US3850949A - Photosensitive material for electrophotography including indoline derivatives - Google Patents

Photosensitive material for electrophotography including indoline derivatives Download PDF

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Publication number
US3850949A
US3850949A US00187190A US18719071A US3850949A US 3850949 A US3850949 A US 3850949A US 00187190 A US00187190 A US 00187190A US 18719071 A US18719071 A US 18719071A US 3850949 A US3850949 A US 3850949A
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United States
Prior art keywords
carbon atoms
alkyl
group
hydrogen atom
compound
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Expired - Lifetime
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US00187190A
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English (en)
Inventor
H Katsuyama
H Ono
S Watarai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US05/455,797 priority Critical patent/US3930851A/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
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
    • G03G5/065—Heterocyclic compounds containing two or more hetero rings in the same ring system containing three relevant rings

Definitions

  • An organic photoconductive material for electrophotography consisting essentially of indoline derivatives represented by the following general formula (A) wherein R is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms, nitro group, or alkylene chain having 1 to 3 carbon atoms, R is hydrogen atom, hydroxyl group, alltoxycarbonyl group having alkyl group having 1 to 4 carbon atoms, cyan or phenyl group, R is substituted phenyl group (where substituted group is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, or alkoxy group having 1 to 4 carbon atoms), alkylene chain having 1 to 3 carbon atoms or phenylene group, In is an integer 1 to 4.
  • This invention relates to an organic photoconductive material for electrophotography.
  • photoconductive materials applicable to electrophotography there are known inorganic substances such as selenium and zinc oxide, organic lower molecular compounds such as anthracene, chrysene and benzidine, and higher molecular compounds such as poly-N-vinylcarbazole, polyvinylnaphthalene and polyvinylanthracene.
  • This invention relates to an organic photoconductive material having a novel structure completely different from known materials, and provides a photosensitive material having as an essential component Z-substitutedmethylene-indoline derivatives represented by the following general formula (A):
  • R1 v H o-u wherein R is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxyl group having 1 to 4 carbon atoms, alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms, nitro group, or methylene chain having 1 to 3 carbon atoms, R is hydrogen atom, hydroxyl group, alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms, cyan or phenyl group, R is substituted phenyl group (wherein substituted group is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms or alkoxyl group having 1 to 4 carbon atoms), methylene chain having 1 to 3 carbon atoms or phenylene group, m is an integer from 1 to 4.
  • R is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxyl group having 1 to 4 carbon atoms, 'alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms or nitro group
  • R is hydrogen atom, hydroxyl group, alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms, cyan or phenyl group
  • R is hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, or alkoXyl group having 1 to 4 carbon atoms
  • R is direct bond of carbon atoms, methylene chain having 1 to 3 carbon atoms or phenylene group
  • In is an integer from 1 to 4, n is zero, an integer 1 or an integer 2, x is degree of polymerization.
  • Nitrile oxides are active intermediates produced by reacting hydroxam ic acid halides with bases and provide ring compounds by 1,3-dipolar cyclo add'ition to multiple bonds such as acetylene, nitrile, carbonyl, olefin and the like. Mechanism of these reactions is known as dipole ring formation reaction, and concerning it R. Huisgen wrote genera-l considerations in Angewandte Chemie, 75, 604 (1963).
  • a high polymer compound obtained by the reaction of 5,5 -methylenebis- 1,3 ,3-trimethyl-2-methylene-indoline) with dichloroglyoxime had a maximum absor-ption in ultraviolet absorption spectrum at 262 m and in NMR spectrum the high molecular compound had peaks at 5 value 1.24 (S), 137 (S), 2.66 (S), 3.01, 3.34, 3.67 (Transition type to A type from AB type) and multiplate ring protons (8H). The intensity ratio of these peaks was 6:6:4:2:6, and infrared absorption spectrum also agreed nearly with spectrum of the above mentioned mono-spiro-compound. From these data it is obvious that the high molecular compound of this invention has a structure containing spiro-(indoline 2,5 isoxazoline) as repetition unit.
  • coatings as light-sensitive layer are made by dissolving the compounds in organic solvents with highly insulating coating-forming resinous binders, applying the solutions to comparatively electroconductive supports and drying, if desired. It is also possible to add plasticizers and sensitizers thereby to improve the characters of coatings and to increase greatly the sensitivity.
