US3314788A - Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines - Google Patents

Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines Download PDF

Info

Publication number
US3314788A
US3314788A US542620A US54262066A US3314788A US 3314788 A US3314788 A US 3314788A US 542620 A US542620 A US 542620A US 54262066 A US54262066 A US 54262066A US 3314788 A US3314788 A US 3314788A
Authority
US
United States
Prior art keywords
photoconductive
tspd
compounds
electrophotographic
phenylenediamines
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
US542620A
Other languages
English (en)
Inventor
Mattor John Alan
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.)
Warren SD Co
Original Assignee
Warren SD Co
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
Priority to NL134044D priority Critical patent/NL134044C/xx
Priority to GB6671/65A priority patent/GB1030220A/en
Priority to DEW38595A priority patent/DE1290428B/de
Priority to NL6503044A priority patent/NL6503044A/xx
Priority to FR9660A priority patent/FR1428747A/fr
Priority to BE661438D priority patent/BE661438A/xx
Priority to CH399465A priority patent/CH436991A/fr
Priority to US542620A priority patent/US3314788A/en
Application filed by Warren SD Co filed Critical Warren SD Co
Priority to JP4017866A priority patent/JPS463712B1/ja
Priority to GB28479/66A priority patent/GB1079838A/en
Priority to DE19661572380 priority patent/DE1572380B2/de
Priority to CH1129766A priority patent/CH459762A/fr
Priority to FR74724A priority patent/FR90786E/fr
Priority to NL666613040A priority patent/NL153685B/xx
Priority to BE688034D priority patent/BE688034A/xx
Application granted granted Critical
Publication of US3314788A publication Critical patent/US3314788A/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
    • 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
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G03G5/0614—Amines
    • G03G5/06142—Amines arylamine
    • G03G5/06144—Amines arylamine diamine

