EP0058839B1 - Composés organiques donneurs d'électrons sensibilisés - Google Patents

Composés organiques donneurs d'électrons sensibilisés Download PDF

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Publication number
EP0058839B1
EP0058839B1 EP19820100686 EP82100686A EP0058839B1 EP 0058839 B1 EP0058839 B1 EP 0058839B1 EP 19820100686 EP19820100686 EP 19820100686 EP 82100686 A EP82100686 A EP 82100686A EP 0058839 B1 EP0058839 B1 EP 0058839B1
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Prior art keywords
group
layer
dye
nucleus
aliphatic
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German (de)
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EP0058839A1 (fr
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Louis M. Leichter
John J. Stofko, Jr.
Terry J. Sonnonstine
Paolo Beretta
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority claimed from US06/236,654 external-priority patent/US4337305A/en
Priority claimed from US06/237,067 external-priority patent/US4357405A/en
Priority claimed from US06/236,653 external-priority patent/US4356244A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0058839A1 publication Critical patent/EP0058839A1/fr
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    • 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
    • G03G5/0698—Compounds of unspecified structure characterised by a substituent only
    • 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
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0629—Heterocyclic compounds containing one hetero ring being five-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
    • G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
    • G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings
    • 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
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs

Definitions

  • the present invention relates to novel photoconductive layers which comprise organic electron donor compounds and sensitizer dyes selected from the group consisting of 1) phenylsulfonyl or benzoyl substituted imidazo-[4,5-b]-quinoxaline dyes, 2) phenylsulfonyl or benzoyl substituted indolenine dyes, and 3) highly fluorinated aliphatic sulfonyl sensitizer dyes. These layers are particularly useful in imaging systems such as electrophotography or electroradiography.
  • Imaging is effected by firstly uniformly electrostatically charging the surface of the photoconductive layer and then exposing the charged layer to an image or pattern of activating electromagnetic radiation, usually visible light or ultraviolet radiation. This exposure selectively enables the charge in the irradiated areas of the photoconductive insulator to dissipate. The charge which remains in the non-irradiated areas forms a latent image which may be further processed to form a more permanent record of the exposing image or pattern.
  • a common electrophotographic construction comprises, in sequence, a substrate, a conductive layer, and a photoconductive insulating layer.
  • Typical classes of photoconductive materials useful in electrophotography include 1) inorganic crystalline photoconductors such as cadmium sulfide, cadmium sulfoselenide, cadmium selenide, zinc sulfide, zinc oxide, and mixtures thereof, 2) inorganic photoconductive glasses such as amorphous selenium, selenium alloys, and selenium-arsenic, and 3) organic photoconductors such as phthalocyanine pigments and polyvinyl carbazole, with or without binders and additives which extend their range of spectral sensitivity.
  • inorganic crystalline photoconductors such as cadmium sulfide, cadmium sulfoselenide, cadmium selenide, zinc sulfide, zinc oxide, and mixtures thereof
  • inorganic photoconductive glasses such as amorphous selenium, selenium alloys, and selenium-arsenic
  • organic photoconductors such as phthal
  • U.S. Patent No. 3,824,099 shows the use of squaric acid methine sensitizing dyes and triaryl pyrazoline charge transport materials as an electrophotographic construction.
  • Cadmium sulfoselenide plates are shown in U.S. Patent No. 3,764,315, and one of the original disclosures of the use of poly-N-vinylcarbazole as a photoconductive insulating layer is provided in U.S. Patent No. 3,037,861.
  • Japanese Patent Publication 52-34735 discloses carbazole organic photoconductor materials which may have substituents thereon which would inherently prevent oligomerization of the carbazoles. This is not recognized in the disclosure and the cabazoles would still be subject to oxidation problems.
  • Electronically active organic donor compounds have been found to be sensitized by 1) phenylsulfonyl or benzoyl substituted imidazo-[4,5-b]-quinoxaline cyanine dyes, 2) indolenine cyanine dyes bearing a phenylsulfonyl or benzoyl substituent on the 5-position thereof, or a dye of the formula: wherein R a represents a monovalent chromophonic radical, M represents sulfonyl, carbonyl or carbonyloxy, R f represents a highly fluorinated aliphatic radical, and R represents a monovalent electron-withdrawing radical.
