US3660084A - Recording process using quinolin-2-one or quinolin-4-one organic photoconductive substances - Google Patents

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

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US3660084A
US3660084A US22376A US3660084DA US3660084A US 3660084 A US3660084 A US 3660084A US 22376 A US22376 A US 22376A US 3660084D A US3660084D A US 3660084DA US 3660084 A US3660084 A US 3660084A
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photoconductive
recording
pattern
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Johannes Joseph Vanheertum
Albert Lucien Poot
Jozef Frans Willems
Wilhelmus Janssens
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Agfa Gevaert NV
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
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    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
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    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
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    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
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    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637—Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
    • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
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    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18—Luminescent screens
    • H01J29/22—Luminescent screens characterised by the binder or adhesive for securing the luminescent material to its support, e.g. vessel
    • H01J29/225—Luminescent screens characterised by the binder or adhesive for securing the luminescent material to its support, e.g. vessel photosensitive adhesive

Definitions

  • 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.
  • .an inorganic or organic photoconductor e.g. selenium, zinc oxide, anthracene, and particular heterocyclic compounds
  • 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.
  • 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
  • n is one or two.
  • the present invention includes also the use in a recording and reproduction process of the tautomeric structures of said compounds.
  • Tautomeric structures are derived from said compounds wherein R represents hydrogen.
  • Photoconductive compounds within the scope of said general formula and that are suitable for use according to the present invention are photoconductive compounds of the quinolin-Z-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 with a carbocyclic or heterocyclic radical of aromatic nature, an oxime group, a hydrazone group or a substituted hydrazone group.
  • a pattern of increased conductivity is produced in a photoconductive insulating recording element containing a heterocyclic organic photoconductive compound having the following structural formula:
  • L and L 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
  • GN group an oxime group, particularly a NOR group wherein v R is hydrogen or an aliphatic group, e.g. an alkyl group, or a hydrazone group or a substituted hydrazone group particularly a /RII III: (B) R1 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 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 (CONH,) 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 fonn and such ring that makes part of a fused ring system;
  • 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 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 CONHCl-i group an aminoacyl group e.g. a NHCC H, group, a sulphamoyl group, a N-substituted sulphamoyl group e.g. a --SO N(CH group, a sulphonylfluoride group, a car bonylalkoxy group e. g. a carbethoxy group,
  • R represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group, e. g. an alkyl group including a substituted alkyl group e.g. a C C 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 ester group e.g. a carbonylal- I koxy group such as a carbethoxy group, a carbamoyl group including a substituted carbamoyl group, an amino group including a substituted amino group,
  • a hydrocarbon group including a substituted hydrocarbon group e. g. an alkyl group including a substituted alkyl group e.g. a C C alkyl group, an aralkyl group including a substituted aralkyl group, a cycloalkyl group including a substituted cycl
  • R represents hydrogen, a hydrocarbon group including a substituted hydrocarbon group e.g. an alkyl group including a substituted alkyl group e.g. a C -C 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, a carboxylic acid group, an ester group e.g. a carbonylalkoxy group such as a carbethoxy group, or a carbarnoyl group including a substituted carbamoyl group, and
  • R and R together represent the necessary atoms to close a homocyclic ring including such ring in substituted form or making part of a fused ring system.
  • Said heterocyclic compounds e.g. those containing the quinolin-2- or 4-one ring system can be introduced into a polymeric chain by known methods, e.g. by introducing in said i system an a,B-ethylenically unsaturated group and by applying a subsequent proper ionic or radical polymerization, or by linking said ring system to an already existing polymer chain by 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 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.
  • quinolin-Z-one compounds also called carbostyril compounds
  • Preferred photoconductive compounds are quinoline compounds, that contain the above indicated value for X and an electron-donating (electron-rich) substituent e.g. a hydroxy, amino, alkyl substituted amino, alkoxy or alkyl group.
  • an electron-donating (electron-rich) substituent e.g. a hydroxy, amino, alkyl substituted amino, alkoxy or alkyl group.
  • a dialkylamino group is present as a substituent on the aromatic ring part of the quinolin-Z-one or quinolin-4-one compound, or photoconductive derivatives 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.
  • n m mmc nmo mm n mmv c 5 0522 2 00 m n G 50 @N 83 506wmz2 m m 0520 m m 50 x 3 8 m m m m m m 6% 2 5m 0 l E 2 m m m m m 2 8E 8 m m 200 m m EQW Q 50 3 s 5 m m 05m m n O 8 83 28.2..