  • coatings for use as a light-sensitive layer are made by dissolving the high molecular compounds in organic solvents without highly insulating coating-forming resinous binder, applying the solution to comparatively electroconductive supports and drying, if desired. It is also possible to add plasticizers and sensitizers thereby to improve the characteristics of the coatings and to increase greatly the sensitivity.
  • coating-forming resinous binders styrene-butadiene copolymers, polystyrenes, chlorinated rubbers, polyvinyl chlorides, vinyl chloride/vinyl acetate copolymers, polyvinylidene chloride, nitrocelluloses, polyvinyl acetates, polyvinylacetals, polyvinyl ethers, silicon resins, methacrylic resins, acrylic resins, phenol resins, alkyd resins, urea/aldehyde resins, etc. may be used, and as electroconductive supports, metallic plates, electroconductive papers, electroconductive plastic films, etc.
  • plasticizers chlorinated biphenyls, chlorinated paraflins, phosphate plasticizers, phthalate plasticizers, etc. may be used, and as sensitizers, conventional sensitizers such as tetracyanoethylene, tetracyanoquinodimethane,
  • chloranil, naphthoquinone, anthraquinone, Methylene Blucei, Crystal Violet and Malachite Green, etc. may be use It is preferred to suitably combine these materials and apply them on an electroconductive support to provide a dried coat of 2 to 20 microns in thickness.
  • organophotoconductive component is more than 25 percent of the total components of the coating, electrophotographically excellent characteristics are obtained.
  • the light-sensitive layer obtained by above-mentioned process is uniformly charged by corona discharge according to the conventional method of electrophotography, and after image-exposure is developed by cascade development, liquid development, etc.
  • cascade development it may be fixed by weakly heating after development or by standing in solvent-vapor capable of dissolving the resin of toner.
  • EXAMPLE 1 Half a gram of compound No. 1 in Table 1 and 20 ml. of 10% polystyrene solution in tetrahydrofuran were blended uniformly, the resulting solution was applied to an aluminum plate support to provide a dried coating of 0.5 micron in thickness.
  • EXAMPLE 4 Compounds No. in Table 3 was applied and dried as described in Example 1. After exposure for about 1 second similar treatments were repeated and a clear positive image was obtained.
  • EXAMPLE 5 Half a gram of compound No. 21 in Table 4 was dissolved in 3 ml. of tetrahydrofuran, then the solution was applied to an aluminum plate to provide a dried coating of 5 microns in thickness. This test plate was exposed for about 1 second as described in Example, and by treating as in Example 1 a clear positive image was obtained.
  • EXAMPLE 6 A similar test plate as in Example 5 was charged with positive electricity in a dark place, and a positive image film was placed upon it; then they were exposed with 100 W. tungsten lamp (Toshiba lamp) from 30 cm. in height and then by treating as described in Example 1 a clear positive image was obtained.
  • tungsten lamp Toshiba lamp
  • EXAMPLE 7 Half a gram of Compound 23 in Table 4 was dissolved in 4 ml. of tetrahydrofuran. After separation of a small amount of insoluble substances, the solution was applied as described in Example 5 and the test plate was exposed for about 3 seconds as in Example 6. Further treatments as described in Example 1 gave a clear image.
  • EXAMPLE 8 A test plate of Example 7 was charged with electricity in a dark place and overlaid with a positive image film, then they were exposed with a diazotype duplicator (for instance Recopy-standard) at full reproduction speed (for instance in the case of Recopy-standard, the dial was set at 'Recopy-standard is a diazo-type wet copying machine equipped with a mercury lamp and manufactured by Ricoh Kabushiki Kaisha, Japan. Further treatments as described in Example 1 gave a clear image.
  • a diazotype duplicator for instance Recopy-standard
  • the dial was set at 'Recopy-standard is a diazo-type wet copying machine equipped with a mercury lamp and manufactured by Ricoh Kabushiki Kaisha, Japan. Further treatments as described in Example 1 gave a clear image.
  • Example 9 To the solution of Example 7 was added 0.001 g. of chloranil, and similarly in Example 7 the solution was ap plied and the test plate was exposed, developed and fixed. When the exposure time was less than even 1 second, a clear image was obtained.
  • R is hydrogen atom, halogen atom, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,
  • R is hydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms, cyan or phenyl
  • R is hydrogen atom, halogen atom, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms
  • m is an integer from 1 to 4
  • n is zero, an integer 1 or an integer 2.
  • R1 R1 0N N-O wherein R is hydrogen atom, halogen atom, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms or nitro, R is hydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms, cyan or phenyl, R is direct bond of carbon atoms, alkylene chain having 1 to 3 carbon atoms or phenylene, and m is an integer from 1 to 4.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US00187190A 1970-10-06 1971-10-06 Photosensitive material for electrophotography including indoline derivatives Expired - Lifetime US3850949A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/455,797 US3930851A (en) 1971-10-06 1974-03-28 Electrophotographic process using methylene indoline photoconductive derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45087788A JPS4917534B1 (enrdf_load_stackoverflow) 1970-10-06 1970-10-06

