US3844782A - Heterocyclic dye sensitised electrophotographic material - Google Patents

Heterocyclic dye sensitised electrophotographic material Download PDF

Info

Publication number
US3844782A
US3844782A US00279251A US27925172A US3844782A US 3844782 A US3844782 A US 3844782A US 00279251 A US00279251 A US 00279251A US 27925172 A US27925172 A US 27925172A US 3844782 A US3844782 A US 3844782A
Authority
US
United States
Prior art keywords
dye
group
electrophotographic
dyes
heterocyclic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00279251A
Other languages
English (en)
Inventor
O Riester
W Gesierich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Application granted granted Critical
Publication of US3844782A publication Critical patent/US3844782A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • G03G5/0631—Heterocyclic compounds containing one hetero ring being five-membered containing two hetero atoms
    • 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
    • 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
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0633—Heterocyclic compounds containing one hetero ring being five-membered containing three hetero atoms
    • 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

Definitions

  • ABSTRACT Primary Examiner-Charles L. Bowers, Jr. Attorney, Agent, or Firm-Connolly and l-lutz [57] ABSTRACT The sensitization of layers containing a photoconductor by the inclusion of a heterocyclic dye compound characterized in that the sensitization is increased while the product exhibits longevity.
  • FIG 6 FIG. 7-
  • the dyes which have been proposed for this purpose belong to a variety of different classes of compounds, e.g. triphenyl methane dyes, phenol sulphonphthaleins, xanthene and acridine dyes as well as cyanines and merocyanines, which exemplify the class of polymethine dyes, and oxonoles.
  • the foregoing dyes suffer the disadvantage that they either do not provide sufficient increase in sensitivity or they add too much colour to the electrophotographic layer. As a rule, only colourless or almost colourless layers are desired. This detrimental discoloration is particularly serious in the case of electrophotographic materials since the sensitising dyes used are not washed out during the usual working up methods, or are not destroyed in the baths. To bleach out the sensitising dyes after the photograph is completed is usually too complicated.
  • the object of the present invention is to provide a method for optically developing sensitised electrophotographic layers which preferably contain zinc oxide as 'photoco'nducter and which are as far as possible, colo'ur'less and are stable on storage, especially in respect of their sensitivity. It has now been found that very good sensitisation in the blue-violet region of the spectrum can ben achieved by the use of methylene dithiocarboxylic acid esters of heterocyclic compounds.
  • R" is (l) a hydrogen atom (2) an alkyl or alkenyl group having preferably 1 to 6 C- atoms, which may be substituted by a hydroxyl, alkoxy, or phenyl group, (3) a cycloalkyl group such as cyclohexyl or (4) an aryl group such as phenyl or naphthyl; R and R" may together denote the ring members required for completing a 5- or 6-membered heterocyclic ring; R' is l) a hydrogen atom, (2) an alkyl or alkenyl
  • 6,7-tetramethylenebenzthiazole those of the selenazole series such as benzoselenazole or those of the indoline series such as 1,3,3-trimethylindoline, 5- methoxyl ,3 ,3-trimethylindoline.
  • the compounds to be used according to the invention are prepared by known methods, eg from heterocyclic quaternary salts which are substituted by a methylene group in the N-Z-position by the addition of carbon disulphide and csterification of of the resulting terminal dithiocarboxylic acids.
  • R represents an alkyl or aralkyl group
  • R represents hydrogen or an alkyl, aryl or aralkyl group
  • R represents an alkyl, aryl or aralkyl group
  • X represents an acid residue
  • This reaction may involve any of known type of heterocyclic quaternary ammonium compounds containing the specified reactive methyl group known for use in the manufacture of cyanine-dyes, as for example the substituted and unsubstituted thiazoles, oxazolcs, selenazoles and their polycyclic homologues such those of the benzene, naphthalene, acenaphthene and anthracene series; pyridine and its polycyclic homologues such as quinoline and a and y naphthaquinolines; lepidines; indolenines; diazines; such as pyrimidines and quinazolines; diazoles (e.g.
  • polycyclic compounds of these series may also be'substituted in. the carbocyclic rings with one or more groups such as alkyl, aryl, amino, hydroxy, alkoxy and methylene dioxy groups, or by halogen atoms.
  • the groups R, R and R may be alkyl groups and examples are the methyl, ethyl, propyl and higher alkyl groups, allyl and similar unsubstituted groups, or they may be aralkyl groups,
  • R and R may be an aryl group, e.g.
  • reaction may take place by heating the reagents together in the presence of a base and a solvent, it is preferred to carry on the reaction in the presence of an excess of a strong base.
