-volatile substances 55 % (135 ⁰ C,

7 hours)

Specific weight (25 ^C C) ■ 1.020 Composition of the functional groups

Functional groups moles of each functional group. Per benzene ring

Ar-CH ₂ -Ar 0.4

Ar-CH ₂ OH ■ 0.5

(II) binder

(a) vinyl acetate resin

This resin was made by polymerizing vinyl acetate

obtain.

properties

Weight average molecular weight 1

Volatile material below 3 wt.%

Viscosity 1 200 cP,

(determined at 3OO with a Solution with 50 wt. ^ Of the resin in methanol)

Transparency 95 %,

(determined with a 10bigen solution at 480 m, below)

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ο, 78 x10 ^j cP 1,
cc 20th
IN THE 87 to 88 ⁰ C 1.47

Apparent density Specific gravity (25 ⁰ C) softening point melting point
Melt viscosity (170 ⁰ C)

(b) acrylic resin

This resin was obtained by polymerizing methyl acrylate, butyl methacrylate and acrylic acid in a weight ratio of 20: 778: 1.
properties

Acid number 3.7

Weight average molecular weight 2500

Solids content 49.8 wt. $ 6

(c) polycarbonate resin

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

Weight average molecular weight about 35,000

Specific weight 1.4

Oxidation initiation temperature ^{300 0 C}

(d) ester resin

This resin was obtained by copolycondensation of an acid component composed of 46 mol% terephthalic acid and 54 mol% isophthalic acid and a glycol component composed of 45 mol % 6 ethylene glycol and 55 mol% neopentyl glycol. Properties

Weight average molecular weight about 1700

Specific gravity 1.26

Intrinsic viscosity 0.53,

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

Softening point 163 ^° C

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(e) polystyrene resin

This consisted of a commercially available styrene resin, obtained by polymerizing styrene monomer and had a weight average molecular weight of about 1,000,000 and a density of 1.045.

(f) vinyl chloride copolymer

This resin was obtained by copolymerizing 91 moles 6 of vinyl chloride, 3 moles of vinyl acetate and 6 moles of 1% vinyl alcohol.
properties

Average size by weight

the polymerization. about 420

Apparent density 0.65

Volatile matter content 3 %

Solution viscosity 220 cP,

determined with a 20% solution in a 1: 1 mixture of methyl isobutyl ketone and toluene at 25 ^c above sea level.

(g) alkyd resin

A commercially available modified alkyd resin was used, which was prepared by reacting glycerine and coconut oil to form a monoglyceride, which was then reacted with phthalic anhydride. 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 VY.
(III) carrier

The following materials were used as a support, on which the electrophotographically sensitive layer was formed.
(a) aluminum pxatte

An aluminum plate with a thickness of 300 μ, the surface of which is polished with emerald of a fineness of 1000 was.

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(b) Electrically conductive drawing paper

A sheet of drawing paper for general engineering drawing was placed in a 10% aqueous solution of polyvinylbenzyltrimethylammonium chloride dipped and dried. Both surfaces of the drawing paper thus had a coating of polyvinylbenzyltrimetl ^ lanimonium chloride in an amount of 2 g / m. This paper is called "T-paper".

(c) Electrically conductive polyethylene terephthalate film

A 100 micron thick biaxially oriented polyethylene terephthalate film was in a 1O ^ ige aqueous solution of polyvinyltrimethylammonium chloride dipped and dried. Both surfaces of the film were thus coated with polyvinylbenzyltrimethylammonium chloride in an amount of 2 g / m. This film is referred to as "PET film".

(d) Metal deposited film

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

(IV) Preparation of the test pieces to determine the light-sensitive 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. A solution containing 1% by weight of the sensitizer in dimethylformamide was prepared and mixed with the above solution and then ent. ' well stirred. The solution obtained was drawn onto a support by means of a window covering device or a carrying handle and applied at 70 ^° C. for 15 hours to form a sensitive layer with a thickness of about 7 μm

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dried on the carrier.

(V) Method for determining the photosensitive properties

A voltage of -6 kV was applied to a square test piece measuring one side about 10 cm below Application of a corona discharge device of the corotron type applied at a "speed of 5 m / min. The surface potential the specimen was then measured by a high level surface potentiometer. The high-level surface potentiometer was connected to a recording device which determined the measured potential. The used The light source was a 30 ¥ - ¥ olefin filament lamp, if nothing other is indicated. It was attached in a position 49 cm from the specimen. The lighting intensity the lamp in this position was 50 lux.

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

Half-waste _{exposure (E ^ 0} ) = L χ t (lux.sec)

An electric charge was applied to the test piece by corona discharge in the dark room, and its potential (V) was read after the lapse of 35 seconds. At the end of this 35 second period, light with an illuminance of L lux was irradiated onto the specimen from a filament lamp. The time (t sec) until the potential (V _Q ) reached the value V _Q / 2 was read. (VI) Method of determining the reproduced images

After measuring the half- _{decay exposure time (Ec 0} ) in the dark room, a corona discharge of -6 kV was applied to the entire surface of the specimen at a speed of 5 m / min. The specimen was exposed imagewise using a test card to light from a 30 W filament lamp which had an amount of illumination 4 times that of the semi-waste exposure. The exposed sample was developed with a liquid or dry

609837/0899

development as indicated below.

