US3852065A - Photoconductive bisphenyl thiocompounds linked by bridging organic group - Google Patents

Photoconductive bisphenyl thiocompounds linked by bridging organic group Download PDF

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Publication number
US3852065A
US3852065A US00143587A US14358771A US3852065A US 3852065 A US3852065 A US 3852065A US 00143587 A US00143587 A US 00143587A US 14358771 A US14358771 A US 14358771A US 3852065 A US3852065 A US 3852065A
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bis
phenylthio
composition according
layer
photoconductive
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US00143587A
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A Hectors
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Canon Production Printing Holding BV
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Oce Van der Grinten NV
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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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/062—Acyclic or carbocyclic compounds containing non-metal elements other than hydrogen, halogen, oxygen or nitrogen

Definitions

  • ABSTRACT V toconductive layer, either self-supported or carried on a support which may be paper or the like or a conductive surface, depending upon the manner of utilization.
  • a fine powder of the composition containing a sensitizing dysestuff is useful in phototoner processes.
  • the photoconductive coating is charged in the dark and exposed to light so as to produce a charge image, after which the charge image is made visible by the selective attraction of pigment (toner) particles to the charged areas.
  • toner particles are fixed onto the photoconductive coating, whereas in the indirect process the particles are transferred to a receiving support and fixed thereon.
  • anuncharged photoconductive coating is imagewise exposed so as to produce a conductivity pattern which can be converted into a charge image ready to be developed with toner particles or can be developed by selective electrolytic deposition of coloring matter in accordance with the conductivity pattern.
  • Electrophotographic processes are also known in which photoconductive particles are attached to a sup port by electrostatic forces and image-formation is based on selective destruction of the electrostatic attraction. These are called phototoner processes.
  • the most familiar photoconductors are amorphous selenium and zinc oxide. Many other substances have been proposed, both organic and inorganic.
  • Organic photoconductors enable the formation of smooth and grainless layers, and thus are particularly useful for reproduction of fine details.
  • Such photoconductors may be polymeric or non-polymeric.
  • the known non-polymeric photoconductors which genereally are used with electrically insulating binders, differ considerably as to chemical constitution and photoconductive behavior. While they relate to many and very different classes of compounds, those in which two phenyl nuclei are linked via a bridging member and at least one of the phenyl nuclei is p-amino-substituted ,show especially interesting properties.
  • the tors of the formula :
  • R represents an alkyl, aralkyl, cycloalkyl or aryl radical
  • Z represents a hydrogen or halogen atom, an alkyl, alkoxy, acylamino, or sulfonamido radical or the group in which R represents a hydrogen atom or an alkyl, aralkyl or cycloalkyl radical and R, a hydrogen atom or an alkyl, aralkyl, cycloalkyl or aryl radical.
  • Y and Y are similar or different and represent a halogen or an alkyl or alkoxy radical; and m and n each is equal to zero, 1 or 2.
  • Non-polymeric photoconductors are highly useful when combined with an electrically insulating binder to provide a photoconductive coating composition.
  • Such a composition on a suitably conductive support gives a material on which excellent copies can be made by electrophotographic reproduction.
  • bridging group X consists of a plurality of identical atoms, such as S S Se or T62, have been found somewhat less light-sensitive than those in which the bridging group consists of a single S, Se or Te atom between the phenyl nuclei.
  • new photoconductive compositions containing an organic photocon ductor and an electrically insulating binder are provided, in which the photoconductor is a monomeric compound having two phenylthio residues, at least one of which carries a tertiary amino group in the para position relative to its sulfur atom, which residues are linked together by means of an organic bridging group between the respective sulfur atoms.
  • the photoconductor is a monomeric compound having two phenylthio residues, at least one of which carries a tertiary amino group in the para position relative to its sulfur atom, which residues are linked together by means of an organic bridging group between the respective sulfur atoms.
  • the photoconductors to be used according to the present invention are, more particularly, compounds having the general formula:
  • R is an alkyl, cycloalkyl or aralkyl radical an R is an alkyl, cycloalkyl or aralkyl radical, or R and R together with the nitrogen atom to which they attach form a saturated heterocyclic ring;
  • Z is a hydrogen or halogen atom, an alkyl or alkoxy :8
  • R and R each is a hydrogen atom or an alkyl, cycloalkyl or aralkyl group, or R and R together with the nitrogen atom to which they attach form a saturated heterocyclic ring.