  • a preferred class of electronically active organic donor compounds particularly useful in the present invention has the formula: where X is wherein R is an aliphatic, aromatic, or mixed aliphatic-aromatic group and Y is an aliphatic, aromatic, heterocyclic, or mixed aliphatic-aromatic group.
  • R and Y may be independently selected from alkyl groups, benzyl groups, phenyl groups, naphthyl groups anthracyl groups, etc., with such various substituents as alkoxy groups, amine groups, alkyl groups, hydroxyl groups, and halogen atoms thereon.
  • These compounds have been found to be electron donor compounds and are useful in forming photoconductive layers when sensitized with cyanine dyes having an imidazo-[4,5-b]quinoxaline nucleus. They may be combined with polymeric binder materials to form photoconductive layers which are solid state molecular solution charge transport layers.
  • the electron donor compounds having a reduced sensitivity to oxidation and oligomerization.
  • All electronically active organic donor compounds may be sensitized to various portions of the electromagnetic spectrum by sensitizing dyes selected from the group consisting of 1) imidazo-[4,5-b]-quinoxatine cyanine dyes, 2) phenylsulfonyl or benzoyl substituted indolenine dyes and 3) highly fluorinated aliphatic sulfonyl, carbonyl or carbonyloxy sensitizer dyes.
  • Typically electronically active organic electron donor compounds are poly-N-vinylcarbazole, polyanthracene, oxadiazoles, . pyrazolines, poly(vinyl acenaphthalene), poly-2,9-methylene fluorene, polyvinyl ferrocene, polybenzocarbazole, polybenzoanthracene, and the like.
  • the electronically active organic donor compounds useful in the practice of the present invention are bis (benzocarbazoles)trisubstituted methanes which may be represented by the formula wherein X is wherein R is an aliphatic, aromatic or mixed aliphatic-aromatic group and
  • Y is an aliphatic, aromatic, heterocyclic or mixed aliphatic-aromatic group.
  • This process can be carried out in a solvent (e.g., ethanol) in the presence of an acid (e.g., HCI) catalyst.
  • the reaction product may be isolated by simple filtration and washing.
  • the reaction product is also stabilized against oxidation of the methine group by the rings ortho to point at which the methine group is bonded to the benzocabazole nucleus.
  • R may, as previously stated, be selected from aliphatic, aromatic and mixed aliphatic-aromatic groups. These groups may or may not be substituted. If they are substituted, it would be preferred that they be electron donating substituents although election withdrawing substituents may be tolerated.
  • R is selected from alkyl groups of 1 to 20 carbon atoms, preferably n-alkyl groups of 2 to 20 carbon atoms, aryl groups such as phenyl or naphthyl groups, with phenyl groups preferred, alkaryl groups, for example benzyl groups, and allyl groups.
  • n-alkyl radical may be only of the formula -(CH Z I " -CH 3 while n-alkyl group may have hydrogen atoms on the n-alkyl radical substituted with other moieties such as halogen atoms, hydroxyl radicals, alkoxy radicals, alkyl radicals, amine radicals, cyano radicals, etc.
  • R moieties are ethyl, n-butyl, n-propyl, 4-methoxybutyl, 3-chloropropyl, 8-hydroxyoctyl, phenyl, benzyl, allyl, p-ethylphenyl, m-tert-butylnaphthyl, p-diethylaminophenyl, stearyl, dodecyl, etc.
  • R preferably has fewer than 20 carbon atoms, but may have up to 30 or more carbon atoms. The main influence of this group, except where electronic induction occurs because of a change of the nature of this group, is in the solubility of the compound.
  • Y may, as previously stated, be selected from aliphatic, aromatic, and mixed aliphatic-aromatic groups. These groups may or may not be substituted. Examples of useful moieties are methyl, ethyl, n-pentyl, nonyl, stearyl, tolyl, anisyl (m-, p-, and o-), p-chlorobenzyl, o-bromobenzyl, p-hydroxybenzyl, veratryl, isobutyl, terphthalyl, p-octyloxybenzyl, p-dimethylaminophenyl, t-butyl, etc.
