Recording process using quinolin-2-one or quinolin-4-one organic photoconductive substances

[57] ABSTRACT

Electrophotographic recording process wherein a pattern of increased conductivity is produced image-wise in a photoconductive insulating recording layer using as the essential photoconductive compound guinolin-2-one, quinolin-4-one, certain analogs and structural derivatives thereof, as well as the bis forms thereof, dispersed in an insulating binder. At least about 10 percent by weight of the recording element is constituted by the photoconductive compound and a spectral sensitizing agent for the photoconductor can be included. This class of photoconductors is also useful in the production of phosphor patterns on cathode-ray tube screens.

Claims, No Drawings

3,660,084

RECORDING PROCESS USING QUINOLIN-2-ONE OR QUINOLIN-4-ONE ORGANIC PHOTOCONDUCTIVE

SUBSTANCES

The present invention relates to recording and reproduction of information-wise modulated electromagnetic radiation and to recording materials applied therefor. More particularly the present invention relates to a photographic recording process utilizing the property of photoconduction of substances as described herein.

A recording element having photoconductive properties and a sufficient insulating power in non-irradiated state can be used for the production of an electrostatic image.

Electrophotographic materials comprising a support and a photoconductive layer containing. an inorganic or organic photoconductor, e.g. selenium, zinc oxide, anthracene, and particular heterocyclic compounds, are well known.

In the production of opaque photoconductive layers generally inorganic photoconductive substances are used, while for preparing transparent photoconductive layers mostly organic photoconductors are applied.

One of the important problems in the production of transparent photoconductive layers is to find organic photoconductive substances that have a photosensitivity comparable with that of commonly used inorganic photoconductive substances and that are easily spectrally sensitizable over the whole visible spectrum range.

An object of the present invention is the use in electrophotographic recording materials of organic compounds that are photoconductive and are easily spectrally sensitizable.

It is another object of the present invention to use such electrophotographic recording materials in photographic recording processes according to which an electrostatic image is formed.

It is still another object of the present invention to provide transparent and semitransparent photoconductive recording elements of particularly high photosensitivity in the ultraviolet range as well as in the visible spectrum range.

Other objects and advantages of the present invention will become apparent from the description but are not limitative for the use of the defined compounds in electrophotographic recording and reproduction processes.

According to the recording process of the present invention a pattern of increased conductivity is produced in a photoconductive insulating recording element containing a heterocyclic organic photoconductive compound having the following structural formula:

group wherein R and R' each represents hydrogen, an alkyl group including a substituted alkyl group, an aralkyl group including a substituted aralkyl group, a cycloakyl group including a substituted cycloalkyl group, an aryl group including a 5 substituted aryl group, an acyl group including a carboxylic acid acyl and sulphonic acid acyl group both either or not in substituted form, a carbamoyl group (—CONH₂) or a substituted carbamoyl group,

Z represents the necessary atoms making part of a carbon 10 chain that closes the nitrogen-containing heterocyclic ring including such ring in substituted form and such ring that makes part of a fused ring system, n is one or two.

The present invention includes also the use in a recording 15 and reproduction process of the tautomeric structures of said compounds. Tautomeric structures are derived from said compounds wherein Ri represents hydrogen.

Compounds within the scope of said general formula and that are suitable for use according to the present invention are 20 photoconductive compounds of the quinolin-2-one and quinolin-4-one series and compounds structurally derived therefrom wherein the oxygen atom in the 2-one and 4-one group is substituted with a sulphur atom, a dicyanomethylene group, an imino group including an imino group substituted 25 with a carbocyclic or heterocyclic radical of aromatic nature, an oxime group, a hydrazone group or a substituted hydrazone group.

Representatives of said quinolin-2-one and quinoline-4-one compounds and structural derivatives thereof are within the 30 scope of the following structural formulae (A) and (B):

(A) ¹

<img file="US3660084A_D0001.tif" />

(B)

<img file="US3660084A_D0002.tif" />

wherein:

R] represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group, e.g. an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group including said groups in substituted form,

X is oxygen, sulphur, an imino group including an imino group substituted with an aryl group, a _z-----z

Ri-N(Li=Ls)_m-C;

x50 wherein:

<img file="US3660084A_D0003.tif" />

L, and each represents a methine group including a substituted methine group or a carbon atom that makes part of a homocyclic ring, e.g. a benzene ring including a substituted homocyclic ring,

R, represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group, e.g. an alkyl group, an aralkyl group, a cycloalkyl group, and an aryl group including said groups in substituted form,

X is an electronegative (electron-attracting) substituent e.g. oxygen, sulphur, an imino group including an imino group substituted with a carbocyclic or heterocyclic radical of aromatic nature, a

ON =0^ ^CN group, an oxime group, particularly a = NOR' group wherein R' is hydrogen or an aliphatic group, e.g. an alkyl group, or a ’ hydrazone group or a substituted hydrazone group particularly a group, an oxime group, particularly a = NOR' group wherein R' is hydrogen or an alkyl group, or a hydrazone group or a substituted hydrazone group particularly a

R =N-N^//^R' group, and R and R' each represents hydrogen, an alkyl group including a substituted alkyl group, an aralkyl group including a substituted aralkyl group, a cycloalkyl group including a substituted cycloalkyl group, an aryl group including a. substituted aryl group, an acyl group including a carboxylic acid acyl and sulphonic acid acyl group either or not in substituted form, a carbamoyl group (—CONH₂) or a substituted carbamoyl group,

Z represents the necessary atoms making part of a carbon chain that closes the nitrogen-containing heterocyclic ring including such ring in substituted form and such ring that makes part of a fused ring system; examples of substituents for the ring closed by Z are alkyl, e.g. methyl, substituted alkyl e.g.

trifluoromethyl, halogen e.g. chlorine and fluorine, an amino

R =N-N^/^R'

3,660,084

<img file="US3660084A_D0004.tif" />

<img file="US3660084A_D0005.tif" />

<img file="US3660084A_D0006.tif" />

group, a substituted amino group e.g. a dialkylamino group, a hydroxyl group, an alkoxyl group e.g. a methoxy group, a carbamoyl group, a substituted carbamoyl group e.g. a — CONHCH3 group, an aminoacyl group e.g. a — NHCOC_e H₅group, a sulphamoyl group, a N-substituted sulphamoyl group 5 e.g. a — SO₂N(CH₃)₂ group, a sulphonylfluoride group, a carbonylalkoxy group e.g. a carbethoxy group,

R₂ represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group, e.g. an alkyl group including a substituted alkyl group e.g. a Cj-C₁₅ alkyl group, an aralkyl 10 group including a substituted aralkyl group, a cycloalkyl group including a substituted cycloalkyl group, an aryl group including a substituted aryl group, an ester group e.g. a carbonylalkoxy group such as a carbethoxy group, a carbamoyl group including a substituted carbamoyl group, an amino group in- 15 eluding a substituted amino group,

Ra represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group e.g. an alkyl group including a substituted alkyl group e.g. a Cr-C₁₅ alkyl group, an aralkyl group including a substituted aralkyl group, a cycloalkyl group ^2υincluding a substituted cycloalkyl group, an aryl group including a substituted aryl group, a carboxylic acid group, an ester group e.g. a carbonylalkoxy group such as a carbethoxy group, or a carbamoyl group including a substituted carbamoyl ₂^ group,and

R₂ and Rs together represent the necessary atoms to close a homocyclic ring including such ring in substituted form or making part of a fused ring system.

Compounds according to the above general formulae that jq are suitable for use in the manufacture of an electrophotographic recording material according to the present invention are listed in the following Tables I, II and ΠΙ. In Table ΠΙ “duplo ’ ’ structures are exemplified.

Said heterocyclic compounds, e.g. those containing the 35 quinolin-2- or 4-one ring system can be introduced into a polymeric chain by known methods, e.g. by introducing in said ^Msystem an α,/3-ethylenically unsaturated group and by apply- j ing a subsequent proper ionic or radical polymerization, or by linking said ring system to an already existing polymer chain 40 ^6-1by means of an addition or substitution reaction, e.g. by using polyvinylbenzyl chloride whose chlorine atoms have been substituted with an active hydrogen atom of the quinolin-2- or quinolin-4- compounds.

Polymers containing heterocyclic organic systems for the 45 purpose of the present invention have not to be of a high molecular weight in order to obtain a practical useful photoconductivity.

The photoconductive heterocyclic compounds used according to the present invention are prepared according to methods known per se. As an illustration of the preparation of quinolin-2-one compounds, also called carbostyril compounds, reference is made to the published Dutch Pat. Specification No. 6,603,985 filed Mar. 25, 1966 by Farbenfabriken Bayer A.G. corresponding with the Canadian Pat. Specifica- ³tion No. 788,892 filed Mar. 24, 1966 by Farbenfabriken Bayer A.G.

The preparation of particular quinolin-4-one compounds is described, e.g., in the French Pat. Specification No. 1,202,105 ,θ filed June 14, 1956 by Badische Anilin- &amp; Soda-Fabrik A.G., Chem. Abstracts 61 (1964) 10657 e, J.Org.Chem. 23 (1958) 762-763,and J.Prakt.Chem. 77(1962) 135-146.

Preferred photoconductive compounds are quinoline compounds, that contain the above indicated value for X and an ¢5 electron-donating (electron-rich) substituent e.g. a hydroxy, amino, alkyl substituted amino, alkoxy or alkyl group. In preferred compounds a dialkylamino group is present as a substituent on the aromatic ring part of the quinolin-2-one or quinolin-4-one compound, or photoconductive derivatives 70 thereof. The quinolin-2-one and quinolin-4-one compounds are further preferably substituted in the o-position to the X substituent with a substituent having an aromatic character, e.g. a phenyl group or a substituent having an electronwithdrawing character such as a nitro group. For substituents 75 a m 1 1

<img file="US3660084A_D0007.tif" />

<td></td><td colspan="5"> 00000</td><td> 0</td><td> 0</td><td> 0</td><td colspan="2"> OO</td>

<td></td><td></td><td></td><td> f:</td><td></td><td></td><td> w</td><td> EU</td><td></td><td></td><td></td>

<td> K</td><td> tc</td><td> s</td><td> Ei</td><td> s</td><td> ϋ</td><td> s</td><td></td><td> w</td><td> K</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 1 K z c c 1</td><td></td><td></td>

<td> t?</td><td> c</td><td> i c</td><td></td><td> 1¾ K</td><td> tr</td><td> c z</td><td> c c c c</td><td> c</td><td> K / z</td><td> K</td>

<td> w</td><td></td><td></td><td></td><td></td><td> ix</td><td></td><td></td><td> !X</td><td></td><td> w</td>

