US3047384A - Sensitized photoconductive compositions comprising polymethine dyes containing a mercapto group - Google Patents

Sensitized photoconductive compositions comprising polymethine dyes containing a mercapto group Download PDF

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US3047384A
US3047384A US805156A US80515659A US3047384A US 3047384 A US3047384 A US 3047384A US 805156 A US805156 A US 805156A US 80515659 A US80515659 A US 80515659A US 3047384 A US3047384 A US 3047384A
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nucleus
zinc oxide
photoconductive
dyes
sensitized
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Jean E Jones
Paul H Stewart
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE563443A priority Critical patent/BE563443A/xx
Priority to GB39804/57A priority patent/GB885717A/en
Priority to FR1188943D priority patent/FR1188943A/fr
Priority to GB39802/57A priority patent/GB885715A/en
Priority to GB39803/57A priority patent/GB885716A/en
Priority to US805156A priority patent/US3047384A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to GB11748/60A priority patent/GB954017A/en
Priority to BE589454A priority patent/BE589454A/xx
Priority to FR823566A priority patent/FR1253157A/fr
Priority to US24122A priority patent/US3110591A/en
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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
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • 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
    • 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

Definitions

  • This invention relates to sensitized photoconductive compositions and layers comprising zinc oxide which are particularly useful in the document copying field.
  • a relatively conducting support such as paper
  • a photoconductive zinc oxide dispersed in an electrically insulating binder material is coated with a photoconductive zinc oxide dispersed in an electrically insulating binder material.
  • the grounded support is then placed beneath a corona discharge so that a blanket negative electrostatic charge on the Zinc oxide surface is accumulated.
  • the zinc oxide is a photoconductive material, it is necessary to perform this charging separation in the substantial absence of any ultra-violet or visible radiation.
  • the charged zinc oxide photoconductive layer can then be exposed to a photographic image in the usual manner, the portions of the zinc oxide which receive light or ultra-violet radiation losing wholly or in part (depending upon the extent of exposure), the negative electrostatic charge, while the unexposed or partially exposed portions of the charged layer retaining their negative electrostatic charge.
  • the resulting latent image can then be developed to a visible image by means of a pigment powder which has a charge opposite to the negative charge remaining on the areas of the photoconductive layer.
  • the pigment powder is thus strongly attracted to the negatively charged areas and can be permanently affixed to the surface of the photoconductive layer by simply melting the vehicle for the powder at some temperature below the charring temperature of the paper support.
  • the sensitivity is not primarily within the visible region of the spectrum, so that such materials have a relatively low speed when an ordinary light source, such as a tungsten lamp or fluorescent lamp, is used as the exposing source.
  • the zinc oxide normally employed in such photoconductive layers has its greatest sensitivity in the ultra-violet region of the spectrum, and normal light sources have "ice very weak radiation in this region.
  • An object of our invention is to provide a convenient means of increasing the sensitivity of photoconductive zinc oxide layers to visible radiation. Another object is to provide photoconductive zinc oxide layers which have much higher speeds than those previously available.
  • Still another object is to provide a means for sensitizingphotoconductive zinc oxide compositions to particular regions of the spectrum so that these compositionscan be used in the manufacture of color materials.
  • the following invention relates to the discovery that certain polymethine dyes containing a mercapto group can be used to usefully extend the sensitivity of photoconductive zinc oxide compositions.
  • the polymethine dyes of our invention conveniently contain a cyclic.
  • FIGURES 1-3 represent the sensitivity of photoconductive zinc oxide compositions sensitized with polymethine dyes according to our invention. Further details regarding such sensitizing action are given below.
  • the polymethine dyes which can be usefully employed according to our invention comprise many of the wellknown classes of sensitizing dyes which have been used in silver ialide photography, and they include dyes containing a cyclic ketomethylene acidic nucleus. Such dyes It has been found that dyes containing a subinclude simple merocyanine dyes, merocarbocyanine dyes, merodicarbocyanine dyes, trinuclear holopolar dyes, complex merocyanine dyes, etc. Many of the useful dyes of our invention contain a H l N .C
  • Polyrnethine dyes of the merocyanine class which can be usefully employed in our invention include those dyes represented by the following general formula:
  • R represents an alkyl radical, Le, a substituted or unsubstituted alkyl group, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, fl-methoxyethyl, p-ethoxyethyl, carboxymethyl, etc.
  • R represents a hydrogen atom or an alkyl group, such as methyl, ethyl, etc, d, m and 11 each represents a positive integer of from 1 to 2,
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the type common in cyanine dye chemistry, such as those selected from the group consisting of a thiazole nucleus (e.g., thi-azole, 4-methylthiazole, 4-phenylthiazole, S-methylthiazcle, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthi azole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole, etc), a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole,
  • a Z-quinoline nucleus e.g., quinoline, 3-methylquinol-ine, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6 chloroquinoline, 8 chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc), a 4-quinoline nucleus (e.g., quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc), a l-isoquinoline nucleus (e.g., isoquinoline, 3,4-dihydroisoquincline, etc), a benzimidazole nucleus (e.g., 1,3-diethylbenzimidazcle, l-ethyl-3- phenylbenzrirnidazole, etc), a 3,3-dialkylindolenine nucleus (e.g., 3,3-dirnethylindolenine, 3,3,5
  • R, R X, n, d and Z have the values given above and Z represents the atoms necessary to complete a cyclohexene ring, which may contain simple substituents, such as alkyl groups (e.g., methyl, ethyl, etc).
  • p represents a positive integer of from 1 t0 2 CH CH K S
  • Z represents the non-metallic atoms necessary to 5 complete a heterocyclic nucleus containing from 5 to 6 I atoms in the heterocyclic ring of the type commonly 5 employed in cyanine dye chemistry, such as are defined by Z above.
  • the merocyanine dyes embraced by our invention can 3 be prepared according to techniques which have been previously described in the prior art.
  • pat- (5) ents describing methods for making such dyes are the (c1 1 following: C NH I 1 Brooker et al. US. Patent 2,161,331, granted June 6, 1939 C CH CE K S Brooker US. Patent 2,170,803, granted August 29, 1939 H Brooker U.S. Patent 2,170,804, granted August 29, 1939 Brooker US. Patent 2,170,807, granted August 29, 1939 3 Brooker US. Patent 2,177,401, granted October 24, 1939 y Brooker US.
  • the polymethine 0 J chain in our dyes can contain conventional substituents.
  • Methods for making such dyes have been previously de- N scribed in the prior art. See, for example, Brooker and 4 N H White U.S. Patent 2,263,757, issued November 25, 1941, H and Kendall and Collins US. Patent 2,319,547, issued 2 5 May 18, 1943. 7