Definitions

  • the photoconductive insulating layer When used, the photoconductive insulating layer is first electrically charged as with a corona discharge so that the coating has a uniform positive or negative charge on its The plate is then exposed to a light image which activates the photoconductive compound. The charge density remaining at any point on the photoconductive insulating layer is inverse y proportional to the intensity of illumination at that point during the exposure.
  • the non-visible charge pattern or image is thereafter developed with an electrostatically attracta'ble toner in a known manner.
  • the developed image composed of colored pigment, together with a thermoplastic resin, is subsequently fixed by heating, or in the case of liquid toners by the air oxidation of the drying oils.
  • the present invention is based on the finding that the TSPD compounds are excellent photoconductive materials for use in the preparation of electrophotographic plates. These compounds have good photoconductivity and are particularly suitable for the preparation of lithographic plates as well as reproduction papers for use in desk type oilice copying devices or in electrophotographic printing.
  • the compounds of this class are, in general, easily prepared, stable compounds with a long shelf life and are soluble in most common resin binder-solvent systems so that they can be readily applied to a supporting substrate.
  • FIG. 1 illustrates the class of photoconductive TSPD compounds of interest
  • FIG. 2 schematically depicts the electrophotographic plate of this invention.
  • the TSPD compounds are used according to this invention in association with clear resinous film-forming polymeric binders having high dielectric characteristics such as a polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polyvinyl acetal, polyvinyl ether, polyacrylic ester, or any other natural or synthetic polymeric substance having the proper electrical characteristics.
  • the organic photoconductor and resinous polymer are dissolved in a sutiable organic solvent such 3,314,788 Patented Apr. 18, 1967 as benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, chloroform or methylene chloride.
  • Mixtures of two or more photoconductive substances can be used, as well as mixtures of two or more mutually miscible soltransparent, radiant energy.
  • the electrophotographic plate or sheet of this invention comprises a support carrying a photoconductive insulating layer which layer consists of a suitable resinous binder and at least 10 weight percent of the TSPD compound having the formula illustrated in drawings.
  • R in the formula is improve some other ferred radicals in the radicals. The benzyl only once.
  • phenylene ring is unsubstituted as substitution would tend to destroy photoconductivity because of steric hindrance of the planar configuration of the amine groups.
  • the preferred compounds are white and have a melt ing point in the range of 50 to 160 C. They are soluble to the extent of at least 2.5 grams in milliliters of chloroform at 25 C.
  • Symmetrical N,N,N'N' tetrabenzyl p phenylenediamine is a preferred example of the TSPD compounds because of its ease of preparation and excellent properties.
  • the alkyl derivatives will produce a photoconductive coating that responds excellently to ultra-violet light without the need of adding sensitizers to the coating.
  • the TSPD compounds can be prepared by condensing the appropriate alkyl halide and paraphenylenediamine in solution with heating.
  • the chloro alkyl halides are preferred. It is important to note that the TSPD compound is the reaction product of a primary aryl diamiue and an alkyl halide and is not the reaction product of a secondary diarylamine and an aryl halide. The latter reaction besides being difficult and expensive gives phenyl instead of benzyl derivatives.
  • TSPD compounds when dissolved in a layer of insulating resin, which layer is electrostatically charged and property such as solubility.
  • Pre- Z position are methyl and halogen radicals are preferably substituted.
  • the spectral sensitivity of the electrophotographic plates can be shifted into sitivity increased by the addition of dyes, to such an ex-
  • the invention is further illustrated in the following specific examples, without being limited thereto:
  • Example I N,N,NN, tetrabenZyl-para-phenylene diamine was prepared and purified as follows: Potassium hydroxide was dissolved in ethanol. 76 grams of benzyl chloride and 10.8 grams of p-phenylenedia mine where mixed in a 500 ml. Erlenmeyer flask with the alcohol solution (containing 9 grams of KOH). The flask was heated on a steam :bath and a vigorous but controllable reaction took place. An additional 27 grams of KOH in ethanol was added over a -minute period, along with enough extra ethanol to keep the system mobile. The reaction product was crystallized after A of an hour by cooling and adding water.
  • the crystals were filtered and washed thoroughly with water and 3060 petroleum ether, which removed large amounts of blackish material.
  • the washed crystals were dried, dissolved in chloroform and decolorized with carbon black, followed by filtration through a Celite filter pad.
  • the solution was then heated and ethanol was added to precipitate the compound as white needles (M.P. 145.5l46.0 C.).
  • the first crop was 36.3 grams, a 77.6% yield (theoretical yield was 46.8 grams).
  • a coating composition is prepared by mixing 1 part by weight of the TSPD compound, 0.0007 part by weight of a sensitizing dye such as Rhodamine B Base; 3 parts by weight of a resinous binder such as Butvar B-76 (a polyvinyl butyral resin; Shawinigan Resins Corp.) and parts by Weight of CHCl as a solvent.
  • This coating solution is applied to a suitable paper or foil substrate for example, Silkote Offset, a high quality printing paper manufactured and sold by the S. D. Warren Paper Company.
  • the amount applied is 2-15 pounds (dry weight) per ream (500 sheets x 38"), preferably in the range of from 4-6 pounds.
  • the coated paper is either air dried or even dried to remove the solvent carrier.
  • the coated paper is either positively or negatively charged under a corona discharge and then exposed under a positive or negative transparency to a light source such as a 60-watt tungsten lamp. After this exposure, a dry electrostatically attractable resinous toner colored with a pigment such as carbon black is applied to the sheet. For best results this is done in reduced light area, preferably under red light. The toner thus applied adheres to the parts of the coating which have not been exposed to the light and a positive image appears. The imaged sheet is heated for a short period at l00130 C. to fuse the resin of the toner and fix the image.
  • N,N,N'N', tetra (4-chlorobenzyl)-p-phenylenediamine (M.P. 141.5-l43 C.) and N,N,NN' tetra (Z-chlorobenzyl)-p-phenylenediamine (M.P. l42145 C.) have been similarily prepared and applied.
  • the electrophotographic plates based thereon performed equally as well.
  • Example 11 Another suitable coating composition is:
  • the images can be used as master copies for any sort of lithographic duplicating process, provided the non-imaged areas are treated to make them ink repellent and water receptive.
  • a sheet of paper which has been prepared to have a hydrophilic surface, e.g., a surface coating composed of titanium dioxide, carboxymethylhydroxyethyl cellulose or similar water soluble cellulose derivative, and melamine formaldehyde resin (see US. Patents 2,778,735 and 2,778,301) is coated with a solution consisting of 1 g.
  • the sheet is dried, then charged and imaged in the above manner and fused at -160 C.
  • the surface of the sheet is washed with methanol, ethanol, isopropanol, or mixtures of same, thereby exposing again the hydrophilic surface in all areas but the hydrophobic imaged areas.
  • the sheet thus formed maybe used in any type of hydrophilic-hydrophobic lithographic duplicating process.
  • the TSPD compounds are unusual in that they are white while still having good electrophotoconductive properties. Many other photoconductive compounds are colored because of chromophoric groups.
  • An electrophot-ographic plate comprising a photoconductive insulating layer on a relatively more conductive support, the photoconductive layer containing a N,N,N'N' tetra-substituted-p-phenylenediamine containing at least one benzyl group each in the N, and N position with the remaining two substituent groups being selected from the group consisting of benzyl radicals and alkyl radicals.
  • the electrophotographic plate of claim 1 wherein said phenylenediamine is N,-N' dialkyl, N,N dibenzyl pphenylene diamine, the alkyl groups of which contain in the range of 3 to 4 carbon atoms and are branche 6.
  • a process for preparing a copy which comprises electrostatically charging the electrophotographic plate of claim 1, exposing said plate to light pattern thereby relieving the electrostatic charge thereon in the background areas and leaving a latent image, toning the imaged areas with a tribe-electric powder and thereafter fusing said tribo-electric powder to fix said image.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US542620A 1965-03-23 1966-04-14 Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines Expired - Lifetime US3314788A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
NL134044D NL134044C (da) 1965-03-23
GB6671/65A GB1030220A (en) 1965-03-23 1965-02-16 Electrophotographic product
DEW38595A DE1290428B (de) 1965-03-23 1965-02-20 Photoleitfaehige Schicht mit einem organischen Photoleiter
NL6503044A NL6503044A (da) 1965-03-23 1965-03-10
FR9660A FR1428747A (fr) 1965-03-23 1965-03-18 Plaque électrophotographique
BE661438D BE661438A (da) 1965-03-23 1965-03-22
CH399465A CH436991A (fr) 1965-03-23 1965-03-23 Plaque électrophotographique
US542620A US3314788A (en) 1965-03-23 1966-04-14 Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines
JP4017866A JPS463712B1 (da) 1966-04-14 1966-06-22
GB28479/66A GB1079838A (en) 1965-03-23 1966-06-24 Electrophotographic product
DE19661572380 DE1572380B2 (de) 1965-03-23 1966-07-05 Fotoleitfaehige schicht mit einem benzylgruppenhaltigen phenylendiaminderivat und gegebenenfalls einem bindemittel
CH1129766A CH459762A (fr) 1965-03-23 1966-08-05 Plaque électrophotographique
FR74724A FR90786E (fr) 1965-03-23 1966-08-31 Plaque électrophotographique
NL666613040A NL153685B (nl) 1965-03-23 1966-09-15 Elektrografische plaat.
BE688034D BE688034A (da) 1965-03-23 1966-10-10