(1) Liquid development

The exposed sample was immersed in a dispersion of a toner (particle size 0.1 to 1.0 μm) for a few seconds. The toner dispersion was obtained by kneading well a mixture of 15 g of Pentarol 20 (trade name), 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 dispersing the mixture in 3 1 isoparaffin (Cg to C.c mixture) has been prepared using ultrasonic oscillation. Pentarol 20 is a phenol modified pentaerythritol ester of rosin (having an acid number of 10, a specific Gev / layer at 2 CFC of 1.09 and a melting point of 110 to 12O ⁰ C).

(2) dry development (magnetic brush development)

200 parts by weight of reduced iron powder with a size from 150 to 300 mesh was made with 5 parts by weight of one Toner from 1 part by weight of a styrene / butadiene copolymer, 0.05 part by weight of polystyrene, 0.1 part by weight of carbon black and 0.18 parts by weight of oil black that had been melt blended, mixed, cooled and pulverized to an average particle size of 10 μ. The toner used had one Particle size from 5 to 25 μ. The obtained mixture was adhered to a bar magnet and exposed by rubbing with it Contacted test piece for its development.

The images obtained were rated on the following scale:

Excellent: Very clear print images were obtained.

Good: Despite a few errors, the printed images were practically satisfactory.

Bad: There was heavy fog and the images were unclear or no printed images were observed.

609837/0899

example 1

(1) Preparation of the soluble aromatic tertiary amine-containing Resin

A 100 ml three-necked flask was filled with 17 g of the xylene / formaldehyde resin, 16.7 g (0.1 mol) of carbazole and 0.17 g of 2,5-diniethylbenzenesulfonic acid, hereinafter referred to as m-xylene sulfonic acid, as The catalyst is charged and the materials are ^{reacted at 200 °} C. in a stream of nitrogen. The reaction product was dissolved in 50 ml of toluene at room temperature. 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 tertiary amine-containing resin which had the following properties:

Melting point 135 ⁰ C

Inherent viscosity 0.26

N content 4.16% by weight

Aromatic · Amine group content: 0.70 per benzene ring

NMR spectrum peak (12.3 ppm) on the ba

sis of> NH of the carbazole was not observed

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

2 g of the above obtained according to (1) tertiary amine-containing resin was dissolved in 10 ml of chlorobenzene at 20 ⁰ C to form a solution.

On the other hand, metallic indium was raised in vacuo

the surface of a polyethylene terephthalate film with a

2 thickness of 75 I- and an area of 10 cm deposited and then oxidized in air to form a transparent conductive film with a resistance of 400 ohms / cm.

The resulting solution was drawn up on the surface of this film using a disk coater

609837/0899

and at 7 (K! for 15 hours to form a light-sensitive Layer with a thickness of 7 μ dried.

The semi-waste exposure (E ₅₀ ) of this photosensitive layer, determined using light with an illumination intensity of 10,000 lux from a 300 W filament lamp, was 1.8 × 10 lux.sec. After the lapse of one month, the coating was still adhered to the polyethylene terephthalate film and no precipitate appeared on the surface, and the photoconductive layer had a transparency of more than 70 %.

Comparative example 1

10 g polyvinyl carbazole (Luvican M-170, product of BASF) were pulverized and dissolved in 100 ml of methylene chloride and reprecipitated with 1000 ml of purified methanol and then dried. This procedure was carried out three times to purify the polyvinyl carbazole. 1 g of the purified Polyvinyl carbazole was dissolved in 10 ml of chlorobenzene to form a 10% solution.

In the same way as in Example 1, the solution drawn onto the aluminum plate to form a coating. The semi-waste exposure (Ej-q) of this coating is determined in the same manner as in Example 1, was 1.6 10 lux.sec.

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

When the polyvinyl carbazole solution on the transparent conductive polyethylene terephthalate film was drawn up in the same manner as in Example 1, the photosensitive one peeled off Coating and it was impossible to determine the photosensitive properties of the coating and evaluate the print images.

609837/0899

Examples 2 to 18

600 mg of the tertiary amine-containing resin obtained according to Example 1 (1), binder and chemical sensitizer, as listed in Table I, were with each of the solvents listed in Table I to form a Mixed solution.

The solution was mixed with a separately prepared solution of each of the sensitizers listed in Table I with 1% by weight of 5 ¹ O in dimethylformamide with stirring at room temperature. The resulting mixture was coated on each of the supports shown in Table I using a rotary coating machine and dried to give a photosensitive layer having a thickness of 7 µm.

The half-waste exposure (E ₅₀ ) of the photosensitive layer and the quality of the printed images were determined and the results are shown in Table I.

609837/0899

Table I. example

Tertiary amine

containing resin

(mg) 600 600 600 600 600 600

Solvent N-methylpyrro- methylethyl- methylethyl- methylethyl- methylethyl- methylethyl- (ml) lidone (3) ketone (3) ketone (3) ketone (3) ketone (3) 'ketone (3)

Binder (mg)

solvent
(ml)

Ester resin (400)

N-methylprrolidone (2.0)

Ester resin
(100)

Ester resin
(100)

Ester resin
(100)

Ester resin (100)

Ester resin (100)

Methylethyl- methylethyl- chlorobenzene
ketone (0.50) ketone (0.50) (0.50)

Methyl ethyl methyl ethyl ketone (0.50) ketone (0.50)

Chemical sensitizer
to (mg)
co

** ί solvents
^ (ml) *

1,4,5,8-naphthalenetetracarboxylic acid (300)

N-methylpyrrolidone (3.0)