  • Such preferred compounds are e.g. l-ethyl-3phenyl-7- dimethylamino-quinolin-Z-one, l-ethyl-3phenyl-7- diethylamino-quinolin-Z-one and which are also called 1- ethyl-3-phenyl-7-dimethylaminocarbostyril and l-ethyl-3- phenyl-7-diethylaminocarbostyril respectively.
  • the former compound can, e.g., be prepared as follows, the parts being by weight:
  • l-methyl-3-(4'-methylphenyl)-7-dimethylaminocarbostyril 6o (l-90 C), l-methyl-3-(4'-methylphenyl) 6-methyl-7- dimethylaminocarbostyril (152-153 C), l-methyl-3-(3,5- dimethylphenyl)-7-dimethylaminocarbostyril (l5 l-153 C), l-ethyl-3-( 3 '-chlorophenyl)-7-dimethyl-aminocarbostyril (l6l-62 C), l-ethyl-3-phenyl-7-monoethylaminocarbostyril (l78-l 80 C), l-ethyl-3-phenyl-7-N-methyl-N- ethylarninocarbostyril (75-78 C).
  • the nitro group is reduced to an amino group, which for the purpose of the present inven- 70 tion preferably is alkylated.
  • alkylation for preparing l-ethyl-3-phenyl-7- diethylarninoquinolin-2-onc preferably is carried out as fol- I lows:
  • 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:
  • 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:
  • R, R, R and R substituents may have the significance of the corresponding substituents of the general formula above Table II.
  • ketoesterfl ketoesterfl
  • aromatic amine (II) is 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 (III) 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 to h. at about C. Thereupon the reaction mass is treated with an aqueous lN sodium hydroxide solution. The precipitate formed is separated by suction and the obtained product V is purified by crystallization.
  • reaction scheme A The operating conditions are the same as explained for reaction scheme A except for the alkylation reaction with ptolusulphonic acid alkyl ester.
  • R 1 represents an alkyl iodide e.g. methyl iodide.
  • 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).
  • quinoline compounds wherein X is an oxime group can be prepared according to a known method for producing an oxirne, e.g. as described by Vogel in Practical Organic Chemistry, 3rd Ed. Longmans, (1959) 741.
  • reaction scheme D is followed:
  • 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:
  • the quinoline compounds wherein X is a hydrazone group can be prepared according to a known method for producing a hydrazone compound starting from a ketone.
  • 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-quinoline- Z-dicyanomethylene.
  • 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.
  • These particles size between 1 and 5 p. 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.
  • 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.
  • reference is made to the Canadian Pat. Specification No. 712,541 filed 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 arable, microcrystalline waxes, modified natural substances such as cellulose 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 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.
  • a material suitable for use in electro-photography comprises a photoconductive layer incorporating an organic monomeric photoconductor and a halogen-containing polymer in such layer or in a juxtaposed layer (if any), e sensitivity of said photoconductor having been increased by making it to interact with said halogen-containing polymer by heating.
  • semi-transparent recording layers are prepared, in which said heterocyclic photoconductive compoundsare used in admixture with (an) inorganic photoconductive substance(s), especially photoconductive substances of the group of zinc oxide, photoconductive lead(ll) oxide and photoconductive cadmium sulphide.
  • an inorganic photoconductive compound such as photoconductive zinc oxide (1.5 g) in respect of 4 g of l-ethyl-3-phenyl-7-diethylaminoquinolin- 2-one ofiers 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 d same or difi'erent sensitizing dyestuffs.
  • an inorganic photoconductive compound such as photoconductive zinc oxide (1.5 g) in respect of 4 g of l-ethyl-3-phenyl-7-diethylaminoquinolin- 2-one ofiers 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 d same or difi'erent sensitizing dyestuff
  • Suitable spectral sensitizing dyestuffs for the organic photoconductor are among others organic dyestufis, known as methine dyes, or xanthene dyes of which the phthaleins and rhodamines are subclasses, and triarylmethane dyes e.g. crystal violet (C.l. 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.
  • methine dyes includes monoas 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.
  • preferred xanthene dyes Rhodamine B (C.l. 45,170), Rose Bengale (C.l. 45,440) and Fluorescein (C.l. 45,350) are mentioned.