<td></td><td> ix</td><td> n</td><td> i c i c</td><td></td><td> ix c L</td><td> [I</td><td> tr</td><td> h·</td><td> 'K</td><td> « 0 0 0 u</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td> fc</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td> c 02 1</td><td> 0.</td><td></td><td></td><td></td>

<td> M</td><td> £ c</td><td> c</td><td> 0</td><td> ix c</td><td> ί c</td><td> 1</td><td> _____Same a* abm</td><td> c T</td><td> O</td><td> .....—NH—CeHi</td>

<td> M</td><td> K</td><td> n</td><td> ί</td><td> w</td><td> a</td><td> n</td><td> &amp;</td><td> Ei</td><td></td><td> ES</td>

<td> nber</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> a z</td><td></td><td> σ</td><td> n</td><td></td><td> «5</td><td></td><td></td><td> CO</td><td> Cb</td><td> 0</td>

3,660,084

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§ S5§§ g

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<td> x ‘a</td><td> o B</td><td> o B</td><td> θ'o'θ'a WBiBiB 1 1</td><td> ______H_________=N—NHSO₂Ci«H₃3_________________________________</td>

<td> M</td><td> B</td><td> B</td><td> &gt; 1 1 : ; : OBJBJB</td><td> B</td>

Jjjj j J co · । , ;

w'm'km m m

<img file="US3660084A_D0010.tif" />

; ; i I m'w'm'S M m

<td> P?</td><td> w</td><td> ΰ z</td><td> p:</td><td> MZir</td><td></td><td> I</td><td>_a</td><td> I co</td><td> s</td><td></td><td> i</td><td> c</td><td> hl</td><td> i</td><td> ΰ</td><td></td><td> &amp;</td><td> B</td><td> B</td><td> B</td><td></td><td></td>

<td></td><td> s</td><td> s</td><td> £</td><td> MWK</td><td> M</td><td> 3</td><td> K</td><td> s</td><td></td><td></td><td></td><td> (I</td><td> s</td><td></td><td> s</td><td> B</td><td> &amp;</td><td> B</td><td> Bi</td><td> B</td><td></td><td> B!</td>

<img file="US3660084A_D0011.tif" />

<img file="US3660084A_D0012.tif" />

a 53 8 K 8 s' 8 8 8 S

3,660,084

<img file="US3660084A_D0013.tif" />

g 8 8', g , §

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w w aww ww

J JU o u

W W W to W w w n wk

<img file="US3660084A_D0015.tif" />

<td rowspan="10"> K₂ Rs</td><td> ... II_________________ .... IL·.-............. II.................</td><td> W</td><td> w</td><td> w</td><td> j</td>

<td></td><td></td><td></td><td></td><td rowspan="9"> .... cais...................—..........</td>

<td></td><td> CO</td><td></td><td> w</td>

<td></td><td> w</td><td></td><td> O</td>

<td></td><td> Q</td><td></td><td> Φ</td>

<td> i</td><td> O ή</td><td> -Π</td><td> OQ .A</td>

<td> nV : W</td><td> u w</td><td>^gV w</td><td> J. w</td>

<td> &lt;ό j? Z</td><td> z</td><td> Z·</td><td> z</td>

<td> SJ £ o</td><td> o</td><td> o</td><td> o</td>

<td> O Q □ 1 ¹ ' 1 i 1 '</td><td> o</td><td> o</td><td> Q</td>

<td></td><td> i * ' i 1 ' &lt; : : : WWW</td><td></td><td> w</td><td> w</td><td> £</td>

<td> W</td><td> O Q □ 1 1 ’ r ' '</td><td> 3</td><td> Q</td><td> o</td><td> o</td>

<td> Number</td><td> 34__________ 35__________ 36_____-----</td><td> co</td><td> 00 co</td><td></td><td> c •r</td>

• w · W : '. ! . ' :

w o W ΰ W WWW WW

<img file="US3660084A_D0016.tif" />

&lt;n co +' » S ft S 5 'Decomposition.

3,660,084

<img file="US3660084A_D0017.tif" />

No. Ri

Rs

Rs

2.

H...

H—

NOs.

H...

OHi. CHs.

3.

CsHs.

<img file="US3660084A_D0018.tif" />

TABLE II

Rj Ri

R&lt; Rs . Η..Ϊ H...

. II- II...

H— H....

Rs

... H—-..

.. CHs-.

(CsHs)sN

Rs X

Η— O...

H—-- O...

H— O

M.p., ⁰ C.

225

115

4.

5.

6.

CHs—— CHs..... H.......

H— CisHsi. H—

CisHsi—. CHs— CisHsi..

H.:;H.-— H.... H.L H.... H— II- H......... Cl„.

H— 0..

H.--_ 0..

H— O78

104

7.

CHs.

H.

<img file="US3660084A_D0019.tif" />

Η- H...

H...

H—. Ο....

214

8....

9....

10—

11...

12...

13...

14...

15...

H-_________

CsHs...----CHs_________ (CHs)sCH.. CHs________CsHs-------CHs-.......

CHs-.......

ΒΗ... H.i. H... ΗΒΗ.;.

-CH=CH-CH=CH- : H„ H— CHs-................. Η— H—^:._

CisHsi—..............Η.. H—

CHs.................... Η- H —

CisHsi—---------------Η.:.' H—..

CisHsi—............H- H—

CisHsi...._____________H— CHs—

H.....................H.-H—

H-.......H.

Hl........ H.

CHsO— H. CHs— CH_si.

ΗΒΗ—

O___________________

O______________—.

______s____________________

H— S..._________________

H..„ S....................

H— S....................

H— S—.............

H— =N—NHCOOCHs.

134

116 93 69

133

159

16..

CHsH—

Η.. H.2.

H..

H— =N-NHS

<img file="US3660084A_D0020.tif" />

210

17.

18.

CsHsCHs...

H... ΗCHs. CFsH— H...

Hli H.I.

H..

H..

H— =N—NHSOsCisHss H—-. Same as above —

109

122

19.

CHs.

H.

CisHsi.

Η— H—

Cl..

H— =N—NH-SOs&gt;—CHs

127

20.

CHs...

H.

CisHsi...

Η— H-—

H—

H.

160

21.

CsHs..

CHs..

H_. H...

H_.

22.

CsHs..

CHs...

H— H...

H.„

23—

CHs.

H—

<img file="US3660084A_D0021.tif" />

NHs

CHs..

Η- H.l.

H.i

24—

CHs.

Hi.

H.i CHsO—. H..

25.

CHs—

H.

CHs..

Hi. H.

H_.

=N-NHCONHs.

H—

H...

H.

HH.

<img file="US3660084A_D0022.tif" />

212 ±250

250

125

205

CN

26.

CHs

H..

CHs

Η— HCHs

H211

CH =C

CHs

CN

27—

28...

29...

30—

31...

32...

CHs. CHs. CsHs. CHs. CHs. ΗHi. H— H— H— HH„ . (CHs)ic-CHs— . CHs........— . (CHs)h—CHs... . (CHs)h-CHs...

. H...............

.CHs............

H-.CHsl—.

Η— H........

H„ II-......

H- H_.......

H- (CsHs)s-.

H- HsCO...

H.._____ . H.......

. H—.....

. HsCO... . H.______ . H-.....

H—— Same as above H„_______do________

H-_______do-......

H.........do________

Hi... S...........H—. =N—NHs—

110 207 116 120 112 125

33.

CHs

H—

H.i H.

H..

H— &gt;N—

<img file="US3660084A_D0023.tif" />

205

34.

35.

36.

CHs.

CHs. CHs.

Hi.... H- — CHs..

. CHs.

. CHs.

. CHs.

Η.. H..

H.i Hi.

Η- H..

ΒΗ— H..

H— S CHs. S. H—. S

160

124

212

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TABLE III

<img file="US3660084A_D0024.tif" />

&gt;260 &gt;260 &gt;260 &gt;260 ±230

<img file="US3660084A_D0025.tif" />

H_______________—CHj—.......

<img file="US3660084A_D0026.tif" />

______________H.______Same as above.--------------ιό:______________H...........-do------------------------&gt;260 —NH—___________ —GHz—___________

C_eHs..............

&gt;260 &gt;260 &gt;260

<img file="US3660084A_D0027.tif" />

-SO₂-.„........

—CH!—...........

- GHz—___________

-CH=CH------0-.............

&gt;260 &gt;260 &gt;260 &gt;260 &gt;260

<img file="US3660084A_D0028.tif" />

Melting point:

&gt;260° C.

with electron-donating an electron-withdrawing character reference is made to Peter Sykes, A Guidebook to Mechanism in Organic Chemistry Longmans, London (1963) p. 106-107. Such preferred compounds are e.g. l-ethyl-3phenyl-7dimethylamino-quinolin-2-one, l-ethyl-3-phenyl-7diethylamino-quinolin-2-one and which are also called 1ethyl-3-phenyl-7-dimethylaminocarbostyril and l-ethyl-3phenyl-7-diethylaminocarbostyril respectively. The former compound can, e.g., be prepared as follows, the parts being by weight:

17.9 parts of 2-ethylamino-4-nitroltoluene, 16.2 parts of phenylglyoxylic acid ethyl ester, and 2 parts of piperidine are heated for 8 hours to 200° C with stirring.

parts of the resulting l-ethyl-3-phenyl-7-nitrocarbostyril in a mixture of 50 parts of alcohol and 50 parts of concentrated hydrochloric acid are heated on a waterbath. A solution of 50 parts of tin(II) chloride in 100 parts of concentrated hydrochloric acid is added to the mixture with stirring. Stirring is continued for 1 hour, whereupon the mixture is allowed to cool. The resulting l-ethyl-3-phenyl-7-aminocarbostyril is filtered off, boiled out with 200 parts of 5 percent aqueous solution of sodium hydroxide, filtered while hot, dried, and recrystallized from xylene. From the resulting l-ethyl-3-phenyl-7-aminocarbostyril(melting point: 170°-172° C) 13.2 parts are dissolved in 150 parts of dioxane. To the solution are added 25 parts of 35 percent solution of formaldehyde in methanol and 10 parts of Raney nickel. The mixture is heated for 4 hours to 110° C in an autoclave with a hydrogen pressure of 110 atm. Subsequently, the Raney nickel is isolated and the dioxan is distilled in vacuo. After recrystallization from ⁵⁰ cyclohexane l-ethyl-3-phenyl-7-dimethylaminocarbostyril is obtained. Melting point: 109°-112° C.

The following products listed with their respective melting point are prepared in an analogous way by a condensation reaction of the proper 2-amino-4-nitrotoluene and phenyl55 glyoxylic acid ethyl ester.