Bis- (4-dime- bis (4-dime- 4-chloro-3-trimellitethylaminophe- thylamino-3-nitrobenzoic acid anhynyl) methane bromophenyl) acid (100) drid (100) (200) methane (200)

Tris (4-dimethylaminophenyl) methane (200)

Methylethyl- methylethyl- methylethyl- methylethyl- chlorobenzene ketone (1.0) ketone (1.0) ketone (1.0) ketone (1.0) (1.0)

Optical sensi
bilizer (mg) - Crystal crystal crystal crystal crystal
yiolet (0.5) purple (0.5) purple (0.5) purple (0.5) purple (0.5) Al Al Al Al carrier Al T-paper 130 360 290 98 Semi-waste
clearance (Ecq)
(lux.sek) 80 163 excellent excellent
net excellent
net excellent
net Evaluation of the
Print images excellent excellent

CT) O OO CD OO NJ

example

Table I (continued
10 11

12th

13th

600

600

600

600

Τθ 3? "Fc i M.3T * ß S containing resin (mg)

Solvent (ml) methylethyl- methylethyl- methylethyl- methylethyl- chlorobenzene methylethyl-

ketone (3) ketone (3) ketone (2) ketone (3) (3) ketone (3)

Binder (mg)

Solvent (ml)

Ester resin (100)

Methyl ethyl ketone (0.50)

Ester resin
(100)

Polystyrene
(100)

Polystyrene
(100)

Polycarbonate
(100)

Ester resin
(100) '

Methylethyl- methylethyl- methylethyl- methylethyl- methyl ketone (0.50) ketone (0.50) ketone (0.50) ketone (0.50) chloride (0.50)

Chemical Sensi- 1,1-bis- (4-bilizer (mg) NjiM'-dibenzyl-

aminophenyl; -butane (200)

(200) 2,2'-Methy- Bis- (4-dime- Bis- (4-dime- Bis- (4-dimelenbis- (4-thylamino-thylamino-thylaminophechlorophenol) phenyl) -me- phenyl) -me- nyl) methane
(200) than (200) than (200) (200)

solvent
(ml) Chlorobenzene
(1.0) Al Chlorobenzene
(1.0) Chlorobenzene
(1.0) Chlorobenzene
(1.0) Chlorobenzene
(1.0) Methylethyl
ketone (1.0) Al T-paper Al Al Optical Sen Crystal
sensitizer (mg) violet (0.5) 228 Crystal crystal crystal crystal crystal
purple (0.5) purple (0.5) purple (0.5) purple (0.5) purple (0.5) 553 163 104 169 carrier excellent
net Al excellent
net excellent
net excellent
net excellent
net Semi-waste
clearance (Ecq)
(lux.sek) 455 Evaluation of the
Print images excellent
net

CD O OO O OO K)

example

Table I (continued) 16 17

18th

19th

Tertiary amine-containing resin (mg)

Solvent (ml)

600

Methyl ethyl ketone (3)

600

600

600

500

Methylethyl- methylethyl- methylethyl- methylethyl- N-methylpyrketone (3) ketone (3) ketone (3) ketone (3) rolidone (5)

Binder (mg)

Solvent (ml)

Ester resin (100)

Methyl ethyl ketone (0.50) ester resin
(100) '

Methyl ethyl ketone (0.50)

Chemical Sensi- 4-Nitrophthalbilizer (mg) acid (200)

co solvent (ml)

Methyl ethyl ketone (1.0) 2,4-dinitro

benzoic acid

Methyl ethyl ketone (1.0)

2,4,7-tri- ( ⁺ 1)
nitrofluo- (300)
renon (300)

300)

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

Methylethyl- methylethyl- tetrahydro- N-methylpyrketone (6) ketone (1.5) furan (6.0) rolidone (1.0)

Optical sensi
bilizer (mg) crystal
purple (0.5) crystal
purple (0, Crystal crystal crystal.
5) purple (0.5) purple (0.5) purple (0.5) - Al Al Al carrier Al Al Al 870 1400 400 Semi-waste
clearing (E ₅₀ )
lux.sec 620 480 14th out
draws out
draws out
draws Evaluation of the
Print images out
draws out
draws out
draws

σ> ο cx> ο co ro

Footnotes

Br

(n is 7 on average)

Copolymer of vinylidene chloride and vinyl chloride (1: 1) having a weight average molecular weight of Burch around 100 000 and a melting point of 85 ⁰ C.

Example 20 and Comparative Example 2

A 100 ml three-necked flask was carried out with 10g of highly condensed xylene / formaldehyde resin, 6.8 g (0.041 mole) of carbazole and 0.10 g of m-xylene sulphonic acid were charged and the reaction for 4 hrs. At 200 ⁰ C in a nitrogen atmosphere . The obtained product was dissolved in 25 ml of toluene at room temperature, and the solution was added to 800 ml of methanol in a mixer with stirring. The resulting precipitate was filtered off and at 7O ³ C and 1 mm Hg abs. dried for 15 hours to give 9.5 g of a white tertiary amine-containing resin having the following properties.

Melting point 115 ⁰ C inherent viscosity 0.12

N content 2.50 %

A peak (12.3 ppm) due to } NH of the carbazole was not observed in the NMR spectrum analysis.

The photosensitive properties of the resulting resin were compared with those of a pure mixture of benzyl

609837/0899

carbazole of the following formula

and the highly condensed xylene / formaldehyde resin (see, Example 2), which has the same nitrogen content as had the above tertiary amine-containing resin. The results are shown in Table II.