  • the spectral sensitizing dyes are preferably added to the recording layer composition in a proportion of 0.01 to percent by weight in respect of the photoconductive substance(s).
  • methine dyes are within the scope of the following general formulae:
  • I. l a 4 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,
  • R stands for hydrogen or has one of the meanings given for 1) R stands for hydrogen, alkyl, alkoxy or halogen or together with R, forms an alkylene bridge such as dirnethylenc and trimethylene,
  • each of R and R stands for hydrogen, alkyl, alkoxy or halogen or together represent the atoms necessary to complete a fused-on benzene nucleus;
  • X represents an anion e.g. Cl, Br, 1', C10 CH SO] or HzC-Q-SO'u,
  • Z represents the atoms necessary to complete a heterocyclic nucleus of the types used in the production of cyanine dyes e.g. such as those of the thiazole series e.g. thiazole, 4- methylthiazole, 4-methyl-5-carbethoxythiazole, 4-phenylthiazole, S-methylthiazole, 5-phenylthiazole, 4-(p-tolyl)- thiazole, 4-(p-bromophenyl)-thiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole, 4-(m-nitrophenyl)-thiazole, those of the benzothiazole series, e.g. benzothiazole, 4-chlorobenz0thiazole, 5-chlorobenzothiazole,
  • naphtho[2,l-d]thiazole 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 series e.g.
  • 4-phenylthiadiazole those of the oxazole series e.g. 4-methyloxazole, S-methyloxazole, 4-phenyloxazole, 4,5- diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5- phenyloxazole, those of the benzoxazole series e.g.
  • benzoxazole S-chlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, -methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, 6-methoxybenzoxazole, S-hyclroxybenzoxazole, 6-hydroxybenzoxazole, those of the naphthoxazole series, e.g. naphtho[2, l -d]oxazole, naphtho[l,2-d]oxazole, those of the selenazole serieseg.
  • quinazoline series those of the l-phthalazine series, those of the Z-pyridine series e.g. pyridine, S-methylpyridine, 3- nitropyridine, those of the 3,3-dia1kylindolenine series e.g. 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7- trimethylindolenine, etc., those of the benzirnidazole series e.g.
  • benzirnidazole 5,6-dichlorobenzimidazole, 5- chlorobenzimidazole, 5,6-dibromobenzimidazole, 5-chloro-6- amino-benzimidazole, S-chloro-G-bromobenzimidazole, 5- phenylbenzimidazole, S-fluorobenzimidazole, 5,6-
  • fluoro-6-cyanobenzimidazole 5-acetylbenzimidazole, 5- chloro-6-fluorobenzimidazole, S-carboxybenzimidazole, 7- carboxybenzimidazole, S-carbethoxybenzimidazole, 7-carbethoxybenzimidazole, S-sulphamylbenzimidazole, or 5-N- ethylsulphamylbenzimidazole, S-ethylsulphonylbenzimidazole and 5-trifluoromethylsulphonylbenzirnidazole;
  • A stands for monomethine or trimethine including substituted monomethine or trimethine,
  • each of R -R and R R" (the same or different) has one of the meanings given for R R X -has the same significance as X,.
  • A has the same meaning as A each of m and p (the same or different) stands for one or two, and
  • each of Z and Z stands for the atoms necessary to complete a heterocyclic nucleus of the thiazole, benzothiazole, naphthothiazole, thionamhtheno[7,6- d]thiazole, thiadiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, 2-quinoline, 4-quinoline, pyrimidine, quinoxaline, quinazoline, 2-pyridine, 3,3-dialkylindolenine or of the benzimidazole series,
  • the dyestuffs corresponding to the above general formulae can be prepared according to the methods known by those skilled in the art of rnethine dye chemistry.
  • 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.
  • a binding agent or a curing agent can act as a sensitizing agent that enhances the total sensitivity of the recording element.
  • 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.
  • electromagnetic radiationsensitive diazonium salts that on exposure to electromagnetic radiation produce (a) radical(s) that irreversibly increase(s) the electroconductivity of the recording layer.
  • 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 UK. Pat. Specification No. 964,872 filed Apr. 22, 1959 by Gevaert Photo-Producten N.V. and the US. 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
  • additives well known in the art of preparing coatings 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 viscosity 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 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.
  • the transparencies obtained 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 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 latter may have the properties of a fluorescent compound or phosphor.