  • Y moieties are phenyl, tolyl, anisyl, and benzyl groups because of their availability.
  • group R the main influence of this group, except with regard to electron induction effects, is on the solubility of the compounds.
  • Y has 20 or fewer carbon atoms, but up to 30 may be readily tolerated.
  • Preferred dyes may be represented by the formulae: wherein W represents:
  • R and R each represents a substituent independently selected from the group consisting of an acyclic hydrocarbon substituent, such as an alkyl group (including substituted alkyl), preferably containing from 1 to 13 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, hexyl, cyclohexyl, dodecyl, octadecyl, hydroxyalkyl (e.g.
  • R 2 represents a 6- or 7-position substituent selected from phenylsulfonyl or benzoyl
  • X- represents an acid anion such as for example, in order of general preference perchlorate, tetrafluoroborate, p-toluenesulfonate, methylsulfate, sulfamate, iodide, bromide, and chloride
  • R 3 represents a substituted or non-sub
  • Q represents a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom, and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom).
  • L represents a cation nucleus of 1-alkyl-2-phenylindol-3-yl, 1-aryl-2-phenylindol-3-yl, 1-alkyl or aryl-2-phenyt-5-nitro-indot-3-yt, 1-alkyl-2-phenyl-5-phenylsulfonylindol-3-yl, 1-aryl-2-phenyl-5-phenylsulfonyl- indol-3-yl,1-aryl-2-phenyl-5-phenylsulfonylindol-3-yl, 1-alkyl-2-phenyl-5-benzoylindol-3-yl, 1-aryl-2-phenyl-5-benzoylindol-3-yl, 9-methyl-carbazol-3-yl, 2-alkyl or substituted alkyl-3-phenyl-5-oxo-3-isooxazolin-4-yl, 2-alkyl or substituted alkyl-3-fury
  • the counterion (the acid anion, X ⁇ ) has been found to significantly affect the sensitizing ability of the dyes according to the present invention.
  • the reason for this is not understood.
  • the general order of preference for the anions is perchlorate (most preferred), tetrafluoroborate, p-toluenesulfonate, methylsulfate, sulfamate, iodide, bromide, and chloride.
  • substituent groups i.e., R, R 1 , R 2 , R 3 , R 4 , R s , Z, Q, L and X'
  • this size of such groups is not believed to be of any substantial significance in the practice of this invention. Size changes may only require modification of solvents necessary to include them in photosensitive systems, but the action of these dyes is believed to be substantially the same, without regard to size. However, for purposes of economics, the following moiety sizes are generally preferred.
  • the second nucleus heterocyclic or paraaminophenyl
  • such second nucleus contains no more than 30 carbon atoms and most preferred no more than 20 carbon atoms.
  • groups R and R 1 it is generally preferred to have no more than 18 carbon atoms and most preferred to have no more than 10 carbon atoms.
  • group R 2 when benzoyl and phenyl-sulfonyl the generally preferred aryl groups of this invention are phenyl and naphthyl and derivatives thereof.
  • R 4 and R s are preferred to have no more than 6 carbon atoms each. None of R 2 , R 4 and R 5 should contain metal atoms.
  • the preferred dyes of this class are those of U.K. Patent No. 1,555,053 in which the imidazo-[4,5-b]-quinoxaline cyanine dye bears a 5-phenylsulfonyl or 5-benzoyl substituent.
  • indolenine sensitizers which are a part of the present invention are disclosed in U.S. Patent No. 4,025,347. This reference teaches the use of the indolenine dyes in silver halide emulsions as sensitizer dyes.
  • the dyes may be represented by the formulae: and wherein A is selected from and B is selected from and n represents a positive integer of from 1 to 4, m and q each represents a positive integer of from 1 to 2, p represents a positive integer of from 1 to 3, r is 0 or 1, R 2 represents a substituent independently selected from the group consisting of an acyclic hydrocarbon substituent (substituted or not), preferably aliphatic, such as an alkyl group (including substituted alkyl), preferably containing from 1 to 13 carbon atoms, e.g.