609837/0899

Table II example

Photo-conductive.es
Resin (mg)

solvent
(ml)

Example 20

Comparative example 2

Tertiary amine-containing mixture of benzylcarbages resin (600) zol (259) and the highly condensed xylene / formaldehyde condensate (300)

Chlorobenzene (3)

Chlorobenzene (3)

Binder (mg)

solvent
(ml)

Ester resin (100) chlorobenzene (0.5)

Ester resin (100)
Chlorobenzene (0.5)

Chemical sensitizer (mg)

solvent
(ml)

Bis (4-dimethylaminophenyl) methane (200)

Bis (4-dimethylaminophenyl) methane (200)

Chlorobenzene (1.0) chlorobenzene (1.0)

Optical sensi
bilizer Crystal violet Crystal violet carrier Aluminum plate Aluminum plate Semi-waste
clearing (E ₅₀ )
lux.sec 330 not sensitive to yourself
when the light source 5 times
was made so bright Evaluation of the ko
pated images excellent bad

609837/0899

Examples 21 to 31

In the same manner as in Example 1 (1), the Reaction at the temperatures and periods of time given in Table III using the various values given in Table III listed aromatic amines instead of carbazole. Yield, melting point, inherent viscosity and N contents of the obtained tertiary amine-containing resins were determined; the results are shown in Table III.

0.6 g of each of the obtained tertiary amine-containing resins was dissolved in 3 ml of methyl ethyl ketone. 0.1 g of the ester resin were dissolved in 0.5 ml of methyl ethyl ketone. Furthermore, 0.2 g of 2,2 »-Methylene bis (4-chlorophenol) in 1 ml of methyl ethyl ketone solved. Furthermore, 0.5 mg of crystal violet was dissolved in 50 ml of dimethylformamide.

These solutions were mixed at room temperature with stirring and the mixture applied to each of the supports listed in Table III using a disk coater and ^{dried at 70 °} C. for 15 hours to form a photosensitive layer with a thickness of about 7 μ.

The semi-waste exposure of each of the obtained specimens was determined and the printed images obtained were evaluated. The results are shown in Table III.

609837/0899

21 - 56 - 22nd 0.2 23 6th 24 2608082 25th 26th 0.1 10 Example I. 20th 200 5 30th 10 20th 20th 200 example Diphenyl aniline
amine (10) (26.7) 3 Benzyl
aniline
(4.4) 0.08 methyl
aniline
(10.28) α-naphthyl indole
amine (9.2) (7.5) 2 Xylene / mold
aldehyde resin
(G) 0.1 24 0.05 3.75 0.1 0.2 12.3 Aromatic
Amine (g) 200 128 200 Al 200 200 74 m-xylene sulphate
fonic acid
(G) 2 0.13 2 293 3 2 0.08 Reaction
temperature
( ⁰ C) 10.7 4.29 10 18th 5.13 Reaction
time (hours) 68-70 T-paper excellent
drawing 65 59-61 Al Yield (g) 0.09 390 0.10 0.07 1120 Enamel
point ( ⁰ C) 3.75 CTI 4.69 2.60 Intrinsic viscosity
sity Al out
draws Al Al out
draws nitrogen
salary (Sa) 228 293 780 carrier ( ⁺ ) Semi-waste
exposure
^(E 50) Rating excellent
the pressure draws
pictures excellent
; draws out
draws lux.sec

() If only the xylene / formaldehyde resin was used, this value was 3.5 × 10 (determined by the same method as in Example 1)

809837/0899

Table III (continued)

example 27 80-82 . Al Semi-waste
exposure 190O ⁺ 28 29 30th Xylene /
Formalde
hyd resin
(G) 10 above
0.07 lux.sec Well 10 ■ 20 20th Aromati
sches
Amine (g) N, N «-diphe-
nyl-p-phe-
nylenediamine
(12.5) nitrogen
content (%) 5.58 valuation
the pressure
pictures Phenothia
z in
(12.8) N, N »-Diami-
no-diphenyl-
methane
(5.1)
Carbazole
(17.1) o-toluidine
(6.85) m-xylene
sulfone
acid (g) 0.1 carrier 0.1 0.2 0.2 Reaction
temperature
( ⁰ C) 200 200 200 200 Reaction
time (hours) 2 2 2 2 Yield (g) 12.9 15.6 36 18.5 Enamel
point ( ⁰ C) 100 73-75 96-98 Own vis
kosity 0.10 0.07 0.10 4.26 5.03 3.68 Al Al Al 970 1200 975 out
draws out
draws out
draws

⁺ Bis- (4-dimethylaminophenyl) methane was used as a chemical sensitizer.

609837/0899

Comparative example 5

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

and the highly condensed xylene / formaldehyde resin, which the had the same nitrogen content, was used instead of the tertiary amine-containing resin used in Example 22. The photosensitive properties of the coated layer obtained were determined, but they did not show any Sensitivity. If a tungsten filament lamp with an illumination intensity 5 times as large as that above was used the layer did not show any sensitivity either.

Example 51

500 mg of the tertiary amine-containing resin which had been formed between the xylene / formaldehyde resin and diphenylamine according to Example 21, and 500 mg of the tertiary amine-containing resin which was formed between xylene / formaldehyde resin and N, N ^f -diphenyl-p-phenylenediamine was formed according to Example 27, each was dissolved in 6 ml of methyl ethyl ketone with a content of 100 mg of trinitrofluorenone. Each obtained solution was drawn up on an aluminum plate using a disk coater and dried. The measured half-waste exposure was 350 lux.sec and 600 lux.sec. The prints were excellent in both cases.