  • luminescent phosphors are used in screens of cathode-ray tubes and more particularly in television, X-ray, radar and oscilloscope screens.
  • 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 compound optionally incorporated in a vaporizable or thermolysable binding agent.
  • 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.
  • the photoconductive layer containing the phosphor powder image is heated in order to remove the volatile substances of the photoconductive recording layer and to make the phosphor pattern adhere to the screen support.
  • the powder image before applying the heating step it is preferably overcoated with a layer of a thennolysable binding agent.
  • the recording layer may further contain boric acid.
  • the photoconductors mentioned in the French patent specification are advantageously partly or wholly substituted by the photoconductive substances applied according to the present invention.
  • Suitable thennolysable binding agents belong to the class of the polyacrylic acid esters and polymethacrylic acid esters e.g. 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 require ments in each individual case. Good results are attained with photoconductive layers of a thickness between 1 and 20 p.
  • 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.
  • 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.
  • electroconductive plate or sheet 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 10ohm/cm and preferably is at least 100 times as small as that of the recording layer. Supports whose resistivity is not higher than 10 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.
  • the recording layers have in non-irradiated state (dark adapted state) a resistivity of at least 10 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 quaternized nitrogen atoms, such as those described in the UK. 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 ohm/cm.
  • a suitable binder for that purpose is gelatin,
  • 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 transparentpolymer layer composed, e.g., of an organic polyionic polymer, e.g. a polymer containing quaternized nitrogen atoms such as a quaternized polyethylene-imine.
  • 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.
  • 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 p l ectrophotographic materials according to the present invention can be used in any of the difierent 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 neednot 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 efiected 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 comprising a negative corona charging as well as in a recording technique comprising a positive corona charging.
  • 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. 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 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 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.
  • a conductivity pattern e.g. electrolysis
  • electrostatic 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)
  • CALGON CON- DUCTIVE POLYMER 261 (registered trademark of Calgon Corporation, lnc., Pittsburgh, Pa., USA. 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:
  • 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 support, e.g. according to the method described in the UK. Pat. Specification No. 658,699 filed Apr. 14, 1949 by Battelle Memorial Institute, and fixed thereon.
  • the said heterocyclic (Iganic photoconductive compounds can also be applied in a thermoplastic recording process to form a ripple-image as described, e.g., in the UK. Pat. Specification No. 964,881 filed May 17, 1960 by Gevaert Photo- BEEF?" -Y;
  • the present invention by no r rieans is limited to one or other particular embodiment of using the electrophotographic material containing the photoconductive compounds 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.
  • 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.
  • the photoconductive substances involved 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.
  • 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.
  • 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.
  • X may be any atom or group having an electronegative character with respect to the carbon atom of the quinoline nucleus to hich it is attached in the 2- or 4- position.
  • X may be any atom or group having an electronegative character with respect to the carbon atom of the quinoline nucleus to hich it is attached in the 2- or 4- position.
  • 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,
  • 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 electronegan've character e. g. a pyrazolone-S nucleus, In that respect are particularly mentioned the following groups in the meaning of X:
  • 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 UK. Pat. Specification No. 869,138 filed July 11, 1957 by Gevaert Photo-Producten NV. and are examplified as suitable substituents in photoconductive compounds in the US. Pat. No. 3,041,165 of Oskar Siis, Kurt-Walter Kliipfel, Wilhelm Neugebauer, Martha Tomanek and Hans Behmenburg issued June 26, 1962. The following examples lllustrate the present invention.
  • EXAMPLE ll To a polyethylene terephthalate support of p. a conductive transparent coating was applied from an aqueous solution of gelatin and CALGON CONDUCI'IVE POLYMER 261 (trade name) in a weight ratio of 2:1. 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 l X 10 ohms per sq. cm.
  • An electrophotographic recording material was prepared by coating onto said conductive layer a solution containing:
  • the solution was applied in such a ratio that the dried recording layer contained 3 g per sq. m. of said quinolin-Z-one compound as photoconductor.
  • the 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.
  • the dried recording layer contained also 2.5 g of l-ethyl-3- phenyl-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 difl'erence of 6,000 V between the corona wires and the ground.