  • the merocyanine dyes of Formula Ib can be prepared according to methods which have been previously de- 07C scribed in the prior art. See, for example, Brooker and C CH CH Heseltine U.S. Patent 2,856,404, issued October 14, 1958.
  • the holopolar dyes of Formula R can be prepared 1 according to methods previously described in the prior 6 5 art. See, for example, Brooker and White Reissue US. 2H5 Patent 24,292, reissued March 19, 1957 (original Patent No. 2,739,964, issued March 27, 1956). (8)
  • Fry and 551 l Kendall US. Patent 2,388,963, issued November 13, 1945, H describes a method of making complex merocyanine dyes which can be usefully employed in our invention. (See 5 Example 18, for instance.) Heseltine and Brooker US.
  • Patent 2,719,151, issued September 27, 1955, describes 603(9) the preparation of trinuclear merocyanine dyes which 5 o c N 3 can be used in our invention.
  • Typical polymethine dyes which can be employed in g practicing our invention include the following: 1 l
  • N N I I c n E, ,1 e 3 dye can be added to the zinc oxide composition while disi solved in an organic solvent. Pyridine, methanol, ethanol, acetone, etc, can be used to dissolve many of the dyes useful in practicing our invention.
  • the zinc oxide can be uniformly dispersed in an organic solution of the binder customarily employed for the zinc oxide and a solution of the sensitizing dye added to this coating solution. After thorough mixing, the sensitized composition can be coated on a paper support and dried in the usual manner.
  • an unsensitized zinc oxide coating can be prepared as described above and after removal of the organic solvent, the-paper coating can be immersed in a solution of the sensitizing dye. This method has been found to be particularly useful in that higher speeds can be frequently obtained.
  • the binders for the zinc oxide comprise many of the resinous compositions which are commercially available. Such resins are sold under trade names, such as Plaskon ST-856, Rezyl 405-18, Pliolite S7 or S-SD, Styresol 4440, DC 804, etc. These resins comprise styrene-butadiene copolymers, silicone resins, styrene-alkyl resins, silicone-alkyd resins, soya-alkyd resins, polyvinyl chloride, polyvinyl acetate, etc. The methods of making such resins have been previously described in the prior art. For example, styrene-alkyd resins can be prepared according to the method described in Gerhart US.
  • binders such as paraffin, mineral waxes, etc.
  • These binders are generally characterized as having marked hydrophobic properties (i.e., being substantially free of any water-solubilizing groups, such as hydroxyl, free acid groups, amide groups, etc.) and as being good electrical insulators or as having high electrical resistivity.
  • These binders can be easily dissolved in organic solvents having a boiling point below the charring temperature of the paper support. Also, these binders have the desirable property of readily dispersing the zinc oxide photoconductive material.
  • Some resinous binders are relatively poor insulators and do not provide coatings which can be stored for prolonged periods of time after the photoconductive coatings have been negatively charged. This is particularly noticeable at relatively high humidities, and the photoconductive coatings should be charged shortly before use in such instances, that is, it is not advisable to charge the photoconductive coatings too long in advance before use. Such problems are well understood by those skilled in the art.
  • Non-polar solvents have been found to be particularly useful in preparing the photoconductive layers in that any residual solvent which cannot be removed does not have a deleterious effect on the keeping qualities of'the photoconductive layers.
  • solvents include the aromatic hydrocarbons, such as benzene, xylenes, toluene, etc;
  • the zinc oxide employed in our invention should generally consist of relatively small particles of less than 0.5 micron mean diameter. Such zinc oxide materials are readily available and can be purchased under a variety of trade names, such as Protox No. 168 (New Jersey Zinc Company), etc. Sufficient binder should be employed to insulate each of the zinc oxide particles from the surrounding particles in the composition. The most useful or optimum quantity of zinc oxide to binder for a particular binder can be readily determined by making a series of test coatings wherein the quantity and relative amounts of zinc oxide to binder are employed.
  • Exposure of the charged photoconductive layer to visible radiation or ultraviolet radiation causes a loss or reduction of the negative charge in those portions of the photoconductive material which are exposed to the radiation.
  • the degree of loss will dependon the intensity and time of exposure to the radiation, in general.
  • the resulting latent electrophotographic image can then be developed to a visible image in a variety of ways, including those which have been previously employed in electrophotographic processes, such as xerography.
  • a particularly useful means of developing the latent electrophotographic image comprises use of a magnetic brush. This magnetic brush development makes use of a ferromagnetic powder, such as iron filings, which has been intimately mixed with pigmented resin, or sulfur.
  • Agitation of the ferromagnetic powder and pigmented resin results in a triboelectric effect wherein the pigmented resin acquires an electric charge depending upon the relative position of the resin to the ferromagnetic powder in the triboelectric series. That is, ordinary iron powder is below most resins in the triboelectric series, and mixture with a resin higher in the series results in the deposition of a positive electrostatic charge on the resin; The result ing mixture can then be picked up by a magnet on which the iron particles, or other ferromagnetic powder, arrange themselves in the conventional pattern, so that the long chains of filings resemble an ordinary brush; This magnetic brush can then be placedin contact with the exposed photoconductive layer and the brush passed across the negative electrostatic latent image whichis on the surface of the photoconductive material.
  • the electrosatic attraction between the charged pigmented resin particles and the oppositely charged image areas in the photoconductive material is greater than the attraction between these particles and the ferromagnetic powder, so that the pigmented resin is deposited on the surface of the photoconductive material roughly in proportion to the residual charge on the surface of the photoconductive layer.
  • the developed image can then be fixed to the surface of the paper by heating to a temperature above the meltingpoint of the resin, but below the charring temperature of the paper.
  • the resin in the pigmented resin compositions can be varied, depending upon the effects desired and the type of copy which is being reproduced.
  • Such resins may be the same as those employed in the insulating layer coated on .thepaper support, such as .styrene-butadiene resins, etc.
  • the particle size of the pigmented resin used in development can vary, although the range of 0.1 to 25 microns is adequate for most purposes.
  • Various pigments can be used in the resin developing compositions. The ability of the pigmented resin charge is dependent upon the type of resin selected. The pigment merely serves to impart color to the resin and probably imparts very little, if any, influence on the overall charge of the pigmented resin.
  • the sensitizing zinc oxide papers were then dried in air in a vertical position. After drying, the paper strips were exposed to a 10,000- volt corona discharge for 15 seconds and then exposed to tungsten illumination for 2 seconds in an intensity scale sensitometer and spectrograph. The exposed coatings were then developed by the magnetic brush technique described above using small iron particles dispersed in black pigmented sulfur. Finally, the images were fixed by fusing the developed image to the paper at a temperature of about the same manner with the sensitizing dye being omitted from the sensitizing solution. This served as a control, the speed of which was arbitrarily set at one. In the following table the dyes are identified by number and in terms of their concentration in the sensitizing solution.