  • Each of the variables n, m and s represent an integer ranging from I upwards, and each of the variable p, q, r, k and 1 represents either zero or an integer ranging from I upwards with the sum of p, q and r being an integer.
  • the ranges of these integers do not have critical upper limits but for practical reasons, such as solubility, they do not exceed values of approximately 10.
  • the bridging group X When the bridging group X is aromatic, it may be an isocyclic aromatic radical, such as a phenylene, polyphenylene 0r naphthylene radical or another condensed ring system, or an aromatic dicarboxylic residue (e.g. of formula CO-C H CO-), or a heterocyclic aromatic radical such as a pyridine, (s)-triazine, furane, pyrrol or thiophene group.
  • an isocyclic aromatic radical such as a phenylene, polyphenylene 0r naphthylene radical or another condensed ring system, or an aromatic dicarboxylic residue (e.g. of formula CO-C H CO-), or a heterocyclic aromatic radical such as a pyridine, (s)-triazine, furane, pyrrol or thiophene group.
  • each phenyl residue either is non-substituted or may carry one or more of usual substituents such as an alkyl or alkoxy group or a halogen atom and in which X and R have the meanings indicated in the fol lowing tabulation:
  • Sensitizers and activators canbe added to the photo conductive compositions of the invention in the conventional way; Examples of dyestuffs suitable for use in them as sensitizers are set-forth in the aforesaid copending application Ser. No. 9,061. Substances useful in them as activators are disclosed in Belgian Pat. No. 570,790.
  • the monomeric photoconductors herein specified are used in combination with insulating polymeric binders.
  • binders that may be used effectively are, for example, plasticized or unplasticized silicon resins, polystyrene, polyacrylic or polymethacrylic esters, colophony resins, chlorinated rubbers, polyvinyl chloride, polyvinyl acetate, vinyl chloride/acetate copolymers, polyvinyl acetals, phenolformaldehyde resins, polyamides, polyesters, cellulose esters, cellulose ethers and alkyd resins or mixtures thereof.
  • the photoconductive compositions herein disclosed may be used in the form of a photoconductive layer, which may be either self-supporting or coated on a suit able support, or may be used in a so-called phototoner process in the form of a powder having more or less spherical particles. They may be coated on flexible or rigid supports such as of metal, paper, metallized plastic foil ornesa glass, so as to provide valuable electrophotographic materials.
  • the specified photoconductors can be used in them individually or mixtures of different compounds of the nature specified or with photoconductors of other constitution.
  • the photoconductors herein disclosed are sensitive to light of wavelength shorter than 3,000 A. Most of them are almost colorless, i.e., highly transparent to visible radiation in the range above 3,000 A. Nevertheless they show excellent sensitivity for visible light when used in admixture with a suitable sensitizing dye and/or activator. It is indeed surprising that these relatively simple and easily producible compounds have not been previously proposed for use as photoconductors, for their properties fulfill the requirements to be met by organic photoconductors.
  • the electrophotographic layers provided according to the present invention are suitable for carrying out conventional electrophotographic processes, such as those in which a photoconductive layer is charged, i magewise exposed and developed and those in which copying is based on a conductivity image resulting from imagewise exposure without a previous or simultaneous charging step.
  • the conductivity image is converted into a ready developable charge image or is developed by electrolytic deposition of coloring matter which may be a powder or a liquid developer.
  • the developed visible image can be fixed directly on the photoconductive surface or can be transferred: onto a receptor surface and fixed'thereon.
  • the electrophotographic materials of the present invention i.e., the materials which comprise a support and a layer thereon of a photoconductive composition herein disclosed, can be used for making single copies and also for the production of transparent copies such as microcopies, micrates or intermediate copies for overhead projection or for further reproduction, e.g. on diazotype paper.
  • the new photoconductive compositions can be applied to suitable supports to make electrophotographic plates for planography, for relief or intaglio printing, or for the production of masters for spirit duplicating or for xeroprinting.
  • the photoconductive compositions are also useful for the formation of a photoconductive layer to'be employed in copying-duplicating machines which make use of the indirect electrophotographic process.
  • a pho toconductive layer made from such a composition can be used in combination with other photoconductive or semiconductor layers, e.g. with a layer containing CdS or Se.
  • the preparation of the compounds to be used as photoconductors according to the present invention can be effected by processes readily practicable by chemists skilled in organic reactions. These compounds may be prepared either by bringing a p-tertiary amino-phenylmercaptan into reaction with an organic di-halogen compound, or by reacting a p-halogen nitrobenzene with an organic dithiol, and subsequently reducing and alkylating or arylating the reaction product.