  • the sample (A) was contact-exposed for 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 l5/ 1 ,000 by means of ISOPAR l-I (trade name for an isoparafiinic hydrocarbon mixture having a boiling range of l77l 88 C sold by Esso Belgium, N.V., Antwerp, Belgium):
  • carbon black (average particle size nm) 30 g. zinc monotridecyl phosphate as dispersing agent l.5 g. *lSOPAR H (trade name) 750 ml. resin solution prepared as described hereinafter 150 g.
  • FORMVAR 1595 E (a trade name for a polyvinylformal marketed by Shawinigan Resins Corporation, Springfield Mass, U.S.A.) 5 g.
  • the solution was applied at such a rate that the dried recording layer contained 2 g of l-ethyl-3-phenyl-7- diethylamino-2(lH)-quinolone per sq. m.
  • the charged recording layer was contact-exposed for 3 see. through a positive transparency of a test chart with incandescent bulbs that together represent watts and were placed at a distance of 30 cm.
  • 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.
  • Example 3 was repeated with the diflerence, 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/ l ,000 by means of SHELL- SOL 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 ASTM norm D 1,133 54 carbon black (average particle size 20 nm) 30 g. lecithine 1.5 g. SHELLSOL T (trade name) 750 m1.
  • the resin binder solution was prepared by heating at 60 C 500 g of ALKYDAL L 67 (trade name of Konverkusen, W. Germany for a linseed oilmodified (67 percent by weight alkyd resin)) and 500 cc. of white spirit containing 1 1 percent by weight of aromatic compounds till a clear solution was obtained, and subsequent cooling.
  • ALKYDAL L 67 trade name of Konverkusen, W. Germany for a linseed oilmodified (67 percent by weight alkyd resin)
  • EXAMPLE 5 A solution of 4 g of l-ethyl-3-phenyl-7dimethylamino-2- (lH)-quinolone and 5 g of copoly( vinyl chloride/vinyl acetate/maleic anhydride)(mole ratio 865/] 3.3/0.2) in a mixture of 50 ml of methylene chloride and 50 ml of acetone was prepared. A sample of this unsensitized photoconductor composition was coated at a ran'o of 2 g of photoconductor per sq. m. on a sheet of aluminum foil laminated to a paper support.
  • Each of the coated samples was negatively charged with a negative corona having a potential ditference 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 developed 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):
  • the resin binder solution was prepared by heating 500 g of ALKYDAL L 67 (trade name of Wegwood Bayer A.G., Leverkusen, W. Germany for a linseed oil (67 percent by weight)modified alkyd resin) and 500 ml of white spirit containing ll 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.
  • photoconductive zinc oxide powder prepared by oxidation of zinc vapour 4 g. acetone 100 ml.
  • 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.
  • the coating proceeded in such a way that the dried recording layer contained 2.5 g of photoconductive compound per
  • 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 WHO fluorescent tubes mainly emitting in the UV. range and the shorter wavelengths of the visible spectrum (OSRAM is a trade name).
  • Example 7 was repeated by using, however, as binding agent MOWlLITl-l 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.
  • MOWlLITl-l 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.
  • EXAMPLE 9 To a polyethylene terephthalate support of 100 p. 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:
  • the solution was applied in such a ratio that the dried recording layer contained 2 g per sq. m of said quinoline2- one compound as photoconductor.
  • the charged recording layer was contact-exposed for 7 sec. through a positive transparency of a test chart with incandescent bulbs that together represent l00 watts and were placed at a distance of 30 cm.
  • EXAMPLE 10 A solution of 5 g of l-ethyl-3-phenyl-7-diethylamino-2- (lH)-quinolone and 5 g of copoly(vinylchloride/vinylace tate/maleic anhydride) (mole ratio 86.5/l3.3/0.2) 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.