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35386965A 1965-03-23 1965-03-23
US542620A US3314788A (en) 1965-03-23 1966-04-14 Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines

Publications (1)

Publication Number Publication Date
US3314788A true US3314788A (en) 1967-04-18

Family

ID=26998122

Family Applications (1)

Application Number Title Priority Date Filing Date
US542620A Expired - Lifetime US3314788A (en) 1965-03-23 1966-04-14 Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines

Country Status (7)

Country Link
US (1) US3314788A (da)
BE (2) BE661438A (da)
CH (2) CH436991A (da)
DE (2) DE1290428B (da)
FR (2) FR1428747A (da)
GB (2) GB1030220A (da)
NL (3) NL6503044A (da)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624226A (en) * 1970-03-09 1971-11-30 Calgon Corp Electrographic organic photoconductor comprising of n,n,n{40 ,n{40 , tetrabenzyl 4,4{40 oxydianaline
US3767393A (en) * 1971-11-11 1973-10-23 Kodak Park Division Alkylaminoaromatic organic photoconductors
US3787208A (en) * 1970-09-25 1974-01-22 Xerox Corp Xerographic imaging member having photoconductive material in inter-locking continuous paths
US3909261A (en) * 1970-09-25 1975-09-30 Xerox Corp Xerographic imaging member having photoconductive material in interlocking continuous paths
EP0034425A2 (en) * 1980-02-04 1981-08-26 Xerox Corporation Process for preparing arylamines
US4728593A (en) * 1985-07-12 1988-03-01 E. I. Du Pont De Nemours And Company Photoconductive polyimide-electron donor charge transfer complexes
US4764625A (en) * 1980-12-12 1988-08-16 Xerox Corporation Process for preparing arylamines
US5059503A (en) * 1989-03-30 1991-10-22 Mita Industrial Co., Ltd. Electrophotosensitive material with combination of charge transfer materials
US5407767A (en) * 1993-02-12 1995-04-18 Fuji Electric Co., Ltd. Photoconductors for electrophotography with indole and benzidine compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0538195A3 (en) * 1991-10-18 1993-06-23 Ciba-Geigy Ag N-allyl/benzyl substituted phenylenediamine stabilizers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938922A (en) * 1958-01-17 1960-05-31 Monsanto Chemicals Nu-nitroso-nu-aryl arylenediamines
US3265496A (en) * 1961-12-29 1966-08-09 Eastman Kodak Co Photoconductive substances for electrophotography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938922A (en) * 1958-01-17 1960-05-31 Monsanto Chemicals Nu-nitroso-nu-aryl arylenediamines
US3265496A (en) * 1961-12-29 1966-08-09 Eastman Kodak Co Photoconductive substances for electrophotography