  • EXAMPLE I A paper support is coated with a solution of 20 g of polyvinyl chloride/acetate 2 g of l.2-bis[4-N.N-diethyl umino-phunyl-thio
  • the electrophotographic paper thus made is charged negatively and then is placed in contact with a photographic diapositive and exposed through it for 5 seconds to light from an incandescent lamp of 40W at a distance of cm.
  • the latent image thus formed is de veloped by applying positively charged toner particles to it with the aid of a magnetic brush, and the developed image is fixed by heating. A clear positive copy of the diapositive results.
  • EXAMPLE ll A paper support is coated with a solution of of a polyvinyl chloride/acetate of l.2his[4-N.N-dihenzyl amino phenyl thiolethene and of Rhodamine B extra in of. chloroform.
  • EXAMPLE III A copy is produced in the way described in Example I, excepting that the coating solution used contains 1,2- bis[4-N-methyl-N-cyclopentyl-amino phenyl thio] eth ene as the photoconductor and acetone as the solvent.
  • a coating is formed on paper by applying to the paper a solution of It) g olpolyvinyl chloride H) g ml a modified colophonium resin ol' I.lLhis-l4-N,N-diuthylamino phcnyl lhiol dichloroethcne and of Rhodamione 8 extra in of acetone 0.07 g ISO ml and drying the coating.
  • R, and R each represents a lower alkyl radical, a 5- or 6-membered cycloalkyl radical or an aryllower alkyl, or R and R together with the nitrogen atom to which they attach form a morpholine ring
  • Z represents a hydrogen or halogen atom, a lower alkyl or lower alkoxy radical, or an amino group in which R and R each represents a hydrogen atom, a lower alkyl radical, a 5- or 6-membered cycloalkyl radical or an aryl-lower alkyl, or R and R together with the nitrogen atom to which they attach form a morpholine ring
  • X is a lower aliphatic or an aryl phcnylthiol-thiosuccinate
  • a solution is made of one part by weight of l,2-bisl 4- N,N-diethylamino-phenylthiol-ethene and 5 parts by weight of polyvinyl
  • the powder particles are applied to a conductive plate in a uniform layer and subsequently charged by a negative corona-discharge. Upon imagewise exposure of the charged powder layer to light the particles in exposed areas of the layer lose their charge and then are easily removed selectively from the plate. The remnant powder image is transferred from the plate onto a receptor paper by use of an electrostatic field, and is fixed on the paper to provide a permanent copy of the original image.
  • a photoconductive composition comprising in admixture with an electrically insulating polymeric organic binder a monomeric organic photoconductor which is a compound having the formula:
  • a photoconductive composition according to claim 1 wherein said photoconductor is selected from the group consisting of l,Z-bisl4-N,N-diethyl-aminophenylthiol-ethene, 1,2-bisl 4-N,N-dibenzylaminophenylthiolethene, 1.2-bisl4-N-methyl-N- cyclopentylamino-phenylthiolethene, l,2-bis[4-N,N- diethylamino-phenylthiol-dichloroethene, l,4-bis l4- N,N-diethylamino-phenylthio]-butane, I ,2-bisl 4-N- butyl-N-benzyl-amino-phenylthio]-ethene, l.2-bisl
  • diethylamino-phenylthio]-aniline bis [4-N,N-diethylamino-phenylthiol-thion, bis[4-N,N-diethylaminophenylthio]-thiolsuccinate, l,2-bis[4-N,N- dimethylamino-Z-methyl-phenylthiol-ethene and 1,2- bis[4-N,N-diethylamino-phenylthiolethane.
  • An electrophotographic material comprising a layer of a photoconductive composition according to claim 1.
  • An electrophotographic material comprising a support having substantial electrical conductivity and carrying thereon a layer of a photoconductive composition according to claim 1.
  • An electrophotographic material comprising a paper support carrying thereon a layer of a photoconductive composition according to claim 1.
  • An electrophotographic material comprising a photoconductive composition according to claim 1 in the form of a fine powder useful as a photoconductive toner.
  • An electrophotographic material according to claim 10 said powder having an average particlesize of the order of approximately microns.
  • a photoconductive composition comprising in admixture with an electrically insulating polymeric organic binder a monomeric organic photoconductor having the formula:
  • R and R each is a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, a 5- or 6-membered cycloalkyl radical or a benzyl radical, or R and R together with the nitrogen atom to which they attach form' a morpholine ring; and
  • X is a residue selected from the group consisting of alkylene, lower alkenylene, aliphatic dicarboxylic and cycloaliphatic residues. aryl or aryl dicarboxylic residues, and heterocyclic aromatic residues containing at least one nitrogen. oxygen or sulfur atom.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Developing Agents For Electrophotography (AREA)
US00143587A 1970-05-14 1971-05-14 Photoconductive bisphenyl thiocompounds linked by bridging organic group Expired - Lifetime US3852065A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4142982A (en) * 1975-06-04 1979-03-06 Canon Kabushiki Kaisha Toner for developing electrostatic latent images comprising resin binder of polyester and solid silicone varnish
US4603097A (en) * 1983-10-28 1986-07-29 Ricoh Company, Limited Styrene derivatives and electrophotographic photoconductor comprising one of the styrene derivatives
US4606988A (en) * 1984-02-21 1986-08-19 Ricoh Company, Ltd. Styryl derivatives and electrophotographic photoconductor comprising one styryl derivative