  • the solid curve represents the sensitivity of zinc oxide, sensitized with -[(l,3,3t1imethyl-2(1H)- indoleninylidene)ethylidene]rhodanine.
  • the sensitizing data for this dye are given in the above table, dye 4.
  • the solid curve represents the sensitivity of a photoconductive zinc oxide sensitized with 5 [(3-ethyl-2 (3H) -benzoxazolylidene)ethylidene] 1- phenyl-Z-thiohydantoin.
  • the sensitizing data for this dye are given in the above table, dye 7.
  • the solid curve represents the sensitivity of a photoconductive zinc oxide material sensitized with 5 (3 ethyl 2(3H)-benzothiazolylidene)ethylideneJ- l-methyl-Z-thiobarbituric acid.
  • the sensitizing data for this dye are given in the above table, dye 17.
  • sensitizing dyes of our invention can be usefully employed to extend the sensitivity of zinc oxide material intended for use in a photoconductographic process.
  • Photoconductographic processes have been previously described in the prior art, such as in Bronk British Patent 188,030, accepted October 23, 1922, and Hana Dutch Patent 5,142, patented June 13, 1920.
  • Dyes 17, 22 and 23 were separately dissolved in a suitable solvent and mixed with a composition comprising photoconductive zinc oxide and a resinous, insulatorbinder comprising a synthetic resin, such as Pliolite 8-7 (a styrene butadiene copolymer), the concentration of the dyes being 5.6 micromoles per 56 grams of zinc oxide.
  • the zinc oxide to binder ratio was 3:1.
  • a solvent mixture comprising 95% toluene and 5% methanol was added to give a mixture containing 35% solids by weight, and the solutions were separately coated at a thickness of 0.010 inch, wet, on paperabacked aluminum foil.
  • each of the coatings was then dried and exposed in the customary manner to daylight-quality radiation in a high intensity wedge spectrograph.
  • the exposed coatings were then developed by contacting the exposed surfaces with a viscose sponge wet with a developer solution comprising sodium thiosulfate saturated with silver chloride.
  • the viscose sponge was held .at a potential of about 70 volts positive with respect to the aluminum foil backing.
  • the sensitizing data for each of the coatings was approximately the same as indicated in the above table for coatings obtained in an electrophotographic process.
  • dye 17 gave a sensitizing maximum of about 520 with sensitivity extending from about 440 to 540 m
  • the invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms
  • d and m each represents a positive integer of from 1 to 2
  • R represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms and an aryl group containing from 6 to 7 carbon atoms
  • X represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a
  • R and R" each represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms and an aryl group containing from 6 to 7 carbon atoms, provided at least one of the members selected from the class consisting of R R and R" is a hydrogen atom
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphtho thiazole nucleus, a thianaphtheno-7',6,4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • a represents a positive integer of from 1 to 2
  • Z represents the atoms necessary to complete a cyclohexene ring
  • R represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 4 carbon'atoms and an aryl group containing from 6 to 7 carbon atoms
  • X represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a
  • Z represents the non-metallic atoms necessary to complete a heterocyclic-nucleus selected from theclass consisting of a thiazole nucleus, 21 benzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno-7,6',4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nu
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms, a! and In each represents a positive integer of from 1 to 2, R represents 2332 1 5 nucleus a 2 Pyudme nucleus and a 4 pyndme 40 a member selected from the class consisting of a hydro- 3.
  • a photoconductive composition comprising sensigen atom an alkyl group i i from 1 to 4 carbon tized photoconductive zinc oxide particles uniformly disatoms gz an i i 2312 225 35?
  • R and R each represents an alkyl group containgroup and a ing from 1 to 4 carbon atoms
  • d represents a positive integer of from 1 to 2
  • R represents a member selected ll l from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms and an aryl group containing from 6 to ,7 carbon atoms
  • X represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a
  • R and R" each represents a member selected from the class consisting of a hydrogen atom, an
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R represents a member selected from the class consisting of an alkyl group containing from 1 to 4 carbon atoms and an aryl group containing from 6 to 7 carbon atoms
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms
  • d represents a positive integer of from 1 to 2
  • R represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms and an aryl group containing from 6 to 7 carbon atoms
  • X represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a
  • R and R" each represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms and an aryl group containing from 6 to 7 carbon atoms, provided at least one of the members selected from the class consisting of R R and R is a hydrogen atom, and Z represents the non-metallic atoms necessary to complete a 3,3-dialkylindolenine nucleus.
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a dye represented by the following formula:
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said Zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R represents an alkyl group containing from- 1 to 4 carbon atoms
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms
  • d and m each represents a positive integer of from 1 to 2
  • X represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a
  • R and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms and an aryl group containing from 6 to 7 carbon atoms, provided at least one of the members selected from the class consisting of R R and R" is a hydrogen atom, and Z represents the non-metallic atoms necessary to complete a benzothiazole nucleus.
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a dye represented by the following formula:
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a merocyanine dye selected from the class represented by the following general formula:
  • R and R each represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms and an aryl group containing from 6 to 7 carbon atoms, provided at least one of the members selected from the class consisting of R R and R is a hydrogen atom, and Z represents the non-metallic atoms necessary to complete a benzoxazole nucleus.
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dis persed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a dye represented by the following formula:
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a holopolar dye selected from the class represented by the following general formula:
  • R and R" each represents a member selected from the class consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms and an aryl group containing from 6 to 7 carbon atoms, provided at least one of the members selected from the class consisting of R R' and R represents a hydrogen atom, and Z and Z each represents the non-metallic atoms necessary to complete a naphthot-hiazole nucleus.
  • a photoconductive composition comprising sensitized photoconductive zinc oxide particles uniformly dispersed in a high dielectric, organic binder-insulating material for said zinc oxide, said zinc oxide being sensitized with a dye represented by the following formula:

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  • General Physics & Mathematics (AREA)
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US805156A 1956-12-26 1959-04-09 Sensitized photoconductive compositions comprising polymethine dyes containing a mercapto group Expired - Lifetime US3047384A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
BE563443A BE563443A (en(2012)) 1956-12-26 1957-12-21
FR1188943D FR1188943A (fr) 1956-12-26 1957-12-23 Nouvelle composition photoconductrice
GB39802/57A GB885715A (en) 1956-12-26 1957-12-23 Photoconductive compositions and photographic elements
GB39803/57A GB885716A (en) 1956-12-26 1957-12-23 Photoconductive compositions and photographic elements
GB39804/57A GB885717A (en) 1956-12-26 1957-12-23 Photoconductive compositions and photographic elements
US805156A US3047384A (en) 1956-12-26 1959-04-09 Sensitized photoconductive compositions comprising polymethine dyes containing a mercapto group
GB11748/60A GB954017A (en) 1956-12-26 1960-04-04 Photoconductive compositions and photographic elements
BE589454A BE589454A (en(2012)) 1956-12-26 1960-04-06
FR823566A FR1253157A (fr) 1956-12-26 1960-04-06 Nouvelle composition photoconductrice et ses applications, notamment pour l'électrophotographie
US24122A US3110591A (en) 1956-12-26 1960-04-22 Merocyanine sensitized photoconductive compositions comprising zinc oxide