  • R 1 represents a 5-position substituent selected from phenylsulfonyl or benzoyl
  • X- represent an acid anion such as for example, in order of general preference perchlorate, tetrafluoroborate, p-toluenesulfonate, methylsulfate, sulfamate, iodide, bromide, and chloride
  • R 3 and R 4 represents a substituted or non-sub
  • Q represents a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom, and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfor atom).
  • the counterion (the acid anion, X-) has been found to significantly affect the sensitizing ability of the dyes according to the present invention.
  • the reason for this is not understood.
  • the general order of preference for the anions is perchlorate (most preferred), tetrafluoroborate, p-toluenesulfonate, methylsulfate, sulfamate, iodide, bromide, and chloride.
  • the preferred dyes are those of U.S. Patent No. 4,025,347 in which the indolenine portion of the dye bears a 5-phenylsulfonyl or 5-benzoyl substituent.
  • the dyes used in the practice of the present invention are themselves well known in the art for use in light filters, photographic elements, and textiles. These dyes are shown, for example, in U.S. Patents Nos. 3,933,914 and 4,018,810. These dyes may be generally described by the formula: wherein R a represents a monovalent chromophoric radical, M represents R, represents a highly fluorinated aliphatic radical, and R represents a monovalent electron-withdrawing radical.
  • R groups may include such materials as a cyano, arylcarbonyl, alkylcarbonyl, perfluoralkyl, alkylsulfonyl, highly fluorinated alkylsulfonyl, perfluoroalkylsulfonyl, arylsulfonyl, nitro, sulfonyl floride, or sufonyl chloride radical.
  • Radicals preferred for R include cyano, highly fluorinated aliphaticsulfonyl, fluoro- alkylsulfonyl or highly fluorinated alkylcarbonyloxy (for example having from 1-18 carbon atoms - preferably 1-8 carbon atoms), and arylsulfonyl (preferably phenylsulfonyl).
  • highly fluorinated aliphatic radical is defined in the present invention as an aliphatic group having its carbon atoms fluorinated except that with two or more carbon atoms present in the group, the terminal carbon atom may have a hydrogen or chloro substituent, and with four or more carbon atoms the last two carbon atoms may have one or two hydrogen or chlorine substituents.
  • R 5 and R 2 are hydrogen, monovalent alkyl of 1 to 20 carbon atoms (preferably methyl or ethyl), cyanoalkyl (preferably cyanomethyl or cyanoethyl), aryl (preferably phenyl), or aralkyl (preferably benzyl); n is the integer 0, 1, or 2, X is halogen (preferably chlorine or bromine), lower alkyl (e.g., having 1-3 carbon atoms), cyano, nitro, lower alkoxy (preferably having 1-3 carbon atoms), hydrogen, hydroxyl, sulfonate, or carboxyl; and m is the integer 1-3; wherein X is as defined above, A is a trivalent alkenylene radical having from 2-4 carbon atoms, and Q is a divalent nitrogen atom, substituted nitrogen (e.g., with such
  • perfluorinated is employed to denote substitution of all carbon-bonded hydrogen atoms by fluorine atoms, in accord with the recognized usage of the term.
  • the above mentioned highly fluorinated aliphatic groups are defined as aliphatic groups which can contain chlorine and hydrogen atoms bonded to the carbon atoms (not more than one chlorine or hydrogen for two adjacent carbons) as well as having fluorine atoms bonded to carbon atom.
  • the fluoroaliphatic radical may be a straight or branched chain, cyclic, or a straight chain including a cyclic portion.
  • the fluoroliphatic group may contain an oxygen atom linking two carbon atoms, e.g., -CF 2 0CFg-, or a nitrogen atom linking three carbon atoms, e.g., (R f CH 2 ) 2 NCF 2 -.
  • Exemplary aliphatic groups include 1,1,1-tris-trifluoroethyl, perfluoromethyl, perfluorobutyl, perfluorooctyl, perfluorododecyl, perfluoroisopropyl, perfluoro-(2-cyclohexylethyl), omega-chloroperfluorohexyl, 2-hydroperfluoropropyl, perfluoro(3-morpholinopropyl), and perfluoro(3-piperidinopropyl).