3-phenyl-7-dimethylaminocarbostyril (258°-262° C), 1methyl-3-phenyl-7-aminocarbostyril (190°-192° C), 1methyl-3-phenyl-7-dimethylaminocarbostyril (170°-173° C),‘ _ l-methyl-3-(4'-methyIphenyl)-7-dimethylaminocarbostyril ⁶⁰ (185°-9O° C), l-methyl-3-(4'-methylphenyl) 6-methyl-7dimethylaminocarbostyril (152°-153° C), l-methyl-3-(3',5'dimethylphenyl)-7-dimethylaminocarbostyril (15Γ-153⁰ C), l-ethyl-3-(3'-chlorophenyl)-7-dimethyl-aminocarbostyril ,, (161°-62° C), l-ethyl-3-phenyl-7-monoethylaminocar⁶⁵ bostyril (178°-180° C), l-ethyl-3-phenyl-7-N-methyl-Nethylaminocarbostyril (75°-78°C).

In th© resulting nitrocarbostyrils the nitro group is reduced to an amino group, which for the purpose of the present inven70 tion preferably is alkylated.

The alkylation for preparing l-ethyl-3-phenyl-7diethylaminoquinolin-2-one preferably is earned out as follows:

79.2 g (0.3 mole) of l-ethyl-3-phenyl-7-amino-quinolin-275 one and 109 g (0.6 mole) of triethyl phosphite are heated for 3 hours on an oil-bath at 190° C.

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The reaction mixture is poured into 1 1 of water and the whole composition is alkalized by means of a 5N aqueous sodium hydroxide solution. The resulting precipitate is isolated and dissolved in 300 ml of warm acetone. A cooling 75.5 g of purified l-ethyl-3-phenyl-7-diethylamino-quinoline-2-one precipitated. Melting point: 115° C (yield: 78 percent).

As an example illustrative for the preparation of a quinoline-4-one the preparation of the compound 8 of Table I is given hereinafter.

This compound was prepared as follows. A mixture of 26 g of methyl ester of p-fluorosulphonyl-benzoylacetic acid, 21.2 g of p-benzoylamido aniline, 300 ml of chloroform and 1 ml of strong hydrochloric acid was refluxed for 8 days with a separator in order to remove the water formed in the reaction mixture. The precipitate formed was filtered off and the chloroform removed by evaporation in vacuum. The reaction product having the following structural formula:

<img file="US3660084A_D0029.tif" />

was isolated as an oily residue.

This residue was added dropwise to 300 ml of boiling (250° C) DIPHYL (trade name of Farbenfabriken Bayer AG, Leverkusen, W. Germany, for a mixture consisting of 27 percent by weight of diphenyl and 73 percent by weight of diphenyl oxide). The reaction mass was maintained for 5 minutes at the boiling temperature of DIPHYL (250° C) while methanol was distilled. Then the reaction mass was cooled. The precipitate formed was filtered with suction, washed with methanol and ether and dried. Yield: 10.5 g of compound 8 of Table I. Melting point: above 260° C.

As an example illustrative for the preparation of “duplo” compounds listed in Table III the preparation of compounds 5 and 11 of said table is given hereinafter.

Preparation of compound 5 of Table ΙΠ g (0.1 mole) of 4,4'-diamino-diphenyl oxide and 52 g (0.2 mole) of methyl ester of p-fluorosulphonyl-benzoylacetic acid were melted together, whereupon 5 g of polyphosphoric acid as water-attracting product were gradually added thereto while stirring.

The reaction mixture was maintained for 10 days at 50° C under vacuum conditions and kept away from contact with moisture from outside by means of a trap containing concentrated sulphuric acid. Thereupon the reaction mass was stirred into chloroform and filtered. The chloroform solution obtained was washed with water and dried on anhydrous sodium sulphate. The chloroform was removed by evaporation in vacuum. The residual product having the following structural formula:

<img file="US3660084A_D0030.tif" />

NH-C=CH—C 0 0 CHs

<img file="US3660084A_D0031.tif" />

SO₂F was separated in the form of an oil.

This oil was added dropwise to 400 ml of boiling DIPHYL (trade name). The reaction mass was maintained for 5 min. at the boiling temperature of DIPHYL (trade name) with stirring, and then cooled till 20° C. The precipitate formed was filtered with suction, washed with methanol and ether, and dried. Yiled: 7.1 g of compound 5 of Table ΙΠ. Melting point: above 260° C.

Preparation of compound 11 of Table ΙΠ

A mixture of 25.7 g (0.1 mole) of the hydrochloric acid salt of 4,4'-diamino-diphenyl and 54.8 g (0.2 mole) of ethyl ester of fluorosulphonyl benzoylacetic acid, 13.2 g (0.19 mole) of 5 waterfree sodium acetate and 150 ml of chloroform were refluxed for 7 days. Then the chloroform was removed by evaporation under vacuum. The product having the following structural formula:

<img file="US3660084A_D0032.tif" />

was separated as an oil. This oil was added dropwise to 400 ml 15 of DIPHYL (trade name). The reaction mass was maintained for 5 min. at the boiling temperature of DIPHYL (trade name) with stirring and then cooled till 20° C. The precipitate formed was filtered with suction, boiled with acetonitrile, washed with methanol and ether, and dried. Yield: 10.2 g of compound 11 20 of Table ΠΙ.

Quinoline-2 compounds as described in Table Π and wherein X is sulphur can be prepared e.g. according to the following reaction scheme A:

<img file="US3660084A_D0033.tif" />

(I) (Π)

R

<img file="US3660084A_D0034.tif" />

RCOCHjCONH(ΠΙ)

H;S0&lt;

<img file="US3660084A_D0035.tif" />

(VI)

The R, R', R and R' substituents may have the significance of the corresponding substituents of the general formula above Table Π.

Equimolar amounts of ketoester(I) and aromatic amine (Π) are dissolved in xylene contained in a distillation flash provided with a fractionating column. The reaction mass is heated till the theoretical amount of alcohol produced in the reaction is distilled off. After removal of the solvent by evaporation the obtained product (ΠΙ) is purified by crystallization.

Product (III) is dissolved in concentrated sulphuric acid (1,350 ml per mole) and the reaction mass after having been kept for 24 H. at room temperature is poured onto ice. The precipitate formed is isolated by suction, washed with water, whereupon product (IV) is recrystallized.

Product (IV) is mixed with an equimolar amount of p-tolusulphonic acid alkyl ester and heated for 70 to 150 h. at about 160° C. Thereupon the reaction mass is treated with an aqueous IN sodium hydroxide solution. The precipitate formed is separated by suction and the obtained product V is purified by crystallization.

This product is then dissolved in pyridine containing an excess (1.2 mole per mole) of phosphorus pentasulphide and maintained at reflux temperature for 1 to 3 h. After cooling the reaction mass is poured into water, and the precipitate

44»

3,660,084 formed is separated by suction, and washed. The obtained product (VI) is purified by crystallization.

Compounds 10, 12, 14, 34 and 35 of Table Π have been prepared that way.

Quinoline-2 compounds as described in Table II, and wherein X is sulphur, can also be prepared according to the following reaction scheme B:

<img file="US3660084A_D0036.tif" />

The substituents R, R', R, R' and R may have the same significance as the corresponding substituents exemplified in the structural formula above Table Π.

The operating conditions are the same as explained for reaction scheme A except for the alkylation reaction with ptolusulphonic acid alkyl ester.

The compounds 11, 13 and 36 of Table Π were prepared that way.

Quinoline-4 compounds as described in Table I, and wherein X is sulphur, can be prepared according to the following reaction scheme C:

<img file="US3660084A_D0037.tif" />

(Hi)

Preparation of compound (II)

2-phenyl-4-chloro-quinoline is mixed with an excess (3 mole per sole) of dimethyl sulphate and for 24 hours heated at 80° C. After cooling and washing with ether, the compound (Π) is obtained in a quantitative yield. Melting point: 50° C. Preparation of compound (ΙΠ)

0.02 mole of compound (Π), 0.04 mole of sodium carbonate and 0.03 mole of hydroxylammonium chloride are dissolved in a mixture of 50 ml of chloroform and 25 ml of methanol and refluxed with stirring for 2 h. After cooling the precipitate is separated by suction and washed with water. This washed precipitate consisting of compound (ΠΙ) was crystallized from ethylene glycol monomethyl ether. Yield: 50 percent. Melting point: 258° C.

The quinoline compounds wherein X is an imino group substituted with an aromatic group can be prepared according to known methods for producing a ketone anil, e.g. according to reaction scheme E as follows:

<img file="US3660084A_D0038.tif" />

(I) (Π) (ΠΙ)

Compound II of reaction scheme D 45

Ar—NHj

<img file="US3660084A_D0039.tif" />

R,I represents an alkyl iodide e.g. methyl iodide.

According to said reaction scheme C, compound 16 of Table I was prepared as follows:

2-methyl-4-chloro-quinoIine (I) was mixed with an excess of methyliodide (5 mole per mole) and the reaction mass was maintained at reflux temperature for 35 h. Then the reaction mixture was washed with ether.

Compound (Π) wherein R, and R₂ were both methyl was obtained in 67 percent yield in the form of a crystalline product melting at 250° C.

This product was dissolved in dry ethanol (1,600 ml per mole) and maintained at reflux temperature for 12 hours in admixture with an excess of sodium hydrogen sulphide (3 moles per mole).

The reaction mass was filtered hot and cooled. Compound (ΠΙ) (Rj and Rj being both methyl) crystallized, whereupon it was recrystallized from ethylene glycol monomethyl ether. Yield: 59 percent. Melting point: 224° C.

The quinoline compounds wherein X is an oxime group can be prepared according to a known method for producing an oxime, e.g. as described by Vogel in Practical Organic Chemistry, 3rd Ed. Longmans, (1959) 741.

According to another method the reaction scheme D is followed:

Ar is e.g. a phenyl group.

Preparation of compound (ΠΓ) wherein Ar=phenyl. Equimolar amounts of compound (II) and aniline are dissolved in chloroform and refluxed for 4 h. Then the chloroform is evaporated under vacuum and the residue is treated with a 20 percent by weight aqueous solution of sodiurn carbonate. The solid product is separated by suction, washed and dried. The yield is quantitative. Melting point of compound (III') (Arbeingphenyl): 150°C.

The quinoline compounds wherein X is a hydrazone group can be prepared according to a known method for producing a ¢5 hydrazone compound starting from a ketone.

Acyl-substituted hydrazone groups in the 2-position of quinoline can be introduced according to preparation methods described in the U.K. Pat. Specification No. 993,749 filed July 30, 1962 by Gevaert Photo-Producten N.V., the U.S. Pat. 70 Nos. 3,245,787 issued Apr. 12, 1966 of Jozef Frans Willems and Jan Jaeken and 3,293,032 issued Dec. 20, 1966 of Jan Jaeken and Maurice Antoine de Ramaix and the U.K. Pat. application Ser. No. 5979/69 filed Feb. 4, 1969 by Gevaert-Agfa N.V.