609837/0899

Examples 52 to 57

Various co-condensation components are used in these examples used.

The xylene / formaldehyde resin, the aromatic amine compound, the co-condensation component and the catalyst (m-xylenesulfonic acid) were in those listed in Table IV Conditions implemented at the temperatures and times indicated in Table IV. Yield, melting point, inherent viscosity and nitrogen content of the obtained tertiary amine-containing resins were determined; the results are in Table IV listed.

Using each of the obtained resins, electrophotographically sensitive layers were made in the same Made as in Example 1 (unsensitized) and the half-waste exposure and the quality of the printed images were rated.

On the other hand, using each of the obtained resins, electrophotographically sensitive layers became correspondingly the approach of Example 19 (in the case of Examples 32 to 35) and the approach according to Example 10 (in the case of Examples 36 and 37) and the semi-waste exposure and the quality of the printed images were determined.

The results are shown in each case in Table IV.

809837/0899

not-
sensitive
lized
sensi-
bili-
sated 32 - 60 - *
34. 35 2608082 37 400 Table IV 40 20th 10 Carbazole
(200) 33 Carbazole
(20) Carbazole
(20) 36 methyl
aniline
(10.2) At Soiel Anthracene
(200) 20th Anthracene
(10)
tert-Bu-
ty! phenol
(10) tert-Bu-
tylphenol
(5) 10 p-chlorine
phenol
(6, S) Xylene / form
aldehyde resin
(G) 4th Carbazole
(20) 0.4 0.2 Benzyl
aniline
(8.8) 0.1 Aromatic
Amine (g) 200 Tetra
chlorine-
xylene
(D 200 170 p-chlorine
phenol
(7.5) 200 Co-condensa-
tion compo-.
nente (g) 2 0.2 4th 4th 0.1 2 m-xylene sulphate
fonsäure (g) 644 200 62 22.9 200 144 Reaction
temperature ( ⁰ C) 129-133 4th 130 154 2 52-53 Reaction
time (hours) 0.12 29.2 0.07 0.07 16.3 0.07 Yield (g) 2.27 151 1.90 3.68 46 5.79 Enamel
point ( ⁰ C) 1.4x1O ⁴
200 0.08 1.6x1O ⁴
150 1.4x10 ⁴
210 0.08 1.7x10 ⁴
488 Own vis
kosity 4.14 4.98 nitrogen
salary (%) 9000
120 1.8x1O ⁴
780 Semi-waste
exposure
Clux.sek)

S09837 // OB'99

Examples 58 to 55

The tertiary amine-containing resin obtained in Example 32 (Co-condensate from xylene / formaldehyde resin, carbazole and Anthracene) was made with all of those listed in Table V. Binders, chemical sensitizers and optical sensitizers in the proportions listed in Table V. mixed. The resulting mixtures were drawn onto each of the supports given in Table V and dried. The photosensitive properties of the photosensitive layers obtained were determined; the results are included in Table V.

6098 3 7/0839 COPY

example

Tertiary amine-containing resin (mg)

Solvent (ml)

38

39

Table V 40

41

42

Solvent (ml)

Chemical sensitizer (mg)

Solvent (ml)

Optical sensitizer (mg)

carrier

Half-waste exposure

(lux.sek)

Evaluation of the print images

600

Methyl ethyl ketone (3)

Binder (mg) ester

ηεΓΖ (400)

Methyl ethyl ketone (2.0)

2,4,7-trinitro-fluorenone (400)

Methyl ethyl ketone (2.0)

Crystal violet (0.5)

Al

130

600

Methyl-

ethyl-

ketone (3)

Ester resin (200)

Methyl ethyl ketone (1.0)

Trimellitic anhydride (100)

Methyl ethyl ketone (0.50)

Crystal violet (0.5)

600

Methylethyl
ketone (3)

Ester resin
(200)

Methylethyl
ketone
(1.0)

- 4-chloro-3-nitrobenzoic acid
(100)

Methyl ethyl ketone
(0.50)

Crystal violet
(0.5)

Al

90

600

Chlorobenzene (3)

Ester resin (200)

Methyl ethyl ketone (1.0)

p-bromine

phenol

(100)

Methyl ethyl ketone (0.50)

Crystal violet (0.5)

Al

120

excellent, excellent, excellent, excellent

600

Chlorobenzene (3)

Polystyrene

(100)

Chlorobenzene (0.5)

Bis (4-dimethylaminophenyl) methane (100)

Methyl ethyl ketone (1.0)

Crystal violet (0.5)

Al

104

excellent

609837/0899

COPY

example

45 Table V (continued;) 45 46

47

Tertiary amine-containing resin (mg)

Solvent (ml)

Binder (mg)

Solvent (ml)

Chemical sensitizer (mg)

Solvent (ml)

Optical sensitizer (mg)

carrier

Half-waste exposure

(lux.sek)

Evaluation of the print images

600

Methylene chloride (3.0)

Polycar

bonat

(100)

Methylene chloride (1.0)

Bis- (4-dimethyl- aminophenyl) methane (200)

Methyl ethyl ketone (1.0)

Crystal violet (0.5)

Al

.169

excellent

600

Methyl ethyl ketone (3.0)

Alkyd resin (100)

Methyl ethyl ketone (0.50)

Bis (4-dimethyl aminophenyl) methane (200)

Methyl ethyl ketone (1.0)