  • binder materials known in the art are useful with the electronically active electron donor compounds of the present invention. It is of course preferred that the binder be essentially optically transparent or at least transparent to the wavelengths of radiation to which the compounds (sensitized or not) are sensitive.
  • the useful binders are poly(vinyl chloride), poly(siloxanes), poly(vinyl butyral), poly(vinyl acetate), styrene/acrylontrile copolymers, polyacrylates, polymethacrylates, polycarbonates, polyepoxides, polyurethanes, polyamides, polyethers, polyesters, polyolefins as well as block, graft, random, and alternating polymers, copolymers, terpolymers and mixtures thereof and the like.
  • the binders are preferably electrically inactive themselves.
  • the preferred polymeric binders are polycarbonates, polyesters, and styrene/acrylonitrile copolymers. Coating aids, lubricants, surface active agents, and other adjuvants may be added to the composition.
  • the organic electron donor compounds should be present as at least 20 per cent by weight of the composition.
  • the donor compound should be present as at least 25 or 35 per cent by weight of the layer, and may comprise up to 100% by weight of the layer, excluding of course the sensitizer dye.
  • the sensitizing dyes should be used in amounts which will increase the sensitivity of the composition. This is defined as an effective sensitizing amount of dye. Ordinarily amounts of up to 10% by weight dye may be used, but certain constructions can be envisaged with as much as 90% by weight of dye and 10% by weight of organic electron donor compounds. Amounts of dye as small as 0.005 per cent by weight can be useful. More preferred concentration ranges are between 0.05 and 5 per cent by weight.
  • the photosensitive materials of the present invention may also be useful as photoconductive toners, photovoltaic devices, organic semiconductors, and the like, and may use concentrations of organic electron donor compounds as low as 5 per cent by weight.
  • benzocarbazole-aldehyde condensation products useful in the present invention are better charge transport materials than the corresponding benzocarbazoles by themselves. This is surprising because it is the benzocarbazole nucleus which is the electronically active portion of both molecules. Even when benzocarbazoles were used in reasonably higher molecular proportions to the binder than were the condensates, the condensates would still perform better.
  • electronically active electron donor compounds of the present invention were obtained by condensing N-ethytbenzo[a]carbazoie with each of the following aldehydes in equimolar replacement for the benzaldehyde:
  • any of the compounds produced in Examples 1-21 to electrically inert polymeric binders formed positive charge transport layers. These layers could be formed on photoconductive layers and were capable of supporting injected photogenerated holes from the photoconductive layer and allowed the transport of these holes through the transport layer to selectively discharge the surface charge.
  • Bulk sensitized photoreceptors were prepared by coating a solution consisting of 0.5 per cent by weight solids of dye, 40 per cent by weight of the same charge transport compound prepared in Example 1, and 59.5 per cent of an organic solvent soluble polyester resin from a dichloromethane, 1,2-dichloroethane (50/50 solution were coated at about 1 x 10- 4 m wet thickness onto an aluminum coated polyethylene- terephthalate film.
  • the sample was air dried at 85°C for approximately 15 minutes.
  • the photoreceptor charged to a maximum voltage (V ° ) under positive corona charging and the exposure energy and wavelength of radiation necessary to reduce the charge to one half V ° (V,) with little dark decay was recorded.
  • V ° maximum voltage
  • Example 25 shows improved properties at its wavelength of maximum absorbance (621) in comparison to the wavelength of maximum absorbance (650) for compound 29.
  • Dye (A) has the structure
  • the wet thickness of the coating was 4 mil (1 x 10 -4 m).
  • the coating was air dried and then oven dried for 1& min. at 80°C.
  • the electrophotographic behaviour of the construction is shown in Table II..
  • the p-toluene sulfonate counterpart of this dye was equivalently prepared using the p-toluene sulfonate indoleninium salt, 0.9 of the cyclohexene, and 80 g of acetic acid.