Related Child Applications (1)

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US05/455,797 Continuation-In-Part US3930851A (en) 1971-10-06 1974-03-28 Electrophotographic process using methylene indoline photoconductive derivatives

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US (1) US3850949A (enrdf_load_stackoverflow)
JP (1) JPS4917534B1 (enrdf_load_stackoverflow)
DE (1) DE2149714B2 (enrdf_load_stackoverflow)
FR (1) FR2111006A5 (enrdf_load_stackoverflow)
GB (1) GB1368079A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923824A (en) * 1970-10-01 1975-12-02 Fuji Photo Film Co Ltd Spiro (indoline-2,5-isoxazoline) compounds
DE2541665A1 (de) * 1974-09-18 1976-04-08 Matsushita Electric Ind Co Ltd Farbaendernde verbindungen und ihre verwendung
US4139274A (en) * 1974-09-18 1979-02-13 Matsushita Electric Industrial Co., Ltd. Apparatus for changing color
EP0337547A1 (en) * 1988-04-11 1989-10-18 Merck Sharp & Dohme Ltd. Spirocyclic compounds incorporating five-membered rings with two heteroatoms
US5534520A (en) * 1990-04-10 1996-07-09 Fisher; Abraham Spiro compounds containing five-membered rings
US5852029A (en) * 1990-04-10 1998-12-22 Israel Institute For Biological Research Aza spiro compounds acting on the cholinergic system with muscarinic agonist activity

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923824A (en) * 1970-10-01 1975-12-02 Fuji Photo Film Co Ltd Spiro (indoline-2,5-isoxazoline) compounds
DE2541665A1 (de) * 1974-09-18 1976-04-08 Matsushita Electric Ind Co Ltd Farbaendernde verbindungen und ihre verwendung
US4139274A (en) * 1974-09-18 1979-02-13 Matsushita Electric Industrial Co., Ltd. Apparatus for changing color
EP0337547A1 (en) * 1988-04-11 1989-10-18 Merck Sharp & Dohme Ltd. Spirocyclic compounds incorporating five-membered rings with two heteroatoms
US5534520A (en) * 1990-04-10 1996-07-09 Fisher; Abraham Spiro compounds containing five-membered rings
US5852029A (en) * 1990-04-10 1998-12-22 Israel Institute For Biological Research Aza spiro compounds acting on the cholinergic system with muscarinic agonist activity

Also Published As

Publication number Publication date
DE2149714A1 (de) 1972-04-13
DE2149714C3 (enrdf_load_stackoverflow) 1974-11-14
JPS4917534B1 (enrdf_load_stackoverflow) 1974-05-01
FR2111006A5 (enrdf_load_stackoverflow) 1972-06-02
GB1368079A (en) 1974-09-25
DE2149714B2 (de) 1974-04-18

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