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US885716XA 1956-12-26 1956-12-26
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US885717XA 1956-12-26 1956-12-26
US805156A US3047384A (en) 1956-12-26 1959-04-09 Sensitized photoconductive compositions comprising polymethine dyes containing a mercapto group
US24122A US3110591A (en) 1956-12-26 1960-04-22 Merocyanine sensitized photoconductive compositions comprising zinc oxide

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US3250613A (en) * 1961-05-01 1966-05-10 Eastman Kodak Co Use of amines in photoconductographic coatings
US3251687A (en) * 1961-07-10 1966-05-17 Itek Corp Electrostatic printing process
US3252835A (en) * 1960-06-01 1966-05-24 Agfa Ag Sensitization of electrophotographic layers
US3380823A (en) * 1966-06-20 1968-04-30 Itek Corp Photocopying method
US3507649A (en) * 1967-01-31 1970-04-21 Lee C Hensley Sensitized photoconductive zinc oxide
US3628951A (en) * 1968-04-01 1971-12-21 Gaf Corp Trinuclear methine dyes for use in electrophotographic system
US3839327A (en) * 1968-04-01 1974-10-01 Gaf Corp Trinuclear methine dyes for use in electrophotographic systems
USB342886I5 (en(2012)) * 1972-03-23 1975-01-28
US3912507A (en) * 1973-06-04 1975-10-14 Itek Corp Polyrhodanine photoconductive materials
WO1992020015A1 (en) 1991-05-02 1992-11-12 Fuji Photo Film Co., Ltd. Electrophotographic photoreceptor
US10095137B2 (en) * 2016-04-04 2018-10-09 Canon Kabushiki Kaisha Electrophotographic photosensitive member, method of producing electrophotographic photosensitive member, process cartridge, and electrophotographic image forming apparatus