  • a solution consisting of 0.6 g Vitel PE-200, 0.4 g of transport material indicated, and 0.005 g of the 5-phenylsulfonyl-indolenine dye indicated in a mixture of 4.5 g of dichloromethane and 4.5 g of 1.2-dichloroethane was prepared, filtered, and knife coated onto an aluminized polyester substrate.
  • the wet thickness of the coating was 4 mil (1 x 10- 4 m).
  • the coating was allowed to air dry and then oven dried for 15 minutes at 80°C.
  • the electrophotographic performance of these constructions, determined by measuring the energy required to discharge the sample to half of their initial values (E V 0/2 ) ' is shown in the accompanying Table III.
  • the wet thickness of the coating was 4 mil (1 x 10- 4 m).
  • the coating was air dried and then oven dried for 15 minutes at 80°C.
  • the electrophotographic behavior of this construction, determined by measuring the energy required to discharge the sample to hatf of its initial voltage (E V o/2 ) is shown in the accompanying Table III.
  • a bulk sensitized photoreceptor was prepared by coating a solution of 10 per cent by weight solids (5.2% of p-dimethylamino-di- -perfluoromethylsulfonylcinnamilidene, 38% bis(N-ethyl-1,2-benzo- carbazolyl)phenyl methane, and 56.8% polycarbonate resin at about 1 x 10- 4 m onto aluminized polyester-(polyethyleneterephthalate). This was air dried for 15 minutes at 85°C. The sample was evaluated for its xerographic response to positive corona charging. The sample displayed a maximum sensitivity at 540 nm. At that wavelength, the construction required approximately 3 Joules/cm 2 to discharge the sheet to one half its potential from 740 volts. The sample displayed an initial discharge rate of 736 volts/sec. with 3.27 watts/cm2.
  • the dye used in this example has the structure The dyes having the structures and were also found to work well in the construction of this example.
  • a coating solution was prepared from 0.6 g polyester (Vitel O PE-200 organic solvent soluble copolyester of terephthalic acid, isophthalic acid, and ethylene glycol), 0.4 g of the compound of Example 1, and 0.005 g of disulfone dye A in a mixture of 4.5 g dichloromethane and 4.5 g of 1,2-dichloroethane, filtered, then knife coated onto an aluminized polyester substrate.
  • the wet thickness of the coating was 1 x 10 -4 m before oven drying for 15 minutes at 80°C.
  • the electrophotographic performance of this coating is shown in Table IV.
  • Coating solutions were prepared of 0.6 g of an organic solvent soluble copolyester derived from terephthalic acid, isophthalic acid and ethylene glycol (Vitel® PE-200), 0.4 g of the indicated charge transport material, and 0.005 g of the disulfone dye indicated in Table IV. These materials were knife coated onto aluminized polyester from a solution with 4.5 g dichloromethane and 4.5 g of 1,2-dichloroethane after filtering. The wet thickness was 1 x 10-'m before air drying then oven drying for 15 minutes at 80°C. The electrophotographic performance of these coatings is shown in Table IV.
  • a coating solution of 1.0 g polyvinylcarbazole and 0.005 g disulfone dye D in a mixture of 4.5 g of dichloromethane and 4.5 g of 1,2-dichloroethane was knife coated at 1 x 10- 4 m wet thickness onto aluminized polyester. The coating was air dried then over dried for 15 minutes at 80°C.
  • the electrophotographic behavior of the construction is shown in Table IV.

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Claims (19)

1. Couche photosensible comprenant un composé organique donneur d'électrons électroniquement actifs, sensibilisé avec une quantité sensibilisante d'un colorant choisi parmi l'ensemble constitué par 1 ) un colorant de cyanine de type imidazo [4,5-b]quinoxaline ayant au moins un substituant phénylsulfonyle ou benzoyle sur un cycle d'imidazo [4,5-b]quinoxaline, 2) un colorant de cyanine de type indolénine portant un substituant phénylsulfonyle ou benzoyle en position 5, et 3) un colorant de formule
Figure imgb0126
dans laquelle R, représente un radical chromophorique monovalent, M représente un groupe sulfonyle
Figure imgb0127
carbonyle
Figure imgb0128
ou carbonyloxy
Figure imgb0129
Rf représente un radical aliphatique fortement fluoré et R représente un radical monovalent arracheur d'électrons.