Acyl-substituted hydrazone groups in the 4-position of quinoline can be introduced according to reaction scheme F:

3,660,084

<img file="US3660084A_D0040.tif" />

R' represents a hydrocarbon group or a heterocylic group which groups may be further substituted. Compound (I) together with an equimolar amount of R'CONHNH₂ or R' SO2NHNH» is refluxed in ethanol for 8 h.

Thereupon ethanol is removed by evaporation. The residue is dissolved in pyridine and 15 min. later the obtained solution is poured into water. The precipitate formed is separated by suction, washed with water, and crystallized.

The compounds wherein X is a dicyanomethylene group can be prepared by allowing to react propane dinitrile with the appropriate heterocyclic quaternary salt having a methylmercapto group in ortho position to the quaternary nitrogen atom. The reaction conditions for such preparation can be learned from the preparation of N-isopropyl-4,7-dimethyl-quinoline2-dicyanomethylene.

3.4 g of N-isopropyl-2-methylmercapto-4,7-dimethylquinolinium iodide together with 1.2 g of propane dinitrile were dissolved in a mixture of 30 ml of pyridine and 0.3 ml of piperidine. The reaction mixture is kept at 20° C for 24 h. and thereupon poured into water.

The precipitate formed was filtered with suction, washed with water and dried. Melting point: 211° C. Yield: 2 g.

The photoconductive compounds applied according to the present invention may be used alone or in combination with substances imparting desired chemical or physical properties to the recording element. So, these substances can be combined with other substances, that either or not are photoconductive and exert an influence e.g. on the dark-resistivity, the dischargeability or conductivity of the recording layer by an exposure to electromagnetic radiation, or on the transparency or the quality of the final image, e.g. by counteracting the fringe effect as described in the U.K. Pat. Specification No. 1,007,349 filed Oct. 12, 1961 by Gevaert Photo-Producten N.V.

The photoconductive compounds used according to the present invention are preferably applied in admixture with (a) compound(s) that cause(s) an increase of the general sensitivity and/or of the sensitivity to electromagnetic rays of a particular part of the spectrum.

Fringe effect occurs when large electrostatically charged areas are developed and is characterized by the deposit of electrostatically charged substances only at the edges of said areas. In order to inhibit or to decrease said effective dispersable particles, e.g. inorganic pigment particles and organic water-insoluble particles, are incorporated into the continuous phase of the recording layer.

Especially suitable for that purpose are zinc oxide pigment particles and a finely divided mineral product (average particle size: 5 μ) known as MICRODOL (trade name of A.S. Norwegian Table, Bergen, Norway, for a mixture having the following composition (percent by weight:

CaCO₃ 54.34 %

MgCO₃ 45.15 %

FeA 0.04 %

A1₂O₃ 0.03 % and DRY-FLO (trade name of National Starch and Chemical Corporation, Plainsfield, N.J., U.S.A., for a starch ester containing hydrophobic groups).

These particles size between 1 and 5 μ and are preferably used in an amount of 2.4 to 24 percent by weight in respect of the homogeneous phase material contained in the recording layer. Optimal results are obtained with an amount of 6 percent by weight.

A proper combination with selected binding agents and/or j curing agents may result in an enhancement of the total sen^J sitivity so that the binder or curing agent applied may be considered as a sensitizing agent. Preferably the recording layer contains at least 10 percent by weight of the photoconductive substance applied according to the present invention. The 2Q electrically insulating binding agent applied to offer to the recording layer the desired mechanical strength preferably has a resistivity of at least 10° ohm/cm.

According to a particular embodiment the recording layer consists of the photoconductor, which, e.g., is applied to a 25 suitable support in molten state forming a microcrystalline or glass-like layer on cooling. This technique can be applied when the photoconductive recording element has not to possess a high mechanical strength. For such technique reference is made to the Canadian Pat. Specification No. 712,541 filed 30 Feb. 5,1960 by Gevaert Photo-Producten N.V.

Macromolecular compounds suitable for use as insulating binding agent for the photo-conductive compounds are, e.g., natural resins such as dammar resin, gum arabic, microcrystalline waxes, modified natural substances such as cellulose 35 diacetate, cellulose triacetate, and ethyl cellulose, pentaerythrite polyesters or modified colophony resins and ester gums, polymerisates such as polyethylene, polystyrene and copolymers of styrene, polyvinyl acetate and copolymers of vinyl acetate, polyvinyl acetals of formaldehyde, acetaldehyde 40 or butyraldehyde, polyacrylic acid esters and polymethacrylic acid esters, coumarine-indene resins; and polycondensates such as glycerol-phthalate resins and other glyceryl polyesters, alkyd resins, diethylene glycol polyesters, formaldehyde resins and silicone resins.

Preferred binding agents are halogen-containing polymers. The preferred recording materials according to the present invention contain the organic photoconductive compounds in admixture with a halogen-containing polymer. Such polymers and a sensitizing treatment therewith are described in the U.K.

Pat. Specification No. 964,878 filed May 3, 1960 by Gevaert Photo-Producten N.V. According to said specification a material suitable for use in electro-photography comprises a photoconductive layer incorporating an organic monomeric photoconductor and a halogen-containing polymer in such ⁵⁵ layer or in a juxtaposed layer (if any), the sensitivity of said photoconductor having been increased by making it to interact with said halogen-containing polymer by heating.

In the following Table IV a list of preferred polymeric bind,. ing agents is given, which may be used in combination with the ^υ heterocyclic organic photoconductors of use according to the present invention as well as the corresponding suitable solvents.

TABLE IV

Polymeric binding agent defined by its structural unit(s)

Solvent

<img file="US3660084A_D0041.tif" />

Methylene chloride.

3,660,084

Polymeric binding agent defined by its structural unlt(s)

<img file="US3660084A_D0042.tif" />

-[o-(CHs)»- OOC-(CH,)i- Co7—

Solvent

Do.

<img file="US3660084A_D0043.tif" />

CH:

<img file="US3660084A_D0044.tif" />

<img file="US3660084A_D0045.tif" />

Do.

Do.

Do.

Do.

Do.

Do.

<img file="US3660084A_D0046.tif" />

H₂N—N--C—(C H 2) 8-N

---C^ N

H₂N—N—--C—C H₂—O—CH₂Do.

CH₂—CH-Methylene chloride/ cyclohexanone (1:1).

<img file="US3660084A_D0047.tif" />

Methylene chloride..

Do.

CHs I

CH

25% by weight

Do.

CH₂—CHi— I 0 ίσο I ch₃J

<td> 21</td><td> 3,660,084 22</td>

<td> Polymeric binding agent defined by its structural unit(s)</td><td> Solvent</td>

CII₃ “1

--CHs-CDo.

I co

I 0 n—CtHio_

<img file="US3660084A_D0048.tif" />

CH2-CH- Do.

CN_

<img file="US3660084A_D0049.tif" />

Do.

<img file="US3660084A_D0050.tif" />

CHr-CH-CHj-CH- O

Do.

Do.

<img file="US3660084A_D0051.tif" />

<img file="US3660084A_D0052.tif" />

85% by weight 14% by weight

1% by weight

Methylene chloride/ acetone (1:1).

Do.

Methylene chloride/ acetone/ethanol (1:1:1).

(CHjJj-CHj ch-o

<img file="US3660084A_D0053.tif" />

The photoconductive compounds applied according to the present invention can be used in admixture with otherknown photoconductive substances, e.g. sulphur, selenium, photoconductive oxides, sulphides, and selenides of zinc, cadmium, mercury, antimony, bismuth, and lead. They can be used in combination with organic monomeric photoconductors e.g. anthracene, anthraquinone, polymers containing Nvinylcarbazole recurring units and other known monomeric and polymeric organic photoconductors, e.g. those described in the published Dutch Pat. application Ser. No. 6,901,214 filed Jan. 24,1969 by Gevaert-Agfa N. V.

The inherent spectral sensitivity of most of the photoconductive compounds listed in Tables I, H, and ΙΠ is mainly situated in the near U. V. range, i.e. in the range of 360 nm to 420 nm.

3,660,084 atoms necessary to complete a fused-on benzene nucleus; X“ represents an anion e.g. Cl^-, Br~, I^-, C1O₄~, CH₃SO~₄, or

It is possible to increase or extend the spectral sensitivity of recording materials according to the present invention in different ways, e.g. by adding so-called spectral sensitizing agents for the photoconductive substances contained in the recording element or by admixing to the said heterocyclic organic photoconductive compounds other photoconductive substances, the inherent sensitivity of which for a particular part of the electromagnetic radiation spectrum is higher than that of said compounds.

So, according to a special embodiment of the present invention semi-transparent recording layers are prepared, in which said heterocyclic photoconductive compounds are used in admixture with (an) inorganic photoconductive substance(s), especially photoconductive substances of the group of zinc oxide, photoconductive lead(II) oxide and photoconductive cadmium sulphide.

So, for instance a small amount of an inorganic photoconductive compound such as photoconductive zinc oxide (1.5 g) in respect of 4 g of l-ethyl-3-phenyl-7-diethylaminoquinolin2-one offers an interesting sensitivity of the recording layer to ultra-violet radiation and allows the extension of the spectral sensitivity of both the heterocyclic organic photoconductor and the inorganic photoconductive substances into the visible part of the spectrum by means of same or different sensitizing dyestuffs.

Suitable spectral sensitizing dyestuffs for the organic photoconductor are among others organic dyestuffs, known as methine dyes, or xanthene dyes of which the phthaleins and rhodamines are subclasses, and triarylmethane dyes e.g. crystal violet (C.I. 42,555) and the triarylmethane dyes described in published Dutch Pat. application Ser. No. 6,704,706 filed Apr. 3, 1967 by Gevaert-Agfa N.V. The term methine dyes includes mono- as well as polymethine dyes which dyes are known to those skilled in the art of the spectral sensitization of light-sensitive silver halide. Preferred methine dyes are of the cationic type and preferably contain one, three, five or seven carbon atoms in straight line in the methine part linking up two heterocyclic nitrogen-containing nuclei of the methine dye. As preferred xanthene dyes Rhodamine B (C.I. 45,170), Rose Bengale (C.I. 45,440) and Fluorescein (C.I. 45,350) are: mentioned. The spectral sensitizing dyes are preferably added to the recording layer composition in a proportion of 0.01 to 5 percent by weight in respect of the photoconductive substance(s).