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4150987A (en) * 1977-10-17 1979-04-24 International Business Machines Corporation Hydrazone containing charge transport element and photoconductive process of using same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2351657A (en) * 1942-12-26 1944-06-20 Carbide & Carbon Chem Corp Lubricant
US2384577A (en) * 1944-03-03 1945-09-11 Du Pont Esters
US2435508A (en) * 1944-11-01 1948-02-03 Us Rubber Co Manufacture of dithio bisarylamines
US2983726A (en) * 1959-08-18 1961-05-09 Goodrich Co B F Method for preparing secondary aminothiazoledisulfides
US3261825A (en) * 1963-03-11 1966-07-19 Martin Marietta Corp Azo-disulfide triazine dyestuffs
US3299040A (en) * 1963-03-11 1967-01-17 Martin Marietta Corp Disazo-disulfide dyes
US3388126A (en) * 1965-10-27 1968-06-11 Monsanto Co Synthesis of sulfenamides in aqueousorganic solvent mixtures

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1216689B (de) * 1960-09-19 1966-05-12 Renker Belipa G M B H Elektrophotographisches Aufzeichnungsmaterial

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2351657A (en) * 1942-12-26 1944-06-20 Carbide & Carbon Chem Corp Lubricant
US2384577A (en) * 1944-03-03 1945-09-11 Du Pont Esters
US2435508A (en) * 1944-11-01 1948-02-03 Us Rubber Co Manufacture of dithio bisarylamines
US2983726A (en) * 1959-08-18 1961-05-09 Goodrich Co B F Method for preparing secondary aminothiazoledisulfides
US3261825A (en) * 1963-03-11 1966-07-19 Martin Marietta Corp Azo-disulfide triazine dyestuffs
US3299040A (en) * 1963-03-11 1967-01-17 Martin Marietta Corp Disazo-disulfide dyes
US3388126A (en) * 1965-10-27 1968-06-11 Monsanto Co Synthesis of sulfenamides in aqueousorganic solvent mixtures

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4142982A (en) * 1975-06-04 1979-03-06 Canon Kabushiki Kaisha Toner for developing electrostatic latent images comprising resin binder of polyester and solid silicone varnish
US4603097A (en) * 1983-10-28 1986-07-29 Ricoh Company, Limited Styrene derivatives and electrophotographic photoconductor comprising one of the styrene derivatives
US5072043A (en) * 1983-10-28 1991-12-10 Ricoh Company, Ltd. Styrene derivatives and electrophotographic photoconductor comprising one of the styrene derivatives
US4606988A (en) * 1984-02-21 1986-08-19 Ricoh Company, Ltd. Styryl derivatives and electrophotographic photoconductor comprising one styryl derivative

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NL163881B (nl) 1980-05-16
DE2123829C3 (de) 1981-10-29
GB1351129A (en) 1974-04-24
DE2123829B2 (de) 1981-02-05
FR2091630A5 (enExample) 1972-01-14
DE2123829A1 (de) 1971-12-02
NL7106405A (enExample) 1971-11-16
NL163881C (nl) 1980-10-15

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