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US3331687A (en) * 1962-09-24 1967-07-18 Render Belipa G M B H Fa Electrophotographic material
DE1447935C3 (de) * 1964-08-14 1974-11-14 The Dow Chemical Co., Midland, Mich. (V.St.A.) Verfahren zur Herstellung einer Beschichtungsflussigkeit fur elektro photographische Druckplatten
GB1282423A (en) * 1968-12-16 1972-07-19 Agfa Gevaert Spectral sensitization of photoconductive compositions
CH728269A4 (en(2012)) * 1969-05-13 1972-03-30
DE3270544D1 (en) * 1981-02-23 1986-05-22 Minnesota Mining & Mfg Sensitized organic electron donor compounds
JPH0823707B2 (ja) * 1987-04-22 1996-03-06 富士写真フイルム株式会社 スキヤンニング露光工程を含む画像形成方法
CN105493385B (zh) * 2013-09-04 2020-04-07 固瑞克明尼苏达有限公司 具有自由旋转风扇的风扇冷却的马达

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US2078233A (en) * 1934-09-14 1937-04-27 Eastman Kodak Co Photographic emulsion
US2177403A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from imidazolones
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh

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US1730505A (en) * 1928-01-30 1929-10-08 Hart Russell Photo-electric cell
US2493748A (en) * 1945-07-16 1950-01-10 Eastman Kodak Co Merocyanine dyes
BE466676A (en(2012)) * 1945-07-16
US2638473A (en) * 1948-10-02 1953-05-12 Ilford Ltd Methine dyestuffs
US2685509A (en) * 1951-10-05 1954-08-03 Eastman Kodak Co Optically sensitized photographic emulsion
US3052540A (en) * 1954-06-02 1962-09-04 Rca Corp Dye sensitization of electrophotographic materials
BE538610A (en(2012)) * 1954-06-02

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US2078233A (en) * 1934-09-14 1937-04-27 Eastman Kodak Co Photographic emulsion
US2177403A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from imidazolones
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252835A (en) * 1960-06-01 1966-05-24 Agfa Ag Sensitization of electrophotographic layers
US3250613A (en) * 1961-05-01 1966-05-10 Eastman Kodak Co Use of amines in photoconductographic coatings
US3251687A (en) * 1961-07-10 1966-05-17 Itek Corp Electrostatic printing process
US3380823A (en) * 1966-06-20 1968-04-30 Itek Corp Photocopying method
US3507649A (en) * 1967-01-31 1970-04-21 Lee C Hensley Sensitized photoconductive zinc oxide
US3628951A (en) * 1968-04-01 1971-12-21 Gaf Corp Trinuclear methine dyes for use in electrophotographic system
US3839327A (en) * 1968-04-01 1974-10-01 Gaf Corp Trinuclear methine dyes for use in electrophotographic systems
USB342886I5 (en(2012)) * 1972-03-23 1975-01-28
US3923507A (en) * 1972-03-23 1975-12-02 Agfa Gevaert Ag Sensitized electrophotographic layers
US3912507A (en) * 1973-06-04 1975-10-14 Itek Corp Polyrhodanine photoconductive materials
WO1992020015A1 (en) 1991-05-02 1992-11-12 Fuji Photo Film Co., Ltd. Electrophotographic photoreceptor
US10095137B2 (en) * 2016-04-04 2018-10-09 Canon Kabushiki Kaisha Electrophotographic photosensitive member, method of producing electrophotographic photosensitive member, process cartridge, and electrophotographic image forming apparatus

Also Published As

Publication number Publication date
BE563443A (en(2012)) 1958-01-15
GB954017A (en) 1964-04-02
GB885716A (en) 1961-12-28
GB885715A (en) 1961-12-28
US3110591A (en) 1963-11-12
GB885717A (en) 1961-12-28
BE589454A (en(2012)) 1960-08-01
FR1188943A (fr) 1959-09-28

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