Crystal-

violet

(0.5)

Al

176 600

Methylethyl
ketone
(3.0)

600

Methyl ethyl ketone (3.0)

Polyvinyl acrylic acetate resin (100) (200)

Methylethyl
ketone
(0.50)

4-chlorine

3-nitro-

benzene

acid

(50)

Methyl ethyl ketone
(1.0)

Crystal violet
(0.5)

PET film

390

Methyl ethyl ketone (1.0)

Trimellitic anhydride (100)

Methyl ethyl ketone (1.0)

Crystal violet (0.5)

T-paper

165

600

Methyl ethyl ketone (3.0)

Ester resin (100)

Methyl ethyl ketone (0.5)

excellent- excellent- awarded

Kayaset-Blue BOH (0.5)

Al

860

excellent

600

Methyl ethyl ketone (-3.0)

Ester resin (100)

Methyl ethyl ketone (0.5)

Vietorit Pure Bl \ BOH (0 ,:

Al

800

excellent

609837/0899

ORIGINAL INSPECTED COPY

example ^? Tabel 50 V (continued 52 600 Ester resin
(100) • Mt - Ester resin
(400) 53 54 Ester resin
(400) crystal
violet
(0.5) crystal
violet
(0.5) Phthalic acid
anhydride
(200) 55 Tertiary amine
containing resin
(mg) 600 600 51 Methylethyl- methylethyl- methylethyl-methylethyl-
ketone (3.0) ketone (3.0) ketone (5.0) ketone (3.0) Methylethyl- methylethyl-
ketone (0.5) ketone (0.5) - - Methylethyl
ketone (2.0) 600 600 Methyl ethyl methyl ethyl
ketone (2.0) ketone (2.0) Al Al • methylethyl
ketone (1.0) 600 solvent
(ml) 600 Ester resin
(100) Methylvio-
lett-pure-
Special
(0.5) 2,4,7-tri-
nitrofluo-
renon 4-chloro-3-
nitrobenzoe-r
acid (100)
Trimellite
acid anhy
drid (100) Methylethylchlorobehzol
ketone (3.0) (3.0) m-nitrobene
zoic acid
(200) 146 260 crystal
violet
(0.5) Tetrahydro
furan (3.0) Binder (mg) - Al Ester resin
(400) Methyl ethyl - methyl ethyl - methyl ethyl
ketone (2.0) ketone (1.0) ketone (1.0) out
draws out
draws Al Ester resin
(400) solvent
(ml) Turqui-
oise blue
776 (0.5) 890 195 Tetrahydro
furan (2.0) More chemical
Sensibilisa
goal (mg) Al out
draws Al out
draws 2,4,6-tri-
chlorphe-
nol (200) O) solvent
(ml) 860 200 Methylethyl
ketone (1.0) O
co
OO Optical Sen
sensitizer
(mg) out
draws out
draws Krista "! 1-
violet
(0.5) 37/08 carrier Al 1 co
co Semi-waste
exposure
(lux.sek) 180 ' Evaluation of the
Print images out
draws
K>
CD
0
00
O
OO

Example 56

500 mg of the tertiary amine-containing used in Example 35 Resin (co-condensate of xylene / formaldehyde resin, carbazole, anthracene and tert-butylphenol) and 100 mg of 2,4,7-trinitrofluorenone were dissolved in 6 ml of methyl ethyl ketone. The obtained solution was coated on the aluminum plate using a rotary coating machine and dried. Half-waste exposure amount of the obtained photoconductive Shift was 95 lux.sec. The printed images were of excellent quality.

Beis-Diele 57 and 58

10g of the same tertiary amine-containing resin as in Example 1 (1) obtained was dissolved in 50 ml of chloroform, and the solution with a solution of 8 g of bromine in 80 ml of chloroform contacted for bromination of the resin. 8.6 g of a modified tertiary amine-containing resin were included obtain the following properties:

Melting point 175 to 178 ^° C

Inherent viscosity 0.09

Bromine content 28.84 wt

Nitrogen content, 2.89 % by weight

Ratio of aromatic amine groups per benzene nucleus 0.78

The obtained tertiary amine-containing resin was mixed with the binder resin, the chemical sensitizer and the optical Sensitizer as shown in Table VI mixed to form the coating solution. The coating solution was mounted on the aluminum plate and dried. The semi-waste exposure of the obtained photosensitive Layers and the quality of the printed images were determined;

609837/0899

the results are given in table VT,

Table VI

Beis-Diel

Tertiary amine-containing resin (mg)

Solvent (ml)

Binder (mg)

Solvent (ml)

Chemical sensitizer

Solvent (ml)

Optical sensitizer (mg)

Half-waste exposure

(lux.sek)

Evaluation of the print images

57

600

600

Methyl ethyl ketone chlorobenzene (3.0) (3.0)

Ester resin (100) Ester resin (100)

Methyl ethyl ketone chlorobenzene (0.5) (0.5)

Bis- (4-dimethyl- 4-chloro-3-nitro-

aminophenyl) benzoic acid

methane (200) (200

Methyl ethyl ketone (1.0)

Crystal violet (0.5)

98

excellent

Chlorobenzene (1.0)

Crystal violet (0.5)

410

excellent

example

500 mg of the brominated tertiary amine-containing resin used in Example 58, 300 mg of 2,4,7-trinitrofluorenone and 50 mg of crystal violet were dissolved in 10 ml of methyl ethyl ketone. The resulting solution was placed on an aluminum plate drawn up using a disc coater and dried. The semi-waste exposure of the obtained photosensitive layer was 14 lux.sec, which is a

609837/0899

means very high sensitivity. The quality of the received The printed image was excellent.