Particularly preferred methine dyes are within the scope of the following general formulae:

I- Ra R₄

<img file="US3660084A_D0054.tif" />

wherein:

A, stands for dimethine or tetramethine including substituted dimethine and tetramethine, n stands for one or two,

R_t stands for alkyl including substituted alkyl, an unsaturated aliphatic group e.g. allyl, aralkyl including substituted aralkyl, aryl including substituted aryl or cycloalkyl,

R₂ stands for alkyl, aryl including substituted aryl, e.g. phenyl and phenyl substituted preferably in the p-position by alkyl, halogen and alkoxy, a five or six membered heterocycle the heteroatom of which is oxygen, sulphur, selenium or nitrogen such as 2-, 3-, or 4-pyridyl, 2-furyl, 2-thienyl, etc. including their quaternary salts,

R₃ stands for hydrogen or has one of the meanings given for Ri&gt;

R, stands for hydrogen, alkyl, alkoxy or halogen or together with Rs forms an alkylene bridge such as dimethylene and trimethylene, each of R₃ and R« (the same or different) stands for hydrogen, alkyl, alkoxy or halogen or together represent the

<img file="US3660084A_D0055.tif" />

and

Z represents the atoms necessary to complete a heterocyclic - nucleus of the types used in the production of cyanine dyes ¹⁰ e.g. such as those of the thiazole series e.g. thiazole, 4methylthiazole, 4-methyl-5-carbethoxythiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4-(p-tolyl)thiazole, 4-(p-bromophenyl)-thiazole, 4,5-dimethylthiazole, 15 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole, 4-(m-nitrophenyl)-thiazole, those of the benzothiazole series, e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methyl20 benzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 6-sulphobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzo thiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5iodobenzothiazole, 6-iodobenzothiazole, 4-ethox25 ybenzothiazole, 5-ethoxybenzothiazole, 4,5,6,7tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6hydroxybenzothiazole, 5,6-dimethylbenzothiazole, those of the naphthothiazole series e.g. naphtho[2,l-d]thiazole, 30 naphtho[ 1,2-d]thiazole, 5-methoxynaphtho[l,2-d]-thiazole, 5-ethoxynaphtho[l,2-d]-thiazole, 8-methoxynaphtho[2,l-d]thiazole, 7-methoxynaphtho[2,l-d]-thiazole, those of the thionaphtheno [ 7,6-d]-thiazole series e.g. 7-methoxythionaphtheno[7,6-d]-thiazole, those of the thiadiazole se35 ries e.g. 4-phenylthiadiazole, those of the oxazole series e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5phenyloxazole, those of the benzoxazole series e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenyl40 benzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, those of the naphthoxazole series, e.g. naphtho[2,1 -djoxazole, naphthofl,2-d]oxazole, those of the selenazole series e.g. 4methylselenazole, 4-phenylselenazoIe, those of the benzoselenazole series e.g. benzoselenazole, 5chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methyl6-methoxy benzoselenazole, 5,6-diox₅₀ ymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole, those of the naphthoselenazole series e.g. naphtho[2,l-d]selenazole, naphthof 1,2-d]selenazole, those of the thiazoline series e.g. thiazoline, 4-methylthiazoline, 4-hydroxymethyl-455 methylthiazoline, 4,6-bis-hydroxymethylthiazoline, those of the oxazoline series e.g. oxazoline, those of the selenazoline series e.g. selenazoline, those of the 2-quinoline series e.g. quinoline, 3-methylquinoline, 5-methylquinoline, 7methylquinoline, 8-methylquinoline, 6-chloroquinoline, 860 chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6hydroxyquinoline, 8-hydroxyquinoline, etc., those of the 4quinoline series e.g. quinoline, 6-methoxyquinoline, 7methylquinoline, 8-methylquinoline, those of the 1-isoquinoline series e.g. 1-isoquinoline, 3,4-dihydroisoquinoline, those 65 of the 3-isoquinoline series e.g. 3-isoquinoline, those of the pyrimidine series, those of the quinoxaline series, those of the, quinazoline series, those of the 1-phthalazine series, those of the 2-pyridine series e.g. pyridine, 5-methylpyridine, 3nitropyridine, those of the 3,3-dialkylindolenine series e.g. 70 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7trimethylindolenine, etc., those of the benzimidazole series e.g. benzimidazole, 5,6-dichlorobenzimidazole, 5chlorobenzimidazole, 5,6-dibromobenzimidazole, 5-chloro-6amino-benzimidazole, 5-chloro-6-bromobenzimidazole, 5'5 phenylbenzimidazole, 5-fluorobenzimidazole, 5,63,660,084 difluorobenzimidazole, 5-cyanobenzimidazole, 5,6dicyanobenzimidazole, 5-chloro6-cyanobenzimidazole, 5fluoro-6-cyanobenzimidazole, 5-acetylbenzimidazole, 5chloro-6-fluorobenzimidazole, 5-carboxybenzimidazole, 7carboxybenzimidazole, 5-carbethoxybenzimidazole, 7-carbethoxybenzimidazole, 5-sulphamylbenzimidazole, or 5-Nethylsulphamylbenzimidazole, 5-ethylsulphonylbenzimidazole and 5 -trifluoromethylsulphonylbenzimidazole;

II.

<img file="US3660084A_D0056.tif" />

wherein:

A₂ stands for monomethine or trimethine including substituted monomethine or trimethine, each of R'₂-R'_e and R''₂-R_e (the same or different) has one of the meanings given for Rj-Re,

X₂^_has the same significance as X/.

III.

I II I —Ri x-3

R'l—N(=CH—CH)m-i=C—As=C (-CH=CH)_p-i-N J +

wherein:

each of R'j and R, (the same or different) has one of the meanings given for R,,

X₃~has the same meaning as X_t~,

A₃ has the same meaning as A₂, each of m and p (the same or different) stands for one or two, and each of Zj and Zj (the same or different) stands for the atoms necessary to complete a heterocyclic nucleus of the thiazole, benzothiazole, naphthothiazole, thionamhtheno[7,6djthiazole, thiadiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, 2-quinoline, 4-quinoline, pyrimidine, quinoxaline, quinazoline, 2-pyridine, 3,3-dialkylindolenine or of the benzimidazole series, representative examples of these heterocyclic nuclei can be found above in the definition of Z in formula I.

The dyestuffs corresponding to the above general formulae can be prepared according to the methods known by those skilled in the art of methine dye chemistry.

According to a further embodiment of the invention, the recording material contains one or more substances that increase the photoconductivity of the recording material in the inherent spectral sensitivity range of the said heterocyclic organic photoconductive compounds. As already has been said a binding agent or a curing agent can act as a sensitizing agent that enhances the total sensitivity of the recording element. In that respect are to be mentioned compounds containing one or more electron-attracting atoms or groups e.g. the compounds according to the structural formula of the Belgian Pat. Specification No. 734,141 filed June 6, 1969 by Gevaert-Agfa N.V. Particularly suited are chlorine-containing compounds and the chlorine containing polymers of Table IV, and curing agents containing epoxy groups such as the tetraglycidyl ether of tetraphenylene-ethane.

Further have to be mentioned electromagnetic radiationsensitive diazonium salts that on exposure to electromagnetic radiation produce (a) radical(s) that irreversibly increase(s) the electroconductivity of the recording layer. Such substances as well as details about their incorporation into a recording layer containing an organic polymeric photoconductive insulating substance are described in the U.K. Pat. Specification No. 964,872 filed Apr. 22, 1959 by Gevaert Photo-Producten N.V. and the U.S. Pat. No. 3,113,022 of Paul Maria Cassiers, Jean Marie Nys, Jozef Frans Willems and Rene Maurice Hart, issued Dec. 3, 1963. A particularly suitable conductivity-increasing diazonium compound is pnitrobenzene-diazonium chloride. The diazonium compounds are preferably used in an amount of 0.01 to 10 percent by weight in respect of the said photoconductive heterocyclic organic compounds.

Other additives well known in the art of preparing coatings 5 for recording purposes may be used, e.g. matting agents, fluorescing compounds, phosphors, optical brightening agents, agents controlling the adhesive power of the recording layer, agents controlling the elasticity, the plasticity and the hardness of the recording layer, agents controlling the viscosi10 ty of the coating composition, antioxidants, gloss-improving agents, etc.

Transparent and semi-transparent recording materials containing the photoconductive heterocyclic organic compounds as described hereinbefore are especially suited for use in 15 recording materials applied for the reproduction of microfilm images. Microfilm images can be copied in contact or enlarged optically on recording materials according to the present invention. According to the type of development, the 2θ transparencies obtained (contact copies and enlargements) can serve as negative or positive intermediate print for further printing, e.g. on diazotype materials.

The semitransparent recording materials according to the present invention preferably have an optical density not larger 25 than 0.30 towards visible light or the copying light used in the printing apparatus wherein it is used as intermediate print.

The photoconductive heterocyclic organic compounds described hereinbefore are further especially suited for being applied in the manufacture of pigment images wherein the 30 latter may have the properties of a fluorescent compound or phosphor. As is generally known luminescent phosphors are used in screens of cathode-ray tubes and more particularly in television, X-ray, radar and oscilloscope screens.

In color television screens phosphors of different color have 35 to be fixed on a screen in a particular pattern.

The described photoconductive compounds are successfully used in a process for the production of color television screens as described in the French Pat. Specification No. 1,336,499 filed Sept. 26, 1962 by Compagnie Francaise 40 Thomson Houston. According to the process described in said specification a pattern of a phosphor on a screen-support is produced by the steps of applying to said support a coating of an electroconductive material and to said coating a layer comprising a vaporizable or thermolysable photoconductive com45 pound optionally incorporated in a vaporizable or thermolysable binding agent. On said coating an electrostatic charge pattern corresponding with the pigment pattern to be produced is formed in an electrophotographic way, and the electrostatic charge pattern is developed with non-volatile powder particles that have the desired phosphorescent or luminescent properties. Subsequently the photoconductive layer containing the phosphor powder image is heated in order to remove the volatile substances of the photoconductive recording layer g 5 and to make the phosphor pattern adhere to the screen support.

In order to fix the powder image before applying the heating step it is preferably overcoated with a layer of a thermolysable binding agent.

¢0 According to said French patent specification photoconductors of the group of anthracene, anthraquinone and xanthone are used. The recording layer may further contain boric acid.

The photoconductors mentioned in the French patent 65 specification are advantageously partly or wholly substituted by the photoconductive substances applied according to the present invention.

Suitable thermolysable binding agents belong to the class of the polyacrylic acid esters and polymethacrylic acid esters e.g. 70 polymethyl methacrylate, polyethyl methacrylate and polyethyl acrylate.

The thickness of the photoconductive layers is not critical but is open to choice within a wide range according to requirements in each individual case. Good results are attained with photoconductive layers of a thickness between 1 and 20 μ

3,660,084

Paper sheets are preferably impermeabilized to organic solvents, e.g. by means of a water-soluble colloid or by strongly hydrating the cellulose fibers such as in the case of glassine preferably between 3 and 10 μ. Too thin layers do not have a sufficient insulating power, in the absence of active electromagnetic radiation whereas too thick layers require extensive exposure times.