2. Couche suivant la revendication 1, dans laquelle ledit composé donneur est un polyvinylcarbazole.
3. Couche suivant la revendication 1, dans laquelle ledit composé donneur est présent dans un liant polymère électroniquement inerte.
4. Couche suivant la revendication 1, dans laquelle ledit composé donneur est un dérivé de benzocarbazole de formule
Figure imgb0130
dans laquelle X est
Figure imgb0131
où R4 et Y sont indépendamment l'un de l'autre choisis parmi l'ensemble constitué par les groupes aliphatiques, aromatiques, hétérocycliques et mixtes aliphatiques-aromatiques.
5. Couche suivant les revendications 2, ou 4, dans laquelle ledit colorant est un colorant de cyanine de type imidazo[4,5-b]quinoxaline représenté par la formule:
Figure imgb0132
dans laquelle W représente:
Figure imgb0133
Figure imgb0134
Figure imgb0135
où
g représente 1, 2 ou 3;
R et R1, qui peuvent être identiques ou différents, représentent chacun un substituant aliphatique ou un groupe phényle;
R2 représente un groupe phénylsulfonyle ou benzoyle substitué en position 6 ou 7;
Z représente les atomes nécessaires pour compléter un cycle de l'ensemble constitué par les thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole sélénazole, benzosélénazole, thiazoline, pyridine, indolénine, 2-quinoline, 4-quinoline, 1-iso-quinoline, 1,1-dialkyl-indolénine, imidazole, benzimidazole, naphthimidazole, imidazo-[4,5-b]-quinoxaline, 3H-pyrrolo-[2,3-b]-pyridine, 3H-nitro-indole, et thiazole-[4,5-b]-quinoline;
R3 représente un groupe aliphatique ou un groupe phényle; L représente un cycle cationique choisi parmi l'ensemble constitué par les groupes indole, carbazole, isoxazole et pyrazole; et
X- représente un anion d'acide.
6. Couche suivant la revendication 5, dans laquelle W représente
Figure imgb0136
et g est 1 ou 2.
7. Couche suivant la revendication 5, dans laquelle W représente
Figure imgb0137
8. Couche suivant la revendication 6, dans laquelle g est 1, Z est choisi parmi l'ensemble constitué par le thiazole, le benzothiazole, l'oxazole et le benzoxazole.
9. Couche suivant la revendication 7, dans laquelle g est 1, et R et R1 sont tous deux le même substituant aliphatique.
10. Couche suivant la revendication 7, dans laquelle g est 1 et R et R1 sont tous deux un groupe phényle.
11. Couche suivant les revendications 2, 3 ou 4 dans laquelle ledit colorant est un colorant d'indolénine représenté par l'une quelconque des formules:
Figure imgb0138
Figure imgb0139
Figure imgb0140
and
Figure imgb0141
dans lesquelles
A est choisi parmi
Figure imgb0142
et
Figure imgb0143
B est choisi parmi
Figure imgb0144
et
Figure imgb0145
n est un entier positif de 1 à 4,
m et q représentent chacun un entier positif de 1 ou 2,
p représente un entier positif de 1 à 3,
r est 0 ou 1,
R2 représente un hydrocarbure acyclique,
R, représente un substituant phénylsulfonyle ou benzoyle en position 5,
R5 et Re sont un groupe aliphatique,
R3 et R4 représentent des groupes alkyle identiques ou différents en C1―C6,
R7 est choisi parmi l'ensemble constitué par H, halogène, cyano, alkyle, alcoxy, phénoxy, aryle, amino, thiophényle et thioalkyle,
Z représente les atomes non métalliques nécessaires pour compléter un noyau hétérocyclique de 5 à 6 sommets et
Q représente les atomes non métalliques nécessaires pour achever un noyau hétérocyclique de 5 ou 6 sommets et
X représente un anion d'acide.