  • This process produces a dithiocarboxylic acid which may be used for the production of the sensitizing dye.
  • the dyes according to the invention can be used to sensitise an electrophotographic layer, in particular a zinc oxide layer, in the blue region of the spectrum with sensitation maxima of 420 to 460 mu.
  • These dyes have a characteristically narrow sensitisation range with steep drop of the sensitisation curve towards the long wave region of the spectrum and have high sensitisation intensity. This makes them eminently suitable for blue sensitisation of electrophotographic materials such as for example, colour materials which are processed with copying light containing a high proportion of blue light.
  • Another advantage of the dyes according to the invention is that discoloration of the photographic layers is almost imperceptible.
  • the sensitisers according to the invention are added to the layers in such quantitiesthat about 0.1 to l mg of sensitiser are present per square metre of completed photoconductive layer.
  • Sensitisation of electrophotographic layers is usually carried out by triturating the photoconductive pigment with the solution of the sensitising dye in a suitable solvent such as methyl or ethyl alcohol and evaporating off the solvent.
  • the sensitising dye precipitates on the surface of the grain of the photoconductive pigment when this operation is carried out.
  • the pigment can now be worked up with a dilute solution of a lacquer binder to produce the electrophotographic layer.
  • the dye according to the invention may equally well be used in other sensitisation methods. In one of these processes, for example, the solution of sensitising dye in a liquid which is inert to the binder is added to the mixture of photoconductor and binder before dispersion.
  • the use of the dye according to the in vention is not limited to any particular types of photoconductors and binders.
  • Compounds which can be used as photoconductors in such systems are, in particular, inorganic and organic compounds which by virtue of their own colour do not already have a sensitivity maximum in the sensitising region of the dyes according to the invention.
  • suitable compounds are zinc oxide, titanium dioxide or arsenious trioxide or organic compounds such as anthracene or phenanthrene.
  • Any of the film-forming agents customarily used in electrophotography such as silicone resins, alkyd resins, polyurethanes on polyvinyl acetate, can be used as binders for the layers sensitized according to the present invention.
  • dye No. III XII, IV, XIV, V and XV.
  • FIG. 1 show the spectral sensitivity curve of a zinc oxide layer which has not been sensitised
  • FIG. 2 the sensitisation properties of the material prepared according to the Example
  • FIGS. 3 to 7 the photoconductive Layers obtained with the use of dyes No. XII (FIG. 3), No. lV (FIG. 4), No. XIV (FIG. 5), No. V (FIG. 6), No. XV (FIG. 7).
  • the sensitisation curves are obtained as follows:
  • the layer which is to to be examined, in contact with an interference graduated line filter VERIL B-60 made by Schott & Genossen is exposed to 4,000 Lux seconds of an image enlarging lamp RADIUM R 226 (230 V/250 W).
  • RADIUM R 226 230 V/250 W
  • the filter is covered with a transparent grey step wedge so that a curve is obtained on the photoconductive layer typical of the image which is capable of being developed, which curve is shown as a line drawing in the appended figures.
  • the effectiveness of the sensitising dye can be assessed by the height of the ordinate at its maximum on this sensitisation curve, whilst the position of the sensitisation maximum in the visible region of the spectrum can be determined from the abscissa.
  • the photoconductive material according to the invention can be used for all electrophotographic processes, for example for development processes which make use of a solid pulverulent toning powder, for aerosol development processes electrophoretic processes and so-called wetting development processes.
  • the materials according to the invention are suitable both for electrostatic charge images and for conductive images.
  • Photosensitive electrophotographic material having a layer of photoconductive material comprised of said dye being present in the amount of 0.1 to 10 mg. per square meter of the photoconductive layer.
  • Photosensitive electrophotographic material according to claim 1 in which the dye is a benzthiazole compound.
  • Photosensitive electrophotographic material according to claim 1 in which the photoconductive material is zinc oxide dispersed in a hinder.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
US00279251A 1965-10-15 1972-08-09 Heterocyclic dye sensitised electrophotographic material Expired - Lifetime US3844782A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA0050509 1965-10-15

Publications (1)

Publication Number Publication Date
US3844782A true US3844782A (en) 1974-10-29

Family

ID=6937439

Family Applications (1)

Application Number Title Priority Date Filing Date
US00279251A Expired - Lifetime US3844782A (en) 1965-10-15 1972-08-09 Heterocyclic dye sensitised electrophotographic material

Country Status (6)