In the manufacture of electrophotographic recording materials according to the present invention, a relatively conductive support for the recording layer is used, e.g. an electroconductive sheet or plate, or an insulating sheet or plate covered with an electroconductive interlayer. Under electroconductive plate or sheet is understood a plate or sheet whose electrical resistivity is smaller than that of the non-irradiated (dark-adapted) photoconductive layer i.e. in general smaller than 10⁹ohm/cm and preferably is at least 100 times as small as that of the recording layer. Supports whose resistivity is not higher than 10⁷ ohm/cm are preferred. The recording layers itself have preferably an electrical insulating power as high as possible without affecting too much the photosensitivity by means of a too high amount of insulating binding agent. Preferably the recording layers have in non-irradiated state (dark adapted state) a resistivity of at least 10⁹ ohm/cm.

Suitable conductive plates are, e.g., plates of metals such as aluminum, zinc, copper, tin, iron, or lead.

Suitable electroconductive interlayers for insulating supports are, e.g., vacuum-coated metal and conductive metal compound (metal oxide or metal salt) layers such as silver, tin aluminum, titanium dioxide and copper iodide conductive layers, transparent conductive polymer layers, e.g. applied from polymers containing quatemized nitrogen atoms, such as those described in the U.K. Pat. Specification No. 950,960 filed Sept. 23, 1960 by Gevaert Photo-Producten N.V. or layers containing conductive particles, e.g. carbon black and metal particles dispersed in a binder. The binder used for said particles has a resistivity preferably lower than 10^e ohm/cm. A suitable binder for that purpose is gelatin.

It is possible to produce transparent photoconductive recording materials by applying the photoconductive compounds together with a suitable binder (if necessary) from a clear solution to a conductive transparent base or a transparent insulating base coated with an electroconductive transparent interlayer.

As transparent bases resin sheets having an optical density of not more than 0.10 are preferred, e.g., a sheet made of polyethylene terephthalate or cellulose triacetate. The conductive interlayer preferably consists of a metal coating, e.g., a vacuum-coated aluminium layer having an optical density of not more than 0.30 or of a conductive transparent polymer layer composed, e.g., of an organic polyionic polymer, e.g. a polymer containing quatemized nitrogen atoms such as a quatemized polyethylene-imine.

In reproduction techniques wherein the prints are to be produced on an opaque background preferably a paper sheet is used as support for the recording layer.

Paper sheets that have an insufficient electrical conductivity are coated or impregnated with substances enhancing their conductivity, e.g. by means of a conductive overcoat such as a metal sheet laminated thereto.

As substances suited for enchancing the conductivity of a paper sheet and which can be applied in the paper mass are particularly mentioned hygroscopic compounds and antistatic agents as described, e.g., in the U.K. Pat. Specification No. 964,877 filed May 2, 1960 by Gevaert Photo-Producten N.V., and antistatic agents of polyionic type, e.g. CALGON CONDUCTIVE POLYMER 261 (registered trademark of Calgon Corporation, Inc., Pittsburgh, Pa., U.S.A, for a solution containing 39.1 percent by weight of active conductive solids, and which contain a conductive polymer having recurring units of the following type:

H3C -f- CH3 ' h₂c^// -Cl

CH-CHi--HC paper.

Electrophotographic materials according to the present invention can be used in any of the different techniques known in recording with the aid of photoconductors. According to a preferred embodiment they are used in a technique based on the discharge of an electrostatically charged recording layer by exposure to light.

Photoconductive recording materials prepared according to the present invention can be used in exposure units equiped with incandescent lamps, so that they need not be exposed with light rays rich in ultraviolet such as those emitted by a high-pressure mercury vapor bulb.

The electrostatic charging of photoconductive recording elements according to the present invention can be effected according to any method known in electrophotography, e.g. by friction with a smooth material, with a material possessing a high electric resistance, e.g. a cylinder coated with polystyrene, by corona discharge, by contact charge, or by discharge of a capacitor.

Recording materials containing the said organic photoconductive substances can be used in a recording technique com²⁵ prising a negative corona charging as well as in a recording technique comprising a positive corona charging.

In order to obtain an electrostatic image, it is possible to effect the charging and exposure steps simultaneously and even ,- to expose the recording layer image-wise before charging ^υ since a conductivity image is formed that is not destroyed immediately, especially if diazonium salts are used in the recording element. It is preferred, however, that the charging is effected before image-wise exposure.

The electrostatic latent image can be converted into a visible image either on the electrophotographic material wherein the latent image was formed, or on a material to which the electrostatic latent image was transferred, e.g. by application of the method described in the Belgian Pat. Specification No.

4q 529,234 filed May 29,1954 by Battelle Development Co.

The conversion of the original or transferred latent image into a visible image can occur according to one of the techniques known in electrophotography, wherein use is made of a conductivity pattern (e.g. electrolysis) or the electrostatic 45 attraction or repulsion of finely divided colored substances, which, e.g. are present in a powder mixture, in an electrically insulating liquid (e.g. in the form of a suspension) or in a gas (e.g. in the form of an aerosol), or wherein electrostatic attraction is used for selectively wetting charged portions of the 50 recording layer, as described in the U.K. Patent Specification Nos. 1,020,505 filed Nov. 8, 1961 and 1,033,419 filed Nov. 26,1962 both by Gevaert Photo-Producten N.V.

When the sign of the charge of the developing powder or developing liquid is properly chosen, either a negative or a 55 positive print can be obtained from any original. If both printing material and developing powder or developing liquid have the same sign of charge, the powder only adheres to the . discharged areas so that a negative print is obtained. If the signs of the recording material and of the developing powder 60 or developing liquid differ, a positive print is obtained.

If a colored powder is used for making visible the latent image, the visible image obtained can, if necessary, be fixed according to one of the methods known in electrophotography, e.g. by heating, or it can be transferred to another sup65 port, e.g. according to the method described in the U.K. Pat. Specification No. 658,699 filed Apr. 14, 1949 by Battelle Memorial Institute, and fixed thereon.

The said heterocyclic organic photoconductive compounds can also be applied in a thermoplastic recording process to 70 form a ripple-image as described, e.g., in the U.K. Pat. Specification No. 964,881 filed May 17, 1960 by Gevaert PhotoProducten N.V. _ _____

Evidently, the present invention by no means is limited to one or other particular embodiment of using the electrophoto75 graphic material containing the photoconductive compounds

Ha

3,660,084

Behmenburg issued June 26, 1962. The following examples illustrate the present invention.

as described herein. The exposure technique the charging method, the formation of the charge pattern, the transfer of such pattern if applied, the developing method, and the fixation or the transfer of the developing material pattern may be modified or adapted.

The composition of the recording materials used in these methods may be adapted to the requirements of the recording process used.

Electrophotographic materials according to the present invention can be employed in reproduction techniques, wherein different kinds of electromagnetic radiations are used, e.g. visible light, U.V. light, X-rays and y-rays.

In order to prepare an electrophotographic material according to the present invention various techniques may be applied.

In practice, the photoconductive substances involved, either alone or together with other additives such as those described above, preferably are first dissolved or dispersed in a suitable organic solvent such as a ketone, e.g. acetone, chlorinated hydrocarbons, e.g. methylene chloride, and aliphatic esters, e.g. ethyl acetate, or in a mixture of two or more of such solvents. The solution or dispersion thus obtained is uniformly spread on a surface of a suitable support, e.g. by centrifuging, spraying, brushing, or coating. Thereupon the layer formed is dried in such a way that a solid photoconductive layer is formed on the surface of the support.

With regard to the structure of the photoconductive compounds used according to the present invention we do not limit said compounds to the particular atoms and groups that have been indicated already for the value of the bivalent substituent X. Indeed, X may be any atom or group having an electronegative character with respect to the carbon atom of the quinoline nucleus to which it is attached in the 2- or 4position. So, in addition to the atoms and groups already mentioned we include also e.g. for the meaning of = X each group introduced by means of an active methylene compound and wherein the carbon atom of the active methylene compound becomes double bonded to the quinoline nucleus in the X substituent position. For example the group

Q =c^z wherein each of Q and Q' represents an electronegative substituent e.g. a cyano group, an aryl group an acyl group e.g. a benzoyl group, a carboxylic ester group, an amide group or a substituted amide group, or Q and Q' represent the necessary atoms to close a heterocyclic ring having an electronegative character e.g. a pyrazolone-5 nucleus. In that respect are particularly mentioned the following groups in the meaning of = X:

<img file="US3660084A_D0057.tif" />

<img file="US3660084A_D0058.tif" />

Groups of that type are generally known from merocyanine dye chemistry and can be introduced in a carbonyl group containing compound e.g. according to a preparation technique described in the U.K. Pat. Specification No. 869,138 filed July 11, 1957 by Gevaert Photo-Producten N.V. and are examplified as suitable substituents in photoconductive compounds in the U.S. Pat. No. 3,041,165 of Oskar Sils, Kurt-Walter Kliipfel, Wilhelm Neugebauer, Martha Tomanek and Hans

EXAMPLE 1

To a polyethylene terephthalate support of 100 μ a conductive transparent coating was applied from an aqueous solution of gelatin and CALGON CONDUCTIVE POLYMER 261 (trade name) in a weight ratio of 2:1. Coating was carried out 10 in such a way that the dried coating contained 2 g of gelatin per sq. m. The electrical resistivity of the coating was 1 X 10“ ohms per sq. cm.

An electrophotographic recording material was prepared by coating onto said conductive layer a solution containing:

¹⁵ C₂H₅ 5 g.

<img file="US3660084A_D0059.tif" />

Copoly(vinyl chloride/vinyl acetate/maleic anhydride) (mol 5 g. ratio: 86.5/13.3/0.2).

Methylene chloride-------------------------------------------- 100 ml.

The solution was applied in such a ratio that the dried recording layer contained 3 g per sq. m. of said quinolin-2-one compound as photoconductor.

After a negative corona charging with a potential difference of —6,000 V between the corona wires and the ground, the 30 charged recording layer was contact-exposed for 5 sec. through a positive transparency of a test chart with incandescent bulbs that together represent 100 watts and were placed at a distance of 30 cm.

After exposure the development was carried out with a 35 triboelectrically charged positive toner on the base of three parts by weight of pitch, four parts by weight of colophony and three parts by weight of carbon black.

A contrasty transparent positive copy of the transparency was obtained.

Analogous results as obtained with said quinolin-2-one compound were obtained with same amounts of heterocyclic organic photoconductive substances having the following structural formulae

<img file="US3660084A_D0060.tif" />

<img file="US3660084A_D0061.tif" />

On applying a positive corona charging with a potential difference of +6,000 V between the corona wires and the ground the exposure time lasted only 3 sec. to obtain a good image with the developer described in Example 4 hereinafter.