Example 60

A 100 ml DreiJialskolben was stirred with 23.5 g (non-volatile content 52%) of a resol resin, 16.7 g of carbazole and 0.2 g of m-xylene sulphonic acid were charged and this at 80 ⁰ C for 1 h. In a nitrogen atmosphere, to to distill off the volatile components contained in the resole resin. The reaction was continued for another 2 hrs. At 230 ⁰ G, giving 22 g of a dark brown tertiary amine-containing resin. 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 resole resin.

The obtained tertiary amine-containing resin had the following properties:

Melting point above 300 ^° C

Inherent viscosity 0.274

Nitrogen content 5.79% by weight

Aromatic amine content

1.41 per benzene nucleus

The obtained product was dissolved in N-methylpyrrolidone to form a solution. The solution was drawn onto the aluminum plate by means of a disk coating device and dried in a vacuum dryer (1 mm Hg abs.) At 70 ³ C for 12 hours. The half-dropout exposure amount of the obtained photoconductive layer, determined using a 100 W filament lamp of 300 lux, was 7,500 lux.sec.

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Comparative example 4

10.7 g (0.10 mol) of N-mono-methyl aniline, 7.5 g (0.10 Hol) 379 & strength formaldehyde (formalin) land 12 ml concentrated hydrochloric acid were added to a 100 ml three-necked flask and stirred at 100 ⁰ C during 8 hours implemented. The reaction product was neutralized to pH 7 using a sodium carbonate solution. The solid was filtered, washed with water ^{and dried at 50 3} C and 1 mm Hg for 12 hours and gave 10.8 g (melting point 85 to 86 ⁰ 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-monomethylaniline and formalin.

The coating was applied in the same manner as in Example 20 using the obtained condensation product tries. However, it had poor solubility in common solvents and was uniform Coating could not be obtained.

609837/0899

Claims (16)