Country Link
US (1) US3844782A (en))
BE (1) BE688309A (en))
CH (1) CH472708A (en))
DE (1) DE1497120A1 (en))
GB (1) GB1098535A (en))
NL (1) NL6614490A (en))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999989A (en) * 1970-12-19 1976-12-28 Fuji Photo Film Co., Ltd. Electrophotographic member having improved sensitizer and process utilizing same
US5310614A (en) * 1991-11-21 1994-05-10 Konica Corporation Electrophotographic photoreceptor having an organic photoelectroconductive light sensitive layer
US20080193700A1 (en) * 2004-05-05 2008-08-14 Ciba Specialty Chemicals Holding Inc. Metal Chelates and Their Use in Optical Recording Media Having High Storage Capacity

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2332517A (en) * 1943-10-26 Ctanine djtesttjff intermediates
US3114633A (en) * 1959-04-18 1963-12-17 Azoplate Corp Material for electrophotographic and electroradiographic purposes
US3287123A (en) * 1961-07-24 1966-11-22 Azoplate Corp Process for the sensitization of photoconductors
US3352670A (en) * 1964-02-14 1967-11-14 Minnesota Mining & Mfg Supersensitizers for optically sensitized photoconductive layers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2332517A (en) * 1943-10-26 Ctanine djtesttjff intermediates
US3114633A (en) * 1959-04-18 1963-12-17 Azoplate Corp Material for electrophotographic and electroradiographic purposes
US3287123A (en) * 1961-07-24 1966-11-22 Azoplate Corp Process for the sensitization of photoconductors
US3352670A (en) * 1964-02-14 1967-11-14 Minnesota Mining & Mfg Supersensitizers for optically sensitized photoconductive layers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999989A (en) * 1970-12-19 1976-12-28 Fuji Photo Film Co., Ltd. Electrophotographic member having improved sensitizer and process utilizing same
US5310614A (en) * 1991-11-21 1994-05-10 Konica Corporation Electrophotographic photoreceptor having an organic photoelectroconductive light sensitive layer
US20080193700A1 (en) * 2004-05-05 2008-08-14 Ciba Specialty Chemicals Holding Inc. Metal Chelates and Their Use in Optical Recording Media Having High Storage Capacity

Also Published As

Publication number Publication date
GB1098535A (en) 1968-01-10
BE688309A (en)) 1967-04-17
NL6614490A (en)) 1967-04-17
CH472708A (de) 1969-05-15
DE1497120A1 (de) 1969-05-14

Similar Documents

Publication Publication Date Title
US3617270A (en) Sensitization of an inorganic photoconductive layer with 1, 3- and 1, 2-squario acid methine dyes
US3830647A (en) Recording process and element employing as photoconductive material fluorene ring system fused 1,2,-dihydro-2,2,4-trialkyl-quinolines
US3709685A (en) Photoconductive zinc oxide sensitized by substituted thiazolidene dyes
GB2084605A (en) Phthalocyanine pigments
US3798031A (en) Photoconductive 1,2,3,4-tetrahydroquinolines employed in electrophotography
GB1328374A (en) Electrophotographic copying process
US3533783A (en) Light adapted photoconductive elements
US4481270A (en) Photoreceptor containing squaric acid methine dyes
US3844782A (en) Heterocyclic dye sensitised electrophotographic material
US4500621A (en) Sensitive electrophotographic plates containing squaric acid methine dyes suspended in a binder
US3635706A (en) Sensitized electrophotographic layers
US3660084A (en) Recording process using quinolin-2-one or quinolin-4-one organic photoconductive substances
US3782933A (en) Sensitized electrophotographic layers
JPS6126904B2 (en))
US3583869A (en) Electrophotographic copying paper containing poly-n-vinyl-3-azo carbazole
US3988513A (en) Silver halide emulsions for recording electron rays
US3579331A (en) Electrophotographic materials containing cyanine dye sensitizers
US3658522A (en) Merocyanine-sensitized zinc oxide photoconductive element
JPH0331847A (ja) 電子写真記録材料
US3560208A (en) Cyanine dye containing a pyrrole nucleus used as a sensitizer for organic photoconductors
US3567438A (en) Organic photoconductors sensitized with pyrylium cyanine dyes
US3765882A (en) Heterocyclic photoconductor containing o, s or se
US3607257A (en) Photoconductive compositions and elements
US3782935A (en) Novel tetranuclear methine dyes,processes for preparing the same,and electrophotographic systems and silver halide emulsions containing the same
US3712811A (en) Electrophotographic material