3,660,084

As spectral sensitizing agent:

Orange Astrazon R (C.I. Basic Orange 22; C.I. 48,040) having 0.020 g.

the following structural formula:

EXAMPLE 2

To an aluminum laminated paper a solution containing:

l-ethyl-3-phenyl-7-diethylamino-2-( 1H)quinolone 7.5 g.

1,2-dichloroethane 100 ml.

copoly(vinyl chloride/vinyl acetate/maleic anhydride) (mol ratio : 86.5/13.3/0.2) 5 g.

were applied with a reverse roller coater.

The coating proceeded in such a way that the dried recording layer contained 2.5 g of l-ethyl-3-phenyl-7-diethylamino2-( 1H) quinolone per sq. m. The obtained recording material was called material (A).

An electrophotographic recording material (B) was prepared by coating onto a same aluminum-laminated paper a solution containing:

-ethyl-3-phenyl-7-diethylamino-2-( 1H) quinolone 7.5 g.

Rhodamine B (C.I. Basic Violet 10; C.I.

45,170) 0.020 g.

The dried recording layer contained also 2.5 g of l-ethyl-3phenyl-7-diethylamino-2-( 1H )quinolone per sq. m.

Each of the coated samples (A) and (B) was negatively charged with a negative corona having a potential difference of—6,000 V between the corona wires and the ground.

The sample (A) was contact-exposed for 15 sec. at a distance of 25 cm through a step wedge having 0.30 log exposure increments by means of an OSRAM L 40 watt A 70 fluorescent tube having an emission maximum at 365 nm.

The sample (B) was contact-exposed for a same period of time at a distance of 25 cm through a step wedge having 0.30 log exposure increments by means of a tungsten filament lamp exposing the recording layer with 2,400 lux and having a color temperature of 2,600° K.

The latent wedge images were electrophoretically developed and contrasty copies were obtained. The electrophoretic developer used in the development was obtained by diluting the concentrated developer composition described hereinafter in a volume ratio of 15/1,000 by means of ISOPAR H (trade name for an isoparaffinic hydrocarbon mixture having a boiling range of 177°-188° C sold by Esso Belgium, N.V., Antwerp, Belgium):

carbon black (average particle size : 20 nm) 30 g.

zinc monotridecyl phosphate as dispersing agent 1.5 g.

ISOPAR H (trade name) 750 ml.

resin solution prepared as described hereinafter 150 g.

The resin binder solution was prepared by heating 500 g of ALKYDAL L 67 (trade name of Farbenfabriken Bayer A.G., Leverkusen, W. Germany, for a linseed oil-modified (67 percent by weight alkyd resin)) and 500 cc. of white spirit containing 11 percent by weight of aromatic compounds at 60° C till a clear solution was obtained, and subsequent cooling.

Analogous results as those obtained above were obtained by using 1 -ethyl-3-phenyl-7-dimethylamino-2-( 1 H)-quinolone instead of the 7-diethylamino quinolone compound.

EXAMPLE 3

To a glassine paper of 60 g per sq. m. the following solution was applied:

l-ethyl-3-phenyl-7-diethylamino-2( 1H)quinolone 7.5 g.

FORMVAR 1595 E (a trade name for a polyvinylformal marketed by Shawinigan Resins Corporation, Springfield Mass., U.S.A.) 5 g.

<img file="US3660084A_D0062.tif" />

Acetone------------------------------------------------------ 75 ml.

The solution was applied at such a rate that the dried recording layer contained 2 g of l-ethyl-3-phenyl-7diethylamino-2(lH)-quinolone per sq. m.

After a negative corona charging with a potential difference of —6,000 V between the corona wires and the ground, the charged recording layer was contact-exposed for 3 sec. through a positive transparency of a test chart with incandescent bulbs that together represent 100 watts and were placed at a distance of 30 cm.

After the exposure the development was carried out with a triboelectrically charged positive toner on the base of three parts by weight of pitch, four parts by weight of colophony and three parts by weight of carbon black.

A constrasty positive copy of the transparency was obtained.

On adapting the exposure intensity analogous results were obtained with each of the compounds exemplified in the Tables I, Π and ΙΠ.

EXAMPLE 4

Example 3 was repeated with the difference, however, that the recording layer was positively corona-charged with a corona potential difference of +6,000 V between the corona wires and the ground.

The positively charged recording layer was exposed for 1 sec. through a test chart by means of tungsten filament lamps irradiating the recording layer with 1,400 lux.

The positive charge image on the exposed recording layer was electrophoretically developed with a developer obtained by diluting the concentrated developer composition described hereinafter in a volume ratio of 15/1,000 by means of SHELLSOL T (trade name for a hydrocarbon solvent marketed by Shell, Belgium, having a boiling range of 175°-200° C, specific gravity at 15° C: 0.764, viscosity at 25° C: 1.62 centipoise, flash point (Pensky-Martens) open cup: 71° C — closed cup: 53° C) Kauri-butanol number: 31 ASTMnorm D- 1,133 - 54 T) carbon black (average particle size : 20 nm) 30 g.

lecithine 1.5 g.

SHELLSOL T (trade name) 750 ml.

resin solution prepared as described hereinafter 150 g.

The resin binder solution was prepared by heating at 60° C

500 g of ALKYDAL L 67 (trade name of Farbenfabriken Bayer A.G., Leverkusen, W. Germany for a linseed oilmodified (67 percent by weight alkyd resin)) and 500 cc. of white spirit containing 11 percent by weight of aromatic compounds till a clear solution was obtained, and subsequent cooling.

An image with high detail reproduction was obtained.

EXAMPLE 5

A solution of 4 g of l-ethyl-3-phenyl-7dimethylamino-2(IH)-quinolone and 5 g of copoly(vinyl chloride/vinyl acetate/maleic anhydride)(mole ratio 86.5/13.3/0.2) in a mixture of 50 ml of methylene chloride and 50 ml of acetone was

3,660,084 prepared. A sample of this unsensitized photoconductor composition was coated at a ratio of 2 g of photoconductor per sq. m. on a sheet of aluminum foil laminated to a paper support.

Other samples of the unsensitized coating composition were sensitized by addition of 0.05 g of the sensitizing compounds 5 mentioned in Table V and coated in the same way as the unsensitized sample.

Each of the coated samples was negatively charged with a negative corona having a potential difference of —6,000 V between the corona wires and the ground and then exposed for 15 sec. with 2,000 lux emitted by means of an incandescent lamp placed at a distance of 25 cm through a step wedge having 0.20 log exposure increments between consecutive steps.

The latent wedge images were electrophoretically ¹⁵developed by means of an electrophoretic developer obtained by diluting the concentrated developer composition described hereinafter in a volume ratio of 15/1,000 by means of the hydrocarbon solvent SHELLSOL T (trade name):

carbon black (average particle size : 20 mu) 30 g.

zinc monotridecyl phosphate 1.5 g.

SHELLSOL T (trade name) 750 ml.

resin solution prepared as described hereinafter 150 g. 25

The resin binder solution was prepared by heating 500 g of ALKYDAL L 67 (trade name of Farbenfabriken Bayer A.G., Leverkusen, W. Germany for a linseed oil (67 percent by weight)—modified alkyd resin) and 500 ml of white spirit con- 30 taining 11 percent by weight of aromatic compounds at 60° C till a clear solution was obtained, and subsequent cooling.

Relative speed values of the developed samples were calculated based on a comparison of the number of visible steps in the wedge images obtained in the sensitized photoconductor materials with the number of visible steps produced in an unsensitized coating, given a relative speed of 100. The visible steps are the area of the wedge image that correspond with the discharge area on exposure.

The following Table V lists the relative speed values for these coatings.

TABLEV

<td> Sensitizing compound number</td><td> Relative speed</td>

<td> none</td><td> 100</td>

<td> 1</td><td> 1700</td>

<td> 2</td><td> 250</td>

<td> 3</td><td> 160</td>

<td> 4</td><td> 250</td>

<td> 5</td><td> 1700</td>

<td> 6</td><td> 160</td>

<td> 7</td><td> 160</td>

<td> 8</td><td> 160</td>

<td> 9</td><td> 160</td>

<td> 10</td><td> 250</td>

<td> 11</td><td> 250</td>

<td> 12</td><td> 4200</td>

<td> 13</td><td> 1000</td>

<td> 14</td><td> 4200</td>

<img file="US3660084A_D0063.tif" />

<img file="US3660084A_D0064.tif" />

<img file="US3660084A_D0065.tif" />

H5C2

C2H5 3,660,084

<img file="US3660084A_D0066.tif" />

<img file="US3660084A_D0067.tif" />

<img file="US3660084A_D0068.tif" />

<img file="US3660084A_D0069.tif" />

EXAMPLE 6

To a polyethylene terephthalate support of 100 μ a conductive transparent coating was applied from an aqueous solution of gelatin and CALGON CONDUCTIVE POLYMER 261 66 (trade name) in a weight ratio of 2:1. The coating was carried out in such a way that the dried coating contained 2 g of gelatin per sq. m. The electrical resistivity of the coating was 1 x 10® ohms per sq. cm.

An electrophotographic recording material was prepared by γθ coating onto said conductive layer a composition containing:

-ethyl-3-phenyl-7-diethylamino-2-( 1H)quinolone 7.5 g.

copoly( vinyl chloride/vinyl acetate/maleic anhydride)(mol ratio: 86.5/13.3/0.2) 5 g.

3,660,084 photoconductive zinc oxide powder prepared by oxidation of zinc vapour 4 g.

acetone 100 ml.

The dried semitransparent recording layer contained 5.6 g of organic photoconductor per sq. m.

After a negative corona charging with a potential difference of —6,000 V between the corona wires and the ground, the recording layer was contact exposed for 5 sec. through a transparent test chart original with a high pressure mercury vapor lamp of 80 watts mainly emitting in the ultraviolet wavelength range of the spectrum and being placed at a distance of 25 cm of the recording layer.

The electrophoretic development was carried out as described in Example 5.

A sharp and contrasty semitransparent copy of the original was obtained.

EXAMPLE 7

To an aluminum-laminated paper a solution was applied containing:

l-ethyl-3-phenyl-7-diethylamino-quinoline-2one 5 g.

ELVACITE 2041 (a trade name for a polymethyl methacrylate marketed by E.I.

du Pont de Nemours &amp; Co. Inc.

Wilmington, Del., U.S.A.) 5 g.

methylene chloride 100 ml.

The coating proceeded in such a way that the dried recording layer contained 2.5 g of photoconductive compound per sq. m.

The obtained recording material was negatively coronacharged with a corona-charging apparatus having a potential difference of —6,000 V between the corona wires and the ground. Thereupon it was contact-exposed for 45 sec. at a distance of 30 cm through a step wedge having 0.20 log exposure increments using 5 OSRAM L 20 W/70 fluorescent tubes mainly emitting in the U. V. range and the shorter wavelengths of the visible spectrum (OSRAM is a trade name).