Claims (Λ J Electrophotographically sensitive layer, characterized in that it contains at least one soluble aromatic tertiary amine-containing
Resin as the photoconductive base contains, the soluble
aromatic tertiary amine-containing resin from a reaction product (1) A soluble low molecular weight polycondensate containing residues of a benzene compound of the following formula 0 (1-A) wherein 0 is the radical of a benzene compound with a valence of at least 1 and with at least one nitrogen-free means electron-donating nucleus substituents, the carbon atoms of the radicals of the benzene compound by a linking group represented by the following formula -CH ₂ (OCH ₂ - ^ (1-B) are connected, wherein m is the number O or a positive one
represents an integer from 1 to 4, and at least one of the radicals of the benzene compound represents at least one pendant (pendant) group of the following formula -CH ₂ X (1-C) 809837/0899 contains, in which X is a hydroxyl group, an alkoxy group, an O-acyl group or a halogen atom, as substituents on the carbon atoms of the benzene ring in principle contains
(2) an aromatic amine compound represented by the following formula H
Ar-4 N - Y) _n (2) wherein Ar represents an aromatic group, the group H
■ f NY) is bonded to the carbon atoms of the aromatic ring, η denotes the numbers 1 or 2 and Y denotes a hydrocarbon residue, which optionally forms a ring with Ar either directly or via a nitrogen, oxygen or sulfur atom and, if η is 1, Y may represent a hydrogen atom, the methylene group bonded to the carbon atom of the benzene ring substituting the hydrogen atom bonded to the nitrogen atom forming the amino group of the aromatic amine compound of the formula (2). 2. Electrophotographically sensitive layer according to claim 1, characterized in that the soluble aromatic tertiary amine-containing resin is a solvent-soluble resin made from a benzene compound the following formula ■ (3) 609837/0899 where 1, 1 «, q and r are positive integers, [1 + qxr] has the fourth 1, 2, 3 or 4, 1 »is a positive integer from 0 to 4 and q is the number O or 1 and, if q has the value O, the grouping denotes a hydrogen atom, r has the value O or 1 and, if r has the value O, the benzene ring C is bonded directly to the carbon atom of the benzene ring B and A and A ^{1 are} identical or different and at least one group from the class of the alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, a hydroxyl group or a halogen atom, and if 1 or I ¹ is 2 or more, A or A ¹ can represent different groups from the above classes and at least one of the radicals A and A ^{1 must represent} an electron-donating group from the above class, the benzene rings B or C being connected essentially via a methylene group and the resin attached to the benzene rings having at least one aromatic N-methyleneamino group of the following formula 809837/0893 "wherein Ar represents an aromatic group which group -4 N - Y) bonded to a core carbon atom of the aromatic group is, η has the value 1 or 2 and Y is a carbon / hydrogen radical or denotes a hydrogen atom and optionally a ring together with Ar either directly or via forms a nitrogen, oxygen or sulfur atom or optionally on the benzene ring B or C of the formula (3) is bound via a methylene group, contains 0.5 to 1 benzene ring. 3. Electrophotographically sensitive layer according to claim 1 or 2, characterized in that that the soluble aromatic tertiary amine-containing resin has an inherent viscosity, determined at 3CK! with a solution this resin dissolved in N-methyl pyrrolidone to a concentration from 0.5 g / 100 ml, from 0.03 to 0.8, 4. Electrophotographically sensitive layer according to claim 1 to 3, characterized in that that the benzene type compound consists of m-xylene. 5. Electrophotographically sensitive layer according to claim 1 to 4, characterized in that that the aromatic amine compound consists of a compound of the formula H Ar -f N - Y) _n (2) .is in which Ar is an aromatic group with a benzene or Means naphthalene nucleus with 6 to 15 carbon atoms, where the benzene or naphthalene nucleus optionally 1 to "609837/0899 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, N, N-di-lower alkyl-substituted amino groups and halogen atoms, η the numbers 1 or 2 and Y is an aliphatic hydrocarbon residue having 1 to 10 carbon atoms or an aromatic group having the same definition as Ar and having the same substituents _; . as listed above with regard to Ar, where, if η is 1, Y can be a hydrogen atom and Y and Ar optionally form a ring which is bonded to one another either directly or via a nitrogen, oxygen or sulfur atom . 6. Electrophotographically sensitive layer according to claim 1 to 5, characterized in that that the aromatic amine compound of aniline, toluidine, N-methylaniline, N-ethy! aniline, N-benzylaniline, carbazole or diphenylamine. 7. Electrophotographically sensitive layer according to claim 1 to 6, characterized in that that in the soluble aromatic tertiary amine-containing resin (1) the ring carbon atoms of the benzene compounds, (2) the nitrogen atom constituting the amino group of the aromatic amine compound and (3) 0.1 to 3 moles, per mole of the aromatic amine compound, from (3a) the ring carbon atoms of the aromatic compound with at least three aromatic rings and / or (3b) the ring carbon atoms of an aromatic phenolic compound with at least one phenolic hydroxyl group 609837/0899 as a substituent on the carbon atom of the aromatic ring,
are practically bound via a methylene group. 8. Electrophotographically sensitive layer according to claim 7, characterized in that the aromatic compound (3a) with at least three aromatic rings consists of anthracene, perylene or phenanthrene and the aromatic phenol compound (3b) consists of phenol, o-cresol, m-cresol, p -Cresol, mixed cresol _f ^: 3 »5-xylenol or tert-butylphenol. 9. Electrophotographically sensitive layer according to claim 1 to 8, characterized in that that the soluble aromatic tertiary amine-containing resin is mixed with at least one optical sensitizer and / or chemical sensitizer and at least one solvent-soluble binder polymer with compatibility with the tertiary amine-containing resin to the extent that when blended with the aromatic tertiary amine-containing resin it allows the formation of a translucent or transparent film. 10. Electrophotographically sensitive layer according to claim 1 to 9, characterized in that it consists of a mixture of the aromatic tertiary amine-containing Resin, the optical sensitizer, the chemical sensitizer and the polymeric binder. 11. Eiektropho ^J .ographically sensitive layer according to claim 9 or 10, characterized in that the chemical sensitizer has the properties of an electron acceptor or consists of a halogen-containing organic compound. 609837/0899 12. Electrophotographically sensitive layer according to claim 9 to 11, characterized in that the chemical sensitizer consists of a halogenated phenol or derivatives thereof. 13. Electrophotographically sensitive layer according to claim 9 to 12, characterized in that that the optical sensitizer consists of a triaryl methane type dye compound. 14. Electrophotographically sensitive layer according to claims 1 to 10 and 13, characterized in that that the soluble aromatic tertiary amine-containing resin has an aromatic tertiary amine group which differs from Carbazole or ring-substituted derivatives derived therefrom, contains and mixes therewith at least one chemical Sensitizer of the following formula V / \ V / wherein fL to R ^ are the same or different and an alkyl group, alicyclic group or aralkyl group with 1 to 7 carbon atoms, R ₁ - at least one hydrogen atom or an alkyl group, alicyclic group, aryl group or aralkyl groups with 1 to 7 carbon atoms or the grouping 609137/0899 and
Rß / Ry are the same or different, and a lower alkyl group having 1 to 3 carbon atoms or a halogen atom and ρ and p ^{f are} an integer from 0 to 2 contains. 15. Soluble aromatic tertiary amine-containing photoconductive resin composed of a reaction product of (1) a soluble low molecular weight polycondensate which is an addition condensation reaction product of (a) a benzene compound having at least one nitrogen-free electron donating core substituent and at least two ring-substituted hydrogen atoms capable of methylol substitution with formaldehyde, with (b) Is formaldehyde or a functional derivative thereof, and wherein at least one of the radicals of the benzene compound a substituent represented by the following formula - CH ₂ X wherein .X is a hydroxyl group, an alkoxy group, an O-acyl means group or a halogen atom, in principle bound to the carbon atoms of the benzene ring as a bonded group contains, with (2) an aromatic amine compound represented by the following formula H Ar ■ £ N - Y) _n H where Ar is an aromatic group, the group 4 ^ -Y) is bonded to the carbon atom of the aromatic ring, η denotes the numbers 1 or 2 and Y denotes an aromatic ring Group which is identical or different to Ar and optionally a ring together with Ar either forms directly or via a nitrogen, oxygen or sulfur atom, means 609837/0899 the one forming the amino group of the aromatic amine Hydrogen atom bonded to nitrogen atom through the methylene group bonded to carbon atoms of the benzene ring is substituted. 16. Method of making an electrophotographic Material, characterized in that a solution in an organic solvent is applied to a carrier the soluble aromatic tertiary amine-containing photoconductive resin and at least one chemical sensitizer and / or optical sensitizer, and a binder polymer be drawn up and the coating for virtually complete removal of the organic solvent is dried. 609837/0899