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624226A (en) * 1970-03-09 1971-11-30 Calgon Corp Electrographic organic photoconductor comprising of n,n,n{40 ,n{40 , tetrabenzyl 4,4{40 oxydianaline
US3787208A (en) * 1970-09-25 1974-01-22 Xerox Corp Xerographic imaging member having photoconductive material in inter-locking continuous paths
US3909261A (en) * 1970-09-25 1975-09-30 Xerox Corp Xerographic imaging member having photoconductive material in interlocking continuous paths
US3767393A (en) * 1971-11-11 1973-10-23 Kodak Park Division Alkylaminoaromatic organic photoconductors
EP0034425A2 (en) * 1980-02-04 1981-08-26 Xerox Corporation Process for preparing arylamines
EP0034425A3 (en) * 1980-02-04 1982-05-05 Xerox Corporation Process for preparing arylamines
US4764625A (en) * 1980-12-12 1988-08-16 Xerox Corporation Process for preparing arylamines
US4728593A (en) * 1985-07-12 1988-03-01 E. I. Du Pont De Nemours And Company Photoconductive polyimide-electron donor charge transfer complexes
US5059503A (en) * 1989-03-30 1991-10-22 Mita Industrial Co., Ltd. Electrophotosensitive material with combination of charge transfer materials
US5407767A (en) * 1993-02-12 1995-04-18 Fuji Electric Co., Ltd. Photoconductors for electrophotography with indole and benzidine compounds

Also Published As

Publication number Publication date
NL6613040A (da) 1967-10-16
NL134044C (da)
GB1079838A (en) 1967-08-16
NL153685B (nl) 1977-06-15
CH436991A (fr) 1967-05-31
DE1572380B2 (de) 1971-05-27
BE688034A (da) 1967-04-10
BE661438A (da) 1965-09-22
FR1428747A (fr) 1966-02-18
DE1572380A1 (de) 1970-08-06
CH459762A (fr) 1968-07-15
NL6503044A (da) 1965-09-24
FR90786E (fr) 1968-02-16
DE1290428B (de) 1969-03-06
GB1030220A (en) 1966-05-18

Similar Documents

Publication Publication Date Title
US3873312A (en) Photoconductive composition and elements containing a styryl amino group containing photoconductor
US3240597A (en) Photoconducting polymers for preparing electrophotographic materials
US3246983A (en) Electrophotographic reproduction process
US3331687A (en) Electrophotographic material
US3488705A (en) Thermally unstable organic acid salts of triarylmethane dyes as sensitizers for organic photoconductors
US3265496A (en) Photoconductive substances for electrophotography
US3066023A (en) Member for electrophotographic reproduction and process therefor
US3677752A (en) Bis(dialkylaminoaryl)ethylene photoconductors
US3314788A (en) Electrophotographic process and element comprising n, n, n,' n', tetrasubstituted-p-phenylenediamines
US3274000A (en) Electrophotographic material and method
US3290147A (en) Electrophotographic organic photoconductors
US3647433A (en) Dinitroarylmethine dyes as sensitizers in electrophotographic layers
US3206306A (en) Material for electrophotographic purposes
GB1588318A (en) Photoconductive composition
US3765884A (en) 1-substituted-2-indoline hydrazone photoconductors
US3655378A (en) Charge-transfer complexes of dibenzofuran-formaldehyde or dibenzothiophene-formaldehyde resins as photoconductive materials
GB1560496A (en) Photoconductive compositions
US3705913A (en) Electrophotographic sensitizers
US3784376A (en) Photoconductive element containing furans, indoles, or thiophenes
US4045220A (en) Low color photoconductive insulating compositions comprising nitrogen-free photoconductor and benzopyrilium sensitizer
US3647431A (en) Substituted bis(p-diakylaminophenyl) methane photoconductors
US3533787A (en) Photoconductive elements containing polymeric binders of nuclear substituted vinyl haloarylates
US3585026A (en) Treatment of background areas of developed electrophotographic elements with carboxy substituted triarylamine photoconductors with an alkaline medium to reduce opacity
US3653887A (en) Novel {60 ,{60 {40 -bis(aminobenzylidene) aryldiacetonitrile photoconductors
US3681068A (en) Organic photoconductors