After the exposure the development was carried out as described in Example 2.

A contrasty opaque positive copy of the step wedge was obtained.

EXAMPLE 8

Example 7 was repeated by using, however, as binding agent MOWILITH 20 (trade name for a polyvinyl acetate marketed by Farbwerke Hoechst A.G., Frankfurt (M) Hochst, W. Germany). The same amounts of polymer and solvent were applied as in Example 7, the solvent, however, now being acetone.

Exposure and processing as described in Example 7 yielded the same image result.

EXAMPLE 9

To a polyethylene terephthalate support of 100 μ a conductive transparent coating was applied from an aqueous solution of gelatin and CALGON CONDUCTIVE POLYMER 261 (trade name) in a weight ratio of 2:1. The coating was carried out in such a way that the dried coating contained 2 g of gelatin per sq. m. The electrical resistivity of the coating was 1 x 10* ohms per sq.cm.

An electrophotographic recording material was prepared by coating onto said conductive layer a solution containing:

C2H5 5 g.

<img file="US3660084A_D0070.tif" />

As chemical sensitizing agent:

Cl -. _2g

I c

HsC^ %-Cl

I I

C1-C:^=C-C1

Copoly(vinyl cholride/vinyl acetate/maleic anhydride) (mol 5 g. ratio: 86.5/13.3/0.2).

Methylene chloride------------------------------------------- 100ml.

The solution was applied in such a ratio that the dried recording layer contained 2 g per sq. m of said quinoline-2one compound as photoconductor.

After a negative corona charging with a potential difference of —6,000 V between the corona wires and the ground, the charged recording layer was contact-exposed for 7 sec. through a positive transparency of a test chart with incandescent bulbs that together represent 100 watts and were placed at a distance of 30 cm.

After the exposure the development was carried out as described in Example 2.

A contrasty transparent positive copy of the original was obtained.

EXAMPLE 10

A solution of 5 g of l-ethyl-3-phenyl-7-diethylamino-2(IH)-quinolone and 5 g of copoly(vinylchloride/vinylace tate/maleic anhydride) (mole ratio 86.5/13.3/0.2) in a mixture of 100 ml of methylene chloride was prepared.

A sample of this unsensitized photoconductor composition was coated in a ratio of 2 g of photoconductor per sq. m on a sheet of aluminum foil laminated to a paper support.

Other samples of the unsensitized coating composition were sensitized by addition of 0.2 g of the sensitizing compounds mentioned in Table VI and coated in the same way as the unsensitized sample.

Each of the coated samples was negatively charged with a negative corona having a potential difference of —6,000 V between the corona wires and the ground and then exposed for 30 sec. with 1,400 lux emitted by means of an incandescent lamp placed at a distance of 25 cm through a step wedge having 0.20 log exposure increments between consecutive steps.

The latent wedge images were electrophoretically developed by means of the electrophoretic developer described in Example 5.

Relative speed values of the developed samples were calculated based on a comparison of the number of visible steps in the wedge images obtained in the sensitized photoconductor materials with the number of visible steps produced in an unsensitized coating, given a relative speed of 100. The visible steps are the area of the wedge image that correspond with the discharged area on exposure.

The following Table VI lists the relative speed values for these coatings.

TABLE VI

<td> Sensitizing compound number</td><td> Relative speed</td>

<td> none</td><td> 100</td>

<td> 1</td><td> 250</td>

<td> 2</td><td> 1600</td>

<td> 3</td><td> 250</td>

<td> 4</td><td> 250</td>

<td> 5</td><td> 2500</td>

<td> 6</td><td> 250</td>

<td> 7</td><td> 2500</td>

<td> 8</td><td> 400</td>

3,660,084

40

COOH

<img file="US3660084A_D0071.tif" />

The coating proceeded in such a way that the dried recording layer contained 2.5 g of photoconductive compound 30 of

Table Π per sq. m.

The obtained recording material was negatively corona5 charged with a corona-charging apparatus having a potential difference of —5,000 V between the corona wires and the ground. Thereupon it was contact-exposed for 30 sec. at a distance of 30 cm through a step wedge having 0.20 log exposure increments using 5 OSRAM L 20 W/70 fluorescent tubes mainly emitting in the U.V. range and the shorter wavelengths of the visible spectrum (OSRAM is a trade name).

After the exposure the development was carried out with triboelectrically charged positive toner on the base of three parts by weight of pitch, four parts by weight of colophonium and three parts by weight of carbon black.

A contrasty transparent positive copy of the wedge was obtained.

<img file="US3660084A_D0072.tif" />

Analogous results as obtained with compound 30 were ob2Q tained with compounds 26,27,28 and 29 of Table Π.

EXAMPLE 12

<img file="US3660084A_D0073.tif" />

<img file="US3660084A_D0074.tif" />

Example 11 was repeated but the material was positively corona-charged with a corona-charging apparatus having a 25 potential difference of +6,000 V between the corona wires and the ground.

After the exposure the positive charged image was developed with an electrophoretic developer obtained by diluting the concentrated developer composition described ³⁰ hereinafter in a volume ratio of 15/1,000 by means of SHELLSOL T (trade name for a hydrocarbon solvent marketed by Shell, Belgium, having a boiling range of 175°-2OO° C, specific gravity at 15° C: 0.764, viscosity at 25° C: 1.62 centipoise, 26 flashpoint (Pensky-Martens open cup: 71° C — closed cup: 53° C) kauri-butanol number: 31 ASTM norm D - 1133-54 T)

<img file="US3660084A_D0075.tif" />

carbon black (average particle size : 20 nm) 30 g.

lecithine 1.5 g.

SHELLSOL T (trade name) 750 ml.

resin solution prepared as described hereinafter 150 g.

<img file="US3660084A_D0076.tif" />

The resin binder solution was prepared by heating at 60° C 45 500 g of ALKYDAL L 67 (trade name of Farbenfabriken Bayer A.G., Leverkusen, W. Germany for a linseed oilmodified alkyd resin (67 percent by weight, alkyd) and 500 cc. of white spirit containing 11 percent by weight of aromatic compounds till a clear solution was obtained, and subsequent cooling.

An image with high detail reproduction was obtained.

<img file="US3660084A_D0077.tif" />

EXAMPLE 11

EXAMPLE 13

Example 11 was repeated with the difference however, that as binding agent instead of said 5 g of copoly( vinyl chloride/vinyl acetate/maleic anhydride) a mixture of 3 g of SILICON HARZ UD 160 (trade name of Farbenfabriken Beyer AG, Leverkusen, W. Germany, for an organic silicon oxide polymeric binding agent) and 3 g of EPON 1031 (trade name of Shell Chemical Co., U.S.A, for a tetraglycidyl ether of tetraphenylene ethane) were used.

Other suitable resin binders for the photoconductive compounds according to the present invention that can be used 65 alone or in admixture are poly-n-vinyl butyral and copoly( vinyl acetate/vinyl laurate) (80/20 by weight).

EXAMPLE 14

To a polyethylene terephthalate support of 100 μ a conductive transparent layer was applied from an aqueous solution of gelatin and CALGON CONDUCTIVE POLYMER 261 (trade name) in a weight ratio of 2:1. The coating was carried out in such a way that the dried coating contained 2 g of gelatin per sq. m. The electrical resistivity of the coating was 1 x 10* ohms per sq. cm.

To an aluminum laminated paper a solution was applied containing:

compound 30 of Table II 10 g.

copoly( vinyl chloride/vinyl acetate/maleic anhydride) mol.ratio: 86.5/13.3/0.2 5 g.

methylene chloride 100 ml.

3,660,084

42

<img file="US3660084A_D0078.tif" />

<img file="US3660084A_D0079.tif" />

Different electrophotographic recording materials were prepared by coating onto said conductive layer a compositioncontaining a 20 percent by weight solution in methylene chloride of copoly( vinyl chloride/vinyl acetate/maleic anhydride)(mol ratio: 86.5/13.3/0.2) and a 20 percent by weight ⁵solution in dimethylformamide or methylene chloride of the hereinafter in Table VH indicated photoconductor.

The solution was applied in such a ratio that the dried recording layer strips contained 3 g of photoconductor per sq. m.

Under the same conditions the dried strips were negatively charged with a corona-charging device having a potential difference of —6,000 V between the corona wires and the ground. . 15

Still under the same conditions all the charged recording layer strips were exposed with ultraviolet light through a step wedge having 0.20 log exposure increments between consecutive steps.

The development of the exposed strips proceeded as ₂θ described in Example 2.

Relative speed values of the developed strips were calculated based on a comparison with the speed of the test material A containing l-ethyl-3-phenyl-7-dimethylamino-2-(lH)quinolone called hereinafter compound A. The speed of the 25 test material A was given arbitrarily the value 100.

TABLE VII

Test material Compound No. Relative speed

<td> A</td><td> A</td><td> 100</td><td> 35</td>

<td> B</td><td> 14 of Table II</td><td> 10</td><td></td>

<td> C</td><td> 32 of Table Π</td><td> 20</td><td></td>

<td> D</td><td> 33 of Table II</td><td> 1</td><td></td>

<td> E</td><td> 31 of Table II</td><td> 100</td><td></td>

<td> F</td><td> 12 of Table I</td><td> 6</td><td></td>

<td> G</td><td> 8 of Table I</td><td> 6</td><td rowspan="2"> 40</td>

<td> H</td><td> 49 of Table I</td><td> 10</td>

Analogous results as obtained with test material G are obtained with the following compounds: 45

Ri I

R's (Π)

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wherein:

Z' represents the necessary atoms to close a benzene nucleus including a benzene nucleus free from any other substituents than hydrogen and a benzene nucleus that is substituted with a substituent selected from the group consisting of an alkyl group, hydroxyl, an alkoxy group, amino, an alkyl substituted amino group, fluorine, chlorine, nitro, sulfonylfluoride, alkoxy carbonyl, phenyl—COHN—, dialkylaminosulfonyl, an alkyl—NH— CO—group or an alkyl—CO—NH—group,

R, represents hydrogen, an alkyl group or a phenyl group, R'₂ represents hydrogen, nitro, an alkyl group or a phenyl group,

R'_s represents hydrogen, hydroxyl, an alkyl group, a phenyl group or linked to the carbon atom in the five-position of the heterocyclic ring system the chain —CH = CH—CH

-CH—,

R_s represents hydrogen, an alkyl group, a phenyl group, a phenyl—NH—group, a phenyl—NHCO—group, a (phenyl),— N—CO— group or represents together with R₃ a closed —CH = CH—CH = CH— chain,

Rs represents hydrogen, an alkyl group, a phenyl group, — COOHor —COO alkyl,

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Melting point: &gt;260°_C.