  • 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 see. 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Quinoline Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US22376A 1969-03-24 1970-03-24 Recording process using quinolin-2-one or quinolin-4-one organic photoconductive substances Expired - Lifetime US3660084A (en)

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BE (1) BE747849A (enrdf_load_stackoverflow)
CA (1) CA933011A (enrdf_load_stackoverflow)
CH (1) CH544326A (enrdf_load_stackoverflow)
FR (1) FR2039653A5 (enrdf_load_stackoverflow)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798031A (en) * 1971-11-10 1974-03-19 Agfa Gevaert Nv Photoconductive 1,2,3,4-tetrahydroquinolines employed in electrophotography
US3830647A (en) * 1970-12-11 1974-08-20 Agfa Gevaert Nv Recording process and element employing as photoconductive material fluorene ring system fused 1,2,-dihydro-2,2,4-trialkyl-quinolines
US4088482A (en) * 1971-07-13 1978-05-09 The Dow Chemical Company Organic photoconducting compositions containing aromatic sulfonyl fluorides and their use in electrophotographic processes
EP0531578A1 (en) * 1991-09-10 1993-03-17 Agfa-Gevaert N.V. Thermally transferable fluorescent compounds
US5242730A (en) * 1990-02-16 1993-09-07 Ricoh Company, Ltd. Optical recording medium
US5340675A (en) * 1990-06-19 1994-08-23 Agfa-Gevaert, N.V. Electrophotographic recording material
US20020197561A1 (en) * 2001-03-28 2002-12-26 Horst Berneth Optical data carrier comprising a cyclizable compound in the information layer
US20090246660A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Additive containing photoconductors
US20090246662A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Hydroxyquinoline containing photoconductors
US20090246666A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Thiadiazole containing photoconductors

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316087A (en) * 1959-10-31 1967-04-25 Azoplate Corp Photoconductor coatings for electrophotography
CA788892A (en) * 1968-07-02 Wirth Wolf-Dieter Brightening agents
US3475169A (en) * 1965-08-20 1969-10-28 Zenith Radio Corp Process of electrostatically screening color cathode-ray tubes
US3514459A (en) * 1963-04-02 1970-05-26 Cassella Farbwerke Mainkur Ag 7-hydroxy-3-aminoalkyl-2-oxo-1,2-dihydroquinoline esters and ethers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA788892A (en) * 1968-07-02 Wirth Wolf-Dieter Brightening agents
US3316087A (en) * 1959-10-31 1967-04-25 Azoplate Corp Photoconductor coatings for electrophotography
US3514459A (en) * 1963-04-02 1970-05-26 Cassella Farbwerke Mainkur Ag 7-hydroxy-3-aminoalkyl-2-oxo-1,2-dihydroquinoline esters and ethers
US3475169A (en) * 1965-08-20 1969-10-28 Zenith Radio Corp Process of electrostatically screening color cathode-ray tubes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830647A (en) * 1970-12-11 1974-08-20 Agfa Gevaert Nv Recording process and element employing as photoconductive material fluorene ring system fused 1,2,-dihydro-2,2,4-trialkyl-quinolines
US4088482A (en) * 1971-07-13 1978-05-09 The Dow Chemical Company Organic photoconducting compositions containing aromatic sulfonyl fluorides and their use in electrophotographic processes
US3798031A (en) * 1971-11-10 1974-03-19 Agfa Gevaert Nv Photoconductive 1,2,3,4-tetrahydroquinolines employed in electrophotography
US5242730A (en) * 1990-02-16 1993-09-07 Ricoh Company, Ltd. Optical recording medium
US5340675A (en) * 1990-06-19 1994-08-23 Agfa-Gevaert, N.V. Electrophotographic recording material
EP0531578A1 (en) * 1991-09-10 1993-03-17 Agfa-Gevaert N.V. Thermally transferable fluorescent compounds
US20020197561A1 (en) * 2001-03-28 2002-12-26 Horst Berneth Optical data carrier comprising a cyclizable compound in the information layer
US20090246660A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Additive containing photoconductors
US20090246662A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Hydroxyquinoline containing photoconductors
US20090246666A1 (en) * 2008-03-31 2009-10-01 Xerox Corporation Thiadiazole containing photoconductors
US7981578B2 (en) * 2008-03-31 2011-07-19 Xerox Corporation Additive containing photoconductors
US7981579B2 (en) * 2008-03-31 2011-07-19 Xerox Corporation Thiadiazole containing photoconductors
US7989129B2 (en) * 2008-03-31 2011-08-02 Xerox Corporation Hydroxyquinoline containing photoconductors

Also Published As

Publication number Publication date
NL7004174A (enrdf_load_stackoverflow) 1970-08-25
CH544326A (de) 1973-11-15
BE747849A (fr) 1970-09-23
SU368775A3 (enrdf_load_stackoverflow) 1973-01-26
JPS4817902B1 (enrdf_load_stackoverflow) 1973-06-01
CA933011A (en) 1973-09-04
FR2039653A5 (enrdf_load_stackoverflow) 1971-01-15

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