12. Couche suivant la revendication 11, dans laquelle ledit colorant d'indolénine est représenté par la formule
Figure imgb0146
dans laquelle
n est 1,
r est 1,
R2 est un groupe aliphatique de 1 à 13 atomes de carbone,
R1 est un groupe phénylsulfonyle ou benzoyle,
R3 et R4 sont choisis parmi l'ensemble constitué par les groupes méthyle, éthyle, propyle, butyle, pentyle et hexyle,
R7 est un halogène et
X- est un anion d'acide.
13. Couche suivant la revendication 11, dans laquelle ledit colorant d'indolénine est représenté par la formule
Figure imgb0147
dans laquelle
A est choisi parmi
Figure imgb0148
et
Figure imgb0149
r est 1,
n est 1,
R2 est un groupe aliphatique en C1―C13,
RI est un groupe phénylsulfonyle ou benzoyle,
R3 et R4 sont choisis parmi l'ensemble constitué par les groupes méthyle, éthyle, propyle, butyle, pentyle et hexyle,
R5 et R6 sont un groupe alkyle en C1―C6,
R7 est un halogène,
X est un anion d'acide
14. Couche suivant les revendications 2, 3 ou 4, dans laauelle ledit colorant est un colorant de formule
Figure imgb0150
dans laquelle M est un groupe sulfonyle.
15. Couche suivant les revendications 8, 9 ou 10, dans laquelle R est un groupe alkyle de 2 à 20 atomes de carbone ou un groupe phényle.
16. Article électrophotographique comprenant un substrat ayant dans l'ordre sur au moins une de ses surfaces une couche conductrice et la couche photosensible des revendications 1, 2, 4, 5, 6, 9, 10,12 ou 13.
EP19820100686 1981-02-23 1982-02-01 Composés organiques donneurs d'électrons sensibilisés Expired EP0058839B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US236654 1981-02-23
US06/236,654 US4337305A (en) 1981-02-23 1981-02-23 Sensitized organic electron donor compounds
US236653 1981-02-23
US06/237,067 US4357405A (en) 1981-02-23 1981-02-23 Fluorinated dye sensitized organic electron donor compound
US06/236,653 US4356244A (en) 1981-02-23 1981-02-23 Quinoxaline cyanine dye sensitized organic electron donor compounds
US237067 1981-02-23

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JPS59216146A (ja) * 1983-05-24 1984-12-06 Sony Corp 電子写真用感光材料
GB8712151D0 (en) * 1987-05-22 1987-06-24 Minnesota Mining & Mfg Dyes
EP0342810A3 (fr) * 1988-05-20 1990-06-06 Minnesota Mining And Manufacturing Company Colorants à la cyanine et leur préparation
US5008043A (en) * 1990-03-16 1991-04-16 Eastman Kodak Company Optical article exhibiting a high level of second order polarization susceptibility

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BE563443A (fr) * 1956-12-26 1958-01-15
US3352670A (en) * 1964-02-14 1967-11-14 Minnesota Mining & Mfg Supersensitizers for optically sensitized photoconductive layers
GB1161797A (en) * 1966-09-08 1969-08-20 Agfa Gevaert Nv Optically Sensitized Light-Sensitive Material
CH494419A (fr) * 1967-04-25 1970-07-31 Eastman Kodak Co Couche électrophotographique
BE758446A (fr) * 1969-11-04 1971-04-16 Fuji Photo Film Co Ltd Materiel electrophotographique
US3723116A (en) * 1970-07-24 1973-03-27 Canon Kk Electrophotographic photosensitive materials
US3933914A (en) * 1972-10-25 1976-01-20 Minnesota Mining And Manufacturing Company Organic dye having fluoroaliphatic substituent
IT988269B (it) * 1973-06-18 1975-04-10 Minnesota Mining & Mfg Coloranti cianinici e loro impiego come sensibilizzatori spettrali in materiali fotografici positivi diretti del tipo ad effetto herschel sensibilizzato spettralmente
IT1057476B (it) * 1976-04-07 1982-03-10 Minnesota Mining & Mfg Coloranti cianinici contenenti un nucleo di imidazo 4.5.b chinossalina sostituita e loro uso in elementi fotografici

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